HHC HC Donchuc Dchuc t1

B Y t
V khoa hc v o to

Hp cht hu c n chc v a chc
(Sch dng o to dc s i hc)
M s: .20.Y.13
Tp I

Nh xut bn Y hc
H ni - 2006
1

Ch bin:
PGS. TS. Trng Th K
Tham gia bin son:
ThS. Nguyn Anh Tun
TS. Phm Khnh Phong Lan
ThS. Th Thu
PGS. TS. ng Vn Tnh
ThS. Trng Ngc Tuyn
Tham gia t chc bn tho
TS. Nguyn Mnh Pha
ThS. Ph Vn Thm

Bn quyn thuc B Y t (V khoa hc v o to)

2
Li gii thiu
Thc hin Ngh nh 43/2000/N-CP ngy 30/08/2000 ca Chnh ph quy
nh chi tit v hng dn trin khai Lut Gio dc, B Gio dc v o to v
B Y t ph duyt, ban hnh cc chng trnh khung cho o to Dc s i
hc. B Y t t chc thm nh sch v ti liu dy hc cc mn hc c s v
chuyn mn theo chng trnh mi nhm tng bc xy dng b sch chun trong
cng tc o to Dc s i hc ngnh Y t.
B sch Ho hu c c bin son theo chng trnh o to mn Ho hc
hu c thuc chng trnh gio dc ca i hc Y Dc thnh ph H Ch Minh
trn c s chng trnh khung c B Gio dc v o to, B Y t ph duyt.
Ni dung b sch ch cp nhng kin thc l thuyt v ho hu c, gm
40 chng v chia lm 2 tp trnh by nhng kin thc c bn v danh php, cu
trc, c ch phn ng, tnh cht l hc v tnh cht ho hc ca cc hp cht
hydrocarbon, cc hp cht n chc, cc hp cht a chc, hp cht tp chc, hp
cht thin nhin v hp cht cao phn t.
i tng s dng chnh ca b sch ny l cc sinh vin ang theo hc ti
Trng i hc Dc khoa Dc cc trng i hc ngnh Y t. ng thi cng
l ti liu tham kho tt cho nhng hc vin sau i hc.
Sch c bin son da theo chng trnh c B Y t ban hnh. Ni
dung sch ch cp nhng kin thc l thuyt v Ho hu c.
Sch Ho hu c c cc ging vin giu kinh nghim ca Khoa Dc - i
hc Y Dc Thnh ph H Ch Minh bin son. Sch c Hi ng chuyn
mn thm nh sch gio khoa v ti liu dy hc chuyn ngnh Dc ca B Y
t thm nh v c B Y t ban hnh lm ti liu dy hc chnh thc dng
o to dc s i hc ca Ngnh Y t trong giai on hin nay. Trong thi gian
t 3 n 5 nm, sch cn c chnh l, b sung v cp nht.
V Khoa hc v o to, B Y t xin chn thnh cm n Khoa Dc - i
hc Y Dc Thnh ph H Ch Minh cng cc tc gi b nhiu cng sc
bin son cun sch ny. V l ln u xut bn nn chc chn cn nhiu thiu
st, chng ti mong nhn c kin ng gp ca ng nghip v bn c
cun sch ngy cng hon thin.

V khoa hc v o to
B Y t

3
4
MC LC

Li gii thiu 3
M u 9
Chng1: Cu trc in t ca nguyn t carbon v s to thnh
cc lin kt trong hp cht hu c 11
ThS. Nguyn Anh Tun
1. Cu trc in t (electron) ca nguyn t carbon 11
2. S to thnh cc lin kt 13
Chng 2: Cc hiu ng in t trong ha hu c 22
ThS. Nguyn Anh Tun
1. Hiu ng cm ng 22
2. Hiu ng lin hp (cng hng) 25
3. Hiu ng siu lin hp (Hyperconjugate effeet) 29
Chng 3: Cu trc phn t hp cht hu c. ng phn v cu dng
ThS. Nguyn Anh Tun
1. ng phn phng 31
2. ng phn lp th - ng phn khng gian 33
Chng 4: Khi nim acid -base trong ha hu c 49
ThS. Nguyn Anh Tun
1. Khi nim acid -base theo Bronsted-Lowry (1923) 49
2. Khi nim acid -base theo Lewis (1923) 51
3. Hng s cn bng acid base 51
4. Yu t nh hng n tnh acid -base ca cht hu c 53
Chng 5: Cc loi phn ng trong ha hu c v khi nim v c ch phn ng 54
ThS. Nguyn Anh Tun
1. Cc loi phn ng trong ha hu c 54
2. Khi nim v c ch phn ng 57
Chng 6: Cc phng php ha hc v vt l xc nh cu to hp cht hu c 67
ThS. Nguyn Anh Tun
1. Phng php ha hc 67
2. Phng php vt l 68
Chng 7: Alkan - Hydrocarbon no
ThS. Th Thy
1. Ngun gc thin nhin - Cu to, ng phn, cu dng 82
5
2. Danh php 85
3. Phng php iu ch alkan 86
4. Tnh cht l hc 88
5. Tnh cht ha hc 89
6. Cht in hnh 93
Chng 8: Cycloalkan
ThS. Th Thy
1. Monocycloalkan 95
2. Hp cht a vng 100
Chng 9: Alken - Hydrocarbon etylenic 102
ThS. Th Thy
1. Cu to ca alken 102
2. ng phn 102
3. Danh php 104
4. Phng php iu ch 105
5. Tnh cht l hc 109
6. Tnh cht ha hc 110
7. Cht in hnh 118
Chng 10: Alkyn - Hydrocarbon acetylenic 120
ThS. Th Thy
1. Cu trc in t 120
2. Danh php v ng phn 121
4. Tnh cht l hc 123
6. Cht in hnh 127
Chng 11: Aren - Hydrocarbon thm 129
PGS. TS. ng Vn Tnh
1. Benzen v nhn thm 129
2. Danh php v ng phn 132
4. Tnh cht l hc 134
Chng 12: Hydrocarbon a nhn thm 150
PGSTS. ng Vn Tnh
1. Cu to v danh php 150
2. Biphenyl 151
3. Biphenylmetan v triphenylmetan 153
4. Naphtalen 154
5. Anthracen 155
6. Phenanthren 156
6
Chng13: H thng lin hp v alkadien 158
PGS. TS. ng Vn Tnh
1. H thng allylic 158
2. Dien 161
3. H thng lin hp bc cao 164
4. Phn ng Diels Alder 165
Chng 14: Dn xut halogen 168
ThS. Trng Ngc Tuyn
1. Danh php 168
2. ng phn 169
4. Tnh cht l hc 173
Chng 15: Hp cht c kim 181
ThS. Trng Ngc Tuyn
1. Cu to 181
2. Danh php 181
3.Tnh cht l hc 182
4. Phng php iu ch cc hp cht c kim 182
5. Cc phn ng ca hp cht c kim 184
Chng 16: Alcol 189
ThS. Trng Ngc Tuyn
1. Monoalcol 189
2. Alcol cha no 200
3. Alcol vng 201
4. Polyalcol alcohol a chc 201
Chng 17: Phenol 207
ThS. Trng Ngc Tuyn
1. Monophenol 207
2. Polyphenol 215
Chng 18: Ether 219
ThS. Trng Ngc Tuyn
1. Ether mch h 219
2. Ether vng 223
Chng 19: Aldehyd , Ceton v Quinon 224
ThS. Nguyn Anh Tun
1. Aldehyd v ceton 224
2. Aldehyd - ceton cha no 245
7
3. Aldehyd - ceton a chc 250
4. Quinon 253
Chng 20: Acid carboxylic 257
ThS. Nguyn Anh Tun
1. Cu to 257
2. Danh php 258
4. Tnh cht l hc 261
6. Acid carboxylic cha no 268
7. Acid a chc polyacid 270
Chng 21: Cc dn xut ca acid carboxylic 273
ThS. Nguyn Anh Tun
1. Ester 274
2. Anhydrid acid 279
3. Ceten 280
4. Halogenid acid - acyl halogenid 281
5. Amid 283
6. Nitril 285
Chng 22: Amin 288
1. Cu to 288
2. Danh php 289
3. iu ch 290
4. Tnh cht l hc 292
5. Tnh base ca amin 292
6. Cc phn ng ca amin 295
7. Amin cha no c mt lin kt i Enamin 300
8. Amin a chc - polyamin 301
Chng 23: Cc hp cht khc cha nit 303
1. Hp cht nitro 303
2. Isocyanat, carbamat v ure 306
3. Hp cht diazo v mui diazoni 308
Chng 24: Hp cht c lu hunh v phosphor 313
ThS. Th Thy
1. Hp cht hu c c lu hunh 313
2. Hp cht cha phosphor 317
Ti liu tham kho 319
8
M U
i tng ca ha hc hu c:
Ha hc hu c l mn khoa hc nghin cu thnh phn v tnh cht cc
hp cht ca carbon.
Trong thnh phn hp cht hu c, ngoi carbon cn c nhiu nguyn t
khc nh H, O, N, S, P, halogen... nhng carbon c xem l nguyn t c bn cu
to nn hp cht hu c.
S lc lch s pht trin ca Ha hc hu c
T xa xa ngi ta bit iu ch v s dng mt s cht hu c trong
i sng nh gim (acid acetic long), ru (ethanol), mt s cht mu hu c.
Thi k gi kim thut cc nh ha hc iu ch c mt s cht hu c nh
ur, ether etylic...
Cui th k 18 u th k 19, cc nh ha hc chit tch t ng, thc
vt nhiu acid hu c nh acid oxalic, acid citric, acid lactic ... v mt s base hu
c (alcaloid). Nm 1806 ln u tin nh ha hc ngi Thy in Berzelius
dng danh t Ha hc hu c ch ngnh ha hc nghin cu cc hp cht c
ngun gc ng vt v thc vt. Thi im ny c th xem nh ct mc nh du
s ra i ca mn ha hc hu c.
Nm 1815 Berzelius a ra thuyt Lc sng cho rng cc hp cht hu c
ch c th c to ra trong c th ng vt v thc vt nh mt lc sng ch
con ngi khng th iu ch c. Thuyt duy tm ny tn ti trong nhiu nm
nhng dn dn b nh bi cc cng trnh tng hp cc cht hu c t cc cht
v c.
Nm 1824, nh ha hc ngi c Wohler tng hp c acid oxalic bng
cch thy phn dixian l mt cht v c. Nm 1828 cng chnh ng, t cht v c
amoni cyanat tng hp c ur. Tip theo Bertholet (Php) tng hp c
cht bo nm 1854 v Bulerov (Nga) tng hp ng glucose t formalin nm
1861.
Cho n nay hng triu cht hu c c tng hp trong phng th
nghim v trn quy m cng nghip. Con ngi khng ch bt chc tng hp cc
cht ging thin nhin m cn sng to ra nhiu cht hu c, nhiu vt liu hu
c cc k quan trng v qu gi m t nhin khng c.
Tuy nhin tn gi hp cht hu c vn c duy tr, nhng khng phi ch
vi ngha l cc cht c ngun gc ng vt v thc vt m mang ni dung mi:
l cc hp cht ca carbon.

9
c im ca cc hp cht hu c v phn ng hu c
Mc d ra i mun hn ha hc v c nhng cc hp cht hu c rt phong
ph v s lng, chng loi. S lng cht hu c cho n nay nhiu gp vi chc
ln cc cht v c bit. Nguyn nhn c bn l do carbon c kh nng to
thnh mch di v tn theo nhiu kiu khc nhau. Ni cch khc hin tng ng
phn (tc l cc cht c cng thnh phn phn t nhng khc nhau v cu to) l
cc k ph bin v c trng trong ha hc hu c.
Cu trc phn t ca hp cht hu c c th n gin nhng cng c th rt
phc tp, vic xc nh cu trc ca chng nhiu khi rt kh khn, phi s dng
nhiu phng php ha hc v vt l hc hin i.
Nu nh lin kt ion kh ph bin trong hp cht v c th lin kt ch
yu gia cc nguyn t trong phn t hu c li l lin kt cng ha tr. c
im ny nh hng nhiu n tnh cht l ha v c bit l kh nng phn
ng ca chng.
Cc phn ng hu c thng xy ra vi tc chm, khng hon ton v
thng theo nhiu hng khc nhau, v vy vai tr ca nhit ng hc, ng hc
v xc tc trong ha hu c rt quan trng.
Vai tr ca ha hc hu c
Cc cht hu c c vai tr rt quan trng trong i sng ca con ngi.
Khng nhng hu ht thc phm chng ta n (glucid, protid, lipid), vt dng
hng ngy (cellulose, si tng hp, cao su, cht do . . .) l cc cht hu c m
nhiu cht hu c cn l c s ca s sng (protid, acid nucleic..). Nhin liu cho
ng c t trong, cho nh my nh xng, du l hn hp hydrocarbon mch di
ngn khc nhau. Cc vt liu hu c nh, khng han g, tin s dng, nhiu mu
sc a dng ang ngy mt thay th cho cc kim loi, hp kim trong nhiu lnh
vc, k c nhng lnh vc tng nh khng th thay th c nh bn dn, siu
dn. . .
Do tt c nhng c im trn, ha hc hu c c tch ra nh mt ngnh
khoa hc ring i hi nhng phng php nghin cu v thit b ngy cng hin
i hn, i hi n lc khng ngng ca cc nh ha hc khng nhng bt
chc thin nhin tng hp nn cc cht phc tp phc v cho nhiu lnh vc ca
cuc sng m cn vt xa hn c thin nhin. T c s ha hc hu c, c rt
nhiu ngnh nghin cu ng dng ra i: ha cng nghip, ha du, cng nghip
dt, ha thc phm, dc phm v ha m phm.

10
Chng 1
CU TRC in t CA NGUYN T CARBON
V S TO THNH CC LIN KT TRONG HP CHT HU C
Mc tiu
1. Trnh by c cu to in t carbon cc trng thi lai ha sp
3
, sp
2
v sp.
2. Gii thch c cch hnh thnh cc loi lin kt:
Cng ha tr
Lin kt phi tr
Lin kt hydro
Ni dung
1. Cu trc in t (electron) ca nguyn t carbon
1.1. Thuyt carbon t din (Vant Hoff- Le Bel 1874)
Nguyn t carbon c 4 ha tr. Bn ha tr ca carbon hng ra bn nh ca
mt t din. Tm ca t din l nguyn t carbon.

C

109
o
28'
CC
109
o
28'

Cc gc ha tr tm u bng nhau v bng 10928'. Khi nguyn t carbon
lin kt vi 4 nguyn t hoc 4 nhm th ng nht ta c mt t din u.
1.2. Cu trc in t ca nguyn t carbon
1.2.1. Carbon trng thi c bn
Carbon c c cu hnh in t C
1S
2
2S
2
2p
x
2p
y
1 1
1S
2
2S
2
2p
2

1s
2
2s
2
2p
2

2 in t n c l p
x
v p
y
. Cn c mt orbital 2p
z
trng khng c in t
1.2.2. Carbon trng thi kch thch C
*
1 1
1S
2
2S

2p
x
2p
y
2p
z
1
1S
2
2S
1
2p
3
1

11
Carbon hp thu nng lng 60-70 kcal/mol, mt in t 2s
2
chuyn ln trng
thi 2p (orbital 2p
z
).
1s
2
2s 2s
2
2p
2
1s
2
C 1s
2
2s
2
2p
2
C 1s
2
2s
1
2p
3
2p
x
2p
y
2p
z

Carbon c cu hnh in t 1s
2
2s
1
2p
3
l carbon kch thch (1s
2
2s
1
2p
x
2p
y
2p
z
).
Kt qu l carbon c 4 in t n c to lin kt. Carbon lun c ha tr 4.
Bn in t ca carbon kch thch c nng lng khc nhau do cc lin kt ca
carbon phi khc nhau. Thc t phn t metan c 4 lin kt C
_
H hon ton ging
nhau .
1.2.3. Carbon trng thi lai ha
Khi to thnh cc lin kt, orbital 2s v mt s orbital 2p c th t hp li
to thnh nhng orbital c dng khc cc orbital ban u v c kh nng xen ph
cao hn do lin kt c hnh thnh cng bn hn. S t hp c gi l s
lai ha.
Lai ha sp
3

Kiu lai ha th nht gi l lai ho sp
3

(cn gi l lai ha t din).
Mt orbital 2s v 3 orbital p t hp vi nhau to thnh 4 orbital lai ha sp
3
.
S to hp 2s va 2p Orbital lai hoa sp
Carbon lai hoa sp3

t hp 2s v 2p bital lai ho sp
Carbon lai ho sp
3
Or S
Cc kt qu tnh ton cho thy rng nu xem kh nng xen ph ca orbital
s l 1 th ca orbital p l 3 v ca orbital sp
3
l 2.
2 1 3

Lai ha sp
2
.
S t hp orbital 2s vi 2 orbital 2p (2p
x
, 2p
y
)
to thnh 3 orbital lai ha sp
2

hay cn gi l lai ha tam gic. Trc i xng ca 3 orbital sp
2
nm trong mt
mt phng v to nn nhng gc 120. Kh nng xen ph tng i ca orbital
sp
2
l 1,99.
12
120
o P
z
S to hp 2s va 2p khong lai ho Carbon lai hoa 2sp
2
Orbital 2p
z

Orbital 2pz khng lai ho Carbon lai ho 2sp
2
S t hp 2s v 2p
Nh vy trn carbon lai ha sp
2
cn c mt in t trn orbital 2p
z
khng lai
ha. Orbital ny c dng hnh khi s 8 ni .
Lai ha sp
T hp mt orbital s v mt orbital 2p
x
to thnh 2 orbital lai ha sp vi kh
nng xen ph tng i 1, 93 v gc to bi trc i xng ca 2 orbital l 180
o
hay
cn

gi l lai ha ng thng.
Trn carbon lai ha sp cn c 2 in t p khng tham gia lai ha 2py v 2pz

S to hp 2s va 2p
Orbital lai hoa sp 2 Orbital 2p
y
va 2p
z

S t hp 2s v 2p Orbital lai ho sp
2 Orbital 2p
y
v 2p
z
S lai ha gia orbital s v p cng xy ra trong cc nguyn t oxy, nit ...
2. S to thnh cc lin kt
2.1. S to thnh lin kt cng ha tr - Lin kt v lin kt
Lin kt c to thnh do s xen ph cc i ca cc orbital nguyn t
thnh orbital phn t. Khi vng xen ph ca cc orbital nguyn t cng ln th
lin kt (orbital phn t) c to thnh cng bn v nng lng thot ra khi
hnh thnh lin kt cng ln. Khuynh hng ca s xen ph l tin ti cc i,
l ni dung ca nguyn l xen ph cc i .
Cc orbital nguyn t tng tc c hiu qu vi nhau thnh orbital
phn t chng phi tha mn 3 iu kin:
Nng lng ca chng gn nhau .
S xen ph mc ln.
Chng phi c cng mt kiu i xng i vi trc ni hai ht nhn nguyn t.
Nh vy 2 orbital s, hoc 1 orbital s v 1 orbital p no c trc i xng trng
vi trc ni 2 ht nhn c th tham gia xen ph nhau thnh orbital phn t.
13
Ty theo c im i xng ca cc orbital nguyn t, s xen ph ca chng
c th theo trc hay bn trc ni gia 2 nguyn t.
S xen ph theo trc orbital to lin kt .
S xen ph bn xy ra s to thnh lin kt .
Xen ph trc - To lin kt
Orbital s
Lin kt
Orbital s Orbital p Lin kt
Orbital p
Orbital p Lin kt

Xen ph bn - To lin kt
Orbital p Orbital p Lien ket
+

2.2. Lin kt v lin kt trong cc hp cht hu c
2.2.1. Trong cc hp cht hu c lin kt to thnh do s xen ph
Orbital s ca nguyn t hydro vi cc orbital lai ha ca carbon sp
3
, sp
2
, sp.
Orbital lai ha ca carbon xen ph vi nhau.
Orbital lai ha s v p ca nguyn t oxy hoc ca nit vi orbital s ca hydro
hoc vi cc orbital lai ha ca carbon sp
3
,

sp
2
, sp trong cc hp cht c lin
kt O-H hoc C-O v trong cc hp cht c lin kt N-H hoc C-N.
2.2.2. Lin kt c to thnh do s xen ph
Orbital P
y
hoc P
z
ca cc nguyn t carbon xen ph vi nhau tng i mt
to thnh lin kt trong C=C hoc trong C C.
Orbital p ca nguyn t oxy, nit xen ph vi orbital p ca nguyn t carbon
to thnh lin kt trong C=O hoc trong C =N, CN.
V d:
S to thnh lin kt trong cc hp cht etan, ethylen, acetylen, alcol
ethylic c th c minh ha nh sau:
14
Cac lien ket
trong phan t etan
H-C-C-H
H H
H H

Cc lin kt trong
phn t etan
Cac lien ket

trong phan t etylen
C

C
H
H
H
H
Cc lin kt trong phn

t ethylen

Cac lien ket
trong phan t acetylen
C C H H
Cc lin kt trong
phn t acetylen

c-c
c-o
o-H
C C
H
H
H
H
H
O H
Cac lien ket
trong phan t
alccol etylic
Cc lin kt trong
phn t alcol ethylic

S to thnh lin kt trong phn t ethylen, acetylen c th minh ha nh sau:
Lin kt trong ethylen c to thnh do s xen ph cc i v 2 pha ca
cc orbital P
z
khng lai ha. Lin kt (orbital phn t ) nm trong mt phng
thng gc vi mt phng cha cc nguyn t C v H.
H H
H H
Lien ket
trong etylen
H
H
H
H

Lin kt
en trong ethyl
Hai lin kt trong acetylen c to thnh do s xen ph cc i v 2 pha
ca cc orbital p
y
v p
z
tng ng. Cc orbital lin kt nm trong 2 mt phng
thng gc vi nhau.
H Cac lien ket

trong phan t acetylen
H H
H

Lin kt
n trong acetyle
15
S to thnh lin kt trong h thng alen C=C=C .
C
H
H

S to thnh lin kt trong h thng lin hp C =CC=C.
C
H
H

H thng lin hp thng thng v n gin l nhng h m hai lin kt
v mt lin kt (hoc mt cp in t cha s dng) phn b cnh nhau (lun
phin, tip cch).
CH
2
=CH
_
CH=CH
_
CH=O ; CH
2
=CH
_
CH=CH
_
CH =CH
_
OCCH
3
Trong h thng lin hp s xen ph bn ca cc orbital p to thnh mt
orbital phn t bao trm ln ton b phn t.

S to thnh cc lin kt v trong h thng lin hp lm cho di
lin kt ngn i v di ca lin kt di ra.
H thng lin hp thng c trong cc cht thuc loi hydrocarbon thm, d vng
thm. Cc lin kt trong h thng lin hp lun nm trong cng mt mt phng.
2.3. Tnh cht ca cc lin kt v
2.3.1. S phn cc ca lin kt
Khi phn t c dng A
_
A ng nht th phn t khng c s phn cc.
Ngha l cp in t lin kt hay l orbital phn t lin kt c phn b
u gia 2 nguyn t v momen lng cc ()bng khng.
V d: H
_
H ; Cl
_
Cl ; O=O ; CH
3
_
CH
3

; Cl
3
C
_
CCl
3

; CH
2
=CH
2

; HCCH .
Khi hai nguyn t lin kt vi nhau khng ng nht (phn t c dng
A
_
B) nh H
_
Cl, CH
3
_
Cl ... cp in t lin kt s lch v pha nguyn t c
m in ln hn. Do trng tm in dng v m khng trng nhau v
lin kt s c momen lng cc khc khng ( 0). l lin kt cng ha
tr phn cc.
S phn cc khng nhng xy ra cc lin kt m cn xy ra cc lin
kt (phn t c dng A =B hoc A B).
16
Trong cc phn t H
2
C =O v CH
3
_
CN, v.v .. c s phn cc ca lin kt .
ch s phn cc ca lin kt ngi ta dng mi tn thng ()v s
phn cc ca lin kt ngi ta dng mi tn cong ( ). Chiu chuyn dch ca
mi tn l chiu chuyn dch in t. Hoc dng k hiu
+
,
-
nhm biu th cc
phn in tch nh nhng nguyn t tham gia lin kt .

CH
3
Cl

;
CH
3
Cl
;
H
2
C=O

;
H
2
C=O

H
2
C==O

V d: hoc:
2.3.2. tan
Cc hp cht hu c c lin kt cng ha tr (l nhng lin kt c phn
cc khng ln) rt t hoc khng tan trong nc, tri li tan nhiu trong cc dung
mi hu c. Dung dch cc cht hu c thng l khng dn in.
Cc cht c lin kt ion d tan trong nc v khng hoc t tan trong dung
mi hu c, dung dch ca chng dn in.
2.3.3. di lin kt
Khong cch gia 2 ht nhn nguyn t lin kt thng gi theo quy c l
di lin kt. di lin kt c o bng cc phng php vt l hin i nh:
phng php nhiu x tia X, ntron, electron, phng php ph hng ngoi.
Ngi ta nhn thy rng:
di lin kt cng ha tr gia carbon v mt nguyn t khc trong cng mt
phn nhm ca h thng tun hon tng theo s th t ca nguyn t .
C
_
F < C
_
Cl < C
_
Br < C
_
I
di ca lin kt cng ha tr gia carbon v mt nguyn t khc trong cng
mt chu k gim khi s th t tng.
C
_
C > C
_
N > C
_
O > C
_
F
di ca lin kt cng ha tr gia 2 nguyn t cng gim nu s orbital
lin kt cng ln.
C
_
C > C= C > CC ; C
_
O > C=O > CO
C
_
N > C=N > C N ; N
_
N > N=N > NN
di lin kt gia carbon vi mt nguyn t khc ph thuc trng thi lai
ha ca carbon. T l orbital s trong orbital lai ha cng cao th di lin kt
cng ngn.
sp
C
__
H
sp
2
C
__
H
sp
3
C
__
H

17
2.3.4. Nng lng lin kt
Nng lng ca lin kt A
_
B l s nng lng thot ra khi hnh thnh lin
kt t 2 nguyn t hay 2 gc A v B. cng chnh l nng lng cn thit
lm t lin kt A
_
B thnh 2 nguyn t hay 2 gc A v B.
Bng 1.1: Nng lng lin kt (kcal/mol)
Lin kt Nng lng lin kt Lin kt Nng lng lin kt
H-H
F-F
Cl-Cl
Br-Br
I-I
N-N
N=N
NN
P-P
C-C
C=C
CC
Si-Si
O-H
N-H
104,2
36,4
58,0
46,1
36,1
38,4
100,0
226,0
51,3
83,1
147,2
194,0
42,2
110,6
93,6
C-H
C-F
C-Cl
C-Br
C-I
C-O
C=O
C
+
-O
C-N
C=N
CN
H-F
H-Cl
H-Br
H-I
98,8
105,4
78,5
65,9
57,4
84,0
171,0
255,8
69,7
147,0
213,0
134,6
103,2
87,5
71,5
Nng lng lin kt l gi tr trung bnh gn ng.
Khi dng khi nim nng lng lin kt c ngha l tt c cc lin kt
C
_
H trong phn t alkan u ging nhau (thc t nng lng ph thuc vo
cu to phn t). Qua bng 1-1 c th thy rng cc lin kt bi (i = ; ba )
khng c tnh cht bi v nng lng. Nng lng lin kt C =C v C C khng
ln gp i v gp 3 ln lin kt C
_
C. Tri li nng lng ca cc lin kt N =N
v N N li gp 3 v gp 6 ln nng lng lin kt N
_
N.
Trong cc phn t c h thng lin hp th gi tr sinh nhit ca n thp hn
tng gi tr nng lng lin kt ca cc lin kt c trong phn t c h thng
khng lin hp.
chnh lch gi l nng lng lin hp hoc nng lng cng hng ca
h thng lin hp.
Cn phn bit nng lng lin kt v nng lng phn ly.
Nng lng phn ly l nhng i lng c trng cho cc lin kt trong phn
t. Nng lng cn lm t lin kt CH th nht khng phi bng 1/4 nng
lng chung phn ct phn t metan thnh carbon v hydro, cng khng hon
ton bng nng lng ca mi lin kt CH trong cc phn t etan v benzen. Mi
lin kt trong phn t c mc nng lng phn ly khc nhau (bng 1-2).
18
Bng 1.2: Nng lng phn ly lin kt R-X (kcal/mol)
X
R
H Br I OH CH
3
R
CH
3
CH
3
CH
2
(CH
3
)
2
CH
(CH
3
)
3
C
C
6
H
5
C
6
H
5
CH
2
102
98
89
85
104
77,5
67
65
65
61
71
48
51
52
47
45
57
39
86,5
87,
84,5
85,
85,
85,
83
82
74
74
91
63
83
82
82
60
103
47
HO-OH --------------------------------- 52 (CH
3
)
2
C N = N C (CH
3
)
2
31

CN CN
C
6
H
5
COO-OCC
6
H
5
----------------- 30 (C
6
H
5
)
3
C N = N C(C
6
H
5
)
3
27

2.4. S to thnh lin kt yu hn lin kt cng ha tr
2.4.1. Lin kt hydro
Lin kt hydro c bn cht tnh in. Nng lng lin kt nh ( 5kcal/mol).
X
___
H
+
... Y
; X

H
+
... Y

iu kin hnh thnh lin kt hydro:
X c m in ln hn hydro sao cho X
__
H phn cc .
Y c cp in t t do e . Kch thc ca X v Y u khng ln .
X v Y thng l nhng nguyn t ph bin nh F, O, N . Trng hp Y l
Cl, S, lin kt th lin kt hydro to thnh s rt yu.
C hai loi lin kt hydro:
Lin kt hydro lin phn t
Lin kt hydro c to thnh gia cc phn t vi nhau.
Khi pha long hp cht c lin kt hydro lin phn t trong dung mi tr
(khng phn cc), lin kt hydro b ct t dn.
...
...
...
...
O
Et
H O
Et
H
O
Et
H
O
Et
H
...
...
O

O H
C
__
H
O

O H
H
__
C

Lin kt hydro ni phn t
Lin kt hydro c to thnh trong cng mt phn t.
Khi pha long hp cht c lin kt hydro ni phn t, lin kt hydro vn
c bo ton. hnh thnh lin kt hydro ni phn t ngoi cc iu kin
19
trn, XH v Y phi gn nhau sao cho khi to lin kt hydro s hnh thnh
nhng vng 5 hoc 6 cnh. Cc hp cht vng c nhm chc v tr 1, 2 thng d
hnh thnh lin kt hydro ni phn t.
.
.
.
C
O
OH
O
H
.
.
.
O
CH
2
CH
2

NH
2

H

2.4.2. nh hng ca lin kt hydro n tnh cht l -ha hc v sinh hc
S to thnh lin kt hydro nh hng n tnh cht ca hp cht hu c.
Nhit nng chy v nhit si
Lin kt hydro lin phn t lm tng nhit nng chy tc v tng nhit
si t
o
s nhng lin kt hydro ni phn t khng c nh hng ny.
V d. Hp cht nitrophenol c 3 ng phn th ng phn p-nitrophenol c lin
kt hydro lin phn t c t
o
c l 144C v t
o
c l 241C. ng phn o-nitrophenol (c
lin kt hydro ni t
o
c phn t) c t
o
c l 44C v t
o
s l 114C .
N O
O
OH N O
O
OH
...
N O
O
OH
...
...
N
O
O
O
H
.
.
.

Lin kt hydro gia cc phn t p -nitrophenol Lin kt hydro ni phn t
o -nitrophenol
tan
Cc cht c kh nng to lin kt hydro vi nc th rt d tan vo nc.
Lin kt hydro lin phn t gia cht tan v dung mi lm tng tan
trong dung mi phn cc. Lin kt hydro ni phn t lm tng tan trong dung
mi khng phn cc.
V d:
Alcol methanol, ethanol rt d tan trong nc.
p-nitrophenol tan c trong nc, cn o -nitrophenol khng tan trong nc.
V vy c th phn ring o -nitrophenol ra khi hn hp bng phng php ct li
cun hi nc.
bn ca phn t
S to thnh lin kt hydro ni phn t, c bit khi lin kt c kh nng
to vng, lm cho ng phn tr nn bn vng hn.
V d: Khi 1,2 -dicloethan dng anti bn vng hn dng syn th ethylenglycol
dng syn li bn hn dng anti. V syn-ethylenglycol c kh nng to lin kt
hydro ni phn t.
20
Anti-dicloetan
Syn-dicloetan Anti-ethylenglycol Syn-ethylenglycol

* Thut ng anti v syn s c trnh by chng ng phn.
nh hng n mt s tnh cht khc
Lin kt hydro lm thay i cc vch c trng trong quang ph hng ngoi (IR),
t ngoi (UV), cng hng t ht nhn (NMR), momen lng cc, di lin kt.
Lin kt hydro cng c tc dng lm thay i s tng tc ca cc cht
trong qu trnh chuyn ha sinh hc trong c th ng vt v thc vt.
2.4.3. Lin kt trong phc chuyn in tch
Phc chuyn in tch to thnh do s chuyn dch mt phn mt in t
t phn t cho in t sang phn t hay ion nhn in t. Phc chuyn in tch
do s chuyn dch mt in t gi l phc .
CH
3
NO
2
O
2
N N
2
O
Phn t nhn

Phc to thnh gia
toluen v trinitrobenzen
Lin kt trong phc chuyn in tch l lin kt yu. Khong cch gia 2
hp phn vo khong 3 - 3,5 ln hn nhiu so vi lin kt cng ha tr. Phc
chuyn in tch c s thay i v phn cc v mu sc ca cc cht ban u.
Bi tp
1. V m hnh orbital nguyn t trng thi xen ph cho cc hp cht sau:
a- Propan, propylen, methylacetylen, ceten (HC
2
=C=O).
b- Cyclobutan, Cyclopentan, Cyclohexan.
c- 1,3-Butadien
2. Hy trnh by mt s nh ngha:
a- Th no l lin kt cng ha tr, lin kt hydro ?
b- Th no l nng lng lin kt v nng lng phn ly, nng lng cng hng ?
3. Trong hn hp phenol - methanol c bao nhiu "dng" lin kt hydro.
Dng no bn nht ? Dng no km bn nht ? Ti sao ?
4. Alcol v ether, cht no d tan trong nc hn. Gii thch ?
21
Chng 2
Cc HIU NG IN T TRONG HA HU C
Mc tiu
1. Nu c cc loi hiu ng cm ng, hiu ng lin hp, hiu ng siu lin
hp v tnh cht ca chng.
2. Bit c mt s ng dng ca cc hiu ng trn.
Ni dung
Mt in t trong lin kt cng ha tr thng c phn b khng ng
u gia 2 nguyn t ca lin kt, khi y phn t cht hu c b phn cc. S
phn cc c th xy ra ngay trng thi tnh hoc cng c th ch xut hin
nht thi trng thi ng (khi phn t b tc ng bi cc yu t ca mi
trng). Bn cht ca s phn cc khc nhau cn tu thuc vo cu to phn t
(phn t c h thng lin kt nh th no). Nh vy cu to phn t c nh
hng n s phn b mt in t. nh hng gi l hiu ng in t
trong phn t.
C cc loi hiu ng:
Hiu ng cm ng I
Hiu ng lin hp C, M
Hiu ng siu lin hp H
1. Hiu ng cm ng (Inductive effect): K hiu l I
Kho st phn t n -propan C
3
H
8
v phn t n-propylclorid C
3
H
7
Cl
C C C H
H H
H
H
H H H
3 1 2
n-propan

C C C Cl
H H
H
H
H H H
1 2 3
+
1 2 3
n-propylclorur
n-propan
n-propyclorid
Trong phn t n -propylclorid, lin kt C
1

Cl b phn cc v pha nguyn
t clor v nguyn t clor c m in ln hn. Nguyn t clor mang mt phn
in tch m
v nguyn t carbon mang mt phn in tch dng

+.
V C
1

mang in tch dng nn cp in t lin kt ca lin kt C
2
C
1
b dch chuyn
v pha carbon C
1
. Kt qu l lin kt C
2
C
1
cng b phn cc theo. Nguyn t C
2

mang mt phn in tch dng. n lt lin kt C
3
C
2
cng chu nh hng
nh vy v kt qu nguyn t carbon C
3
mang mt phn in tch dng. Nhng
1
+
>
2
+
>
3
+
. Cc lin kt cng chu nh hng nh th v kt qu c s phn cc
22
ca lin kt C H. Hydro tr nn linh ng hn. Hin tng ny khng ch xy
ra vi phn t propan. Nh vy nh hng s phn cc ca lin kt C -Cl lm cho
cc lin kt khc b phn cc theo v ton phn t b phn cc.
Nguyn t clor l nguyn t gy nh hng cm ng.
S phn cc hay s chuyn dch mt in t trong cc lin kt gi l hiu
ng cm ng. Hiu ng cm ng k hiu l I hoc I
(ch u ca inductive)
phn loi cc nhm nguyn t theo hiu ng cm ng ngi ta quy c
rng nguyn t hydro lin kt vi carbon trong C
__
H c hiu ng I = 0. Nhng
nguyn t hay nhm nguyn t X c kh nng ht in t (CX) mnh hn
hydro c coi l c hiu ng - I (hiu ng cm ng m). Nhng nguyn t hay
nhm nguyn t Y c kh nng y in t (YC) mnh hn hydro c coi l
nhng nhm c hiu ng +I (hiu ng cm ng dng)
C X
Y C C H
+I
-I
I=0

1.1. Hiu ng cm ng + I
Thng thy cc nhm alkyl (R-) v cc nhm mang in tch m.
Trong dy cc nhm alkyl, hiu ng cm ng +I tng theo phn nhnh
hay l bc ca nhm .
CH
3
CH
2
CH
3
CH CH
3
CH
3
C CH
3
CH
3
CH
3
+ I

Trong dy cc nhm mang in tch m, nhm c m in nh hn l
nhm c hiu ng + I ln hn .
-O
-
< -S
-
< -Se
-

1.2. Hiu ng cm ng - I
L hiu ng rt ph bin cc nhm khng no, cc nhm mang in tch
dng v cc nhm ng vi nhng nguyn t c m in ln (nh cc halogen,
oxy, nit).
S bin thin mc mnh yu ca hiu ng - I trong cc nhm nguyn t
tun theo mt s quy lut:
Nguyn t carbon lai ha sp c -I ln hn nguyn t carbon lai ha sp
2
v sp
3

-CCR > -CR
1
=CR
2
> -CR
2
_
CR
3
.
Nhm mang in tch dng c hiu ng -I ln hn nhm c cng cu to
nhng khng mang in tch.
-OR
2
> -OR
+
-NR
3
> -NR
2
+

23
Cc nguyn t ca nhng nguyn t trong cng mt chu k nh hay trong
cng mt phn nhm chnh ca h thng tun hon, hiu ng -I cng ln
khi nguyn t tng ng cng bn phi (trong cng chu k) hoc cng
pha trn trong cng phn nhm).
-F >

-Cl >

-Br >

-I
-F >

-OR >

-NR
2
>

-CH
3
.
-OR > -SR > -SeR
m in cng tng th hiu ng cm ng - I cng ln
Biu hin c th ca hiu ng cm ng l nh hng ca cc nhm th khc
nhau n lc acid v lc base ca cc acid carboxylic no v ca cc amin.
Trn bng 2-1, ngi ta nhn thy rng nu thay th hydro ca acid formic
bng cc gc alkyl c + I tng th kh nng phn ly ca acid gim. Cn ln lt thay
th cc hydro ca amoniac bng cc gc alkyl c +I tng th tnh base tng ln.
Hiu ng + I tng lm cho lin kt O
__
H km phn ly.
CH
3
C
O
O H H
_
COOH

Khi thay th hydro ca amoniac bng cc nhm c hiu ng + I, mt in
t trn nguyn t nit tng ln do tnh base ca amin tng.
.. ..
CH
3
NH
2
H
_
NH
2

CH
3
N
CH
3
CH
3
:

Bng 2.1. nh hng hiu ng cm ng n tnh acid base
Acid hu c
pKa (H
2
O.25
o
)
Base hu c
pKa (H
2
O.25
o
)
4,76
3,75
CH
3
NH
2
10,62
4,87
CH
3
CH
2
NH
2
10,63
(CH
3
)
2
NH
10.77
(CH
3
)
3
N
9,8
*
HCOOH
CH
3
COOH
CH
3
CH
2
COOH
4,86
4,82 CH
3
CH
2
CH
2
COOH
(CH
3
)
2
CHCOOH
NH
3
Lc acid giam khi +I tang
Lc base tang khi +I tang
9,10

Ch : *S d tnh base ca trimethylamin khng tng l do hiu ng khng gian.
Hiu ng - I tng, lc acid tng. Khi thay th hydro ca CH
3
trong acid
acetic bng cc halogen c m in khc nhau th tnh acid thay i. Nguyn
t halogen c hiu ng -I ht in t nh hng n s phn ly ca nhm O
_
H.
2,58
3,16
2,85
2,9 4,76
pKa
CH
2
I C O H
O
C O H
O
CH
2
Br C O H
O
C O H
O
C O H
O
CH
2
Cl CH
2
F
CH
2
H

24
c im quan trng ca hiu ng cm ng l hiu ng cm ng lan truyn
trn mch lin kt v yu dn khi chiu di ca mch carbon tng ln.
CH
3
CH
2
CH
2
COOH
CH
3
CH
2
CHClCOOH CH
3
CHClCH
2
COOH CH
2
ClCH
2
CH
2
COOH
pKa 2,86 4,05
4,42
4,82

2. Hiu ng lin hp (cng hng)
2.1. H thng lin hp
H thng lin hp l mt h thng:
Cc lin kt bi (i, ba) lun phin vi lin kt n.
C=C-C=C-C=C-

(- ) C=C-C=C-C=O-

(- ).
H thng cha nguyn t cn cp in t p t do khng lin kt trc tip
vi nguyn t carbon c lin kt bi.
-C=C-O-R -C=C-Cl
.. ..
( p- )

Phn t cha h thng lin hp l phn t lin hp.
2.1.1. Phn loi h thng lin hp nh sau:
H thng lin hp -
H thng lin hp khng vng
2-methyl-1,3-butadien (izopren)
1,3-Butadien
CH
3
CH
2
=C
_
CH=CH
2 CH
2
=CH
_
CH=CH
2

CH
2
= CH CH = O CH
2
= CH C N CH
2
= CH C = O
Aldehyd acrylic Acrylonitril Acid acrylic OH
H thng vng
O
..

H thng lin hp p -
H thng lin kt lin hp do tng tc gia in t p t do vi lin kt .
: :
Anilin Phenol
NH
2
OH
Methylvinyl ether
Vinylclorid
..
CH
2
=CH
_
OCH
3
..
CH
2
=CH
_
Cl

2.1.2. c im ca h thng lin hp
Trong phn t khng ch c lin kt i hoc lin kt n ring:
25
CH
2
=CH
_
CH
2
_
CH=CH
2
; CH
2
=CH
_
CH=CH
_
CH
3

;

CH=CH
_
CH
2
_
OCH
3
Khng lin hp Lin hp Khng lin hp
Cc nguyn t to h lin hp lun nm trong mt mt phng v trc ca
cc oirbtal p song song vi nhau v thng gc vi mt phng cha cc lin kt .
phenol Benzen Butadien

Phn t lin hp bao gi cng c nng lng thp hn nng lng ca nhng
phn t khng lin hp tng ng. V mt in t gn nh gii ta ng u
trn cc nguyn t to h thng lin hp v to thnh mt orbital phn t gii
ta trn ton b phn t.
C
C
C
C

Orbital phn t trong h thng lin hp rt d bin dng v d phn cc khi
cu to ca phn t lin hp c mt nguyn t chnh lch v m in.
Nh vy trong h lin hp c s tng tc gia cc orbital p vi nhau. S
tng tc gi l hiu ng lin hp.
2.2. Hiu ng lin hp C (M)
Hiu ng lin hp l hiu ng sinh ra do s phn cc ca lin kt c lan
truyn trong h thng lin hp
Hiu ng lin hp c k hiu l C (Conjugate effect) hoc M (Mesomeric effect)
2.2.1. Phn loi hiu ng lin hp
Cn c vo s dch chuyn in t ca cc in t . C hai loi hiu ng
lin hp: Hiu ng lin hp + C v Hiu ng lin hp - C
Hiu ng lin hp - C
Nu thay th nguyn t hydro trong nhm CH
2
ca butadien bng nhm
CH = O, nhm ny tham gia lin hp vi orbital phn t ca butadien. Nh c
c tnh phn cc ca nhm CH =O nn ton b orbital mi hnh thnh ca
phn t b dch chuyn mt phn v pha nguyn t oxy.
CH
2
CH CH CH CH O

Nhm CH = O c hiu ng lin hp theo c ch ht in t nn c gi l
nhm c hiu ng - C.
26
Cc nhm c hiu ng - C l nhng nhm khng no c cng thc chung
C =Y, CZ v mt s nhm khc khng cha carbon nh - NO
2
, - SO
3
H...
Hng chuyn dch in t trong h thng c nhm vi hiu ng - C c m
t bng mi tn cong. Nhm c hiu ng -C thng c thm hiu ng cm ng - I.
Cc nhm chc c hiu ng -C :
-
: :
..
.. .. .. .. ..
.. .. .. .. .. ..
.. ..
..
:
: :
..
..
..
:
..
C O
NH
2
C O
CH
3
C O
O
C O
OH
C O
OR
C O
H
C O
Cl

CR = O > CR > CR = CR
2
NO
2
> O N > O CR
Hiu ng lin hp +C
Cc nguyn t hay nhm nguyn t c hiu ng lin hp +C l nhng
nhm c kh nng y in t. Cc nhm ny thng c nguyn t mang
cp in t p t do. Chnh cp in t p ny lin hp vi cc lin kt
trong h thng lin hp.
CH
2
=CH
_
OCH
3
CH
2
=CH
_
Cl:
.. ..
..

Cc nhm c hiu ng + C : -NH
2

> -OH ; -O
-
> -OH
-F > -Cl > -Br > -I
-NR
2
> -OR > -SR > -SeR
Cc nhm c hiu ng + C thng c thm hiu ng cm ng - I.
Hiu ng lin hp c ng dng rng ri gii thch c ch phn ng,
cc cu to trung gian, bn ca cc ion, tnh acid -base ...
Hiu ng lin hp c nh hng n s dch chuyn in t. Chng c cc
cng thc trung gian hay cn gi l cng thc gii hn nh sau:
V d:
Butadien-1,3:
CH CH CH
2
CH
2
CH CH CH
2
CH
2
+
-
CH CH CH
2
CH
2
+ -

Aldehyd crotonic:
CH CH CH CH
3
O
+
CH CH
CH
CH
3
O
CH CH CH CH
3
O
+ -
-

OH
:
OH
+
-
OH
+
-
OH
+
-
OH

Phenol
Hp cht c h thng lin hp cng di th c nhiu cng thc gii hn.
bn ca cc cng thc gii hn ph thuc vo khong cch gia 2 in tch tri
du. in tch tri du cng xa nhau th cng thc gii hn cng bn.
27
Khc vi hiu ng cm ng, nh hng ca hiu ng lin hp khng b
gim i khi h lin hp ko di.
V d: Nguyn t hydro trong nhm CH
3
ca aldehyd crotonic linh ng do
nh hng ca hiu ng lin hp.
CH
3
CH CH CH H O :
aldehid crotonic

Aldehyd crotonic
Nu ko di mch aldehyd crotonic bng cc nhm vinyl th hydro ca nhm
CH
3
vn cn linh ng.
: CH
2
CH CH CH H CH CH CH CH O

Hiu ng lin hp lm thay i trung tm phn ng:
V d: C hp cht sau:
..
NH
2 C
O
CH CH
NH
2 C
O
CH CH
+
-

Trong h thng lin hp p -, cp in t p khng lin kt trn nguyn t N
lin hp vi h thng lin kt . Nhm NH
2
gy hiu ng lin hp + C.
Nhm NH
2
c tnh base c kh nng tc dng vi proton H
+
. Nhng do hiu ng
lin hp, H
+
khng tc dng vo nhm amin NH
2
m tc dng vo nguyn t oxy
ca nhm carbonyl.
+
+ H
-
+
C
O
CH CH NH
2
+
C
OH
CH CH
NH
2

nh hng ca hiu ng lin hp ch xy ra trong h thng phng:
V d: Phenol (I) c tnh acid v nhm OH c hiu ng lin hp +C.
p-Nitrophenol (II) c tnh acid mnh hn phenol v nhm -NO
2
c hiu ng lin hp
- C. Thay 2 nhm CH
3
vo v tr orto so vi nhm OH c cht (III). Cht (III) c
tnh acid gim cht t so vi (II). Nhng a 2 nhm CH
3
vo v tr orto so vi nhm
NO
2
c cht (IV). Cht (IV) c tnh acid yu hn (II). iu chng t 2 nhm
CH
3
lm cho nhm NO
2
khng c hiu ng lin hp - C nh hng n chc phenol.
I
9.98 pKa
OH
OH
NO
2
7,16
II

OH
NO
2
CH
3
CH
3
7,21
III

OH
NO
2
CH
3 CH
3
8,24
IV

S d c iu v trong (III) nhm NO
2
khng nm trong cng mt phng
vi vng benzen. Hai nhm CH
3
c cn tr khng gian lm cho nhm NO
2
b lch
ra khi mt phng ca vng benzen. Hiu ng lin hp ca nhm NO
2
khng pht
huy tc dng.
28
..
HO N O
O
HO N O
O
CH
3
CH
3
..
II
IV

3. Hiu ng siu lin hp (Hyperconjugate effect)
Ngoi s lin hp - v p - nu trn cn c s lin hp - gia cc
orbital ca cc lin kt C H trong nhm alkyl v orbital ca ni i, ni ba
hay vng thm.
3 lien ket 1lien ket 2 lien ket
C C C H
H
H
H
C C C CH
3
H
H
H
C C C CH
3
H
CH
3
H
C
H
H
CH
3
3 lien ket

3 lin kt 2 lin kt 1 lin kt 3 lin kt
S tng tc lin hp gia orbital ca lin kt C - H vi orbital ca lin
kt i, ba hoc h thng lin hp gi l hiu ng siu lin hp.
Hiu ng siu lin hp c k hiu l H.
Hiu ng siu lin hp khng nhng lm thay i bn cht ca lin kt
i m cn lm thay i c tnh cht ca lin kt n C - H.
Hiu ng siu lin hp lm thay i hng cng hp vo lin kt i.
V d: Trong phn t 2-penten, nhm C
2
H
5
c hiu ng + I ln hn nhm CH
3
.
Phn t 2-penten cng hp vi HBr ng l phi to thnh 3-bromopentan.
Nhng thc t thu c 2-bromopentan. iu chng t nh hng siu lin
hp ca nhm CH
3
ln hn nh hng siu lin hp ca nhm C
2
H
5
nh hng
n hng cng hp.
C CHBr CH
2
CH
2
CH
3
H
H
H +HBr C CH CH CH
2
CH
3
H
H
H

Hiu ng siu lin hp nh hng n tnh cht linh ng ca lin kt C -
H trong gc alkyl.
V d: Nguyn t hydro trong nhm CH
3
ca aldehyd acetic d dng b ct
t trong mi trng kim to carbanion.
Carbanion
+ HO
-
+ H
2
O C CH O
H
H C CH O
H
H
H

Carbanion to thnh c h thng lin hp p - . V vy carbanion ny c th
c cng thc gii hn:
H C
H
CH O H C
H
CH O
-
-

Hin tng trn cn th hin trong hp cht ester ethylacetoacetat
CH
3
COCH
2
COOC
2
H
5
. Lin kt C H ca nhm CH
2
c siu lin hp vi nhm
29
carbonyl C =O. Hydro ca CH2 tr nn linh ng v d dng b ct t trong mi
trng base to thnh carbanion.
Carbanion
+ H
2
O
CH
3
C C C
OC
2
H
5
O O
H
+ OH
-
CH
3
C C C
OC
2
H
5
O O
H
H
. .

Carbanion to thnh c h thng lin hp p - do c th c cc cng thc
gii hn.
..
: : :
..
CH
3
C C C OC
2
H
5
O O
H
Carbanion
CH
3
C C C OC
2
H
5
O O
H

Hiu ng siu lin hp tng theo s lng lin kt C
_
H v tr .
CH
3
- > CH
3
CH
2
-

> (CH
3
)
2
CH- > (CH
3
)
3
C -
Hiu ng siu lin hp v hiu ng cm ng +I lun xy ra cng hng.
Hin tng phn b li mt in t cn c th c trong cc trng hp
h thng carbanion v carbocation.
V d: Carbocation allylic CH
2
=CHCH
+

v carbanion allylic

CH
2
=CHCH
-
.
CH
2
=CH
_
CH
2
+
CH
2
=CH
_
CH
2
-

Trong carbocation c hin tng dch chuyn in t t lin kt n orbital
trng ca nguyn t carbon. Trong carbanion c hin tng dch chuyn cp in
t t do ca carbon n lin kt .
Bi tp
1. Pht biu nh ngha v hiu ng cm ng, hiu ng lin hp v siu lin hp.
2. So snh hiu ng cm ng v hiu ng lin hp v bn cht, c tnh v quy lut.
3. Cn c vo hiu ng in t c th c so snh v gii thch tnh acid ca cc
cht trong cc dy sau:
a- n-C
4
H
8
ClCOOH, nguyn t clo cc v tr khc nhau .
b- m-ClC
6
H
4
(CH
2
)
n
COOHn = 0,1,2 .
c- m-ClC
6
H
4
(CH
2
)
n
COOHn = 0,1,2
4. Vit cng thc gii hn ca sn phm to thnh khi:
NH
2
C NH
2
NH
Guanidin
+ H
+
a-
C CH
2
C
O O
CH
2
+ HO
-
b-

30
Chng 3
CU TRC PHN T HP CHT HU C
NG PHN V CU DNG
Mc tiu hc tp
1. Trnh by c cc loi ng phn gp trong Ha hu c.
2. c c tn cu hnh cc hp cht hu c dng Z, E v R,S.
3. Xc nh c cu dng gh ca dn cht cycloalkan.
Ni dung
Cc hp cht hu c c cu to theo mt trt t xc nh. Cng thc
phn t cho bit thnh phn v s lng nguyn t c trong mt phn t. Cng
thc cu to phn nh bn cht v th t sp xp cc lin kt trong phn t.
Mt cng thc phn t c th c nhiu cng thc cu to khc nhau hoc nhng
cht khc nhau.
Hin tng mt cng thc phn t ng vi hai hoc nhiu cng thc cu to
khc nhau c gi l hin tng ng phn (isomery).
Thut ng isomery xut pht t ting Hy Lp "isos" c ngha l "cng" v
"meros"c ngha l "phn".
Da vo c im cu trc ngi ta chia thnh 2 loi ng phn: ng
phn phng v ng phn lp th (ng phn khng gian)
1. ng phn phng
Cc nguyn t v nhm nguyn t trong phn t cht hu c u cng nm
trong mt mt phng. Cc ng phn ch khc nhau v v tr v th t lin kt
gia cc nguyn t to thnh phn t. ng phn phng c cc loi sau:
1.1. ng phn mch carbon
C mch carbon sp xp khc nhau. Mch thng hoc phn nhnh.
iso Butan
CH
3
CH CH
3
CH
3
n- Butan
CH
3
CH
2
CH
2
CH
3

neo Pentan
CH
3
C CH
3
CH
3
CH
3
iso Pentan n- Pentan
CH
3
CH CH
2
CH
3
CH
3
CH
3
CH
2
CH
2
CH
2
CH
3

31
1.2. ng phn v tr nhm nh chc
Nhm nh chc trn mch carbon cc v tr khc nhau. Dng cc ch s
ch v tr nhm chc trn mch chnh ca mch carbon.
2-methyl-2-propanol
CH
3
C OH
CH
3
CH
3
2- Butanol 1-Butanol
CH
3
CH CH CH
3
OH
CH
3
CH
2
CH
2
CH
2
OH

2- Buten
1-Buten
CH
3
CH CH CH
3
CH
3
CH
2
CH CH
2

1.3. ng phn nhm chc
C nhm chc khc nhau.
Aldehyd propionic Aceton Acid acetic Aldehyd glycolic Ester methyl formiat
CH
3
COOH HO CH
2
CHO H COOCH
3
CH
3
CH
2
CHO CH
3
C CH
3
O

1.4. ng phn lin kt
Cc nguyn t trong phn t c cch lin kt khc nhau
Cyclobutan
CH
2
CH
2
CH
2
CH
2
1- Buten
CH
3
CH
2
CH CH
2

CH
2
=CH-CH=CH
2
CH
3
-CH-CCH CH
3
-CC-CH
3
1,3-Butadien 1-Butyn 2-Butyn
S h bin
C cc trng hp cc ng phn vi nhau nhng chng khng bn trong
nhng iu kin xc nh v chng c th thay i cho nhau to thnh hn hp
cn bng.
Hin tng ny gi l s h bin (hin tng tautomer - mesomer)
V d: Ester ethyl acetoacetat CH
3
COCH
2
COOC
2
H
5
c 2 ng phn. Hai
ng phn ny c th phn ring tng cht ch nhit -78C. Hai ng phn c
dng ceton v dng enol. nhit cao hn khng th phn ring chng c.
Chng tn ti nh l mt hn hp 2 cht trng thi cn bng. Dng ceton lun
bin i thnh dng enol v ngc li. Khi nng cc cht trong hn hp c
xc nh th chng t n trng thi cn bng. Chng l 2 ng phn h bin
(mesomer).
32
Ester ethyl acetoacetat Ester ethyl acetoacetat
Dng enol Dng ceton
CH
3
C CH COOOC
2
H
5
OH
CH
3
C CH
2
COOOC
2
H
5
O

2. ng phn lp th - ng phn khng gian
ng phn lp th hay cn gi l ng phn khng gian c cng cng thc
cu to nhng khc nhau v s phn b khng gian (phn b lp th) ca cc
nguyn t hay nhm nguyn t trong phn t. Tnh cht v phn ng ca cc
cht hu c lin quan cht ch vi s phn b khng gian ca cc nguyn t trong
cu trc ca chng.
C cc loi ng phn khng gian:
ng phn hnh hc
ng phn quang hc
ng phn cu dng
2.1. ng phn hnh hc
2.1.1. Cu to v danh php ng phn hnh hc
C th biu din cng thc ca ethylen theo dng khng gian:

H
H
H
H
H
H H
H

S phn b ca cc nguyn t hydro nm v 2 pha ca mt phng cha lin
kt (mt phng ). Cc nguyn t carbon khng th quay t do xung quanh lin
kt c v s cn tr ca mt phng . Nu thay th cc nguyn t hydro ca
etylen bng cc nguyn t hoc nhm nguyn t khc nhau th s phn b khng
gian ca chng so vi mt phng s khc nhau.
S phn b v 2 pha ca mt phng cng thng gp trong hp cht vng.
H
H
H
H
H
H
H
H
H
H
H
H
H
H

S phn b khng gian ca cc nguyn t hay nhm nguyn t v 2 pha ca
mt phng hay mt phng ca vng lm xut hin mt loi ng phn. l
ng phn hnh hc.
ng phn hnh hc l nhng hp cht c cng cng thc phn t nhng c
v tr khng gian ca cc nguyn t hay nhm nguyn t khc nhau i vi mt
phng hoc mt phng ca vng.
33
2.1.2. Phn loi ng phn hnh hc
C 2 loi ng phn hnh hc: ng phn cis v ng phn trans.
+ Dng cis ch ng phn c 2 nguyn t hoc nhm nguyn t ging
nhau cng mt pha i vi mt phng hay mt phng vng.
+ Dng trans ch ng phn c 2 nguyn t hoc nhm nguyn t khc
pha vi mt phng hay mt phng vng.
Mat phang
C C
CH
3
H
H
CH
3
C C
CH
3
CH
3
H
H
Cis 2-buten
Cis
C C
CH
3
H
CH
3
H
Trans 2-buten
Trans
C C
H
CH
3
CH
3
H

Tng qut: Hp cht c lin kt c dng abC =Cab , acC=Cab lun tn ti
ng phn hnh hc cis v trans.
abC=Cab
Cau hnh trans Cau hnh cis
C C
b
a
a
b
C C
a
b
a
b
acC=Cab
Cau hnh cis
C C
a
b
a
c
Cau hnh trans
C C
b
a
a
c

V d:
Acid crotonic
trans
cis
Acid isocrotonic
C C
CH
3
H
HOOC
H
C C
H
CH
3
H
HOOC
trans
Acid fumaric
cis
Acid maleic
C C
COOH
H
HOOC
H
C C
H
COOH
H
HOOC

Trng hp hp cht c dng tng qut abC =Ccd cng c ng phn hnh hc
vi a,b,c, d l nhng nguyn t hay nhm th hon ton khc nhau v " ln ".
S phn b khng gian cc nhm th ln v mt pha ta c ng phn Z
v khc pha ta c ng phn E. Z v E l nhng ch u ca Zusammen
(cng pha) v Eintgegen (khc pha).
Nu a > b, c > d.
a > b ; c > d
Cau hnh E (trans)
Cau hnh Z (cis)
abC=Ccd
C C
d
c
a
b
C C
c
d
a
b

V d:
C C
Cl
H
I
Br
C C
H
Cl
I
Br
1-Brom-1-Iod-2-Cloethylen
Z
E

I > Br > Cl > H V th I > Br ; Cl > E
34
C C
COOH
H
OHC
H
3
C
C C
H
COOH
OHC
H
3
C
Z
E
COOH > CHO > CH
3
> H
COOH > H CHO > CH
3
; ;

Nguyn tc xc nh ln ca nguyn t v nhm nguyn t:
+ Nguyn t c s th t trong bng tun hon cng ln th ln ca n
cng ln
I > Br > Cl > S > P > F > O > N > C > H
-CH
2
Cl > -CH
2
OH > -CH
2
CH
3
CH
OCH
3
CH
2
CH
3
CH
OH
CH
2
CH
3
>

+ Nu trong mt nhm nguyn t c mt nguyn t lin kt vi ni i, ni
ba th xem nh nguyn t c 2 ln, 3 ln lin kt vi nguyn t kia.
CH = CH
2
CH CH
2
C C
CH = O
C
C O
O

Cho nn:
CH
CH
3
CH
2
CH
3
CH
CH
3
CH
3
> > CH CH
2

-COOCH
3
> -COOH > -CONH
2
> -COCH
3
> -CHO
-CN > -C
6
H
5
> -CCH > -CH=CH
2
S ng phn hnh hc tng ln nu phn t c nhiu lin kt i
V d: Phn t 1,4-diphenyl-1, 3-butadien c 3 ng phn hnh hc
Cis-cis Trans-cis Trans-trans
C C
C
6
H
5
H
H
C C
H
H
C
6
H
5
C C
C
6
H
5
H
H
C C
H
C
6
H
5
H
C C
H
C
6
H
5
H
C C
H
C
6
H
5
H

35
ng phn hnh hc trong cc hp cht vng
1,3-Diclocyclohexan
trans
cis
Cl
H
Cl
H
Cl
H
1,3-Dimethylcyclobutan
cis trans
H
CH
3
CH
3
H
CH
3
H
CH
3
H
H
Cl

Cc trng hp khc v ng phn hnh hc.
ng phn hnh hc trong h thng ethylen phc tp
O O
CH
3 CH
3
O O
CH
3
CH
3
Cis
Trans

ng phn hnh hc trong hp cht c ni i C=N v N =N
Azobenzen
E (anti)
Z ( syn )
..
.. ..
..
N N
C
6
H
5
C
6
H
5
N N
C
6
H
5
C
6
H
5
Butanoxim E (anti)
Z ( syn )
..
C N
CH
3
CH
3
CH
2
OH
..
C N
OH
CH
3
CH
3
CH
2

Ch : Cc thut ng trans, cis, E, Z, anti v syn l cc h thng danh php
gi tn cc ng phn hnh hc.
2.1.3. Tnh cht ca cc ng phn hnh hc
Do s khc nhau v khong cch gia nhm th v mc n ng khng
gian, hai ng phn hnh hc c nhiu tnh cht l -ha khc nhau.
Tnh cht vt l
Nhit nng chy (t
nc
) : ng phn trans (E, anti ) c nhit nng
chy cao hn ng phn cis (Z, syn).
Nhit si (t
s
): ng phn trans (E, anti ) c nhit si thp hn
nhit si ca ng phn cis (Z, syn) .
Momen lng cc: Tu thuc vo bn cht ca cc nhm th phn b
chung quanh lin kt i hoc vng, momen lng cc cc ng phn
hnh hc c khc nhau. Nu hp cht c dng aCH =CHa th momen
lng cc ca ng phn E (trans) bng khng
E

= 0 v momen lng cc
ca ng phn Z (cis) ln hn khng
Z

> 0.
36
Hp cht c dng aCH =CHb : Nu a v b cng c bn cht in t (ngha l
a v b u cng ht hoc cng y in t th
Z

>
E
Nu a v b khc nhau v
bn cht in t (a ht in t cn b y in t hoc ngc li) th
E

>
Z
.

Ch : Xc nh momen lng cc theo nguyn tc hnh bnh hnh c th
minh ha nh sau:
aCH=CHa
Z
> 0
E
= 0
a
H
a
H
C C
C C
a
H
H
a
>
E
C C
H
b
H
a
C C
b
H
H
a
E
<
Z
C C
H
a
H
b
C C
H
H
b
a
aCH=CHb
a hut, b ay electron
aHC=CHb
a,b u ht electron

Bng 3.1. Tnh cht vt l ca mt s ng phn hnh hc
p-O
2
NC
6
H
5
CH=CHNO
2
Cis (Z) Trans(E) Cis (Z) Trans(E)
68,0
o
c 134,0
o
c
PhCH=CHCOOH
2,0D 1,7D
CH
3
CH=CHCl
7,4D
0,5D
Nhiet o nong chay Nhiet o soi
Trans (E ) Cis (Z)
Hp chat
Momen lng cc
ClCH=CHCl
-80,5
o
c -50
o
c 48,4
o
c 60,2
o
c 0 D 2,95D

bn
ng phn trans bn hn ng phn cis v nhit . Di tc dng ca
nhit ng phn cis c th chuyn thnh ng phn trans.
S chuyn i cis trans
Quay
trans (E , anti) cis (Z , syn)
C C
a
H
H
a
. .
C C
H
a
H
a
C C
H
a
H
a

Cc gi tr ph t ngoi, ph hng ngoi ca cc ng phn hnh hc cng
khc nhau.
37
Tnh cht ha hc
ng phn cis d tham gia mt s phn ng loi nc, to vng.
COOH
COOH
H
H
C
O
C
H
H
O
O
+ H
2
O
t
o
Acid cis butendioic
Anhydrid maleic

2.2. ng phn quang hc
ng phn quang hc l nhng cht ha hc c tc dng quay mt phng
nh sng phn cc.
Cht c tc dng vi nh sng phn cc l cht quang hot.
nh sng t nhin
Theo l thuyt v nh sng th nh sng t nhin gm nhiu sng in t c
vect in trng hng theo tt c cc hng trong khng gian v thng gc vi
phng truyn sng.
Anh sang t nhien
Vect ien trng
Phng truyen song

nh sng phn cc, mt phng nh sng phn cc
Khi cho nh sng t nhin i qua lng knh Nicon hoc mt cht phn cc
no (nh HgS, KClO
3
....) th cc vect in trng s hng theo mt phng
dao ng xc nh v vung gc vi phng truyn sng. nh sng i ra khi cht
phn cc gi l nh sng phn cc. Mt phng nh sng phn cc (mt
phng phn cc) l mt phng vung gc vi phng dao ng ca nh sng
phn cc.
Anh sang t nhien
Lang knh Nicon
Anh sang phan cc
Mat phang anh sang phan cc Phng truyen song

Cht quang hot (cht hot ng quang hc)
Khi cho nh sng phn cc qua dung dch cht hu c hoc mt cht no ,
nu cht ny lm quay mt phng nh sng phn cc mt gc c gi tr + hoc
- th gi cht l cht quang hot (cht hot ng quang hc).
38
Mat phang phan cc
Mat phat phang phan cc
sau khi qua chat quang hoat
Chat quang hoat
Goc quay

c trng kh nng quang hot ca mt hp cht quang hot ngi ta
dng i lng quay cc ring hay cn gi l nng sut quay cc ring v k hiu
l [].
= 100
__
L C
t
o

Trong :
l gc quay cc xc nh trn my phn cc k, c th c 2 gi tr .
Ga tr + ch mt phng phn cc quay phi.
Ga tr - ch mt phng phn cc quay tri.
L b dy lp cht quang hot m nh sng phn cc i qua n v tnh l dm.
C l s gam cht ha tan trong 100ml dung mi.
l bc sng ca nh sng.
t l nhit o.
Nh vy tnh quang hot ca mt cht l tnh cht ca phn t gn lin vi
cu trc phn t. S phn b khng gian lm cho cu to phn t tr thnh
khng i xng l nguyn nhn ch yu gy ra ng phn quang hc.
2.2.1. Phn t c nguyn t carbon khng i xng
2.2.1.1. Phn t c nguyn t carbon bt i xng
Nu nguyn t carbon lin kt trc tip vi 4 nguyn t hoc 4 nhm
nguyn t hon ton khc nhau th gi l carbon khng i xng (bt i xng,
phi i xng).
hay
a
d
b
C c
a
d
b
C c
*
*

a,b,c, d l cc nguyn t hay nhm nguyn t khc nhau. Carbon khng i
xng k hiu l C*. Phn t c carbon khng i xng th khng c cc yu t i
xng (mt phng i xng, tm i xng v trc i xng) v phn t c ng
phn quang hc.
39
V d: Acid lactic c mt carbon bt i xng CH
3
*
CH(OH)COOH.
hay
C
C
COOH
CH
3
OH H
H OH
CH
3
COOH
CH
3
CHOHCOOH
C
COOH
CH
3
OH
H

Nu xem m hnh t din ca acid lactic l mt vt tht th nh ca n qua
gng l mt vt th th hai. Vt v nh khng bao gi trng kht ln nhau khi
quay vt hay nh chung quanh mt phng mt gc 180.
Gng phang
H
3
C
HO

Anh Vat
H
C
OH
CH
3
COOH
H
C
HOOC
(+
) (-
)
Gng phng
nh
t
V

nh v gng l hai ng phn quang hc ca nhau, c cu to hon ton
ging nhau, ch khc nhau l nu vt quay mt phng nh sng phn cc mt gc
+ th nh quay mt phng phn cc mt gc - .
Quan h gia phn t (vt) v nh gng ca n nh bn tay phi v bn
tay tri.
Vt v nh khng trng ln nhau (chirality).
Hai ng phn vt v nh l 2 i quang (2 cht nghch quang).
2.2.1.2. Phn t c mt nguyn t carbon bt i xng
Cc ng phn i quang (enantiomer, gc t ting Hy Lp enantio l ngc
chiu) c khong cch gia cc nguyn t trong phn t nh nhau. Chng ng
nht v cc tnh cht vt l, ch khc nhau v s tng tc vi nh sng phn cc.
Hp cht c mt nguyn t carbon khng i xng c 2 ng phn quang hc.
Mt ng phn quay mt phng phn cc bn phi vi gc (+) gi l ng
phn quay phi (+)hay l ng phn hu tuyn (cn gi l ng phn d =
dextrogyre).
Mt ng phn quay mt phng phn cc v bn tri (-)gi l ng phn quay
tri (-) hay l ng phn t tuyn (trc y gi l ng phn l = levogyre).
Nu trn nhng lng bng nhau ca 2 cht i quang (50% ng phn quay
phi v 50% ng phn quay tri) s c mt hn hp khng c kh nng quay mt
phng nh sng phn cc. Hn hp gi l bin th racemic k hiu l ( ).
40
thun tin khi biu din cc ng phn quang hc, ngi ta biu din
cng thc theo hnh chiu Fischer (xem mc ng phn cu dng) nh sau:
Cc ng phn quang hc ca acid lactic
Cong thc chieu Fisher Cong thc t dien
Cong thc chieu Fisher
(+
)
Cong thc t dien
;
H HO
CH
3 CH
3
H
H OH OH
COOH
COOH
COOH
C C H
3
C
HO H OH
CH
3
COOH
(+
)
(-
)
CH
3
CHOH COOH

2.2.1.3. Phn t c nhiu nguyn t carbon bt i xng
Hp cht c nhiu carbon bt i xng th s dng phn quang hc tng ln.
Trong phn t, cc nguyn t carbon bt i xng c cu to khc nhau th
s ng phn quang hc l 2
n
; n l s nguyn t carbon bt i xng.
V d: Monosachcarid C
6
H
12
O
6
vi 4 nguyn t carbon bt i xng c
2
4
= 16 ng phn quang hc . D - Glucose l mt trong 16 i quang .
CH
2
OH CHOH CHOH CHOH CHOH CHO

Phn t acid ,-dihydroxybutyric c 2 nguyn t carbon bt i xng nn
c 4 ng phn quang hc. C th minh ha cc ng phn nh sau:
Cc ng phn quang hc ca , - dihydroxybutyric
IV III II I
HO
HO
HO
HO
H
OH
H
CH
3
COOH
H
H
CH
3
OH
COOH
H
H
CH
3
COOH
H
OH
H
CH
3
OH
COOH

CH
3
CHOH CHOH COOH

I v II l 2 i quang, III v IV l 2 i quang vi nhau.
Cn I v III, I v IV, II v III, II v IV l cc cp ng phn quang hc
khng i quang vi nhau (diastereoisomer).
Trong phn t, nhng nguyn t carbon c cu to ging nhau (tng ng
nhau) lm cho phn t c mt phng i xng trong phn t th s ng phn
quang hc s t hn 2
n
v c thm ng phn meso.
V d: Phn t acid tartaric c 2 nguyn t carbon bt i xng ging nhau nn
ch c 2 ng phn quang hc v mt ng phn meso. C th minh ha nh sau:
41
Cc ng phn quang hc v ng phn meso ca acid tartaric
Acid mesotartaric Acid(-) tartaric Acid(+) tartaric
HOOC CHOH CHOH COOH
COOH
OH
COOH
H
OH H
COOH
COOH
H
H
COOH
OH
COOH
H
H
COOH
COOH
H
OH
H
HO
HO HO
HO
I II
III
IV
mp oi xng
* *

Trong :
I v II l 2 i quang (2 ng phn quang hc). III v IV c mt phng i
xng trong phn t nn chng khng quay mt phng phn cc, chng khng c
tnh quang hot. Ngi ta gi l ng phn meso.
Ch : III v IV ch l mt cng thc.
C th gii thch s ng phn trong cc trng hp s carbon bt i xng
c cu to khc nhau v ging nhau nh sau: Carbon bt i xng c cu to khc
nhau th gc quay mt phng phn cc khc nhau. Trong trng hp acid ,-
dihydroxybutyric, gi s gc quay ca mi carbon bt i l a v b, a>b. Acid
tartaric c 2 carbon bt i vi cu to ging nhau, gc quay mt phng phn cc
ca mi carbon bt i ging nhau (a= b).
Gc quay mt phng phn cc l tng gi tr gc quay ca tt c carbon bt
i trong phn t.
C cc trng hp:
a=b
a>b
2 oi quang
2 oi quang
2

= ( -a ) + (+b ) = ( -)
1

= ( +a ) + (+b ) = (+)
2

= ( -a ) + (-b ) = (-)
2

= ( +a ) + (-b ) = ( +)
mot ong pham meso
2 oi quang
4

= ( -a ) + (+b) = (0)
3

= ( +a ) + (-b) = (0)
2

= ( -a ) + (-b ) = (+)
1

= ( +a ) + (+b) = (+)
HOOCCHOHCHOHCOOH
CH
3
CHOHCHOHCOOH

Kt qu: Acid , -dihydroxybutyric c 4 ng phn quang hc v acid
tartaric ch c 2 ng phn quang hc v 1 ng phn meso.
2.2.2. Danh php ng phn quang hc
Danh php ny dng k hiu cu hnh ca nguyn t carbon bt i.
C 2 loi danh php: Danh php D, L v danh php R,S
2.2.2.1. Danh php D,L
Ngi ta chia cc cht quang hot thnh hai dy: dy D v dy L. Loi danh
php ny c tnh cht so snh, ngha l ngi ta ly cu hnh khng gian ca
aldehyd glyceric CHOHCHOHCHO lm chun so snh.
42
Aldehyd glyceric c mt carbon bt i xng c 2 ng phn quang hc. Cu
hnh ca chng c m t di y:
Cu hnh chun ca aldehyd glyceric
CH
2
OH CHOH CHO
Cong thc chieu Fisher Cong thc t dien Cong thc chieu Fisher
Cong thc t dien
II
I
va
L ( - ) Aldehid glyceric
D ( + ) Aldehid glyceric
CH
2
OH
H OH OH
CHO
H HO
CH
2
OH
CHO
H
CHO
C HOH
2
C
HO
H
C
OH
CH
2
OH
CHO

Trong cng thc I nhm OH bn phi ngi ta quy c n c cu hnh D.
Trong cng thc II nhm OH bn tri, quy c n c cu hnh L.
Nhng hp cht quang hot c carbon bt i xng vi s th t cao nht c
cu hnh ging cu hnh ca D - aldehyd glyceric th chng thuc dy D.
Nhng hp cht quang hot c carbon bt i xng vi s th t cao nht c
cu hnh ging cu hnh ca L - aldehyd glyceric th chng thuc dy L .
V d: D- Glucose v L - Glucose c cu hnh nh sau:
Trong phn t glucose carbon bt i xng s 5 (s th t cao nht ca C
*
)
c cu hnh ging D - aldehyd glyceric c gi l D - Glucose v ging L -aldehyd
glyceric l L -Glucose.
Cu hnh ca D - Glucose v L - Glucose
CHO
H
HO
OH
CH
2
OH
OH
OH
H
H
H
CH
2
OH
_
CHOH
_
CHOH
_
CHOH
_
CHOH
_
CHO
2
1
3
4
5
6
D(+) - Glucose L(-) - Glucose
1 5 6 3 2 4
CHO
H
HO
CH
2
OH
H
H
H
2
1
3
4
5
6
HO
HO
OH

Du (+) v du ( - ) ch chiu quay mt phng nh sng phn cc.
Danh php D, L cng p dng cho cch gi tn ca cc acid amin.
2.2.2.2. Danh php R, S (danh php Cahn - Ingold-Prelog ).
R t ch Rectus (phi), S t ch Sinister (tri).
Danh php D, L c nhiu hn ch l khng ch r ht cu hnh ca cc
nguyn t carbon trong phn t v c tnh cht so snh. Danh php R, S khc
43
phc iu . Theo h danh php ny th 4 nhm th chung quanh nguyn t
carbon bt i xng c sp xp theo th t gim dn v ln" .
V d: C
*
abcd a > b > c > d
Xt s phn b cc nhm th a,b,d,c chung quanh carbon bt i xng ca vt
v nh trn hnh t din sao cho nhm th nh nht d vo nh t din xa nht so
vi mt ngi nhn v ba nhm th a,b,c cn li chim 3 gc ca y t din. Nu
theo th t " ln " ca 3 nhm th a,b, c theo chiu quay kim ng h ta c cu
hnh R, nu th t ngc chiu kim ng h ta c cu hnh S.
Cau hnh S
Cau hnh R
a,b,c theo chieu quay
ngc chieu kim ong ho
a,b,c theo chieu quay
cung chieu kim ong ho
Gng phang
II I
c b
a
C
c b
a
C
d
c
C
b
a
d d
c b
a
C C
*
*
*
*

V d: Phn t acid lactic c 2 ng phn: acid R- Lactic v acid S Lactic

OH
HOOC
OH
o ln cac nhom the OH > COOH > CH
3
> H
CH
3
HOOC
H
H
3
C
OH
COOH
H
3
C
H
OH
CH
3
COOH
CH
3
_
CHOH
_
COOH
C C
C C
Gng phang
acid R Lactic
acid S-Lactic
*
* *
*

i vi cc hp cht c nhiu carbon bt i xng c danh php theo h
thng R, S ngi ta ln lt xc nh cu hnh ca tng carbon bt i.
V d: i vi acid tartaric HOOC
_
CHOH
_
CHOH
_
COOH ta c cc ng phn:
acid (2R, 3R )-tartaric
acid (2S, 3S )-tartaric
acid (2R, 3S )-tartaric (aid mesotartaric ).
Phng php xc nh cu hnh R,S
Chuyn cng thc dng t din v hnh chiu Fischer.
Xt ln lt tng carbon bt i xng vi 4 nhm th c ln khc nhau.

44
Theo qui tc:
Nu thay i v tr nhm th 1 ln th cu hnh thay i.
Nu thay i v tr nhm th 2 ln th khng thay i cu hnh.
(Ch thay i sao cho nhm th b nht v pha di).
Xt chiu theo th t gim dn ln ca cc nhm th.
V d: Xt cu hnh ca aldehyd D Glyceric HOCH
2

_
C*HOH
_
CHO.
C mt carbon bt i v 4 nhm th chung quanh
C* l HO > CHO > CH
2
OH > H
Cong thc chieu Fisher
Cong thc t dien
HOCH
2
_
CHOH
_
CHO
III II I
oi v tr lan 2 oi v tr lan 1
R R
CH
2
OH
H
CH
2
OH CHO
OH
OH
CH
2
OH
H
H
CH
2
OH
OH
CHO CHO
OH
H
CH
2
OH
CHO
C CH
2
OH
H OH
CHO
C * *
*
*

T cng th t din chuyn v cng thc chiu Fischer (I). Cu hnh I l cu
hnh ca aldehyd D -glyceric. T (I) thay i v tr ln 1 thu c (II). i v tr
tip tc ln 2 ta c (III). Cho H l nhm th b nht v pha di. Cu hnh ca
(III) l cu hnh ca (I)
Xt chiu quay ca 3 nhm th OH, CHO, CH
2
OH. Ta c OH CHO CH
2
OH
theo chiu kim ng h. (III) c cu hnh R v suy ra (I) phi c cu hnh R.
Vy D- aldehyd glyceric l R - aldehyd glyceric .
2.2.2.3. Danh php Erythro v Threo
phn bit cc ng phn quang hc khng i quang ca cc hp cht
quang hot c 2 nguyn t carbon bt i xng ngi ta gi tn theo danh php
erythro v threo.
Dng erythro l dng trong 2 i nhm th tng t nhau c th a v
v tr che khut, cn dng threo ch c mt i nhm th tng t nhau c th v
tr che khut
V d: 2-Phenyl -2-butanol c dng ng phn erythro v threo nh sau:
45
CH
3
_
CH(Ph)
_
CHOH
_
CH
3
CH
3
Ph
H OH
HO
CH
3
H
CH
3
Ph H
CH
3
H
CH
3
Ph
H
CH
3
H
CH
3
Ph
H OH
CH
3
H
HO
[] = -0,69
o
25
D
[] = +0,69
o
25
D
[] = -30,2
o
25
D
[] = +30,2
o
25
D
2 ong phan erythro
2 ong phan threo
S
R
S
S
S
R
R
R

2.2.3. Cc ng phn quang hc khng c carbon bt i xng
C mt s hp cht trong phn t khng c carbon bt i xng, nhng do
s cn quay lm cho phn t tr thnh bt i xng nn phn t c tnh quang
hot (c ng phn quang hc). Cc hp cht thuc dy allen, diphenyl,
paracyclophan, thuc loi cht quang hot khng c carbon bt i xng.
C C C
c
d
a
b
R
R'
R"
R'''
Hp chat allen Hp chat diphenyl Hp chat paracyclophan
(CH
2
)
n
O
O

2.3. ng phn cu dng
Cu dng hay cn gi l hnh th (Conformation) ca mt phn t dng
ch cc dng cu trc khng gian c th hnh thnh khi cc nhm th quay t do
chung quanh lin kt n.
Mt cht hu c c th c trnh by theo cc dng cng thc sau:
Cng thc t din
Cng thc chiu Fischer
Cng thc phi cnh
Cng thc Newman
V d: Phn t etan c th c trnh by cc dng cng thc:
CT t dien
H
H
H
H
H
H
H
CT Newman CT phoi canh CT chieu Fisher
H
H
H
H
H
H
H
H
H
H
H
H H
H
H
H
H

46
Cng thc phi cnh v cng thc Newman thng c dng bin din
cu dng cc cht hu c.
Cng thc phi cnh c m t trong khng gian 3 chiu, lin kt gia 2
nguyn t carbon hng theo ng cho t tri sang phi v xa dn ngi
quan st.
C 2 loi cng thc phi cnh l dng xen k v dng che khut.
Dng che khut
Dng xen k
c
c
b
b
a
a
C
C
c
b
a
c
b
a
C
C

a,b,c l nhng nguyn t hoc nhm nguyn t phn b chung quanh
nguyn t carbon. Cng c th m t theo ng m nt ( ),ng chm chm
(
.....
)v ng nht (
__
). ng m nt ch r lin kt hng v pha trc mt
phng. ng chm chm hng v pha sau mt phng. ng nt nht nm
trong mt phng.
c
c
b
b
a
a
C
C
c
b
a
c
b
a
C
C
Dng xen k Dng che khut

Cu dng xen k c nng lng thp hn (bn hn) cu dng che khut (km
bn). T cng thc phi cnh c th m t theo cng thc Newman bng cch nhn
phn t theo dc trc lin kt C
1
C
2
. Ta biu din C
2
b che khut bng vng
trn, cn C
1
tm vng trn. Ba lin kt xut pht t mi nguyn t carbon to
nn nhng gc 120 trn mt phng giy.
CT Newman CT phoi canh
C
C
a
b
c
a
b
c
C
C
a
a
b
b
c
c
Dang xen ke
Dang che khuat
1
2
a
a
b
c
c
b
a
b
c
a
b
c
CT Newman CT phoi canh
1
2
2
1
1
2

Trong cc hp cht vng cc nguyn t khng phn b trn cng mt phng.
Chng c cc cu dng khc nhau. Phn t cyclohexan c hai loi cu dng: cu
dng gh v cu dng thuyn.
47
H
H
H
H
H
H
H
H
H
H
H
H H
H
H
H
H H
H
H
H
H
H
Cau dang ghe
Cau dang thuyen

dng gh cc nguyn t hydro trn 2 carbon cnh nhau phn b theo cch
xen k. Cn dng thuyn cc nguyn t hydro trn 2 carbon cnh nhau phn b
theo cch che khut. V vy cu dng gh bn hn cu dng thuyn (xem phn
cycloalkan).
2.4. Tc dng sinh hc ca cc ng phn quang hc
Cc ng phn quang hc ng vai tr quan trng trong i sng t nhin
ca con ngi v th gii sinh vt. Cc cht chuyn ha, cc cht men l nhng h
thng hp cht quang hot. Thay i cc dng i quang dn n s thay i qu
trnh v c ch ca s chuyn ha.
Acid Lactic tn ti (+) Lactic, (-)Lactic v L () Lactic (racemic). Chng c
cc tc dng sinh hc khc nhau. D -(+)-glucose l ng c tc dng sinh hc lm
cht tim truyn. Ngc li L -(-)-glucose hon ton khng c tnh cht ...
Bi tp
1- Cng thc phn t mt hydrocarbon l C
7
H
14
. Bao nhiu ng phn c th c ?
2- Cng thc phn t C
5
H
12
. Bao nhiu ng phn c th c?
3- Vit cng thc cu to cc ng phn hnh hc ca cc cht sau:
a- 2-Penten ; b-2-Phenyl-2-buten ; c- 1,2-Dimethylcyclopentan.
d-1-Phenyl-1-clo-2,3,3-trimethyl-1-buten.
Cho bit danh php cu hnh ca cc ng phn .
Dng ng phn no bn hn. Gii thch.
4- C hp cht CH
2
Cl-CHOH-CHOH-CH
2
Cl.
a- Hp cht ny c bao nhiu nguyn t carbon i xng, bt i xng .
b- Hp cht c bao nhiu i quang v c loi ng phn no.
c- V cng thc t din, cng thc chiu Fischer, cng thc phi cnh v
cng thc Newman .
d- Gi tn cc ng phn theo danh php D, L; danh php R, S v
danh php Erythro -Threo .
5- V cc cu dng gh v thuyn ca cc cht sau y:
a- cis-1,2-dimethylcyclohexan b- trans-1,2-dimethylcyclohexan.
c- cis-1,3-dimethylcyclohexan d- trans-1,3-dimethylcyclohexan
e- cis-1,4-dimethylcyclohexan f-trans-1,4-dimethylcyclohexan
48
Chng 4
KHI NIM ACID -BASE TRONG HA HU C
Mc tiu hc tp
1. Trnh by c cc quan nim v acid v base trong ha hu c.
2. Gii thch v so snh c mnh tng i tnh acid hoc base ca mt
s hp cht hu c.
3. Nm c khi nim acid -base lin quan n phn ng ca cc hp cht
hu c.
4. S dng khi nim acid -base ca Bronsted - Lowry v Lewis trong ho hu
c gii thch v tnh acid -base ca cc cht v c ch phn ng.
Ni dung
1. Khi nim acid - base theo Bronsted -Lowry (1923)
Acid l nhng tiu phn c khuynh hng cho proton. Base l nhng tiu
phn c khuynh hng nhn proton. V d c cht HA cho proton H
+
.

HA A
-

+ H
+

Theo phng trnh trn th s phn ly to H
+
l mt qu trnh thun nghch.
HA l acid v cho proton H
+
. A
to thnh gi l base, v A
nhn proton
to thnh acid HA. V vy c th gi HA l acid lin hp ca base A
v A
l
base lin hp ca acid HA. Trong bng 4-1 trnh by mt s acid -base lin hp.
Bng 4.1. S phn ly ca cp acid base lin hp
Proton
..
..
+
H
+
CH
3
_
O
_
CH
3
H
CH
3
_
O
_
CH
3
H
+
NH
3
+
NH
4
H
+
CH
3
O
-
CH
3
OH
CH
3
COO
-
H
+
CH
3
COOH
Base lien hp Acid lien hp
HA H
+
+ A
-

49
Theo bng trn khi BH
+
phn ly to thnh base khng c in tch ( - )

BH
+
H
+
B +

Kt hp c 2 trng hp ta c

HA
BH
+
B + A
-
+

Vy phn ng gia mt acid HA v mt base B l s chuyn dch proton t
acid sang base hay l phn ng proton ha. Tnh cht ca acid hoc base khng
ph thuc in tch ca tiu phn. Nh vy c nhng phn t acid khng mang
in (H
2
SO
4
, HCl, CH
3
COOH), c phn t acid tch in dng (NH
4
+
, [CH
3
OCH
3
]H
+
),
c phn t base mang in tch m (CH
3
COO
-
, CH
3
O
-
), c phn t base khng c
in tch (NH
3
,

CH
3
OCH
3
) .
Acid ha tan vo nc c s tng tc acid base: Nc l dung mi c tnh base.
CH
3
COOH +

H
2
O H
3
O
+

+

CH
3
COO
-
Acid Base Acid
Base

Ho tan mui ca acid hu c vo nc, c s tng tc acid -base : Nc l
dung mi c tnh acid.
Acid Base
Acid Base
H
2
O CH
3
COO
-
CH
3
COOH HO
- +
+

Nc l mt dung mi lng tnh ph thuc vo tnh cht ca cht ha tan.

Mt s phn ng ha hc c xc tc acid, thc cht l s tng tc acid - base.
V d: Phn ng to ether t alcol c xc tc acid l s tng tc acid (H
+
)
vi base (alcol) to cht trung gian khng bn trc khi hnh thnh ether.
Acid
Base Acid Base
+ R
_
O
_
H H
2
SO
4
R
_
O
_
H
H
+
HSO
4
-
+

Phn ng cng hp nc vo olefin c xc tc acid cng l qu trnh tng
tc acid -base, to carbocation trung gian trc lc to thnh alcol.
H
3
PO
4
+
Base Acid
+
H
2
PO
4 CH
3
CH
_
CH
3
- +
Base
Acid
CH
3
CH=CH
2

Mt s phn ng c xc tc base cng c qu trnh tng tc acid base to
carbanion trung gian.
Base (carbanion)
Acid
CH
3
_
CHO + HO
-
H
2
O + CH
2
_
CHO
-
Base Acid

Ch : Mt acid rt mnh th base lin hp ca n l mt base rt yu.
Mt acid rt yu th base lin hp ca n l mt base rt mnh.
50
CH
3
Acid rt yu Base rt mnh Base rt mnh Acid rt yu
+ B BH
+
+
CH
2
-
HO
-
, CH
3
O
-
l nhng base mnh
H
2
O, CH
3
OH l nhng acid yu

2. Khi nim acid - base theo Lewis

(1923)
Base l phn t c kh nng cung cp cp in t (c cp in t khng lin
kt). Acid l phn t c nguyn t m in t lp ngoi cng cha y (c
kh nng kt hp vi cp in t ca base).
Cc cht sau y l nhng base Lewis:
R
_
O
_
R R
_
NH
2
R
_
OH
HO RO NH
3
.. .. .. ..
- -
; ; ; ; ;

Cc cht sau y l acid Lewis:
BF
3
, AlCl
3
, FeCl
3
, ZnCl
2
, SO
3
,NH
4
+

Acid Lewis c kh nng to lin kt cng tr (lin kt phi tr cng l mt
dng ca lin kt cng tr) vi cc base Lewis nh H
2
O, R
2
O, NH
3

.
Base Lewis
+
H
H
H
N
..
:
..
:
Acid Lewis
F
F
F
B
..
..
:
H
H
H
N
F
F
F
B
..
:
..
:
..
..
:

3. Hng s cn bng acid - base
Acid phn ly trong nc. Cc ion b hydrat ha (solvat ha)
HA H
+
+ A
-
HA( nc ) H
+
(nc)

+ A
-
(nc) hay

S solvat ha H
+
(nc) v A
-
(nc) c th minh ha:
H
A
H
O
H
O
H
H
O
H
H
H
O
O
H
H H OH
2
H
2
O
OH
2
+
H
3
O (H
2
O)
n
A(H
2
O)
n
+
-
-

51
Bng 4.2. Gi tr pK
a
ca mt s cht hu c
-10.7
-9.0
-8.0
-6.5
-6.0
-3.6
-2.2
-1.7
00
+
+
+
+
+
+
+
+
CH
3
C NH
CH
3
C Cl
OH
CH
3
C H
OH
CH
3
C OC
2
H
5
OH
CH
3
C OH
OH
(CH
3
CH
2
)
2
OH
CH
3
OH
2
H
3
O
+
CH
3
C NH
2
OH
CH
3
CN
CH
3
COCl
CH
3
CHO
CH
3
COOC
2
H
5
CH
3
COOH
(CH
3
CH
2
)
2
O
CH
3
OH
H
2
O
CH
3
CONH
2
pK
a Acid lien hp Hp chat

Hng s cn bng ca phn ng:
HA( n c ) H
+
(n c)

+ A
-
(n c)
K

K
a
=
[H
+
][A
-
]
[HA]

K
a
> 1 thuc nhng acid mnh
K
a
< 10
-4

thuc nhng acid yu
Gi tr K
a
rt b thuc nhng acid rt yu
S dng i lng pK
a
= -logK
a
nh gi mnh yu ca acid
pK
a
cng b th acid cng mnh v ngc li
pK
a

< -1 thuc acid mnh .
pK
a
> 3 thuc acid yu.
Tng t ta c hng s cn bng ca base.
B + H
2
O BH

+ HO
-

K
b +

K
b
=
[ BH

][HO
-
]
[B]
v [H
2
O] = 55,5 M
+

S dng i lng pKb = - logKb nh gi mnh ca base.
K
b
cng ln th tnh base cng yu
pK
b
cng ln th tnh base cng mnh v ngc li
52
Bng 4.3. nh hng ca cc hiu ng n tnh acid
4,31
2,46
4,87
3,32
4,35
3,54
3,83
3,18
2,90
0,64
1,26
2,86
0,23
2,59
HC CCH
2
COOH
0,23
4,9.10
-5
3,4.10
-3
1,3.10
-5
4,8.10
-4
4,5.10
-5
2,9.10
-4
1,5.10
-4
6,7.10
-4
1,3.10
-3
4,74
5,5.10
-2
1,4.10
-3
0,59
2,6.10
-3
1,8.10
-5
C
6
H
5
CH
3
COOH
NCCH
2
COOH
CH
3
CH
2
COOH
CH
2
=CHCH
2
COOH
CH
3
OCH
2
COOH
HOCH
2
COOH
ICH
2
COOH
BrCH
2
COOH
Cl
3
CCOOH
Cl
2
CHCOOH
ClCH
2
COOH
F
3
CCOOH
FCH
2
COOH
CH
3
COOH
pK
a
K
a
,M Acid

Ch : Tnh acid v tnh base ca mt cht l mi quan h bin chng. Mt
cht c tnh acid mnh th n l mt base yu. Mt cht c tnh base mnh th n
l mt acid yu. Ether ethylic C
2
H
5
OC
2
H
5
l mt base yu, v vy n ch tc dng
vi mt s acid mnh .
CH
3
CH
2
OCH
2
CH
3
+

H
+
CH
3
CH
2
OCH
2
CH
3

+
H
..

4. Yu t nh hng n tnh acid -base ca cht hu c
Cu trc in t ca phn t nh hng n tnh acid -base
Cc nguyn t, nhm nguyn t gy nh hng cm ng, nh hng lin
hp, nh hng siu lin hp c nh hng n tnh acid -base.
Hiu ng - I, - C lm cho tnh acid ca mt cht tng (tnh base gim).
Hiu ng + I, + C lm cho tnh acid ca mt cht gim (tnh base tng).
Cc s liu ghi trong bng 4-3 chng t iu .
Bi tp
1- Vit cng thc ca cc base lin hp ca cc acid sau:
C
6
H
5
COOH, C
6
H
5
CH
2
COOH, CH
3
CH
2
NO
2
, C
6
H
5
OH, (CH
3
)
3
NH
+
2- Vit cng thc cc acid lin hp ca cc base sau:
NH
3
, C
6
H
5
NH
2
, CH
3
OCH
3
, CH
3
COCH
3
, HCC
-
, RO
-

3- V sao AlCl
3
, ZnCl
2
, NH
4
+
, BF
3
l nhng acid.
53
Chng 5
CC LOI PHN NG TRONG HA HU C v
KHI NIM V C CH PHN NG
Mc tiu hc tp
1. Trnh by c cc c ch phn ng thng gp trong ha hu c.
2. Vit v gii thch c cc c ch phn ng: th (S), cng hp (A), tch loi (E)
Ni dung
C nhiu phng php phn loi phn ng trong ha hu c. Trong gio
trnh ny cc phn ng c phn loi theo hng phn ng. C cc loi phn
ng nh sau:
1. Cc loi phn ng trong ha hu c
1.1. Phn ng th (Substitution)
Phn ng th (k hiu S) l phn ng trong mt nguyn t hay nhm nguyn
t trong phn t c thay th bng mt nguyn t hay nhm nguyn t khc.
R
_
I + CN
-
R
_
CN + I
-

R
_
Li + H
2
O R
_
H + LiOH
Tng qut: R
_
A + Y

R
_
Y + A
A l nhm b th (nhm i ra) A = I
-
, Li
+
, ...
Y l nhm th ( nhm i vo) Y = CN
-
, H
+

Trong ha hu c tn gi ca mt s phn ng c lit k trong bng 5-1.
Bng 5.1. Tn gi mt s phn ng th
Phan ng azo hoa
Phan ng formyl hoa
Phan ng ester hoa
Phan ng acyl hoa
Phan ng aryl hoa
Phan ng alkyl koa
Phan ng sulfonic hoa.
Phan ng nitro hoa
Phan ng halogen hoa
Ten phan ng San pham the R
_
Y Nhom the Y
N=N
_
Ar
CHO
R'COO
R'CO
Ar
R'
SO
3
H
NO
2
Halogen X
R
_
N=N
_
Ar
R
_
CHO
R'COO
_
R
R'CO
_
R
R
_
Ar
R
_
R'
R
_
SO
3
H
R
_
NO
2
R
_
X

R A + Y R Y + A
54
Mt s phn ng th c km theo s loi nc, alcol, amoniac ...cn gi l
phn ng ngng t. V d:
R
_
CHO + CH
3
COC
6
H
5
R
_
CH=NR' + H
2
O
RCOOC
2
H
5

+ CH
3
COC
6
H
5
RCOCH
2
CO C
6
H
5
+ C
2
H
5
OH
Tu theo c ch phn ng v tc nhn phn ng, phn ng th cn chia
thnh cc loi phn ng th khc nhau:
Phn ng th i nhn.
Phn ng th gc t do.
Phn ng th i in t.
1.1.1. Phn ng th i nhn S
N

R-A + Y
-
R-Y + A
-

Y- gi l tc nhn i nhn
V d: CH
3
Cl + HO
-

CH
3
OH + Cl
-

1.1.2. Phn ng th gc t do S
R

R-A + R
.
R-R + A
.

R
l gc t do (nhng gc c mt in t)
V d: SO
2
Cl
2

+

C
6
H
5
C
6
H
5
Cl +

SO
2
Cl
1.1.3. Phn ng th i in t S
E

R
_
A + E
+

R
_
E + A
+
E
+
l tc nhn i in t
V d: Ar
_
H +
+
NO
2

Ar
_
NO
2

+ H
+
Trong phn c ch phn ng s cp v cc qu trnh xy ra phn ng th.
1.2. Phn ng cng hp (Addition)
Phn ng cng hp (k hiu Ad) l phn ng trong hai phn t (hoc ion)
kt hp vi nhau thnh mt phn t (hoc ion) cht mi.
Phn ng thng xy ra trong cc hp cht c ni i, ni ba:
C=C, CC, C=O, C=NH, CN.
Phn ng cng hp xy ra c s thay i trng thi lai ha ca nguyn t carbon.
HCCH + HCl H
2
C=CHCl: Carbon trng thi sp thnh sp
2

R
_
CH=CH
2

+ Br
2

R
_
CHBr
_
CH
2
Br: Carbon trng thi sp thnh sp
3
55
Ty theo cu to cht phn ng, ngi ta chia phn ng cng hp thnh cc loi:
Phn ng cng hp i in t P (Ad
E
, A
E
)
Phn ng cng hp i nhn P (Ad
N
, A
N
)
Phn ng cng hp gc P (Ad
R
, A
R
)
1.2.1. Phn ng cng hp i in t (Ad
E
, A
E
)
R
_
CH=CH
2

+ H
2
O R
_
CHOH
_
CH
3
1.2.2. Phn ng cng hp i nhn (Ad
N
, A
N
)
R
_
CH=O + HCN R
_
CH(CN)
_
OH
1.2.3. Phn ng cng hp gc (Ad
R ,

A
R
)
;
Cl
Cl
+ Cl
.
.
Cl
.
Cl
+ Cl
.
+ Cl
2

Phn ng cng gc c nh sng lm xc tc l phn ng dy chuyn.
Phn ng cng hp hydro vo lin kt i, ta cn c th gi l phn ng
hydro ha hay phn ng kh.
1.3. Phn ng tch loi (Elimination)
Phn ng tch loi (k hiu E) l phn ng m 2 nguyn t hay nhm
nguyn t tch ra khi phn t v khng c nguyn t hay nhm nguyn t no
thay th.
Phn ng xy ra c s thay i trng thi lai ha ca nguyn t carbon.
H
_
CH
2
_
CH
2
_
OH CH
2
=CH
2
+ H
2
O: Carbon trng thi sp thnh sp
2
.
Br
_
CH
2
_
CH
2
_
Br + Zn CH
2
=CH
2

+ ZnBr
2
: Carbon trng thi sp thnh sp
2

1.4. Phn ng chuyn v (Rearrangement)
Trong cc loi phn ng k trn c lc c th xy ra s chuyn v lm
chuyn ch mt nguyn t hay nhm nguyn t no trong phn t. Phn ng
xy ra c s chuyn i v tr trong phn t gi l phn ng chuyn v.
R C
R
R
CH
2
X
R C
R
R
CH
2
R C
R
CH
2
R
- X
-
+
Chuyen v tr
+
. .

Mt s phn ng th, tch loi, cng hp c th xem l phn ng oxy ha -
kh. V trong qu trnh phn ng c s thay i s oxy ha ca mt hay nhiu
nguyn t trong phn t. Cc phn ng c s tng v gim s oxy ha (hay s
nhng v thu in t) gi l phn ng oxy -ha kh.
56
2. Khi nim v c ch phn ng
Phng trnh ha hc thng thng ch trnh by cc cht u v cui ca
h phn ng m khng cho bit qu trnh ha hc c thc hin bng cch no
v tin trnh din bin ca phn ng.
C ch phn ng ha hc l con ng chi tit m h cc cht phn ng phi
i qua to ra sn phm. Cc qu trnh phn nh cc bc c bn ca phn ng,
s ct t lin kt, s hnh thnh lin kt mi, hnh thnh cht trung gian v
phc hot ng (trng thi chuyn tip); tin trnh lp th, s solvat ha ...
2.1. Ct t lin kt v hnh thnh cc tiu phn phn ng
Mt lin kt c th b ct t theo kiu d ly hoc ng ly.
V d c lin kt cng ha tr gia hai nguyn t hoc hai nhm nguyn t
A v B:
2.1.1. S ct t d ly
Khi lin kt b ct t, cp in t lin kt thuc A hoc B
hoac .
.
A
__
B A
-
+ B
.
.
A
__
B A

+ B
-
+ +

A
+
v B
-
l cc ion.
Nu tiu phn to thnh A
+
hoc B
+
l R
+
th tiu phn gi l
carbocation.
Nu tiu phn B
-
hoc A
-
l R
-
th tiu phn gi l carbanion.
Carbocation v carbanion l nhng tiu phn ng vai tr quan trng trong
cc phn ng th, cng hp v tch loi.
2.1.2. S ct t ng ly
Khi lin kt b ct t, cp in t c phn i. Trn mi tiu phn mang
mt in t t do. Cc tiu phn gi l gc t do.
A
__
B A + B
.
.
. .

CH
3
-CH
2
CH
2
=CH-CH
2
.
.
,
la cac goc t do

Cc gc t do tham gia cc phn ng theo c ch gc.
2.1.3. Cu to v tnh cht tiu phn to thnh khi ct t lin kt
Carbocation
Carbocation (k hiu R
+
) l nhng cation m trung tm in tch dng
nguyn t carbon (trn orbital p khng c electron - orbital trng).
Carbocation c to thnh khi ct t d ly lin kt cng tr hoc khi cng
hp proton H
+
vo ni i, ni ba.
57
CH
3
CH=CH
2
+ H

CH
3
CH
_
CH
+ +

Carbocation c cu trc phng. Ba lin kt ca carbon C
+
nm trong mt
mt phng. Orbital trng (khng c in t) c trc i xng thng gc vi mt
phng .
Carbanion
Carbanion (k hiu R
) l nhng anion m in tch m (2 in t) tp trung

ch yu nguyn t carbon (trn orbital p c 2 in t). Carbanion c to
thnh khi ct t d ly lin kt cng ha tr .
H
_
CH
2
CHO + HO
-
-
CH
2
CHO + H
2
O
Carbanion c cu trc hnh thp, tm l nguyn t carbon v 4 nh l 3
nhm th v cp in t.
Gc t do
Gc t do (k hiu R
) l nhng tiu phn c cha 1 in t t do (khng cp

i) nguyn t carbon (trn orbital p c 1 in t). Gc t do c to thnh do
s ct t ng ly lin kt cng tr di tc dng ca nh sng hoc nhit. Gc t
do c cu trc phng. Ba lin kt ca carbon C
.
nm trong mt mt phng.
Orbital p cha mt in t thng gc vi mt phng . Hnh 5.1 minh ho trng
thi khng gian ca carbocation, carbanion v gc t do.
:
CH
3
CH
3
H
C
+
CH
3
CHCH
3
Cau truc phang cua carbocation
H CH
3
CH
3
CH
3
CH
3
H
CH
3
CH
3
H
orbital p khong co eletron
Cau truc hnh thap cua carbanion Cau truc phang cua goc t do
CH
3
CHCH
3 CH
3
CHCH
3
.
H CH
3
CH
3
H
orbital p vi 2 electron
orbital p vi 1 elctron

-

Hnh 5.1. Cu trc khng gian ca carbocation, carbanion v gc t do.
Carben
Carben k hiu RR'C: l tiu phn c 2 in t khng lin kt lp ngoi
cng ca nguyn t carbon .
V d: H
2
C: , Cl
2
C: , CH
2
=CHCH:
Nu 2 in t phn phi trn 2 orbital p, carben dng lng gc. Nu 2 in
t cng phn phi trn mt orbital p, trn carbon c mt orbital p trng khng c
in t. Carben c dng mt ion dng ng vai tr mt tc nhn i in t .
58
Ion dng Lng goc
orbital sp
2
orbital trong
H
H
H H

Hnh 5.2. Cu trc ca carben H
2
+
C: v lng gc CH
2
bn ca cc tiu phn
bn ca cc tiu phn ph thuc vo cu trc in t. Mt in tch
trn carbocation v carbanion cng gim th nng lng ca chng cng thp v
chng cng bn (d tn ti trong cc qu trnh phn ng).
Cc hiu ng electron I, C v H lm gim mt in tch c nh hng
quyt nh n bn vng ca cc tiu phn.
Carbocation bn vng kh in tch dng c gii ta. Cc hiu ng
+
I v
+
C c tc dng lm cho carbocation bn vng hn.
V d: CH
3
+
< CH
3
CH
2
+
< (CH
3
)
2
CH
+
< (CH
3
)
3
C
+
do hiu ng
+
I ca CH
3
.
CH
3
+
< C
6
H
5
CH
2
+
< (C
6
H
5
)
2
CH
+
< (C
6
H
5
)
3
C
+
do hiu ng
+
C ca C
6
H
5
Carbanion bn vng khi c cc nhm ht in t . Hiu ng -I v -C lm
tng bn ca carbanion.
V d: CH
3
< (CF
3
)
2
CH- < (C
6
H
5
)
2
CH

CH
3
CH
2
CH
2
-
< CH
2
= CH CH
2
< (CH
2
=CH)
2
CH

Cc gc t do km bn v c kh nng phn ng cao. Cc nhm alkyl, aryl
lm tng bn. Gc phenyl C
6
H
5
- c kh nng c hiu ng
+
C hoc -C
V d: CH
3
.
< CH
3
CH
2
.
< (CH
3
)
2
CH
.
< (CH
3
)
3
C

CH3
.
< C
6
H
5
CH
2
.
< (C
6
H
5
)
2
CH
.
< (C
6
H
5
)
3
C
.
Cc nhm th c hiu ng I , C v H v tr para trong gc p-X-C
6
H
4
CH
2
.

lm cho bn ca gc tng ln.
2.2. Tc phn ng
Tc v ca phn ng A + B C c th c th hin qua phng trnh .
v = k [A].[B] = k c
Trong : c = [A].[B]
k l hng s tc phn ng .
[A],[B] l nng ca cc cht A v B .
Theo phng trnh Arrhenius ta c .
-
RT
E
A
k
=
P.Z .e

59
Theo th k t l thun vi s va chm Z. Nhng khng phi tt c cc va chm
u dn n phn ng ha hc. V vy cn c mt nng lng ti thiu E
A
gi l nng
lng hot ha a cc phn t n " trng thi kch thch " lm cho cc phn t
thnh cc tiu phn giu nng lng (carbocation, carbanion, gc t do).
xy ra phn ng, s cc tiu phn c nng lng ti thiu bng nng
lng hot ha E
A
c xc nh bi nh lut phn b nng lng Boltzmann.
Kt qu l tc phn ng ph thuc mnh vo nhit T. Theo phng trnh
trn, khi nhit tng ln khong 10
o
C th tc cc phn ng ha hc tng ln
gp 2 n 3 ln.
Khi cc tiu phn nng lng cn thit th ch c nhng va chm ca cc
tiu phn nhng v tr khng gian thch hp mi lm cho phn ng xy ra. Tr
s k thc nghim thng nh hn rt nhiu so vi gi tr tnh ton c t E
A
, T
v Z. Gi tr k l thuyt v k thc nghim khc nhau bi mt i lng P. i
lng P c gi l h s khng gian hay l h s xc sut .
Khi nghin cu v c ch phn ng, tc phn ng cn c tnh ton theo
l thuyt phc cht hot ng (hay cn gi l trng thi chuyn tip) gii thch
cc trng thi ng hc ca phn ng.
L thuyt ny gi thit rng trn bc ng n sn phm cui cng, cc
phn t tham gia phn ng hp li vi nhau thnh mt phc cht hot ng (hay
l trng thi chuyn tip). Trng thi chuyn tip c c trng bng mt cc i
nng lng (im A trong hnh 5-3a) ca cc phn t tham gia phn ng. Phc
cht hot ng khng phi l mt cht trung gian v n khng c cc tiu nng
lng. Cc tiu nng lng ca cht trung gian trnh by trn hnh
5-3b (im B).
(b)
(a)
E
A1
E
A1
Phc chat hoat ong A2
Phc chat hoat ong A1
Tin trnh phn ng
E
Nang lng hoat hoaE
A
Chat cuoi
Chat ban au
Chat trung gian B
A2
A
AH
B
A1
E
Tin trnh phn ng

Hnh 5.3. Gin nng lng v tin trnh phn ng
C th xem nng lng hot ha E
A
tng ng vi entanpi hot ha H
.
Mc trt t khng gian trng thi chuyn tip c c trng bi i lng
Entropi S
hot ha. Gi tr S
hot ho ca trng thi chuyn tip cng m s

phn nh mc cc cht phn ng tng tc a phn t hay n phn t. Bit
gi tr S
v H
tc l bit c tin trnh v c ch phn ng xy ra.

60
Thc t khng phi nng lng hot ha E
A
m l nng lng t do F
hot
ha mi l yu t quyt nh chuyn phn t t trng thi u ln trng thi
chuyn tip .
F

=

H

- TS

2.3. C ch phn ng th
2.3.1. C ch phn ng th i nhn
Phn ng th i nhn xy ra theo 2 c ch chnh.
C ch lng phn t S
N2
v c ch n phn t S
N1
.
C ch S
N2

C ch lng phn t S
N2
th hin trong phng trnh tc phn ng c
nng ca 2 cht phn ng. Phn ng xy ra mt giai on v c trng thi
chuyn tip gia cht phn ng v tc nhn i nhn Y
-
.
V d: CH
3
Cl + HO
-
CH
3
OH + Cl
-

Phng trnh tc phn ng: v = k [CH
3
Cl] [HO
-
]
Trng thi chuyn tip:
San pham cuoi Chat phan ng
Tac nhan ai nhan
Trang thai chuyen tiep
+
Cl
-
+

-

-
H
H
H
HO Cl C
H
H
H
C
H
H
Cl
H
HO
- HO

trng thi chuyn tip lin kt c sp b ct t v lin kt mi sp to
thnh. Tc nhn i nhn HO
-
(tng qut Y
-
) tn cng vo carbon t pha sau ca
Cl (nhm i ra X) Sn phm ca phn ng c thay i cu hnh. Nu cht phn
ng ban u c cu hnh R th sn phm phn ng s c cu hnh S v ngc li.
C ch S
N1

Xy ra theo 2 giai on. Giai on chm l giai on quyt nh tc
phn ng. Trong phng trnh tc phn ng ch c nng ca cht phn
ng. Giai on chm quyt nh tc phn ng l giai on to ra carbocation
trung gian R
+
.
V d: HO
-
+ (CH
3
)
3
C
_
Br (CH
3
)
3
C
_
OH + Br
-

Phng trnh tc phn ng: v = k [(CH
3
)
3
C
_
Br]
Giai on chm: (CH
3
)
3
C
_
Br (CH
3
)
3
C
+
+

Br
-
Giai on nhanh: (CH
3
)
3
C
+
+ HO
-
(CH
3
)
3
C
_
OH
61
Phn ng xy ra theo c ch S
N1
c s racemic ha. C s racemic ha v
carbocation R
+
to ra giai on chm c cu trc phng v tc nhn i nhn
HO
tn cng vo carbon v 2 pha ca mt phng vi kh nng nh nhau. V vy

c 2 sn phm vi cu hnh ngc nhau c to thnh v c s racemic ha.
C th minh ha qu trnh lp th nh sau:
HO
-
C
CH
3
CH
3
OH
CH
3
C
CH
3
CH
3
HO
CH
3
CH
3
C
CH
3
CH
3
San pham cuoi
HO
-
+
San pham cuoi
Carbocation

Phn ng xy ra theo c ch S
N1
, c carbocation R
+
hnh thnh nn kh
nng c s chuyn v v to thnh sn ph l th hoc tch loi (xem thm
phn alcol).
Cc tc nhn i nhn Y
trong phn th i nhn c th l anion (HO-, Cl-,

Br -, I-), carbanion (-CH
2
CHO ...), cc tiu phn c cp in t lin kt (anion
CH
3
O- ..), hoc cc phn t c cp in t khng lin kt (NH
3
...)
Ch : Tnh base ca Y
-
cng mnh th tnh i nhn ca Y
-
cng mnh.
Ngc li tnh i nhn ca Y
-
mnh khng nht thit n l mt base mnh.
V d: HO
l mt base mnh ng thi HO
cng l mt tc nhn i nhn mnh.

Ngc li ion I
l mt base rt yu nhng n l mt tc nhn i nhn mnh.

C ch phn ng th S
N1
xy ra c tnh cht ion gia tc nhn i nhn Y
-
v
carbocation R
+

(hnh thnh giai on chm).
Phn ng th nhm X trong phn t R
_
X v tc nhn i nhn Y
-
, nu X gn
trc tip vi carbon bc nht RCH
2
_
X phn ng ch yu xy ra theo c ch S
N2

RCH
2
_
X + HO
-
RCH
2
_
OH + X
-
: c ch S
N2
.
Phn ng th nhm X trong phn t R X v tc nhn i nhn Y-, nu X gn
trc tip vi carbon bc ba (R)
3
C X phn ng ch yu xy ra theo c ch S
N1

(R)
3
C
_
X + HO
-
(R)
3
C
_
OH + X
-
c ch S
N1
Phn ng th nhm X trong phn t R
_
X v tc nhn i nhn Y
-
, nu X gn
trc tip vi carbon bc hai (R)
2
CH
_
X phn ng xy ra theo c ch S
N1
hoc S
N1

ph thuc vo cc yu t cu trc hoc dung mi.

(R)
2
CH
_
X + HO
-
(R)
2
CH
_
OH + X
-
c ch S
N1
hoc S
N2
Dung mi c nh hng n c ch phn ng. Dung mi phn cc lm cho
phn ng u tin xy ra theo c ch S
N1
. Dung mi khng hoc t phn cc lm
cho phn ng u tin xy ra theo c ch S
N2
.

62
2.3.2. C ch phn ng th i in t S
E
Phn ng th i in t ch yu xy ra cc hp cht ca hydrocarbon thm
v d vng thm (xem thm phn hydrocarbon thm v d vng). Tc nhn i
in t Y
+
l nhng tc nhn mang in tch dng (
+
NO
2
, Br
+
) hoc phn t
thiu in t (SO
3
, CO
2
...). Cht phn ng l nhng hp cht vng c cu trc
thm Ar -H (ph hp vi cng thc Huckel) .
H E
Hnh 5-4. Cac qua trnh cua phan ng the ai ien t
Tien trnh phan ng
E
Chat trung gian
E
+
E
H
H
+
E
H
Phc
Phc
San pham
Chat phan ng

Hnh 5.4: Cc qu trnh ca phn ng th i in t
Phn ng th i in t xy ra qua nhiu giai on.
Giai on tng tc gia E
+
v Ar -H to phc .
Giai on chuyn phc hnh thnh phc .
Giai on to sn phm cui cng.
Thc t trong phn ng th i in t thng c vai tr ca xc tc (xem
phn hydrocarbon thm).
San pham Phc
Phc
+
+ H
+
+
+
E
E
H
E
+
E
+
E
H
H

T cht phn ng ban u n sn phm cui tri qua s hnh thnh cc
phc hot ng (trng thi chuyn tip ng vi cc cc i nng lng trn gin
nng lng (hnh 5-4).
2.3.3. C ch phn ng th gc t do S
R
Phn ng th theo c ch gc l phn ng dy chuyn c ba giai on:
Giai on khi mo.
Giai on pht trin mch v to sn phm.
Giai on tt mch v kt thc phn ng .

63
V d: Phn ng clor ha alkan xy ra nh sau .
Giai on khi mo: Cl
_
Cl Cl
.
+ Cl
.

Giai on pht trin mch: R
_
H + Cl
.
R
.
+ HCl
tip tc...............................

Giai on tt mch v kt thc phn ng: R
.
+ R
.
R
_
R
Cl
.
+ Cl
.
CL - CL
Giai on quyt nh tc phn ng l giai on pht trin mch .
Gc t do c cu trc phng, phn t Cl
2
tn cng t 2 pha ca mt phng
(tng t c ch th S
N1
) v vy sn phm phn ng dn n s racemic ha.
2.4. C ch phn ng cng hp (k hiu Ad)
2.4.1. C ch phn ng cng hp i in t Ad
E
Phn ng cng hp xy ra gi phn t E
_
Y v cht phn ng c lin kt i
C =C v lin kt ba C C l phn ng cng hp i in t c cc giai on:
Giai on to tc nhn i in t E
+
v anion Y
-
t phn t E Y
Tng tc ca E
+
vi cht phn ng c ni i, ba to thnh carbocation R
+

Tng tc gia carbocation R
+
v Y
-
v to thnh sn phm cng hp.
Tng tc ca E
+
vi cht phn ng c ni i, ba to thnh carbocation R
+

xy
ra chm nn n l giai on quyt nh tc phn ng.
V d: Phn ng cng hp ca HBr vo propylen CH
3
CH=CH
2
xy ra nh sau:
H
_
Br H
+

+ Br
-
H
+
l tc nhn i in t E
+
; Br
l Y
-
.
Cham
+
+
CH
3
CH
2
CH
2

CH
3
CH CH
3

hoac
+
CH CH
2
H
CH
3
+ H
+
CH
3
CH CH
2

+
+
CH
3
CH CH
3

+
CH
3
CH
2
CH
2

+
Br
-
CH
3
CHBr CH
3

CH
3
CH
2
CH
2
Br Br
-
Nhanh

Carbocation to thnh l vng tam gic cu to phng. Mt in tch
dng trn hai nguyn t carbon l nh nhau. Y
-
(Br
-
) tn cng v hai pha ca
mt phng vi xc sut nh nhau. V vy cng lc hai sn phm cng hp c
to thnh. Gii thch iu theo s di y:
CH CH
3
Br
CH
2
H
Br
-
Br
-
+
CH CH
2
H
CH
3
CH CH
3
H
CH
2
Br

64
Dung mi v cu to phn t E
_
Y c nh hng quyt nh n s hnh
thnh tc nhn i in t E
+
.
2.4.2. C ch phn ng cng hp i nhn
Phn ng cng hp i nhn thng xy ra gia tc nhn i nhn Y
-
vi cc
hp cht c ni i C =O, C=N
_ ....

Phn ng c cc giai on nh sau:
S tng tc gia tc nhn i nhn Y - vo trung tm mang in tch dng
ca carbon trong nhm carbonyl ( C=O
+
C O
) to thnh ion mang

in tch m trn oxy.
RCH=O + Y
-
RCHY
_
O
-

Ion m to thnh s kt hp ion dng (H
+
) to thnh sn phm cui cng.
RCHY
_
O
-
+ H
+

RCHY
_
OH
Nhiu hp cht c cha nhm chc carbonyl tham gia phn ng cng hp i
nhn v ng thi km theo s tch loi. C th xem loi phn ng ny nh l
mt loi phn ng th hoc phn ng cng v tch''
R C X
O
+ Y
-
R C Y
O
+ X
-

in tch dng trn nguyn t carbon ca C =O cng ln th kh nng
phn ng cng cao. Thay X bng nhm th c nh hng in t th kh nng
phn ng thay i.

R C Cl
O
R C O
O
C R'
O
R C O
O
R C O
O
R'
..
..
R C O
O
H
..
-
> > >
>

2.5. C ch phn ng tch loi (k hiu E)
Phn ng tch loi to lin kt i xy ra theo 2 c ch: c ch lng phn
t E
2
v c ch n phn t E
1
.
2.5.1. C ch tch loi E
2

Phn ng xy ra theo cc giai on.
Tng tc gia mt base mnh vi cht phn ng hnh thnh trng thi
chuyn tip.
S tch loi xy ra v to sn phm c lin kt i.
Tng qut:
Y
-
+
H C C X H C C X Y

C C YH + + X
-
Trang tha i chuye n tiep Base manh San pham Chat phan ng

65
V d: Phn ng tch loi HBr t ethylbromid di tc dng ca C
2
H
5
O
l
mt base mnh to thnh ethylen c c ch nh sau:

+ Br
-
+
+
C
2
H
5
OH
C
2
H
5
O C
2
H
5
O
-
H
C
CH
3
H
C
H
H
C
H
CH
3
H
H
C
Br H
C
H
CH
3
H
H
C
Br

iu kin v ha lp th cho c ch E
2
xy ra khi 4 trung tm phn ng
(H C C Br) trn mt mt phng. H v Br v tr trans vi nhau (v tr anti).
Minh ha c ch theo cch biu din hnh chiu Newman:
+ C
2
H
5
O
-
C
C
H
CH
3
H
H
+ C
2
H
5
O
-
- C
2
H
5
OH
- Br
-
CH
3
H
H
Br
H
H
CH
3
H
H
Br
H
H

2.5.2. C ch tch loi E
1

Phn ng xy ra theo 2 giai on.
Cht phn ng to carbocation R
+

l giai on chm
.

Tch H
+

v to ni i l giai on nhanh.
Tng qut:
Chat phan ng
Sa n pha m
+ X
-
C C
H C C
H C C X +
H C C
+ + H
+
Carbocation
Cha m
Nhanh
Carbocation

V d: Tch HBr khi 2-Brom-2,3-dimethylbutan .
C C
H C C Br
+
- H
+
Carbocation
CH
3
CH
3
CH
3
CH
3
H C C
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3 - Br
-

Cc phn ng c s cnh tranh ln nhau. Khi tin hnh phn ng th
thng km theo phn ng tch loi. Cc iu kin nh dung mi, nng , nhit
c nh hng ng k n c ch phn ng.
66
Chng 6
CC PHNG PHP HA HC V VT L
XC NH CU TO CHT HU C
Mc tiu hc tp
1. Hiu v bit cch s dng cc phng php ha hc v vt l xc nh
cu trc ca phn t
2. ng dng ca quang ph t ngoi, hng ngoi v cng hng t ht nhn
trong vic xc nh cu trc phn t.
Ni dung
Mt cht hu c c ng dng trong thc t phi bo m tinh khit,
phi tha mn v thnh phn cc nguyn t ha hc v cng thc cu to. Xc
nh cng thc cu to ca mt cht hu c tch/chit c t ngun gc thin
nhin hay tng hp c l cng vic rt cn thit v quan trng trong ha hu
c. C th xc nh cu to cht hu c bng phng php ha hc hay vt l.
1. Phng php ha hc
ng dng phng php php ha hc xc nh cng thc phn t v
nhm chc ha hc bng cc phn ng c trng.
1.1. nh tnh v nh lng nguyn t
nh tnh v nh lng cc cht hu c l xc nh s hin din cc nguyn
t v thnh phn nh lng ca cc nguyn t trong mt cht hu c.
1.1.1. nh tnh cc nguyn t v nhm chc
xc nh s c mt cc nguyn t c trong cht hu c, thng tin hnh
v c ha, ngha l chuyn cc nguyn t v dng ion v dng cc phn ng nh
tnh xc nh cc ion .
V d: V c ha hp cht hu c th carbon s chuyn thnh CO
2
hoc CO
3
2-
,
nguyn t halogen (X ) chuyn thnh X
-
, nguyn t N chuyn thnh CN
-
...
Dng cc phn ng nh tnh c trng xc nh cc ion CO
3
2-
, ion X
-
, ion CN
-
.

nh tnh cc nhm chc bng cc phn ng c trng. V d: Chc OH
alcol tc dng vi natri c hydro thot ra. Chc aldehyd cho phn ng trng
gng vi thuc th Tollens...
Ngy nay c cc phng php vt l xc nh cc nhm chc mt cch
nhanh chng v chnh xc.
67
1.1.2. nh lng cc nguyn t
Xc nh thnh phn phn trm v khi lng cc nguyn t trong cht hu
c theo 2 phng php ch yu sau:
Phng php Dumas
nh lng cc nguyn t C, H, N, S v halogen c trong cc cht hu c.
Nguyn tc: t chy cht hu c bng mt lung kh oxy. Cc nguyn t
chuyn thnh CO
2
, H
2
O, N
2
, SO
2
, X
2
. Hp thu cc kh sinh ra vo cc cht thch
hp. Xc nh khi lng cc kh v suy ra thnh phn phn trm cc nguyn
t c trong hp cht hu c. Ngy nay c cc my mc tinh vi nh lng chnh
xc cc nguyn t.
Phng php Kjendall
ng dng phng php Kjendall nh lng nguyn t nit c trong cc
cht hu c. Phng php ny rt ph bin xc nh nit trong cc cht amin
v acid amin. Nguyn tc ca phng php Kjendall l chuyn nit v dng NH
3

hay NH
4
+
sau dng phng php chun xc nh hm lng NH
3
hay NH
4
+

v suy ra thnh phn phn trm ca nit c trong cht hu c.
2. Phng php vt l
ng dng cc phng php vt l xc nh cc tiu chun v tinh
khit v xc nh cc nhm chc, cc lin kt c trong hp cht hu c.
2.1. Cc tiu chun vt l
2.1.1. Nhit nng chy v nhit si
Nhit nng chy
Cc cht hu c dng rn tinh khit c nhit nng chy xc nh. Nhit
nng chy ca mt cht l nhit m tng rn v tng lng nng chy ca
cht trng thi cn bng vi nhau. Nhit m tt c cc tinh th u nng
chy c coi l im kt thc ca khong nhit nng chy.
Nhit si
Cht hu c lng tinh khit c c trng bng nhit si. Nhit si
ca mt cht l nhit m ti cht lng bin thnh hi. Tng lng v tng
hi trng thi cn bng. Nhit si ca cht lng ph thuc vo p sut. Cht
lng tinh khit lun c nhit si xc nh.
Nhit nng chy, nhit si l nhng tiu chun xc nh tinh khit
ca cht rn hoc cht lng.
2.1.2. Ch s khc x
Ch s khc x l mt tiu chun nh gi tinh khit ca cht lng.
Theo nh lut Snellius, nu nh sng n sc b khc x ti b mt ranh gii
gia hai mi trng ta c:
68
sin
sin
=
C
2
C
1
n =
Moi trng 1
Moi trng 2
C
1
va C
2
la toc o ang sang trong moi trng 1 va 2

Thng ngi ta ly khng kh lm mi trng so snh. Ch s khc x ph
thuc vo nng , nhit v bc sng ca nh sng.
2.2. Cc phng php sc k
S dng cc phng php sc k tch ring cc cht trong hn hp v cn
dng phng php sc k xc nh tinh khit ca mt cht.
Sc k l mt phng php vt l dng tch cc thnh phn ra khi hn
hp bng cch phn b chng thnh 2 pha: mt pha c b mt rng gi l pha c
nh v pha kia l mt cht lng hoc cht kh gi l pha di ng, di chuyn i
qua pha c nh. C 2 loi sc k: sc k lng v sc k kh.
2.2.1. Sc k lng
Sc k lng l phng php sc k dng cht lng lm pha di ng. Trong
sc k lng c cc k thut:
Sc k giy: Pha tnh (pha c nh) l giy.
Sc k lp mng: Pha tnh l mt lp mng cht hp ph c trng bng
phng v u n trn mt tm knh hoc kim loi.
Sc k ct: Pha tnh l cht rn c nhi thnh ct. Trong k thut sc
k ct, ty theo bn cht ca cht rn lm ct cn c chia thnh:
+ Ct c in: Ct n gin vi cht hp ph thng thng v c hoc hu c.
Ct trao i ion: Ct l cht trao i ion m (anion) hoc dng (cation).
+ Ct gel hoc lc gel (gel filtration) : Pha c nh l mt loi gel tng hp
c l xp xc nh dng lc cc cht c kch thc phn t khc nhau.
Sc k lng cao p (high pressure liquid chromatography) cn gi l sc k lng
hiu nng cao HPLC (high performance liquid chromatography).
2.2.1. Sc k kh
Sc k kh l phng php sc k dng cht kh lm pha di ng. Da vo
pha c nh, cn chia ra:
Sc k kh -rn: Pha c nh l cht rn.
Sc k kh -lng: Pha c nh l cht lng.

69
2.3. Cc phng php ph
Khi mt cht hu c hp th nng lng bc x in t th phn t c th
tri qua nhiu dng kch thch. Cc kch thch c th l kch thch chuyn dch
in t, kch thch quay, kch thch lm thay i spin ht nhn nguyn t, kch
thch lm bin dng lin kt, nu nng lng cao c th gy ion ha phn t.
Bng 6.1: Vng bc x in t
Vng ph in t di sng Nng lng kch thch Dng kch thch
Bc x gama, tia X
V tia v tr
< 100 nm > 286 Kcal
- Tia t ngoi
Xa (vng chn khng)
Gn (vng thch anh)

100-200 nm
200-300 nm

286 - 143 Kcal
143 - 82 Kcal

in t
in t
- Kh kin 350-800nm 82 - 86 Kcal in t
- Hng ngoi
Hng ngoi gn
Hng ngoi
Hng ngoi xa

0,8-2,0 m
2-16,0 m
16,0-300 m

36 - 14,3 Kcal
14,3 - 1,8 Kcal
1,8 - 0,1 Kcal

Bin dng lin kt
-nt-
-nt-
- Vi sng cm
10
-4
Kcal
Quay
- Tn s radio mt
10
-6
Kcal
Thay i spin ht nhn
Mi dng kch thch u cn n mt nng lng nht nh v s hp th
tng ng vi mi mc nng lng s xy ra mi vng khc nhau trn ph
in t .
Bng 6-1 lit k vng ph electron, di sng, nng lng kch thch v
dng kch thch khi chiu bc x vo cht hu c.
Nu chng ta v th ph thuc ca nng lng bc x c truyn qua vi
tn s (), s sng (), bc sng (),chng ta nhn c mt ph hp th. Cc
phn t hu c c cu to khc nhau th c ph hp th khc nhau. V vy quang
ph hp th l phng php xc nh cu trc phn t rt chnh xc v hiu qu.
Ghi nhng ph hp th c tin hnh bng nhng thit b (my quang
ph) gm c nhng b phn ch yu l ngun bc x A, mt cuvet o B ng
cht kho st, mt my n sc C (cch t hay lng knh) v mt thit b pht
hin bc x D vi my ghi cc tn hiu c phng i E.
A B
C D
E

Hnh 6.1: S mt quang ph k
Ty thuc vo v tr tn s hp th trong di tn s ca bc x in t m ta
gi chng l quang ph Rnghen, quang ph electron, quang ph hng ngoi hay
quang ph vi sng. Ngy nay quang ph t ngoi (UV), quang ph hng ngoi
(IR), quang ph cng hng t ht nhn (NMR) v khi ph l nhng phng tin
quan trng v chnh xc xc nh cu to cc cht hu c.
70
2.3.1. Quang ph t ngoi (UV)
S hp th trong vng t ngoi v kh kin ph thuc vo cu trc in t
ca phn t. S hp th y gy ra s chuyn dch cc in t t orbital c bn ln
orbital c nng lng cao hn trng thi kch thch.
Ph t ngoi ch p dng xc nh cu trc ca phn t c h thng lin
kt - v p -. Trn ph t ngoi cc v tr bng (hay cn gi l di) hp th c
o bng di sng (lam- a).
n v di sng trong vng t ngoi thng c biu th bng nanomet
(1nm = 10
-7
cm). Cng hp th c biu th bng hp th phn t
max

hoc log
max
. S hp th c nhiu ng dng trong quang ph t ngoi l trong
vng t 200 - 380 nm, gi l vng t ngoi gn.
Nng lng ca mt phn t l tng cc nng lng electron, nng lng dao
ng v nng lng quay ca chng. ln cc nng lng ny gim theo th t:
Nng lng in t > Nng lng dao ng > Nng lng quay
Nng lng hp th trong vng t ngoi gy ra s bin i nng lng
electron, do s chuyn dch in t ha tr trong phn t t orbital trong trng
thi c bn (thng l orbital p khng lin kt hoc orbital lin kt) ln orbital
c nng lng cao hn (orbital phn lin kt * hoc *).
Bng 6.2: Trnh by cu trc in t v s chuyn dch ca chng
trong mt s hp cht hu c.
Cu trc
electron
Hp cht Chuyn dch
electron
max
(nm)
max
Bng
hp th
Etan

*

135 - -
n H
2
O
Methanol
n
*
n
*

167
183
7.000
500
-
-
Ethylen
Acetylen

*

*

165
173
10.000
6.000
-
-

v n

Aceton

*
n
*
n
*

150
188
279
-
1.860
15
-
-
R
- 1,3-Butadien

*

217 21.000 K
v n Acrolein

*

210 11.500 K

thm

Benzen

*
thm

*
thm

*
thm
180
200
255
60.000
8.000
215
E
1
E
2

B
- Toluen

*
thm

*
thm
208
262
2.460
174
E
2
B
-n thm Phenol

*
thm

*
thm
210
270
6.200
1.450
E
2
B
71
Mt s thut ng thng dng trong quang ph t ngoi:
Nhm mang mu (Chromophore): l nhng nhm khng no gy ra hp
th in t. Cc nhm nhm mang mu c: C=C, C=O, NO
2
.
Nhm tng mu (Auxochrome): l nhng nhm chc no hoc c in t p
khng lin kt. Cc nhm chc ny c tc dng ko di h thng lin hp.
Khi gn cc nhm ny vi nhm mang mu th nh hng n di
sng hp th v cng hp th.
Cc nhm tng mu thng gp: -OH, -NH
2
, - Cl
Hypecromic (Hypechromic): l s tng cng hp th.
Hypocromic (Hypochromic): l s gim cng hp th.
Chuyn v hng hng hay chuyn v bathocromic (Bathocromic shift): l
s chuyn dch bng hp th sang bc sng di hn do c cc nhm th
hoc nh hng ca dung mi.
Chuyn v hng lam hay chuyn v hypsocromic (Hypsochromic shift): l
s chuyn dch bng hp th sang bc sng ngn hn do cc nhm th
hoc dung mi. C th trnh by s chuyn dch in t trong mt s hp
cht nh sau:
+ S chuyn dch in t ca phn t butadien v hexatrien c m t
theo m hnh di y:
h
Trang thai c ban
cua butadien
Trang thai kch thch
cua butadien
6
217 nm
258 nm
Trang thai c ban
cua hexatrien
Trang thai kch thch
cua hexatrien

+ S chuyn dch in t ca phn t aceton v methylvinylceton:

1
n
h
n
h
(n-
)
h
4
Aceton Methyl vinyl ceton

72
Hp th c trng ca mt s nhm chc hu c.
+ Cc hp cht no ch c lin kt hoc electron khng lin kt (n hoc p)
khng cho cc bng hp th trong vng t ngoi gn. V vy alcol thng
c dng lm dung mi trong vic o quang ph t ngoi.
+ Cc hp cht hu c cha nhm chc c lin kt (C=C, C=N-, C=O,
N=O, S=O) thng c cc bng hp th c trng trn ph t ngoi. Cc
nhm chc ny gi l nhm mang mu.
Bng 6.3: di sng v chuyn dch in t cc nhm mang mu
Nhm mang
mu
Cu to V d
max
(nm)
max
Chuyn dch
electron
Ethylenic RCH=CHR CH
2
=CH
2
165
193
15.00
10.00
-
*
-
*
Acethylenic RCCR CHCH 173 6.000 -
*
Carbonyl RR
1
C=O

RCH=O
CH
3
COCH
3

CH
3
CHO
188
279
290
900
15
16
-
*
n -
*
n -
*
Carboxyl RCOOH CH
3
COOH 204 60 n -
*
Amid RCONH
2
CH
3
CONH
2
208 - n -
*
Azometin C=N- (CH
3
)
2
C=N-OH 190 5.000 -
*
Nitril -CN CH
3
CN 160 - -
*
Azo -N=N- CH
2
-N=N 347 4.500 n -
*
Nitroso -N=O C
4
H
9
-N=O 300 100
Nitrat -ONO
2
C
2
H
5
ONO
2
270 12 n -
*
Nitrit -ONO C
5
H
11
NO 218 1.120 -
*
Nitro -NO
2
CH
3
NO
2
271 18.60 n -
*
Sulfon - SO
2
- (CH
3
)
2
SO
2
180 -
+ Nu trong phn t c nhm tng mu hoc c h thng lin hp th bc
sng s tng ln. V d:
Bng 6.4: nh hng cc nhm tng mu n bc sng
Hp cht
1
3
CH
3
COOH 204 - -
CH
3
(CH=CH)
2
COOH 254 - -
C
6
H
6
204 256 -
C
6
H
5
Cl 210 265 -
C
6
H
5
OH 210 270 -
C
6
H
5
NO
2
252 280 330

73
200 250 300 350 400
0,0
0,5
0,1
0,2
0,3
1,5
1,4
1,3
1.2
1.1
1,0
0,9
0,8
0,7
0,6
0,4
(nm)

Hnh 6.2: Ph t ngoi ca ceton oxyd mesityl (CH
3
)
2
C=CHCOCH
3
2.3.2. Quang ph hng ngoi (IR)
Cc cht hu c hp th bc x hng ngoi nhng tn s trong vng t
10.000 -100cm
-1
(1-100m) v bin thnh nng lng dao ng ca phn t. Trong
nhng dao ng ca phn t, cc nguyn t c th chuyn ng theo chiu ca
lin kt gi l dao ng ha tr hoc chuyn ng ca nguyn t lm bin dng
(quay) lin kt gi l dao ng bin dng. Nng lng dao ng bin dng thp
hn nng lng dao ng ha tr.
Phn t H
2
O c cc dao ng nh sau:
Dao ong hoa tr
khong oi xng
1595cm
-1
3655cm
-1
3756cm
-1
Dao ong hoa tr
oi xng

Dao ong bien dang
goc len ket

Hnh 6.3: Cc dao ng ca phn t nc
Tn s hay di sng hp th ca mi cht ph thuc vo khi lng
tng i ca cc nguyn t, vo hng s lc lin kt, vo cu trc hnh hc ca
phn t.
d
=
1
2
K
=
m
1
.m
2
m
1
+m
2

74
l tn s dao ng ca lin kt.
l khi lng rt gn
m
1
v m
2
l khi lng ca 2 nguyn t lin kt vi nhau
K l hng s lc lin kt.
V tr di hp th c o bng di sng hoc bng s sng

.
n v di sng s dng trong vng hng ngoi l micromet - m (m =
10
-6
m). n v s sng c dng l cm
-1
.
cm
-1
=
m
1
10
4

Cng hp th c biu th bng truyn nh sng (Transmittance)
vit tt l T, hoc bng hp th (Absorbance) vit tt l A.
A = log ( )
1
T

Xut hin mt s di hp th nht nh trong ph hng ngoi l c trng
s c mt ca mt s nhm chc xc nh trong phn t. V vy ph hng ngoi c
ngha phn tch cu trc phn t cc cht hu c. Cc cht hu c thng
hp th trong vng hng ngoi t 4.000 - 400cm
-1
(2,5-25m).
Bng 6.5: Tn s c trng cc chc hu c
Hp cht Tn s cm -1 Cng Dao ng lin kt
Alkan 2850-3000
1450-1470
1370-1380
720 - 725
s
s
s
m
C-H dao ng ho tr

CH
2
v CH
3
bin dng
Alken
RCH=CH
2

3080-3140
1800-1860
1645
990
910

m
m
m
s
s

=C-H

C=C
C-H
R
2
C=CH
2
3080-3140
1750-1800
1650
890
m
m
m
f
=C-H

C=C
C-H
Alkyn
RCCH

RCCR

3300
2100-2140
600-700
2190-2260

f
m
f
tf

C-H
CC
C-H
CC
75
Bng 6.5 (tip)
Hp cht Tn s cm -1 Cng Dao ng lin kt
Alkyl halogenid
R-F
R-Cl
R-Br
R-I

1000-1350
700-850
500-600
200-500

tf
f
f
f

C-F
C-Cl
C-Br
C-I
Alcol
RCH
2
OH

R
2
CHOH

R
3
COH

3600
3400
1050
3600
3400
1150
3600
3400
1200

v
f
f
v
f
f
v
f
f

O-H
O-H
C-O
O-H
O-H
C-O
O-H
O-H
C-O
Ether 1070-1150 f C-O
Acid R-COOH

2500-3300
1760
v
f
O-H
C=O
Aldehyd R - CHO 1725
2720, 2820
f
m
C=O
C-H
Hnh 6.4 l ph hng ngoi IR ca phn t 2-methylprophanol
3360 1200
4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 600 800 400

Hnh 6.4: Ph hng ngoi (IR) ca phn t 2-methylpropanol.
2.3.3. Quang ph cng hng t ht nhn (RMN)
Cc ht nhn nguyn t c proton v ntron. Nhng ht nhn c s l
proton hoc s l ntron u c momen t .
76
Bng 6.6: T tnh ca mt vi ht nhn nguyn t
Ht nhn S proton S ntron Spin Momen t
1
H 1 0 1/2 2,79267
12
C 6 6 0 0.00
13
C 6 7 1/2 0,70216
14
N 7 7 1 0,40357
16
O 8 8 0 0,00
19
F 9 10 1/2 2,6275
31
P 15 16 1/2 1,1306
32
S 16 16 0 0,00
Nu mt ht nhn nh vy nm trong mt t trng ng dng H
o
(t trng
tnh, t trng c nh, t trng bn ngoi) th momen t ca ht nhn c hai
kh nng nh hng khc nhau. Kh nng nh hng ca ph thuc vo s
lng t spin ca ht nhn. nh hng th nht song song vi hng ca t
trng ng dng H
o
k hiu l spin . nh hng th hai i song vi t trng
ng dng k hiu spin .
Momen t hat nhan
Momen t hat nhan trong t trng

H
o

Hnh 6.5: S nh hng ca momen t ht nhn
Spin trng thi nh hng song song - spin c mc nng lng thp.
Nu tc dng mt tn s bc x thch hp ln phn t hu c ang t trong t
trng H
o
, proton c spin hp th nng lng, b kch thch v chuyn dch ln
mc nng lng cao hn lm thay i nh hng thnh spin . Hin tng gi
l s cng hng t ht nhn. Ghi li nhng tn hiu cng hng, thu c ph
cng hng t ht nhn (NMR).
h
H
o

Hnh 6.6: S thay i nh hng spin do hp th nng lng
o trng hp cng hng, ngi ta a mu hp cht kho st (cht
lng hay rn) vo t trng khng i H
o
(trng ng dng). Hp cht c bao
quanh bi mt bobin cm ng to ra mt trng xoay chiu cao tn c tn s .
77
Cng H
o
ca trng c thay i cho n khi thu c trng hp cng
hng. Mu tip nhn nng lng ca trng xoay chiu v nhn bit bi s bin
thin ca ngun pht sng cao tn. S bin thin dng in c o v ghi li bi
my ghi.
S my cng hng t ht nhn c trnh by trn hnh 6-7
H
H
o
o
Nguon phat song cao tan
Cc t trng
Cc t trng
Ong ng mau
May ghi
...
...
...
...
...
...
N S

Hnh 6.7: S my cng hng t ht nhn
Hnh 6.8 l ph cng hng t ht nhn ca ethanol vi phn gii thp
CH
3
CH
2
HO

Hnh 6.8: Ph RMN ca ethanol vi phn gii thp.
Cc thng s phn tch ph RMN:
Hng s chn v chuyn dch ha hc
Nu ht nhn b che chn bi mt v in t th v in t lm yu t
trng chung quanh ht nhn. Ta c biu thc:
H
hiu dng
= H
o
- H
o

l hng s che t (hng s chn)
Tn hiu cng hng ch xut hin mt cng t trng bn ngoi H
o

ln hn so vi mt ht nhn khng b che chn. Hiu ng ny c gi l chuyn
dch ha hc (Chemical shift), bi v n ph thuc vo thuc tnh in t bao
quanh ht nhn (cu trc ha hc). chuyn dch ha hc k hiu l .
78
xc nh v tr ca mi dng proton trn ph NMR ngi ta dng mt
cht lm chun. Cht chun thng dng l TMS (tetramethyl silan (CH
3
)
4
Si).
Mc chnh lch v v tr hp th gia proton cht th v proton cht chun l
chuyn dch ha hc ca cht th. n v dng biu th chuyn dch ha
hc l (delta) hoc ppm (phn triu).
Nu pic ca TMS ti v tr hp th 60 Hz ( 60) trong tn s bc x in t
60MHz th s l 1, 00 hoc 1, 00 ppm.
60
= 1,00
.10
6
( hoac ppm ) =
60.10
6

Trong h thng n v (hoc ppm) ngi ta qui c v tr hp th ca TMS
l 0 Hz ( = 0 ppm). chuyn dch ha hc ca proton cht th s c so snh
vi tr s ny.
Cn c h thng n v khc gi l (tao) cng c s dng o chuyn
dch ha hc. Theo h thng n v ny th tr s hp th ca TMS l 10.
= 10,00 -
Ph NMR ca ethanol (hnh 6-8) c 3 tn hiu cng hng tng ng vi
nhn hydro ca nhm OH, CH
2
v nhm CH
3
, v proton ca cc nhm trn c
min ph cn khc nhau v mt ha hc. Cc proton ca nhm methyl b che
chn mnh nht, proton ca nhm OH b che chn yu nht.
S tng tc spin - spin v hng s tng tc spin -spin J
Khng phi lc no mi dng proton ng lng cng cho mt nh ring
bit. Nhiu trng hp, mt dng proton li th hin s hp th ca n bng mt
vch hp th nhiu nh. C hin tng l do cc proton ng cnh nhau
tng tc spin - spin vi nhau.
Hin tng tng tc spin -spin xy ra l v cc in t lin kt c xu hng
ghp i spin ca n vi spin ca proton gn nht bn cnh. Spin ghp i ny li
nh hng n proton bn cnh tip theo v gy nn cc t trng ca cc ht
nhn bn cnh. T trng ny tc ng ln proton v xut hin s cng hng
ng thi cho cc tn hiu. Cc tn hiu ny chnh l cc nh i (doublet), nh
ba (triplet), nh t (quartet)..., nh a (multiplet) trn ph NMR. Khong cch
gia 2 nh tch ra c o bng Hz gi l hng s tng tc spin -spin k hiu J
(cn gi l hng s ghp spin).
Cn c vo cc gi tr v J thu c trn ph NMR ngi ta bin lun v
tm cng thc cu to ph hp ca cht hu c.
V d: o ethanol trn my c phn gii cao, ph NMR ca ethanol c cc
nh 3, nh 4.., (hnh 6-9).
79
-CH
2
-
-CH
3
TMS
0 5
4
3 2
1 ppm
-OH

Hnh 6.9: Ph RMN ca C
2
H
5
OH vi phn gii cao
2.3.4. Ph khi (MS)
Ph khi l phng php phn tch s dng mt chm in t c nng lng
cao (70 von electron) bn vo cht cn xc nh cu trc, ph chng thnh tng
mnh (fragmentation) ion mang in tch dng. My pht hin cc ion ny v
ghi thnh pic vi cng khc nhau tng ng vi khi lng ca chng. l
khi ph.
V d: Cc mnh ion to thnh khi bn chm in t vo phn t
2-methylpentan. Trc tin phn t mt mt in t v b ion ha. Phn t ion
ny b phn chia thnh cc mnh mang in tch dng c khi lng tng ng:
+ e
-
2e
-
+
CH
3
CH
2
CH
2
CHCH
3
CH
3
+
.
CH
3
CH
2
CH
2
CHCH
3
CH
3

CH
3
.
.
CH
3
CH
2
m/e 71
m/e 57
+
+
+
CH
3
CH
2
CH
2
.
m/e 86
+
.
CH
3
CH
2
CH
2
CHCH
3
CH
3
CH
3
CH
2
CH
2
CH
CH
3
+
m/e 43
+
CHCH
3
CH
3
CH
3
CHCH
3
CH
3
+

Cc tn hiu v khi lng v cng ca cc mnh c ghi li trn ph
khi. Hnh 6-10 l khi ph ca phn t 2-metylpentan.
Ngy nay cc my quang ph c thm cc b phn my tnh, cho nn cc qu
trnh tnh ton v v ph u c t ng v kt qu phn tch ngy cng c
hon thin hn.

80
10
20
71
57
60
70
80
90 100
40
20 30 40 50 60 80
100
43
86 M
+
m/e
Cng o

Hnh 6.10: Ph khi ca 2-methylphentan
Trn y ch trnh by khi qut cc phng php ha hc v phng php
vt l xc nh cu trc cht hu c. C nhiu ti liu chuyn su v lnh vc
ny. C th tm tt cc giai on xc nh cu to cht hu c theo s sau:
S o cac giai oan xac nh cau tao chat hu c
Chat hu c tach chiet
hoac tong hp
Tinh che (ket tinh, chng cat, sac ky)
Chat hu c tinh khiet
Xac nh cac hang so vat ly
t

s t c
n
nh tnh, nh lng
cac nguyen to
nh tnh nhom chc
UV IR RMN
MS
Ket luan ve cau truc
cua chat hu c
o o

81
Chng 7
ALKAN - HYDROCARBON NO
(C
n
H
2n+2
)
Mc tiu hc tp
1. c c tn cc alkan thng dng
2. Nu c ha tnh ca alkan v ng dng ca chng trong cuc sng.
Ni dung
1. Ngun gc thin nhin - Cu to, ng phn, cu dng
1.1. Ngun gc thin nhin
Alkan l nguyn liu t nhin c t du m, kh thin nhin.
Kh thin nhin cha cc kh vi thnh phn khng c nh, thng cha
75% metan, 15% etan, 5% propan, phn cn li l cc alkan cao hn v nhiu cht
khc. Kh thin nhin c dng lm nhin liu v trong qu trnh k ngh.
Ngun alkan ch yu l du m, thng thu c cc cht sau:
Bng 7.1: Cc alkan trong du m
Cc cht Thnh phn t si
Kh C
1
C
4
< 20
Ether du ha C
5
C
6
20-60
Xng C
6
C
8
60-200
Ligroin C
7
60-90
Gazolin C
6
C
12
85-200
Keroxin C
12
C
15
200-300
Du mazut C
16
C
23
200-400
Du bi trn C
18
C
22
300
Atphan dng phng php hydro ha than nu bng cch nghin nh than
vi du nng c xc tc st v H
2
nhit 450C, p sut 200-300 atm, thu c
sn phm th, sau khi chng ct thu c kh, xng v sn phm du nng.
1.2. Cu to
Alkan l hydrocarbon no (hydrocarbon bo ha, parafin) c cng thc chung
C
n
H
2n+2
. Cht n gin nht l metan CH
4
. Cu to mch thng hay phn nhnh.
82
metan
H H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H H
H
H
H
H
H
H
H H
H
H
n-pentan isopentan

1.3. ng phn
Alkan c ng phn mch thng v phn nhnh. S ng phn tng khi s
carbon tng.
Bng 7.2: S ng phn ca mt s alkan
S carbon Tn cht S ng phn S carbon Tn cht S ng phn
1
2
3
4
5
6
Metan
Etan
Propan
Butan
Pentan
Hexan
1
1
1
2
3
5
7
8
9
10
20
30
Heptan
Octan
Nonan
Decan
Eicozan
Tricozan
9
18
35
75
366319
4,11.10
9
1.4. Cu dng
Do tnh cht i xng trc ca lin kt , hai nguyn t carbon lin kt vi
nhau c th quay t do quanh trc lin kt. S quay t do km theo s tiu
hao nng lng. Chnh v c s quay t do quanh trc lin kt C C nn cc
alkan c cc ng phn cu dng (ng phn hnh th - conformer).
Etan tn ti di nhiu cu dng khc nhau. Hai dng cu dng thng
thng nht l dng che khut (t bn) v dng lch (bn), hnh 7-1
H
H
H
H
H
H
H
H
H
H
H
H
H
Khuat
Lech
Cong thc Newman
Lech Khuat
Cong thc phoi canh
H
H
H
H
H
H
H
H
H
H
H H
Cong thc lap the
thong thng
H
H
H
H
H
H
H
H
H
H
H

Hnh 7.1: Cch biu din cc cu dng ca etan
Che khut Lch
M hnh phn t etan

83
Khi gc nh din bng 0; 120 ; 240 ; 360 c cc dng che khut.
Khi gc nh din bng 60; 180 ; 300

c cc dng lch.
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
goc quay
Kj/mol
E
360 300 240 180 120 60 0
11,7

Hnh 7.2: Gin ph thuc nng lng v gc quay ca cc cu dng ca etan

H
H
H
H
H H
HH
H
H
H H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
(goc quay)
360 300 240 180 120 60
14,2
0
3,4
25,5
E
(Kj/mol)

Hnh 7.3: Gin ph thuc nng lng v gc quay cc cu dng ca n-butan
k hiu l
CH
3

Dng che khut c nng lng cao hn dng lch.
S ph thuc nng lng c biu din trn hnh 7-2. Etan c mt cc i
v mt cc tiu nng lng. S chnh lch c gi tr 11,7 kj / mol
Phn t butan tn ti nhiu cu dng v gin nng lng cng phc
tp hn.
Gin nng lng ca phn t butan CH
3
CH
2
CH
2
CH
3
trnh by trn
hnh 7-3

84
2. Danh php
Cc hydrocarbon no u c tip v ng l an
2.1. Tn gi cc gc hydrocarbon thng gp
C
n
H
2n+2

C
n
H
2n+1
_

an yl
Nguyn tc:
Thay v ng ''an'' trong tn gi ca hydrocarbon no bng tip v ng ''yl"
Cc gc bc 1
n-propyl ethyl
methyl
CH
3
CH
2
CH
2
CH
3
CH
2
CH
3

CH
3
CH CH
2
CH
3
CH
3
CH
2
CH
2
CH
2
-
n-butyl
isobutyl

neopentyl
CH
3
CH
3
CCH
2
-
CH
3
isopentyl
CH
3
CHCH
2
CH
2
-
CH
3
n-pentyl
CH
3
CH
2
CH
2
CH
2
CH
2
-

neohexyl isohexyl
n-hexyl
CH
3
CCH
2
CH
2
-
CH
3
CHCH
2
CH
2
CH
2
- CH
3
CH
2
CH
2
CH
2
CH
2
CH
2
-
CH
3
CH
3 CH
3

Cc gc bc hai
CH
3
CH
3
CH
2
CH-
CH
3
CH-
CH
3
isopropyl
sec-butyl

Cc gc bc ba
tert-pentyl
tert-butyl
CH
3
CH
3
CH
2
C-
CH
3
CH
3
CH
3
CH
3
C-

2.2. Danh php quc t
Chn mch chnh l mch thng di nht.
nh s carbon trn mch chnh sao cho tng cc ch s ch v tr ca nhm
th l mt s nh nht (theo IUPAC). Nu mch nhnh khc nhau khong
cch nh nhau so vi hai carbon u mch chnh th phi nh s t u
no c mch nhnh vi s carbon t nht (theo danh php Genve).
85
Nu mch nhnh c s phn nhnh th phi nh s mch nhnh bt u t
v tr gn vi mch chnh.
8 7 6 5 3 2 4 1
CH
3
CH
2
CH
3
CH
3
_
CH
2
_
CH
_
CH
2
_
CH
_
CH
2
_
CH
2
_
CH
3
1' 2' 3'
3-etyl-5-methyl octan
4' 5' 6' 7' 8'
anh so theo nguyen tac tong so nho nhat
3+5 < 4'+6'
Nhom methyl quyet nh v tr anh so
8 7 6
5 4 2 1 3
CH
2
CH
3
CH
3
CH
3
_
CH
2
_
CH
_
CH
2
_
CH
2
_
CH
_
CH
2
_
CH
3
3-methyl ,6-ethyl octan
1 8 7 6 5
4 3 2
CH
3
CH
3
CH
3
1'
2'
CH
3
_
CH
_
CH
2
_
CH
2
_
CH
2
_
CH
_
CH
_
CH
3
3' 4' 5'
6' 7'
8'
anh so theo nguyen tac tong so nho nhat
2+3+7 < 2'+6'+7'
2,3,7-trimethyl octan
1',1'-dimethylpropyl
2,3,6,7-tetramethyl -5-(1',1'-dimethylpropyl) nonan
Mach nhanh co phan nhanh va anh so
mach nhanh tai v tr gan vao mach chnh
va anh so theo quy tac tong so nho nhat
2+3+6+7 < 3+4+5+7
3'
2'
Chon mach chnh la mach dai mhat

1'
CH
2
C CH
3
CH
3
CH
3
3' 2' 1'
8
7
1
CH CH
3
CH
2
CH CH CH CH
3
CH CH
3
C CH
3
CH
2
CH
3
CH
2
CH
3
CH
3
CH
3
2
3 4 5 6
9
CH
3

Cch gi tn:
Tn cc gc (mch nhnh) v ch s ch v tr cc gc gn vo mch chnh.
Tn gc (mch nhnh) ln lt t n gin n phc tp.
Dng cc t Hylp (di, tri, tetra, penta, hexa, hepta, octa) ch s lng
cc nhm th ging nhau v gi tn ca hydrocarbon no c s carbon tng ng
vi s carbon trong mch chnh.
3. Phng php iu ch alkan
3.1. Phng php gi nguyn mch carbon
3.1.1. Kh ha hydrocarbon cha no
Tc nhn kh l hydro phn t vi xc tc c hot tnh cao nh kim loi Pt,
Pd, Ni. Phn ng c th xy ra nhit thng.
R CH
2
CH
2
R'
Ni
+ H
2
R CH CH R'
R CH + 2H
2
Ni
R CH
2
CH
2
R'
CH R'

86
3.1.2. Kh ha dn xut halogen
Tc nhn kh c th l Zn /H
+
hoc acid hydroiodic c (HI)
R-X + Zn +H
+
R-H + Zn
2+
+ X
-
R-I + HI R-H + I
2
3.1.3. Kh ho alcol
Tc nhn kh l HI c (80%), nhit 180-200C v c mt phosphos
Khi un nng: 2HI 2H + I
2
Ban u alcol chuyn thnh sn phm trung gian l dn xut iod v cht
ny li b kh nhit cao hn thnh alkan
R-OH + HI R-I + HOH
R-I + HI R-H + I
2
V d:
CH
3
-CH
2
-CH
2
-CH
2
-OH + 2HI CH
3
-CH
2
-CH
2
-CH
3
+ H
2
O + I
2
Alcol n-butylic butan
S c mt ca phosphor lm tng cng kh nng kh ha ca HI.
Phosphor tc dng iod to phosphor triiodid PI
3
v cht ny khi tc dng vi nc
li ti to HI.
3.1.4. Kh ha acid v dn xut acid
R-COOH + 6HI R-CH
3
+ 2H
2
O + 3I
2
Phn ng dng iu ch alkan c mch carbon ln.
Kh ester d hn acid.
3.1.5. Thy phn hp cht c kim
C
n
H
2n+1
Br + Mg / ether khan C
n
H
2n+1
MgBr
C
n
H
2n+1
MgBr C
n
H
2n+2
+ MgBrOH
3.2. Phng php lm tng mch carbon
3.2.1. Phn ng Wurtz
Dn xut halogen tc dng natri kim loi s to hydrocarbon no do hai gc
ca dn xut halogen kt hp li nn mch carbon s tng gp i.
2 R-X + 2Na R-R + 2NaX (hiu sut 80%)
V d:
2CH
3
-CH
2
-I + 2Na CH
3
-CH
2
-CH
2
-CH
3
+ 2NaI
Phn ng dng hn ch trong tng hp cc dn xut i xng. Nu dng hai
dn xut khc nhau s thu c hn hp sn phm:
3R-X + 6Na + 3X-R R-R + R-R + R-R + 6 NaX
87
3.2.2. Phn ng in phn dung dch mui acid (phn ng Kolbe)
NaOH + H
2
H
2
O
Na
CH
3
CH
2
CH
2
CH
3
CH
3
CH
3
+ CH
2
chnh ph
.
CH
3
CH
2
- CO
2
.
CH
3
CH
2
COO
+ e
- e
catod
anod
Na
+
CH
3
CH
2
COO
-
CH
3
CH
2
COONa
CH
2

3.3. Phng php lm gim mch carbon
Ct khan mui kim, kim th ca acid carboxylic vi vi ti, xt s thu
c hydrocarbon c mch gim 1 carbon so vi acid carboxylic.
R-COONa + NaOH R-H + Na
2
CO
3
CH
3
COONa + NaOH CH
4
+ Na
2
CO
3
4. Tnh cht l hc
Nhit si v nhit nng chy tng dn khi s carbon tng.
Cc alkan phn nhnh c nhit si thp. Alkan khng tan trong nc. D
tan trong ether, trong cc hydrocarbon khc v trong cc dn xut halogen.
Ph hng ngoi:
Cc tn s dao ng ha tr :
Lin kt CH c dao ng ha tr trong khong 2850-3000 cm
-1
; lin kt
C
_
C c dao ng yu v thay i.
Cc tn s dao ng bin dng
Gc methyl CH
3
v methylen CH
2
c dao ng bin dng c trng ca
CH t 1400-1700 cm
-1

88
Bng 7.3: Tnh cht vt l ca mt s alkan
Hydrocarbon Nhit si Nhit chy T khi
Metan CH
4
Etan C
2
H
6
Propan C
3
H
8
Butan C
4
H
10
Pentan C
5
H
12
HexanC
6
H
14
Heptan C
7
H
16
Octan C
8
H
18
Nonan C
9
H
20
Decan C
10
H
22
Undecan C
11
H
24
Dodecan C
12
H
26
Tridecan C
13
H
28
Tetradecan C
14
H
30
Pentadecan C
15
H
32
Eicosan C
20
H
42
Triacontan C
30
H
62
-161,7
- 88,6
42,6
- 0,5
6,1
68,7
98,4
125,7
150,8
170,4
195,8
216,3
235,4
253,7
270,6
343,0
449,7
-182,0
-183.3
-187,7
-138,3
-129,8
- 95,3
- 90,6
- 56,8
- 53,5
- 29,7
- 25,6
- 9,6
- 5,5
5,9
10,0
36,8
65,8
-
-
0,5005
0,5787
0,5572
0,6603
0,6837
0,7026
0,7177
0,7299
0,7402
0,7487
0,7564
0,7628
0,7685
0,7886
0,8097
5. Tnh cht ha hc
Trong phn t alkan ch c 2 loi lin kt: C
_
H v C
_
C. Chng l nhng lin
kt hu nh khng phn cc.
5.1. Phn ng th - Tnh cht ca lin kt C - H
5.1.1. Phn ng halogen ha -Tc dng vi halogen
C
n
H
2n+2

+ X
2
C
n
H
2n+1
X + HX
Phn ng xy ra theo c ch gc t do, c xc tc nh sng hoc nhit cao.
Kh nng phn ng ca halogen sp xp theo F
2
> Cl
2
> Br
2
> I
2
.
Kh nng phn ng ca C
_
H bc 3 > C
_
H bc 2 > C
_
H bc 1
CH
4
+ 2F
2

C + 4HF
Phn ng clor ha metan xy ra qua cc giai on sau:
CH
4

+ Cl
2 CH
3
Cl + HCl

H = -23kcal
H = -1kcal
H = +270kcal
.
CH
3

+ Cl
2 CH
3
Cl + Cl
.

Cl
2
2Cl
.
h
CH
4
+ Cl
.
CH
3
+ HCl
.

89
Thc t phn ng to thnh hn hp sn phm CH
3
Cl, CH
2
Cl
2
,

CHCl
3
,

CCl
4
Phn ng s ngng hn khi cc gc t do kt hp vi nhau.
; ; Cl
.
+ Cl
.
Cl
2
.
CH
3
+ CH
3 CH
3
CH
3
.
. .
Cl + CH
3
CH
3
Cl

Phn ng clor ha phn t propan to ra nhiu cht:
h
+ Cl
2
+ Cl
2
+ Cl
2
+ Cl
2
+ Cl
2
+
+ +
+
CH
2
CH
3
CH
3
CH
2
CH
2
Cl CH
3
CHCl CH
3
CH
3
CH
2
CH
2
Cl CH
2
Cl CHCl CH
2
Cl CH
3
CCl
2
CH
3
CH
3
CHCl CH
2
Cl CH
2
Cl CCl
2
CH
2
Cl CH
3

Brom ha c tnh chn lc cao hn qu trnh clor ha. Khi clor ha isopentan
thu c hn hp sn phm. Cn khi brom ha isopentan sn phm th brom ch
yu xy ra lin kt C
_
H bc 3.
Theo nh lut Hess, hiu ng nhit H
0
l hiu s nng lng lin kt mi
c to thnh trong phn ng v nng lng phn ly ca lin kt b phn ct.
Lien ket phan ly
o
Cl
.
+ H
_
CH
2
CH
3
Cl
_
H

CH
2
CH
3

.
+
H = 98 - 103 = - 5 kcal. mol
-1

Lien ket tao thanh Lien ket phan ly Lien ket tao thanh Lien ket tao thanh

Lin kt HCl bn vng hn lin kt CH. Phn ng ca gc F
vi mt lin
kt CH c hiu ng nhit ln, ngha l phn ng xy ra mnh lit. Phn ng
gia gc brom Br
vi lin kt CH xy ra chm hn. Nh vy chng t rng hot

tnh halogen cng ln th chn lc cng nh v ngc li.
Clor ha:
22% 33%
15%
30%
h
+ +
+
CH
2
CH
3
C CH
3
Cl
CH
3
CHCl CH
3
C CH
3
H
CH
3
CH
2
CH
2
Cl C CH
3
H
CH
3
CH
2
CH
3
C CH
2
Cl
CH
3
H
+ Cl
2
CH
2
CH
3
C CH
3
H
CH
3

90
Brom ha:
+ HBr
h
CH
2
CH
3
C CH
3
Br
CH
3
+ Br
2
CH
2
CH
3
C CH
3
H
CH
3

Phn ng iod ha alkan l qu trnh thun nghch:
RH + I
2
RI + H

Trong iu kin thng, phn ng c khuynh hng chuyn v pha tri ti
to alkan. Ngi ta thm mt cht oxy ha nh acid iodic HIO
3
tch HI v
phn ng chuyn v pha to iodoalkan.
5.1.2. Phn ng nitro ha - Tc dng vi HNO
3
Phn ng nitro ha l phn ng th nguyn t hydro ca alkan bng gc NO
2
.
nhit thng alkan khng phn ng vi acid nitric. nhit cao (150-
450C) alkan tc dng vi acid nitric long hoc kh NO
2
to thnh dn xut
nitro. Nu dng acid nitric c th alkan b oxy ha.
RNO
2
+ H
2
O
RH + HO
_
NO
2
( long )
450
o

Trong phn ng nitro ha ngoi sn phm th, c th xy ra s ct mch
carbon. V d khi nitro ha propan to thnh hn hp sn phm sau:
25%
25% 10%
Nitrometan Nitroetan 2-Nitropropan
1-Nitropropan
+ +
40%
+
+ HNO
3
NO
2
CH
3
_
NO
2
CH
3
_
CH
2
_
NO
2
CH
3
_
CH
_
CH
3
CH
3
_
CH
2
_
CH
2
_
NO
2
CH
3
_
CH
2
_
CH
3

Phn ng nitro ha xy ra u tin th vo hydro carbon bc cao.
Gc NO
2
sinh ra do tc dng ca nhit :

+
t
o
.
H
2
O HNO
3
2 NO
2
+ HNO
3

Vai tr ca gc NO
2
trong phn ng nitro ha ging vai tr X

.
trong phn
ng halogen ho.
5.1.3. Phn ng sulfon ha
Tc dng vi acid sulfuric
Acid H
2
SO
4
m c nhit thng khng tc dng vi alkan. Acid
sulfuric bc khi (c ho tan SO
3
- oleum) tc dng vi nhng alkan c mch 6- 8
carbon v to thnh alkansulfoacid.
C
6
H
13
SO
3
H
H
2
SO
4
C
6
H
14

SO
3

91

Tc dng vi SO
2
v Cl
2
- Phn ng sulfoclor ha

Alkan tc dng trc tip vi hn hp SO
2
v Cl
2
nhit 20 - 30C c
chiu sng bng n t ngoi hoc c peroxyd lm cht khi mo th thu c
alkansulfoclorid.
RH + SO
2
+ Cl
2

RSO
2
Cl + HCl
h
hoc peroxyd

Khi thy phn hp cht alkansulfoclorid c mch carbon ln (> 10 carbon)
bng NaOH s thu c cc mui sulfonat l nhng cht c tc dng ty ra tt.
RSO
2
Cl + 2NaOH RSO
3
Na + H
2
O + NaCl

Sulfo oxy ha
Khi cho hn hp SO
2
v O
2
vi t l ng phn t tc dng vi alkan c mch
6- 8 carbon nhit 20-30C, c chiu sng s thu c hp cht alkansulfoacid.
RH + SO
2

+ O
2
RSO
3
H
h
2
1

5.2. Cc phn ng thuc lin kt CC
5.2.1. Nhit phn v cracking
nhit cao khng c oxy khng kh, cc phn t alkan b phn hy hoc
b gy mch carbon to thnh alkan v hydrocarbon cha no c mch carbon
ngn hn. Qu trnh gi l qu trnh cracking.
C
n
H
2n+2
C
x
H
2x+2
+ C
y
H
2y
(n = x +y )
Khi cracking n-pentan, phn ng xy ra theo c ch gc.
CH
3
CH
2
CH
2
CH
2
CH
3
+
+
CH
3
.
CH
3
CH
2
.
CH
3
CH
2
CH
2
CH
2
.
CH
3
CH
2
CH
2
.

+
CH
3
CH
3
CH
3
.
CH
3
.

CH
3
CH
2
CH
3
+ CH
3
.
CH
3
CH
2
.

CH
3
CH
2
CH
2
CH
2
CH
2
CH
3
+
CH
3
CH
2
.
CH
3
CH
2
CH
2
CH
2
.

+ CH
3
CH=CH
2
CH
3
CH
3
+
.
CH
3
CH
2
.
CH
3
CH
2
CH
2

92
5.2.2. Oxy ha v t chy
iu kin bnh thng, alkan khng tc dng vi oxy khng kh v cc
cht oxy ha mnh nh H
2
SO
4
c, KMnO
4
. Nhng nhit cao, alkan b oxy
ho to thnh cc sn phm cha oxy. Khi un nng c xc tc, cc alkan b oxy
ha bi oxy khng kh to thnh acid hu c tng ng.
RCH
3
+ O
2

RCOOH + H
2
O
2
3
t
o

xuc tac

Nu oxy ha mnh hn c th xy ra s ct t lin kt CC v sau oxy
ha tip to thnh cc acid c s nguyn t carbon t hn.
oxy ho
CH
3
_
(CH
2
)
n
CH
3

CH
3
(CH
2
)xCOOH + CH
3
(CH
2
)
y
COOH
n = x + y + 2

Khi t chy alkan to CO
2
v hi nc ng thi gii phng nng lng.
+ Q C
n
H
2
n
+
2

+ n CO
2

+ (n+1) H
2
O
O
2
3n + 1
2

CH
4

+ 2 O
2

CO
2
+ 2 H
2
O + 885 kj

Chnh v vy cc alkan nh metan, butan, octan ... c dng lm nhin liu.
6. Cht in hnh
Metan CH
4
Tng hp metan:
Be
2
C + 4H
2
O CH
4
+ 2Be(OH)
2
Al
4
C
3
+ 12H
2
O 3CH
4
+ 3Al(OH)
3
CS
2
+ 2H
2
S + 8Cu CH
4
+ 4Cu
2
S
Trong phng th nghim, iu ch metan bng cch nhit phn mui acetat
kim loi kim
CH
3
COONa + NaOH CH
4
+ Na
2
CO
3
Tnh cht v ng dng:
Metan l kh khng mu, khng mi, t tan trong nc, chy cho ngn la
xanh nht v to nhiu nhit (8560 kcal/m
3
) v vy lng ln metan c dng
lm nhin liu.
t metan trong iu kin thiu khng kh v trong thit b c bit to ra
carbon dng bt mn dng lm cht n trong sn xut cao su.
CH
4
+ O
2
C + H
2
O

93
Cho metan qua hi nc xc tc Ni 850C thu c hn hp hydro v
carbon monooxyd dng lm nguyn liu trong tng hp.
CH
4
+ H
2
O CO + 3H
2
Metan cn dng lm nguyn liu tng hp acetylen, cc dn xut clorometan,
acid cyanhydric. . .
Bi tp
1. Nhng tn gi sau y c ng khng :
a- 2-Ethylhexan
b- 2,2,5-Trimethylheptan
c- 3-Ethylheptan
d- 2-Methyl,3-isopropylpentan
e- 1-Methyl,3- ethylnonan
Hy vit li nhng tn gi ng.
2- Etan phn ng vi clor theo t l th tch v trng lng no khi iu ch
ethylclorid ?
3- Khi nitro ha v clor ha cc hydrocarbon sau:
Butan, isobutan, n-pentan, 3-methylbutan th c bao nhiu dn xut mt
ln th c th c to thnh ? .
94
Chng 8
CYCLOALKAN
Mc tiu
1. Gi c tn cc loi cycloalkan: 1 vng, 2 vng.
2. Vit v trnh by c cu dng ca cyclohexan.
Ni dung
Cycloalkan l nhng hydrocarbon no mch vng. Nguyn t carbon trng
thi lai ha sp
3
. C nhiu loi hp cht vng no.
Hp cht n vng: Monocycloalkan
Hp cht a vng: Polycycloalkan.
Phn chia hp cht a vng thnh cc loi sau:
Hp cht a vng ngng t,
Hp cht a vng c mch cu carbon,
Hp cht a vng spiran.
1. Monocycloalkan
1.1. Danh php
Gi tn alkan tng ng v thm tip u ng ''cyclo''
Nu trong phn t c mch nhnh th gi tn mch nhnh t n gin
n phc tp.
nh s cc nguyn t carbon trn mch vng xut pht t mch nhnh
n gin v nh s theo chiu sao cho tng s cc ch s ch mch
nhnh l nh nht.
CH
3
CH
2
CH
2
CH
3
CH
3
CH
2
CH
3
CH
3
CH
3
Methylcyclopropan Methylcyclobutan 1-Methyl 3-ethylcyclopentan 1-Methyl, 3-(n-propyl) cyclohexan
1
2
3
1
2
3

1.2. ng phn
Monocycloalkan c s ng phn nhiu hn s ng phn ca alkan c s
carbon tng ng. V d: C
8
H
16
c cc ng phn vng 3, 4, 6, 7, 8 cnh.
95
Trn mi loi ng phn vng c cc mch nhnh nn s ng phn tng ln.
CH
2
CH
3 CH
3
CH
3
1
2
1
CH
3
CH
3
3
2
1
CH
3
CH
3
4
Ethylcyclohexan 1,2-dimethylcyclohexan 1,3-dimethycyclohexan 1,4-dimethycyclohexan

Khc vi cc alkan, cycloalkan c ng phn hnh hc cis - trans

cis 1,2-dimethylcyclohexan
CH
3
CH
3
CH
3
CH
3
trans 1,2-dimethylcyclohexan

1.3. bn vng ca vng
Cc hp cht c vng 3, 4 cnh km bn hn so vi vng 5, 6 cnh. gii
thch hin tng , Bayer a ra gi thuyt rng: Tt c cc vng u c cu to
phng. Gc lin kt b bin dng (c ln khc 10928' - gc t din) v xut
hin sc cng ca vng (Sc cng Bayer). bin dng ca gc lin kt cng ln
th sc cng Bayer cng ln. V vy vng c nng lng cao nn km bn.
Gc bin dng c tnh nh sau:
2
1
= [109
o
28' - (goc lien ket trong vong phang) ]

Bng 8.1: Sc cng Bayer ca mt s cycloalkan
Hp cht
H
o (
*
)

Cyclopropan
Cyclobutan
Cyclopentan
Cyclohexan
Cycloheptan
Cyclooctan
60
90
108
120
12834
135
+2464'
+964'
+064'
-536'
-953'
-1286'
+12,7
+6,8
-18,4
-29,5
-28,2
-29,7
(*) kcal.mol
-1

Theo thuyt sc cng Bayer th cyclopentan l hp cht bn nht, t
cyclohexan tnh bn gim dn. iu ny khng ph hp v thc t cyclohexan l
hp cht rt bn vng. Cyclohexan khng c cu to phng, chng t rng thuyt
sc cng Bayer ch ng vi nhng cht c cu to phng .
bn ca hp cht vng cn ph thuc nhiu yu t khc c bit l cu
hnh v nhit to thnh. Nhit to thnh cng thp th vng cng bn.
96
Cc hp cht cu hnh lch c nng lng thp. Do nu cc nhm CH
2

k nhau ca vng khng cu hnh lch m cu hnh che khut th phi c s
tng tc ln nhau. S tng tc gi l Sc cng Pitzer .
gim bt sc cng Bayer, sc cng Pitzer, hp cht vng c xu hng phn b
khng ng phng sao cho thun li v nng lng (nng lng thp nht).
1.4. Cu dng ca cycloalkan
1.4.1. Cyclopropan
Ba nguyn t carbon cng nm trn mt mt phng. Bayer gii thch tnh
khng bn ca vng bng s bin dng ca lin kt. Trong cyclopropan cc lin
kt H
_
C
_
H to thnh gc 120. Do ngi ta cho rng cc lin kt C -C b un
cong v s xen ph cc i b vi phm mt phn (hnh 8-1).
C
C
C
H H
H
H
H
H
S xen ph ca cc orbital sp
2
to thnh cyclopropan
S xen ph cc i b vi phm
v lin kt C-C b un cong
S xen ph cc i

Hnh 8.1
1.4.2. Cyclobutan
Cyclobutan c cu dng gy gp - cu dng xp (hnh 8-2)

S tng tac gay ra sc cangPitzer
H
H H
H
H
H
H
H
H
H
H
H
H
H H
H

Hnh 8.2: Cu to khng ng phng ca phn t cyclobutan
1.4.3. Cyclopentan
Cyclopentan c cu to khng phng. Bn nguyn t carbon ca cyclopentan
nm trn mt mt phng. Nguyn t carbon th 5 nm ngoi mt phng ny.
Vng cyclopentan c hin tng " gi quay " (pseudorotation) (hnh 8-3).
97
3
5
4
2
1
H
H
H
H
H
H
4
3
5
2
1
H
H
H
H
H
H
5
4
3
2
1
H
H
H
H
H
H
M hnh phn t cyclopentan S tng tc gy ra sc cng Pitzer

Hnh 8.3: S bin i ca phn t cyclopentan
1.4.4. Cyclohexan
Cyclohexan c 2 cu dng: dng gh v dng thuyn (hnh 8- 4) .
Dang thuyen
Dang ghe
H
H H
H
H
H
H H
H H
H H
H
H
H
H H
H
H
H
H
H
H
H
S tng tac gay ra sc cang Pitzer

Hnh 8.4
Trong cu dng gh ca cyclohexan khng c sc cng Bayer v sc cng
Pitzer, v vy dng gh c nng lng thp v bn vng hn cyclohexan cu dng
thuyn. Cc lin kt C H trong cu dng gh c chia thnh 2 loi.
Su lin kt C

H song song vi trc i xng gi l lin kt axial (a, lin
kt trc).
Su lin kt C H sp xp gn song song vi mt phng trung bnh gi l
lin kt equatorial (e, lin kt xch o, lin kt vnh) (hnh 8-5).
Lien ket equatorial
Lien ket axial
H
H
H
H
H
H
H
Truc oi xng
H
H
H
H
H

Hnh 8.5. Lin kt axial v lin kt equatorial
Lin kt equatorial c nng lng thp v bn vng hn lin kt axial (hnh 8-6).
CH
3
(e)-Methylcyclohexan
(a)-Methylcyclohexan
CH
3
e
a
Axial Equaterial

Hnh 8.6: S chuyn i lin kt axial thnh lin kt equatorial
98
Cc nhm th c th tch ln v cu to phc tp thng tn ti dng
equatorial. Hp cht th 2 ln ca cyclohexan tn ti cc ng phn hnh hc.
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
Trans1,2
Cis 1,2
Trans1,3 Cis1,3 Trans1,4 Cis1,2

Hnh 8.7: Cc ng phn hnh hc ca dimethylcyclohexan
T cc ng phn hnh hc (hnh 8-7) li c cc cu dng khc nhau.
CH
3
CH
3
H
H CH
3
CH
3
H
H
CH
3
CH
3
CH
3
CH
3
a
a
e
e
CH
3
CH
3
CH
3
CH
3
a
a
e
e e
a
a
e
Cis a,e
Cis e,a
Cis a,a Cis e,e Cis a,e
Cis e,a

Hnh 8.8: Cc ng phn cu dng ca cis - dimethylcyclohexan
Trn hnh 8-8 l cc cu dng ca cis-dimethylcyclohexan cc v tr khc
nhau. Tng t cng c cc cu dng trans-dimethylcyclohexan (hnh 8-9)
Trans e,e
CH
3
CH
3
H
H
a
a
Trans e,e
CH
3
CH
3
H CH
3
H
CH
3
H
CH
3
CH
3
CH
3
CH
3
a
a
e
e
CH
3
H
CH
3
a
e
e
e
e
Trans a,a
Trans a,e
Trans e,a
Trans a,a

Hnh 8.9: Cc ng phn cu dng ca trans - dimethylcyclohexan
1.5. Tnh cht ha hc ca cycloalkan
Cc vng 3, 4 cnh th hin tnh cht cha no. Phn ng cng hp v vng
b ph v.
Cc cyclopropan khng tc dng vi kali permanganat v ozon.
;
CH
2
Br-CH
2
-CH
2
Br
Br
2 HBr
CH
3
-CH
2
-CH
2
Br
2 H
CH
3
-CH
2
-CH
3
;

Cc cyclohexan th hin tnh cht ca hydrocarbon no. C phn ng th halogen
khi c xc tc l nh sng. Khi c mt xc tc thch hp, cyclohexan c th b oxy ha
to thnh cyclohexanol, cyclohexanon hoc vng b ph v to acid adipic.
Cyclohexan b dehydro ha khi c xc tc l Pt hoc Pd.
h
6Cl
2
+ 6HCl
H
H
H
H
H
H
+
Cl
Cl
Cl
Cl
Cl
Cl

99
HOOC (CH
2
)
4
COOH
+ 3 H
2
OH
O
O
2
Cyclohexanol
Cyclohexanon
Acid adipic
Xuc tac
Xuc tac
Xuc tac
Pt
;

Tnh cht c bit ca cc hp cht cycloalkan l c th tham gia phn ng
chuyn v tng hay gim ln ca vng.
Methylcyclohexan Cycloheptan Methylcyclopentan
Ethylcyclobutan
;
AlCl
3
CH
3
AlCl
3
CH
3
CH
2
CH
3

2. Hp cht a vng
2.1. Hp cht a vng c lp
Hp cht c 2 vng c lp lin kt vi nhau trc tip hoc bi mt mch carbon.
1,2-Bicyclohexyletan
_
CH
2
CH
2
_
Bicyclohexyl

2.2. Danh php hp cht vng ngng t
Hp cht vng ngng t l nhng hp cht m cc vng c cnh chung vi nhau.
9
8
7
6
5
4
3
1
2
Bicyclo[4.3.0] nonan
10
Bicyclo[4.4.0] decan
7
6
9
5
4
3
1
8
2

2.3. Hp cht a vng c mch cu carbon
Hp cht vng c cu l hp cht khng c cnh chung nhng c cc nguyn
t carbon chung cho cc vng. Nguyn t carbon chung l nguyn t u cu.
Bicyclo[2.2.2] octan
8
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
Bicyclo[2.2.1] heptan
1
2
3
4
5
6
7
1
2
3
4
5
6
7

100
C th c hp cht 3, 4 vng
1
2
3
4
5 6
7
8
10
8
9
Tricyclo[3.3.1.
3,7
] decan
1
2
3
4
5
6
7
8
9
Tricyclo[3.3.1.0
2,9
] decan
1
2
3
4
5
Tetracyclo [2.1.1.0
2,6
. 0
3,5
] hexan
6

Ch : 1
3,7
ch r mch c 1 carbon v 2 carbon u cu l carbon s 3 v s
7; 0
2,6
ch r mch khng c carbon v 2 carbon u cu l carbon s 2 v s 6.
H thng hp cht a vng c danh php phc tp. Theo danh php IUPAC,
gi tn hp cht a vng phi xc nh s mch carbon. S mch carbon tng
ng vi s vng (bicyclo, tricyclo, tetracyclo). Tm vng chnh c s carbon nhiu
nht. Chn mch cu l mch di nht to bicyclo chnh. nh s trn vng
bicyclo chnh xut pht t carbon u cu v n u cu kia t mch cu di
nht n ngn nht (ch nguyn tc tng s nh nht). Sau xc nh tip cc
mch cu cn li v ch r s nguyn t carbon c trn mch cu . S nguyn t
carbon trn mi mch cu (khng k carbon u cu) c t trong ngoc vung
theo th t t ln n nh. Tn ca hp cht a vng l tn ca hydrocarbon c
tng s carbon to vng.
2.4. Hp cht vng spiran
T ''spiro'' c ngha l xon. Hydrocarbon no loi ny ch r cc vng lin kt
vi nhau bng nguyn t carbon chung. Nguyn t carbon ny gi l carbon spiro.
C hp cht spiro, dispiro, trispiro .. .
nh s carbon xut pht t vng b v bt u carbon gn carbon spiro
v theo chiu sao cho carbon spiro (carbon chung) c s b nht. S carbon trn
mi mch t trong du mc v theo chiu nh s.
Spiro[3.4] octan
8
7
6
5
4
3
2
1
Spiro[2.4] heptan
7 6
5
4
3
2
1
Spiro[4.5] decan
9
8
7 6
5
4
3
2
1
10
Dispiro[2.1.4.1] decan
10
9
8
7
6
5
4
3
2
1
Dispiro[2.1.5.2] dodecan
11 12
1
9
8
7
6
5
4
3
2
10

Bi tp
1. V cc ng phn hnh hc c th c ca cc ng phn ca cyclohexan c
CTPT C
9
H
18
. Gi tn cc ng phn .
2. V cc cu dng c th c ca diclocyclohexan.
3. Vit CTCT ca cc cht c tn gi sau:
a. Bicyclo[4.1.0] heptan; b-Bicyclo[3.2.0]heptan ; c-Tricyclo[5.1.0.0
3,5
]octan
d. Spiro [3.3] heptan; e-Spiro [4.4] nonan; f- Dispiro [5.1.6.2] hexadecan
4. Gi tn theo danh php IUPAC ca cc cht c cng thc sau:
CH
3
CH
3

101
Chng 9
ALKEN - HYDROCARBON ETYLENIC
(C
n
H
2n
)
Mc tiu hc tp
1. Trnh by c cu to alken, xc nh ng phn hnh hc v danh php
Z -E ca chng.
2. Nu c cc tnh cht ha hc ca alken.
Alken cn gi l olefin. Chng l nhng hydrocarbon cha no, khng vng,
trong phn t c mt ni i. Alken c cng thc tng qut C
n
H
2n
.
i vi hp cht vng c mt ni i c cng thc tng qut C
n
H
2n-2
v gi l
cycloalken, cycloolefin, hydrocarbon vng cha no.
1. Cu to ca alken
Su nguyn t ca phn t ethylen nm trong mt mt phng. Lin kt
ca C
_
C to thnh do xen ph ca orbital sp
2
. Lin kt c to thnh do 2
orbital p t do xen ph vi nhau. Mt phng cha lin kt thng gc vi mt
phng cha cc nguyn t carbon v hydro ca ethylen. Orbital s ca hydro v
orbital sp
2
ca carbon xen ph vi nhau to thnh lin kt ca HC (hnh 9-1).
Lien ket tao thanh do
2 carbon lai hoa sp
2

Lien ket tao thanh
do 2 orbital p t do
Cac nguyen t H ,C cua ethylen
nam tren mot mat phang
C
sp
2
C
sp
2
Hnh 9.1:

di lin kt ca HC l 1,076 A, ca C =C l 1,330 A
o o
Gc lin kt HCH l 116, 6
o
. Gc lin kt H
_
C=C l 121,7
o .

2. ng phn
2.1. ng phn cu to
Ngoi ng phn v mch carbon, alken cn c cc ng phn do v tr ca
ni i. Do alken c s ng phn cu to nhiu hn alkan c cng s carbon
tng ng.
102
Alken S ng phn Alkan S ng phn
Buten C
4
H
8
3

Butan C
4
H
10
2
Penten C
5
H
10
5

Pentan C
5
H
12
3

Hexen C
6
H
12
12 Hexan C
6
H
14
5

2.2. ng phn hnh hc - ng phn cis-trans

Cc nhm th khng th quay t do chung quanh lin kt i m tn ti mt
cch tng i v hai pha ca lin kt i. Do alken c ng phn hnh hc.
Hai nhm th cng pha so vi mt phng th gi l ng phn cis. Hai nhm
th khc pha so vi mt phng th gi l ng phn trans.

Trans -2-buten Cis -2-buten
H
C C
H
CH
3
CH
3
H
C C
CH
3
H
CH
3
C C
a
b
c
d
Co ong phan Z-E
C C
a
b
Co ong phan cis-trans
a
b

C th hnh dung m hnh phn t 2-buten nh sau.

Dng trans bn hn dng cis v dng trans c nng lng thp. Trong dng
cis cc nhm th cng pha c tc dng y nhau.
Trans -2-buten (74%)
C C
CH
3
H
CH
3
H
C C
H
CH
3
CH
3
H
Cis-2-buten (23% )
CH
3
CH
2
CH=CH
2
1-buten (3%)

ng phn cis-trans tn ti khi cc nhm th chung quanh lin kt i c a b
Cc nhm th chung quanh lin kt i c a b c d th c ng phn Z - E.
E -3-ethyl-2-hexen
H
C C
CH
2
CH
3
CH
2
CH
2
CH
3
CH
3
C C
CH
2
CH
2
CH
3
CH
2
CH
3
CH
3
H
Z -3-ethyl-2-hexen

Ch : Cc t cis - trans hoc Z (zusammen - cng pha) - E (eintgegen -
khc pha) l cc danh php ch ng phn hnh hc trong cc trng hp
khc nhau.
103
3. Danh php
3.1. Danh php thng thng
Gi tn alken bng cch ly tn alkan c s carbon tng ng thay tip v
ng ''an'' thnh ''ylen''.
CH
2
=CH
2
CH
3
CH=CH
2
CH
3
CH
2
CH=CH
2

Ethylen Propylen Butylen
Danh php ny ch gi tn nhng alken n gin
3.2. Danh php ethylen
C th xem cc alken n gin nh l dn xut ca ethylen. Nguyn t
hydro ca ethylen ln lt c thay th bi cc gc alkyl. S thay th ny c th
i xng hoc khng i xng hai u lin kt i.
CH
3
Dimethylethylen khong oi xng Dimethylethylen oi xng Methylethylen
CH
3
_
C=CH
2
CH
3
_
CH=CH
_
CH
3
CH
3
CH=CH
2

3.3. Danh php IUPAC
Gi tn nh hydrocarbon no v thay v ng ''an'' bng v ng ''en''
Chn mch chnh l mch di nht cha lin kt i .
nh s carbon trn mch chnh sao cho ni i c s b nht.
V tr nhnh + Tn nhnh + S ch v tr ni i + Tn mch chnh + en
; ; ;
6-Methyl-3-ethyl-3-hepten
CH
3
4 4
3 3
2
1
7 6 5 4 3
2
CH
3
CH
CH
3
_
CH
_
CH
2
_
CH
2
_
C
_
CH
2
_
CH
3
2-Methyl-2-buten 2-Buten
CH
3
Propen
CH
3
_
C=CH
_
CH
3
CH
3
_
CH=CH
_
CH
3
CH
3
CH=CH
2
1

3.4. Danh php Z - E
Danh php Z- E dng gi tn cc ng phn hnh hc m cc nhm th
chung quanh lin kt i hon ton khc nhau. Theo quy c 2 nhm th trn 2
carbon ca lin kt i c ln nht sp xp v mt pha ca mt phng th gi
l ng phn Z v ngc li gi l ng phn E.
C C
a
b
c
d
ong phan Z
C C
a
b
c
d
ong phan E
Khi a > b va c > d

Xc nh ln nhm th theo quy c Cahn -Ingold-Prelog, danh php R,S
104
R- Rectus - bn phi, S - Sinister - bn tri
E -1,4-diclo,2-methyl-3-(2-clorethyl) -2-penten
CH
3
CH
Cl
C C
CH
2
Cl
CH
3
ClCH
2
CH
2
C C
CH
2
CH
3
H
CH
3
CH
2
CH
3
Z -3-methyl-3-hexen

4. Phng php iu ch
4.1. Tch hydro halogenid t cc dn xut monohalogen
Cc dn xut monohalogen no, c bit l dn xut bc ba, khi tng tc vi
cc dung dch base mnh nh KOH, NaOH, EtONa trong alcol v un nng s b
tch mt phn t hydrohalogenid to ra alken tng ng. Ty cu to ca dn
xut halogen no, alken thu c c th l mt hn hp ng phn v mt lng
nh sn phm ca phn ng th i nhn l ether.
S tch loi HX theo kh nng: R-I > R-Br > R-Cl > R-F .
V nng lng lin kt: C-I 51 kcal.mol
-1
; C-Br 58
;
C-Cl 81 ; C-F 116
C CH
3
CH
3
CH R
X H
Dung dch KOH / alcol
CH
3
R
_
CH=C
_
CH
3
+ HX

Dung dch KOH/alcol khi un nng xy ra s cn bng sau:
ROH + OH
-

RO
-
+ H
2
O

S tch loi HX tun theo qui tc Zaixep.
Khi tch HX khi dn xut halogen, X s b tch cng vi nguyn t hydro
gn ti nguyn t carbon lin bn cnh c bc cao nht.
Qui tc Zaixep ng c trong hai trng hp tch loi E
1
v E
2
.
4.1.1. Phn ng tch loi E
1
alkylhalogenid
R
_
CH
2
_
CH
_
CH
3
X
R
_
CH
2
_
CH
_
CH
3
+
+ X
-
Cham
( II )
( I )
Nhanh
+ H
+
+ H
+
R
_
CH
2
_
CH=CH
2
R
_
CH=CH
_
CH
3
+
R
_
CH
2
_
CH
_
CH
3

Nu X cng tch loi vi H bc cao hn s hnh thnh olefin (I). Olefin (I)
c nng lng thp hn so vi olefin (II) v hiu ng siu lin hp ca CH
3
vi lin
kt i C =C c s lin kt C -H nhiu hn.
105
CH CH
3
C R
H
H
+
R
_
CH
2
_
CH
_
CH
3
+
CH C CH
2
R H
H
H
+
Co 3 lien ket C-H sieu lien hp Co 2 lien ket C-H sieu lien hp

R
_
CH=CH
_
C
_
H R
_
C
_
CH=CH
2
Co 3 lien ket C-H
( I )
( I I )
H
H
H
H
Ch co 2 lien ket C-H ;

4.1.2. Phn ng tch loi E
2
alkylhalogenid
Phn ng E
2
xy ra trong iu kin c base mnh v dung mi km phn cc.
20% 25%
41%
CH
3
CH
2
CH
2
CHBrCH
3
EtOK
EtOH
CH
3
CH
2
CH=CHCH
3
CH
3
CH
2
CH
2
CH=CH
2
CH
3
CH
2
CH
2
CH(OEt)CH
3
+ +

Trong c ch E
2
c th hnh thnh trng thi chuyn tip sau:
CH
3
CH
2
CH
_
CHCH
3
H

-
HO
-
.....
Br
.
.
.
.
CH
3
CH
2
CH
2
_
CH
_
CH
2
H

-
..... OH
-
Br
.
.
.
.

Trong trng hp tch loi theo c ch E
2

(cng nh E
1
) sn phm to thnh
tun theo quy tc:
Khi tch HX khi dn xut halogen s thu c olefin c s nguyn t H
i
vi lin kt i l ln nht
CH
3
_
CH
_
CH
2
_
CH
_
CH
2
_
CH
3
X
CH
3
Co 5 H
CH
3
_
CH
_
CH
2
_
CH=CH
_
CH
3
CH
3
CH
3
_
CH
_
CH=CH
_
CH
2
_
CH
3
CH
3
Co 3 H

Hiu sut olefin thu c ph thuc vo iu kin phn ng .
89% 11%
72% 28%
29%
71%
+ CH
3
CH
2
C=CH
2
CH
3
CH=C(CH
3
)
2
(CH
3
)
3
COK

EtOH
EtOK
CH
3
CH
2
CBr(CH
3
)
2
(CH
3
)
3
COH

(C
2
H
5
)
3
COK

(C
2
H
5
)
3
COH

CH
3

Tc phn ng E
2
ph thuc vo nng ca alkylhalogenid, nng base
v ph thuc vo bn cht ca nhm X.
106
Phn ng c nh hng bi cc lin kt: Lin kt CX d b ct t hn lin
kt CH.
Phn ng c tnh lp th: Nguyn t hydro v nguyn t X b tch phi lun
lun trn cng mt mt phng.
Br
H
C
6
H
5
C
6
H
5
Br
H
C
6
H
5
Br
H
(Z) 1-bromo-1,2-diphenyl ethylen
(R,R) 1,2 -dibromo-1,2-diphenyl etan
HBr
+
Base
H
Br
C
6
H
5
C
6
H
5
C C
Br
H
C
6
H
5
Br
H
C
6
H
5
C C
C
6
H
5
HBr
+
Base
H
Br
C
6
H
5
C
6
H
5
C C
Br
H
C
6
H
5
Br
H
C
6
H
5
C C
(E) 1-bromo 1,2-diphenyl ethylen
Meso-1,2 -dibromo-1,2- diphenyl etan
Br
H
C
6
H
5
C
6
H
5
C
6
H
5
C
6
H
5
Br
H
H
H

4.2. Tch loi nc t alcol
C th tin hnh tch loi nc khi alcol no theo 2 phng php:
4.2.1. pha lng
un nng alcol vi acid mnh (H
2
SO
4
, H
3
PO
4
) hoc vi KHSO
4
s to alken.
+ H
2
O RCH=CH
2
RCH
2
CH
2
OH
180
o
C
H
2
SO
4

Phn ng xy ra qua giai on to ester v c sau s hnh thnh alken
hoc sn phm ph l ether .
+ H
2
O RCH
2
CH
2
OSO
3
H RCH
2
CH
2
OH
140
o
C
H
2
SO
4

RCH=CH
2
+ H
2
SO
4
RCH
2
CH
2
OSO
3
H

RCH
2
CH
2
OH
RCH
2
CH
2
OCH
2
CH
2
R + H
2
SO
4
RCH
2
CH
2
OSO
3
H

i vi nhng alcol bc 1 c s carbon n 4 th to hn hp cc alken. V d
khi loi nc khi 1- octanol c th to thnh hn hp cc alken:
CH
3
(CH
2
)
6
CH
2
OH
+
H
3
PO
4
,
CH
3
(CH
2
)
5
CH=CH
2
CH
3
(CH
2
)
4
CH=CHCH
3

C hin tng trn l do s chuyn v ca hydro trong carbocation to thnh.
H
+
- H
2
O
..
H
+
CH
3
(CH
2
)
4
CH
_
CH
_
CH
2
_
CH
3
H
+
CH
3
(CH
2
)
5
CH
_
CH
_
CH
3
H
CH
3
(CH
2
)
6
CH
2
OH
+
CH
3
(CH
2
)
6
CH
_
CH
2

107
Phng php ny c dng thay i v tr ca chc alcol.
Alcol bc 2, bc 3 d loi nc trong mi trng acid. Phn ng theo c ch E
1
.
CH
3
CH
2
CH
2
CHCH
3
OH
CH
3
CH
2
CH
2
CHCH
3
CH
3
CH
2
CH=CHCH
3
+ H
2
O
H
2
SO
4
62% H
2
SO
4
62%
95
o

C ch E
1
CH
3
CH
2
CH
2
CHCH
3
OH
CH
3
CH
2
CH
2
CHCH
3
CH
3
CH
2
CH
2
CHCH
3
OH
CH
3
CH
2
CH
2
CHCH
3
CH
3
CH
2
CH
2
CHCH
3
OH
2
CH
3
CH
2
CH
2
CHCH
3
CH
3
CH
2
CH
2
CHCH
3
CH
3
CH
2
CH
2
CHCH
3
CH
3
CH
2
CH=CHCH
3
H
+
H
+
+
+
- H
2
O -H
+

C trng hp xy ra s chuyn v:
+
CH
3
-C
__
CH-CH
3
CH
3
CH
3
OH CH
3
CH
3
+
CH
3
CH
3
H
+
t
o
CH
3
-C
__
CH-CH
3
CH
3
-C
__
CH-CH
3

CH
3
CH
3
CH
3
CH
3
CH
3
_
C=C
_
CH
3
CH
2
=C
_
CH
_
CH
3
CH
3
CH
3
-H
+
+
+ CH
3
_
C
_
CH
_
CH
3

4.2.2. pha hi
Alcol di tc dng ca Al
2
O
3
350 - 400C cng to alken theo c ch:
300-400
o
C
Al
2
O
3
H
2
O +
CH
2
=CH
2
CH
3
CH
2
OH

-
+
+
H
2
O
+
alken
+
OH
2
Al
+ R
+
OH
R
H
O
Al Al
Al
Al

4.3. T dn xut dihalogen
S tng tc gia dihalogen trn 2 carbon lin nhau vi bt kim loi (Zn,Cu)
s thu c alken.
RCH=CHR' + ZnCl
2
Zn + RCH
_
CHR'
Cl Cl

4.4. Phng php dehydro ho, cracking hydrocarbon no
Trong cng nghip cc alken thng c iu ch bng cch dehydro ha
cc alkan di tc dng ca xc tc thch hp (V d crom trioxyd 450
C). T
butan, isobutan iu ch c buten v isobutylen.
108
CH
3
CH
2
CH=CH
2
+ H
2
CrO
3
450
o
C
CH
3
CH
2
CH
2
CH
3

Cc alken cng c to thnh khi nhit phnC, cracking cc hydrocarbon no.
CH
2
=CH
2
+
700-800
o
C C
6
H
14
CH
4 CH
3
CH=CH
2
+ +
15%
40% 20%
25%
San pham khac
n-

Propen l nguyn liu sn xut polypropylen. Alken quan trng trong
cng nghip l buten v ethylen c iu ch bng phng php dehydro ha
hoc cracking nguyn liu thu c t du m.
5. Tnh cht l hc
Ba thnh phn u tin ca dy ng ng iu kin thng l cc cht
kh. Cc thnh phn trung bnh l nhng cht lng. Cc thnh phn cao hn l
cht rn. Tnh cht vt l c trng ca mt vi cht hu c c trnh by trong
bng 9-1.
Bng 9: Tnh cht l hc ca cc alken
CH
2
=CH
2
CH
3
CH=CH
2
CH
3
CH
2
CH=CH
2
CH
3
CH=CHCH
3
CH
3
C=CH
2
CH
3
CH
2
CH
2
CH=CH
2
CH
3
CH
2
CH=CHCH
3
CH
3
CH
3
CHCH=CH
2
CH
3
C=CHCH
3
CH
3
CH
3
Ethylen
Propylen
1-Buten
cis 2-Buten
isoButylen
1-Penten
2-Penten
3-Methyl-1-buten
2-Methyl -2-buten
-169,4
-185,2
-130,0
-139,0
-140,0
-138,0
-139,0
-135,0
-124,0
-103,9
- 47,0
-5,0
-3,5
-6,0
+29,9
+36,4
+25,0
+38,4
0,566
0,609
0,668
0,635
0,566
0,640
0,651
0,648
0,668
Cong thc Ten goi
t
o
chay t
o
soi Ty khoi

Ph hng ngoi:
Lin kt -C=C- alken c vch hp th gn 1650 cm
-1
. Tuy nhin cng
v tr s ca vch ny cn ph thuc vo cu to phn t ca alken (lin hp vi -
C=C- hoc -C=O). Cc vch hp th do dao ng ca lin kt C -H ca nhm
-CH=CH
2
c tn s khong 3100, 1420 v 915 cm
-1

Lin kt i d b phn cc. Phn t alken c momen lng cc thay i ty
thuc vo cu to ca alken.
109
R CH=CH
2
C
C
H
H
Cl
C
C
Cl
Cl
C
C
H
H
Cl
C
C
Cl
Cl
=
2,95D = 0
C
C
CH
3
H
Cl
C
C
Cl
H
1,97D =
C
C
H
H
Cl
C
C
Cl
CH
3
1,71D =

6. Tnh cht ha hc
Trong lin kt i, nng lng lin kt ln hn nng lng lin kt .
chnh lch vo khong 20 kcal.mol
1
. iu ny gii thch tnh km bn ca lin
kt v kh nng phn ng cao ca lin kt i. Lin kt i l trung tm phn
ng ca alken. Cc phn ng quan trng nht i vi alken l phn ng cng,
phn ng oxy ha v phn ng trng hp.
6.1. Phn ng cng hp
Lin kt b b gy v kt hp vi hai nguyn t hoc 2 nhm nguyn t
mi to hp cht no. Lin kt i -C=C- c tnh i nhn. S chung ca phn
ng cng hp vo ni i nh sau:
C=C
+ X
_
Y C
_
C
X Y

6.1.1. Phn ng hydro ho c xc tc
Cng hp hydro vo alken to alkan. Phn ng ch xy ra khi c xc tc. Xc
tc thng dng l Pt, Pd hoc Ni. Phn ng ta nhit (

= - 32,7 kcal.mol
-1
) .
C=C
+
xu c ta c
H
2
C
_
C
H H

Dng nickel hot ng mnh l ''nickel Raney''. Nickel Raney c iu ch
t hp kim nickel -nhm. Khi ch ha hp kim ny vi dung dch NaOH, nhm b
ha tan. Nickel thu c trng thi bt rt mn v d bc chy. Nickel Raney
hnh thnh theo phn ng.
2Ni-Al + 2HO + 2H
2
O

2Ni + 2AlO
2
+ 3H
2
-
-

Cc hp cht ca lu hunh, phosphor, arsen lm mt tc dng hot ha
ca cc xc tc. Phn ng hydro ha alken xy ra trn b mt ca xc tc v theo
c ch cng hp cis.
H H
H H H
2
CH
2
=CH
2
C
2
H
4
Be mat xuc tac
H
_
CH
2
_
CH
2
_
H

S cng hp cis vo lin kt i c th trnh by trong phn ng sau:
Pd
H
2
H
H
3
C
HOOC
H
CH
3
COOH
C C
H
H
3
C
HOOC
H
CH
3
COOH
COOH
C
H
3
C
H
3
C
C C
COOH
C

Phn ng hydro ha c xc tc do Sabachie v Sendoren pht minh nm
1899 v tr thnh phng php quan trng v ph bin ca ha hu c.
110
6.1.2. Phn ng cng hp i in t (A
E
)
Phn ng xy ra gia alken v tc nhn i in t (electrophile). C 2 giai
on sau:
Giai on I
Tc nhn i in t kt hp vi carbon ca lin kt i giu in t hn
hnh thnh ion carboni. y l giai on chm quyt nh tc phn ng.
Cham
X C
__
C
+ C== C
+

+
-
Y X
-
+
+ Y
-

Giai on II
Ion carboni kt hp vi phn cn li ca tc nhn tch in m.
Y C
__
C X Y
-
+
+
Nhanh
C
__
C X

Cc tc nhn phn ng halogen X
2

(Cl
2
, Br
2
, I
2
), cc hydrohalogenid HX
(HCl, HBr), cc acid hypohalogen HOX (HOCl, HOBr), nc, acid sulfuric u
cng hp vo lin kt i ca alken theo c ch i in t v to thnh hp cht
no tng ng.
Alcol n chc
Hp chat monoclor
Ester cua acid sulfuric
Hp chat clorhydrin
C== C
+
C
__
C
Br Br
C
__
C
Cl OH
C
__
C
H OSO
3
H
C
__
C
H Cl
C
__
C
OH
+ Br
2
+ HOCl
+ H
2
SO
4
+ HCl
+ H
2
O , H
+
Hp chat dibromo

Cng hp HX
2-Methylpropen cng hp vi HCl. Trc tin lin kt i tc dng vi
proton H
+
to thnh carbocation trung gian. Sau carbocation kt hp vi ion
clorid Cl
-
v to thnh tert butylcloid.
H Cl
C
C
C
CH
3
H
CH
3
H
+
CH
3
CH
3
C
C
H
H
H
CH
3
CH
3
Cl
+ Cl
-
C
H
H
H

111
Alken khng i xng tc dng vi proton to thnh carbocation bn vng.
H
khong tao thanh
+
+
CH
3
CH
3
_
C
_
CH
2
CH
3
CH
3
_
C
_
CH
3
+ HCl
CH
3
CH
3
C=CH
2

Phn ng xy ra theo qui tc Markonikov
Cc hydrohalogenid cng vo lin kt i theo kh nng HI > HBr > HCl
Tc dng ca dung dch nc clor hoc brom vi alken to sn phm
halogenohydrin. Trong trng hp ny tc nhn phn ng l acid hypoclor HOCl
hoc hypobrom HOBr
CH
3
CH
2
CH=CH
2
+ HOCl CH
3
CH
2
CHOH-CH
2
Cl (Butylen clorohydrin)
Carbocation trung gian c th b chuyn v hydro cho nn khi alken tc dng
vi HX c th to ra hn hp cc alkylhalogenid.
2-Penten
2-Bromopentan
+
+
CH
3
CH
2
CH
2
-CHBrCH
3
CH
3
CH
2
CHBr -CH
2
CH
3
CH
3
CH
2
CH
2
-CHCH
3

Br
-
CH
3
CH
2
CH -CH
2
CH
3

Br
-
CH
3
CH
2
CH = CHCH
3
+ HBr 3-Bromopentan

Cng hp vi nc H
2
O
Hydrat ha alken l phng php quan trng iu ch alcol trong cng
nghip. Phn ng cng hp nc thng xy ra trong mi trng acid. Phn ng
qua giai on to carbocation trung gian. Carbocation tc dng vi nc to
thnh alcol.
t-Butanol
Carbocation Isobuten
+
CH
3
C = CH
2
+ H
+
CH
3
CH
3
C
_
CH
3

CH
3
CH
3
C
_
CH
3

CH
3
OH
2
+ H
+

+ H
2
O
+
CH
3
C
_
CH
3

CH
3
OH

Cc quy tc nh hng trong phn ng cng hp vo alken
Quy tc Markonikov
Trong phn ng cng hp, tc nhn khng i xng (HX...) tc dng vi mt
alken khng i xng th nguyn t hydro ca HX s tn cng vo nguyn t
carbon ca ni i c nhiu hydro hn, cn X s tn cng vo nguyn t carbon
cn li ca ni i.
isopropylclorid
CH
3
CH
_
CH
3

Propylen
Cl
CH
3
CH = CH
2
+ HCl

C th gii thch theo cc trng thi ca phn ng.
Trng thi tnh
Trong phn t propylen do tc dng y in t ca nhm metyl v pha
lin kt i (hiu ng +I v hiu ng siu lin hp) lm cho lin kt ny phn cc.
112
Mt in t dch chuyn v pha nhm CH
2
(carbon bc thp) v nhm ny
mang mt phn in tch m
-
, cn nhm methyl CH mang mt phn in tch
dng
+
.
Do s phn b mt in t trong phn t propylen c th trnh by
nh sau.
-
H
H
H
_
C

CH = CH
2

Khi cho H
+
Cl
tc dng vi propylen, phn cation H

+
(tc nhn i in t) s
tn cng vo carbon mang in tch m
v phn anion Cl
tn cng vo carbon
c in tch dng
+
.
Trng thi ng
V phn ng xy ra theo c ch cng hp i in t (A
E
), giai on quyt
nh tc phn ng l giai on ca H
+
tn cng vo phn t propylen. Gi thit
c 2 carbocation to thnh:

H
H
+
CH
3
_
C
_
CH
2
( II )
H
H
H
_
C
_
CH
_
C
_
H ( I ) CH
3
_
CH
_
CH
3
( I )
CH
3
_
CH
2

_
CH
2
( II )
+
+
va
H
H
+

Phn ng xy ra theo qu trnh no l ph thuc vo nng lng v bn
ca carbocation trung gian. Carbocation c nng lng cng thp v bn cng
ln khi in tch dng trn nguyn t carbon ca carbocation cng c gii ta.
iu xy ra khi in tch dng ca carbon lin hp vi cng nhiu in
t ca cc lin kt C -H.
Carbocation c bn cng ln th thi gian tn ti cng lu v d hnh thnh.
Carbocation (I ) lin hp vi 6 lin kt
C
_
H
. Carbocation (II) ch lin hp vi
2 lin kt
C
_
H
. Do ion (I) bn v d hnh thnh hn ion (II).
iu gii thch v sao khi cng hp HCl vo propylen th isopropylclorid
l sn phm ch yu. Trn c s gii thch s cng hp vo alken theo quan im
trng thi ng, c th pht biu quy tc Markonikov nh sau:
Phn ng cng hp i in t vo alken xy ra ch yu qua dng ion carboni
trung gian c bn ln nht
Phn ng cng tri qui tc Markonikov - Hiu ng Kharasch
Khi cng hp HBr vo hp cht c ni i vi s c mt ca mt t peroxyd
th sn phm to thnh tri quy tc Markonikov
peroxyd
CH
3
CH=CH
2
+ HBr CH
3
CH
2
_
CH
2
Br
peroxyd
CH
2
=CHCH
2
Br + HBr BrCH
2
_
CH
2
CH
2
B

Cc peroxyd nh dibenzoylperoxyd (C
6
H
5
CO)
2
O
2
, Peracetic CH
3
COOOH.

113
nh hng ca peroxyd i vi phn ng cng hp gi l hiu ng peroxyd
hoc hiu ng Kharasch. Phn ng xy ra theo c ch cng hp gc qua cc giai
on sau:
+ HBr CH
3
CH
2
_
CH
2
Br + Br
.
H = -11 kc
H = -5 kcal
H = -23 kcal
R-O
.
+ HBr ROH + Br
.

Br
.
+ CH
3
CH=CH
2
H = +35 kcal
R-O-O-R 2R-O
.
.
CH
3
CH
_
CH
2
Br
.
CH
3
CH
_
CH
2
Br

Phn ng kt thc khi cc gc t do kt hp vi nhau Br
.
+ Br
.
Br
2
C th gii thch s to ra sn phm tri vi sn phm Markonikov bng
bn ca gc t do to thnh. Khi nguyn t brom Br
.
tc dng vi alken c kh
nng to ra 2 gc t do (I) v (II). Gc t do (I ) bn v d hnh thnh hn ( II).
Gc t do (I) chu nh hng ca 2 gc y in t v pha carbon mang in t
n c .
.
CH
3
CH

CH
2
Br
Br
.
+ CH
3
CH=CH
2
.
CH
3
CH
_
CH
2
Br (I )
.
CH
3
CHBr
_
CH
2
(II)
CH
3
CHBr

CH
2
.

Kh nng to thnh v bn ca gc t do gim dn theo th t:
Gc bc 3 > Gc bc 2 > Gc bc 1
Qui tc Wagner
Tc nhn khng i xng tc dng vi alken, trong hai nguyn t carbon
mang ni i l ng bc lin kt vi 2 gc alkyl khc nhau l methyl th phn
anion X
ca tc nhn s kt hp vi carbon ca ni i mang nhm methyl.

CH
3
CH
2
_
CH=CH
_
CH
3
+ HBr CH
3
CH
2
_
CH
2
_
CHBr
_
CH
3

C th gii thch quy tc trn theo quan nim:
To carbocation trung gian bn vng.
Gii thch theo hiu ng cm ng v hiu ng siu lin hp.
Cng hp Halogen
L phn ng quan trng ca lin kt i
X
2
+ X
__
C
__
C
__
X C==C (X
2
= Cl
2
, Br
2
..)

Phn ng xy ra nhanh. C th xem phn ng ny nh l mt phn ng th
i nhn vo nguyn t halogen. Alken l tc nhn i nhn. Phn t alken tn
cng vo phn t halogen theo s sau:
114
; +
Br
__
C
__
C
_
Br
Br
-
+
C
C
+
Br Br
C
C
Br
+ Br
-
Br
__
C
__
C

Trn carbocation c nguyn t carbon thiu in t v nguyn t halogen
c 3 cp in t khng lin kt. Chng c kh nng to thnh ion halonium vng.
:
..
S tao thanh ion halonium vong
+
+
X
C C
X
C C
:
..
C C
:
..
:
X
X
C C
.
.

V vy s cng hp halogen c tnh lp th. Anion halogen X
-
tng tc vi
vng halonium t pha ngc vi halogen trong vng. S cng hp halogen thng
to thnh sn phm trans. iu thng thy trong cc hp cht vng cha no.
..
:
+
..
C C
X
+
..
:
C C
X
X
X
-
H
Br
Br
H
Br
H
Br
2
CCl
4
- 5
o
Br
-
Cyclopenten
Trans 1,2-dibromocyclopentan
;

Sn phm cng hp halogen vi alken l cht trung gian trong tng hp hu c.
6.2. Hydroboran ha
Phn ng ca lin kt i vi diboran B
2
H
6
l mt phn ng quan trng ca
alken. Lin kt BH cng vo lin kt i vi hiu sut cao v nhanh to thnh
trialkylboran
6RCH=CH
2

+ B
2
H
6

2(RCH
2
CH
2
)
3
B
6.3. Phn ng oxy ha
Alken b oxy ha bi cc cht oxy ha khc nhau.
6.3.1. Vi KMnO
4

Alken tc dng nhanh vi kali permanganat KMnO
4
. Sn phm to thnh
ph thuc vo nng ca cc cht phn ng.
Vi dung dch kali permanganat long th to thnh diol cnh nhau (glycol)
3
OH
OH
C C + C
C
2KMnO
4
4H
2
O
+
2MnO
2
2KOH + +
3
loang

Phn ng xy ra theo c ch cng hp cis
KMnO
4
+
O
O
-
H
OH
OH
H
H
2
O
loang
t
o
O
Mn
O
H
H
-

115
Vi dung dch kali permanganat m c, lin kt i b ct v to hn hp
ceton v acid carboxylic.
KMnO
4
RCOOH + CO
2
RCH=CH
2

KMnO
4
O
R''
R'
R HO
_
C C==O +
R''
R'
H
R
;
C==C

6.3.2. Vi ozon (O
3
)
Phn ng oxy ha alken bng ozon to thnh aldehyd, ceton hoc acid ty thuc
cu to ca alken. Phn ng tri qua giai on to cht trung gian l ozonid.
Ozonid kh phn ring c v b thu phn to thnh sn phm.
H
2
O C C +
O O
C
O
C
O O + H
2
O
2
+
C C
O
C C
O
O
O O
C
O
C
O
3
Molozonid Ozonid

C th dng phn ng ny xc nh cu trc ca alken.
H
2
O
+ CH
3
CH
2
CHO
O
CH
3
_
C
_
CH
3
Ozonid
O
3
O O
C
O
C
CH
2
CH
3
H
CH
3
CH
3
C C
CH
3
CH
2
CH
3
CH
3
H
+ H
2
O
2

6.3.3. Vi cc peroxyd
Alken b oxy ha bng cc peracid. Sn phm to thnh l cc oxiran (epoxyd)
C
6
H
5
H
H
C
6
H
5
C C
+ CH
3
COOOH C C
O
C
6
H
5
H
C
6
H
5
H
CH
3
COOH +
Trans-Stilben
Trans-2,3-diphenyl oxiran

CH
3
(CH
2
)
3
CH=CH
2

1-butyl oxiran
COOH
Cl
O
CH
3
(CH
2
)
3
CH
__
CH
2

O
COOH
Cl 1-2-epoxyhexan
1-oxydhexen
Acid 3-cloro peroxybenzoic
+
+
Acid 3-cloro benzoic
1-Hexen

6.4. Phn ng trng hp (phn ng polymer ha)
Phn ng trng hp cc alken hoc cc hp cht cha no khc c tm quan
trng c bit trong cng nghip ha hc. C th c s chung nA (A)
n
.
A l cc monomer, (A) n l cht cao phn t (polymer), n l h s trng hp.
116
Ty theo bn cht v iu kin phn ng, s trng hp xy ra theo cc c ch
khc nhau. Polymer to thnh c cu to khc nhau v h s trng hp khc nhau.
C ch phn ng trng hp c th l c ch gc, c ch ion (anion hoc cation)
6.4.1. Phn ng polymer ha theo c ch gc t do
Xy ra qua cc giai on.
S to gc t do:
+ CH
2
=CH
2
Y
.
Y-CH
2
CH
2
.

S pht trin mch:
Y-(CH
2
CH
2
)
n
-CH
2
CH
2
.
Y-CH
2
CH
2
-CH
2
CH
2
CH
2
=CH
2
.
Y-CH
2
CH
2
+
.

S kt thc phn ng:
Y-(CH
2
CH
2
)
n
-CH
2
CH
2
-CH
2
CH
2
-(CH
2
CH
2
)
n
-Y
+ Y-(CH
2
CH
2
)
n
-CH
2
CH
2
.
Y-(CH
2
CH
2
)
n
-CH
2
CH
3
Y-(CH
2
CH
2
)
n
-CH=CH
2
Y-(CH
2
CH
2
)
n
-CH
2
CH
2
.

6.4.2. Phn ng polymer ho theo c ch cation
C cc qu trnh
Qu trnh to cation: (CH
3
)
2
C=CH
2
+ H
+
(CH
3
)
3
C
+

Qu trnh pht trin mch polymer.
Qu trnh kt thc
Trong qu trnh trng hp c cc dimer, trimer c to thnh
20%
+ (CH
3
)
3
C-CH=C(CH
3
)
2
cham +
(CH
3
)
3
C-CH
2
-C(CH
3
)
2
(CH
3
)
2
C=CH
2
(CH
3
)
3
C-CH
2
-C=CH
2
80%
CH
3

6.4.3. Phn ng theo c ch anion
Xc tc to anion thng l cc hp cht c kim.
(CH
3
)
3
-
Li
+

+ CH
2
=CH
2

(CH
3
)
3
C-CH
2
-CH
2
-
Li
+
Hn hp gm R
3
Al + TiCl
4
gi l xc tc Zigler -Natta c s dng trong
phn ng polymer ha theo c ch anion.
Cc polymer thng gp: Polyethylen (PE), Polypropylen (PP), Teflon X-(CF-
CF)
n
_
Y, Polystyren.
6.5. Phn ng th
6.5.1. Th v tr allyl
Tu theo cu to s th vo v tr allyl xy ra cc iu kin khc nhau
117
CH
3
_
CH=CH
2
+ Cl
2
ClCH
2
_
CH=CH
2
+ HCl
500-600
o

CH
3
CH
3
Nhiet o phong
CH
3
C=CH
2
+ Cl
2
ClCH
2
C=CH
2
+ HCl

Phn ng xy ra theo c ch nh sau:
CH
3
CH
3
_
C=CH
2
+ Cl
_
Cl CH
3
_
C
_
CH
2
Cl + Cl
-
CH
3
+

San pham phu
- H
+
San pham chnh
+ Cl
-
CH
3
_
C
_
CH
2
Cl

CH
3
CH
2
=C
_
CH
2
Cl

CH
3
+
Cl
CH
3
_
C
_
CH
2
Cl

CH
3

6.5.2. Th vo v tr vinyl
Xy ra iu kin kh hn s th vo v tr allyl. Nguyn t hydro lin kt vi
carbon c ni i (gi l hydro vinyl) bng lin kt
C
_
H
. Lin kt
C
_
H
c nng lng
lin kt ln hn nhiu so vi cc lin kt C
_
H khc. Phn ng theo c ch gc.
CH
2
=CH
2
+ Cl
2
CH
2
= CH
_
Cl + HCl
200-600
o

S th v tr allyl cn th hin qua phn ng t oxy ha
Cc alken d xy ra phn ng oxy ha ti v tr allyl v to thnh cc
peroxyd. S oxy ha xy ra nhit thng v bng oxy khng kh. Phn ng
ny l nguyn nhn cc du, m b oxy ha.
CH
3
CH
2
CH
2
_
CH=CH
2
+ O
2
CH
3
CH
2
CH
_
CH = CH
2
O
_
O
_
H

7. Cht in hnh
Ethylen CH
2
=CH
2
Cht kh khng mu, khng mi, hu nh khng tan trong nc, ha lng
-105C. Ethylen chy cho ngn la sng hn metan, to thnh CO
2
v hi nc
Hn hp ethylen v oxy n mnh v phn ng t chy ta nhiu nhit, c
th dng hn hp ny ct hn kim loi nh acetylen.
Ethylen kt hp vi nc to alcol ethylic.
Ethylen tc dng vi dung dch clor trong nc to ethylen clorhydrin v t
clorhydrin c th iu ch ethylen oxyd
118
ethylen clorhydrin ethylen oxyd
CH
2
CH
2
O
KOH
CH
2
CH
2
Cl OH
H
2
O
Cl
2
CH
2
CH
2

Ethylen tc dng vi benzen xc tc AlCl
3
to ethylbenzen, t ethylbenzen
to styren dng sn xut polystyren v cao su tng hp BuNa -S.
styren
ethylbenzen
H
2
AlCl
3
+ CH
2
CH
2 CH
2
CH
3
CH = CH
2

Trng hp ethylen to polyethylen l hp cht cao phn t c nhiu ng
dng trong k thut v i sng
Ethylen c tc dng kch thch s hot ng ca cc enzym lm qu mau
chn, c dng dm chn qu xanh nh c chua, chui . . . nng rt long.
Bi tp
1. Vit cng thc cu to ca cc cht sau:
a. 3-Methyl-1-penten; c. 2,2-Dimethyl-3-ethyl-1-octen.
b. 2,4-dimethyl-1-penten; d. Dipropylethylen khng i xng.
e. Diisopropylethylen i xng.
Gi tn theo IUPAC ca cc cht c CTCT di y:
Cl
C C
CH
2
CH
3
CH
3
CH
3
H
C C
CH
3
CH
2
C(CH
3
)
3
BrCH
2
CH
3
C C
CH
2
CH
3
H
CH
3
CH
2
CHCH
2
H
CH
2
C
CH
2
CH
2
CH(CH
3
)
2
CH
2
CH
2
Br
a- b-
c-
d- ;
;
;

2. Khi un nng 3- bromo-2-methyl pentan vi kim ru thu c mt
hydrocarbon cha no. Vit phng trnh phn ng. Trong cc iu kin y s
nhn c hydrocarbon no, nu i t:
a. Isobutyl iodid. d. 4- Bromo-2,2 -dimethyl pentan.
b. 2-bromopentan. e. 2- Bromo-2-methyl butan.
c. 3-cloropentan.
3. Nhng hp cht no c to thnh khi oxy ha cc cht di y bng dung
dch KMnO
4
long nhit thp:
a. 2-Hepten. b. Metyl isopropyl ethylen i xng. c. Trimethylethylen.
4. Hy vit CTCT ca cc hydrocarbon ethylenic bit rng ozonid ca chng b
thy phn trong mi trng acid th to thnh cc cht:
a. Formaldehyd HCHO v aldehyd methylacetic CH
3
CH
2
CHO
b. Aceton v aldehyd propionic CH
3
CH
2
CHO
c. Methylisopropylceton CH
3
COCH(CH
3
)
2

v formaldehyd.
119
Chng 10
ALKYN - HYDROCARBON ACETYLENIC
(C
n
H
2n-2
)
Mc tiu hc tp
1. Trnh by c cu to v gi tn cc alkyn.
2. Nu c cc tnh cht ha hc ca alkyn.
3. Vit c s cc phn ng chuyn ha to thnh sn phm.
Alkyn hoc hydrocarbon acetylenic l hp cht khng vng cha no c cha
mt lin kt ba ng vi cng thc chung C
n
H
2n-2
1. Cu trc in t
Alkyn l nhng cht cha lin kt ba -CC-. Nguyn t carbon ca ni ba
trng thi lai ha sp. Lin kt ba gm mt lin kt v 2 lin kt . Lin kt
C
_
C c to thnh do s xen ph vi nhau ca 2 orbital lai ha sp ca carbon.
S xen ph ca orbital lai ha sp ca carbon vi orbital s ca hydro to thnh
lin kt C
_
H. Lin kt ca alkyn c to thnh do s xen ph tng i mt
ca cc orbital p t do ca nguyn t carbon lai ha sp. Hai lin kt ca alkyn
nm trong 2 mt phng thng gc vi nhau.
Carbon lai hoa sp
__
C C
_
__
C C
_
.
.
.
.

Cac electron p t do cua carbon
2 orbital p t do cua carbon orbital s cua hydro

Acetylen c cu to thng. di lin kt C C (1,2 ) ngn hn lin kt C -C.
o
A
Lin kt C -H (1,06 ) ngn hn lin kt C -H trong ethylen (1,08 ) v trong
etan (1,10
A
). Hnh di y m t s to thnh lin kt ba:
o
A
o
A
o
C
H C
C
sp
H
1s
C
sp
H
C
sp
C
sp
H
1s
o
o
A
o
A
180
1,20
C C H
H
S xen phu cua cac orbital p
S tao lien ket trong phan t acetylen o dai va goc lien ket
1,06

Nng lng kin kt:
i vi lin kt ba l 199,6 kcal.mol
1
, ca lin kt i l 145,8 kcal.mol
1
v
ca lin kt n l 82,6 kcal.mol
1
. Mt in t tp trung ch yu khong
120
gia hai ht nhn ca 2 nguyn t carbon. m in ca carbon lai ha Csp >
Csp
2

>

Csp
3
. iu gii thch kh nng phn ng cng hp i in t ca lin
kt ba km hn so vi lin kt i.
2. Danh php v ng phn
2.1. Danh php IUPAC
Cc alkyn u c tn cng l yn. Mch chnh l mch di nht c lin kt
ba. nh s mch chnh sao cho lin kt ba c s nh nht.
V tr nhnh + Tn nhnh + V tr lin kt ba + Tn mch chnh + yn
;
CH
3
_
CH
_
C
CH
CH
3
_
C C
_
CH
2
_
CH
2
_
CH
_
CH
3
6-Methyl-2-heptyn
7
6
5 4
3 2
1
CH
3
3-Methyl-1-butyn
4 3 2 1
CH
3

2.2. Danh php hp l - Danh php acetylen
Cc alkyn n gin c xem nh dn xut ca acetylen
CH
3
CCH Methyl acetylen
(CH
3
)
2
CHCCCH
3

Methylisopropylacetylen
F
3
C
_
CCH Trifluoromethyl acetylen
2.3. Tn cc gc
-CCH Etynyl CH
3
-
CCH Propynyl CH
3
_
CC-CH
2
- 2-Butynyl
;
Methylcyclohexylacetylen
Propynylcyclohexan
C CCH
3
Cyclopentylacetylen
C CH
Etynylcyclopentan

2.4. ng phn
Cc alkyn c ng phn cu to v mch carbon v ng phn c v tr ca
ni ba . Khc vi alken, cc alkyn khng c ng phn lp th.
3. Phng php iu ch
3.1. Tch loi 2 phn t HX t hp cht gem v vic -dihalogen
Nguyn tc: T gem dihalogen - -C C- + 2HX
T vic -dihalogen - CHX-CHX- -C C- + 2HX
Phn ng xy ra qua 2 giai on:
-CBr
2
-CH
2
-
-CX=CH-
-C C-
_
_
_
-CHBr-CHBr-
Nhanh
Cham

121
S tch loi xy ra khi c mt ca KOH hoc NaOH trong alcol v nhit .
CH
3
CH
2
CHBr
2

CH
3
_
C CH 2 HBr +
t
alcol KOH
o

(66-69%) (77-81%)
Stilben
t
alcol
KOH
ete
Br
2
Br
C
6
H
5
CH-CHC
6
H
5
C
6
H
5
CH=CHC
6
H
5
Br
C
6
H
5
_
C C
_
C
6
H
5
2 HBr +
Diphenylacetylen 1,2-Dibrom-1,2-diphenyletan
o

Propen
CH
3
CH=CH
2

+ Br
2

CH
3
CH
_
CH
2

Br Br
KOH alcol
t
CH
3
_
C CH 2

HBr +
Methylacetylen 1,2-dibromopropan
o

Natri amidid NaNH
2
l mt base mnh c th s dng tch HX trong
phn ng iu ch cc 1-alkyn.
R
_
C C
_
H R
_
C C
-
_
Na
+
R
_
C C
_
H
R
_
C C
-
_
Na
+
NaNH
2
+ +
3
+ H
2
O
2NaNH
2
RCH
2
-CHX
2
RCHX-CH
2
X
RCX
2
-CH
3
NH
+ NaOH

- NaX
- NH
3

Phn ng tch HX trong iu kin c mt base mnh v nhit thng c
th xy ra s chuyn v ca ni ba.
t alcol KOH
CH
3
CH
2
_
C C
_
H CH
3
_
C C
_
CH
3
1-Butyn 2-Butyn
o

3.2. Phng php alkyl ha acetylen
Anion acetylid l mt tc nhn i nhn mnh (mt base mnh) d dng tc
dng vi alkylhalogenid to thnh alkyn c mch carbon di hn.
H
_
C C
_
H + Na
H
_
C C
_
Na
+ RX
H
_
C C
_
R + NaX

2-Pentyn
CH
3
_
C C
_
CH
2
CH
3

+ NaI
+ CH
3
CH
2
I
CH
3
_
C C
_
Na
+ Na
Propyn
CH
3
_
C C
_
H

C th s dng natri amidid to acetylid trong phn ng alkyl ha acetylen.
Hexyn-1 (89%)
n-C
4
H
9
Br
(lng)
+
NH
3
NaNH
2
CH
3
(CH
2
)
3
_
C C
_
H
H
_
C C
_
Na
H
_
C C
_
H
Natri acetylid
-33
o
C

3.3. T hp cht tetrahalogen
Cc hp cht c 4 halogen gn trn 2 carbon cnh nhau tc dng vi bt Zn
kim loi trong iu kin thch hp cng to c lin kt ba.
122
R
_
C C
_
R' + 2 Zn R
_
C C
_
R' ZnX
2
2 +
X X
X X

4. Tnh cht l hc
S to thnh lin kt C
_
C c to thnh do xen ph ca orbital lai ha
Csp
3
ca metyl v orbital lai ha ca carbon acetylenic . Mt orbital sp c tnh
cht ca orbital S nhiu hn orbital sp
3
. Kt qu l lin kt c chnh lch v
m in. Mt in t trn lin kt C
_
C l khng i xng v xut hin
momen lng cc.
CH
3
CH
2
CCH (sp
3
v sp) CH
3
CH
2
CH=CH
2

(sp
3
v sp
2
) CH
3
CCCH
3
= 0,80 D = 0,30 D = 0
Hp cht alkyn khng c ng phn hnh hc nh hp cht alken v acetylen
c cu trc thng.
Mt vi tnh cht vt l ca alkyn c trnh by bng 10-1.
Bng 10: Tnh cht vt l ca cc hp cht alkyn
Hp cht t
o
si t
o
nng chy T khi
Etyn
Propyn
Butyn-1
Butyn-2
Pentyn-1
Pentyn-2
Hexyn-1
Hexyn-2
Hexyn-3
Phenylacetylen
Diphenylacetylen

- 84,0

- 23,2
8,1
27,0
39,3
55,5
71,0
84,0
81,0
143,0
300,0
- 8,9
- 102,7
- 122,5
- 32,3
- 90.0
- 10,0
-132,0
- 88,0
-105,0
- 43,0
- 63,5

0,7152
0,7317
0,7231
5. Tnh cht ha hc
5.1. Tnh acid ca alkyn
Lin kt C -H phn cc mnh v pha carbon ca lin kt ba
CC
-
H
+
lm
tng momen lng cc ca lin kt v tng kh nng tch hydro di dng
proton. Do tnh acid ca acetylen ln hn so vi etylen v etan.
Gi tr pKa ca mt s cht sau y:
Hp cht H
2
O Alcol Acetylen NH
3
Ethylen Metan
pK
a
15,7 16-19 25 35 44 50
123
HC C
-
L c acid
Lc base
CH
2
=CH
2
CH
4
-
-
CH
2
=CH
CH
3
HC CH

Tnh base ca cc anion khc nhau v nguyn t carbon mang in tch m
cc trng thi lai ha khc nhau.
.
.
:
:
sp
sp
2
sp
3
H
H
H
H
H
H
Anion acetylid Anion vinyl Anion methyl
C C
H
_
C C
C

Cc alkyn c ni ba u mch (cc 1- alkyn) cng rt d to carbanion khi
tc dng vi anion amidid trong amoniac lng.
+ NH
3
+ NH
2
-
R
_
C C
_
H R
_
C C
-

Cc carbanion RC C
-
, CH
2
=CH
-
v H
3
C
-
c bn khc nhau.
Nguyn t hydro trong lin kt C H cn th hin cc phn ng sau y:
Acetylen v 1-alkyn tc dng vi kim loi kim, CuCl trong amoniac,
AgNO
3
trong amoniac u to thnh acetylid hoc alkynylid kim loi.

R
_
C C
_
H AgNO
3
NH
3
NH
4
NO
3
+ R
_
C C
_
Ag
+ +

R
_
C C
_
H + CuCl + NH
3
R
_
C C
_
Cu + NH
4
Cl

Acetylen cng hp vi aldehyd formic nh l mt tc nhn i nhn.
1,4-Butyndiol
HOCH
2
_
C C
_
CH
2
OH
Aldehyd formic
+ 2HCHO H
_
C C
_
H

Alkyl lithium tch proton khi alkyn.
CH
3
(CH
3
)
2
CCH + n-C
4
H
9
Li CH
3
(CH
3
)
2
CCLi + n-C
4
H
10
5.2. Phn ng cng hp
5.2.1. Cng hp vi hydro
Alkyn tc dng vi hydro c xc tc to thnh alkan
Pt ,( Pd , Ni)
+ 2H
2
R-CH
2
CH
2
-R'
R
_
C C
_
R'

Phn ng thng xy ra 2 giai on. Giai on mt to nhit hn giai on hai.
HCCH + H
2

CH
2
=CH
2

H = -41.9 kcal mol
-1

H
2
C=CH
2
+ H
2
CH
3
_
CH
3

H = -32,7 kcal mol
-1

124
S hydro ha c th dng li giai on to alken khi dng xc tc c
lm gim kh nng hot ha mt phn. Hn hp xc tc l PdCaCO
3
, Pd-
BaSO
4
-Quinolin.
+
cis-3-Hexen
H
C
2
H
5
H
C
2
H
5
C C
CH
3
CH
2
_
C C
_
CH
2
CH
5
3-Hexyn
Quinolin
Pd- BaSO
4
H
2

S cng hydro cng c th xy ra khi s dng natri kim loi trong amoniac lng.
Na/NH
3
(lng)
NH
4
OH
5-Dekyn
C
4
H
5
C CC
4
H
9
C C
H
9
C
4
H
C
4
H
9
H
Trans- 5-deken

5.2.2. Phn ng cng hp i in t
Phn ng cng hp i in t xy ra ti lin kt ba theo 2 giai on v
tun theo qui tc Markonikov. Cc tc nhn cng i in t c th l X
2

(halogen), HX, H
2
O.
+ X
2
RC CH
RCX
2
CX
2
R' RC CR' RCX CXR'
RCX CH
2
RCX
2
CH
3
+ X
2
+ HX + HX

Khi cng hp vo ni ba, carbocation dng vinylic R -C
+
=CH
2
c to thnh
v d dng tc dng vi cc tc cht i nhn c trong mi trng phn ng. V d
s to thnh vinyl clorid:
CHCH + H
+
CH
2
=CH
+
; CH
2
=CH
+
+ Cl
-
CH
2
=CHCl
+ H
+
HC C CH=CH
2
H
2
C C CH=CH
2
+ Cl
- +
H
2
C CCl CH=CH
2

Phn ng cng hp vi nc c xc tc xy ra qua giai on to cht trung
gian enol. Enol khng bn d b chuyn v to thnh aldehyd hoc ceton .
+ H
2
O
HgSO
4
-H
2
SO
4
O
OH
C CH
3
R
C CH
2
R
C C R H C C R H
Ceton
1- Alkyn
Dang enol
C CH
3
C
4
H
9
1- Hexyn
Methylbutylceton
C C C
4
H
9
H
O
HgSO
4
-H
2
SO
4
+ H
2
O

5.2.3. Cng hp i nhn
Khc vi alken, cc alkyn tham gia phn ng cng hp vi cc cht i nhn
nh alcol, amin, acid carboxylic, amid, HCN to thnh cc hp cht tng ng.
125
HCN
RCONH
2
R
2
NH
RCOOH
Acrylonitril
Amid
Ester vinylic
Vinyl amin
Ether vinylic
ROH
H
2
C CH CN
H
2
C CH NHCOR
H
2
C CH OCOR
H
2
C CH NR
2
H
2
C CH OR
C C H H

5.2.4. Phn ng carbonyl ho vo lin kt ba
Khi c xc tc l cc carbonyl kim loi v p sut, acetylen tng tc vi hn
hp gm carbon oxyd (CO) v cc cht c hydro linh ng (nc, alcol, amin bc
mt v hai) th to cc cht nh acid, ester, amid...
CO + R
2
NH
CO + ROH
CO + H
2
O
Amid cua acid acrylic
Ester acrylat
Acid acrylic
H
2
C CH CONR
2
H
2
C CH COOR
H
2
C CH COOH
H C C H

5.2.5. Phn ng vi diboran B
2
H
6
Alkyn tc dng diboran 0
C to cc cht trung gian trivinylboran. Khi c

mt ca acid acetic th to thnh alken dng cis.
3 CH
3
COOH
3 CH
3
COOH
H
H
H
H
R
C C
R'
H
R
C C
3
H
H
R
C C
B
+
2
1
B
2
H
6
3
2
1
3
3
R'
H
R
C C R R' C C
C C R H
+ B
2
H
6
B

Phn ng cng c th xy ra vi bor dialkyl v theo c ch cng cis
0
o
C
H
CH
2
CH
3
CH
3
CH
2
C C
B
R
R
R
R
B
H
CH
3
COOH
H
cis 3-Hexen (90%)
+
CH
2
CH
3
H
CH
3
CH
2
C C
C C CH
3
CH
2
CH
2
CH
3

Lin kt CB trong hp cht vinylboran d b oxy ha bi nc oxy gi
(H
2
O
2
) to thnh enol v sau chuyn v thnh aldehyd hoc ceton.
Hexanal OH
-
H
2
O
2
1-Hexyn
B
2
H
6
C
4
H
9
C CH
C
4
H
9
CH
2
CHO
OH
H C
4
H
9
C C
H

126
5.3. Phn ng trng hp
cc iu kin thch hp v xc tc, nhit v p sut, cc alkyn c th b
nh hp, tam hp to thnh cc cht tng ng.
Cu(NH
3
)
2
Cl
Vinylacetylen 2
HC C CH=CH
2
HC CH
Carbon ,600
o
C
3HC CH
Benzen

200 - 300
C khi c bt ng lm xc tc, acetylen b trng hp to polyacetylen

cn gi l cht cao phn t Cupren.
Cu
hay viet (CH)n
n
n - CH=CH- Cupren
HC CH
200-300
o
C

6. Cht in hnh
Acetylen C
2
H
2
iu ch
Thy phn carbur calci (t n)
CaC
2
+ 2H
2
O HCCH + Ca(OH)
2
T kh thin nhin: Phn ng quan trng trong cng nghip iu ch
acetylen l in cracking v cracking oxy ha nhit metan.
+ in cracking:
Cho CH
4
i qua cc in cc, in th mt chiu 8000V, nhit phn ng
1600C, tc dng kh 1000 m /s. Hn hp kh thot ra c lm lnh ngay.
2CH
4
HCCH + 3H
2
H
0
298
= 91 kcal/mol
Hn hp kh cha 13% acetylen
+ Cracking oxy ha nhit
6CH
4
+ 4O
2
HCCH + 8H
2
+ 3CO + CO
2
+3H
2
O
T l CH
4
: O
2
= 1 : 0.65. Nhit l phn ng 1500C, tc kh i qua l
rt ln. Lm nhanh s thu c hn hp kh vi khong 8% acetylen.
Tnh cht v ng dng.
Acetylen l cht kh khng mu, nguyn cht khng mi, nh hn khng
kh, t tan trong nc, tan nhiu trong cc dung mi hu c nh alcol, ether, tan
rt nhiu trong aceton.
Acetylen khng bn v mt nhit ng, n c th b phn hy to C v H
2

km theo hin tng n. Phn ng n to nhiu nhit, H
0
298
= -54.9 kcal/mol,
nhit kh lc ln ti hng ngn .
127
Acetylen chy trong khng kh cho ngn la sng, to CO
2
v nc, nhit
lng ta ra rt ln. Khi dng hn hp C
2
H
2
-O
2
lm kh hn, ct kim loi mu,
mun hn tt phi dng kh tr (Argon) oxy khng tip xc trc tip ln b
mt kim loi hn.
Bi tp
1. Vit cng thc cu to ca hydrocarbon sau:
a- 2- butyn; b- 2- methyl-3-hexyn; c- 2,2,5-trimethyl-4-hexyn; d- isopropylacetylen.
2. Gi tn nhng hp cht sau:
HC C
CH
3
_
C
_
CH
2
_
CH
2
_
CH
CH
3
_
CH
2
CH
3
CH
3
CH
3
CH
3
_
C
_ _
C
_
CH
3

CH
3
C C
CH
3
CH
3
C CH
a-
b-
c-
; ;

3. Vit phng trnh phn ng gia dung dch kim - ru d vi cc cht di y:
a- 1,1- dibromobutan;
b- 2,2- dibromo-3,3- dimethylbutan;
c- 2,2- diclopentan
4. Vit phng trnh phn ng gia B
2
H
6
-H
2
O
2

- OH
-
vi cc cht sau:
a- 1-butyn; b- 2-butyn; c- 2- pentyn; d- methylisopropylacetylen.
5. Vit s phn ng ca acetylen vi nhng cht sau:
a- alcol ethylic;
b- acid cyanhydric;
c- aldehyd formic;
d- aldehyd acetic;
e - aceton .

128
Chng 11
AREN - HYDROCARBON THM
Mc tiu hc tp
1. Gii thch cu to ca nhn thm.
2. Gi tn c cc hydrocarbon thm.
3. Trnh by cc tnh cht ha hc ca benzen: c ch S
E
.
Aren hay l hydrocarbon m trong phn t c mt ca mt hay nhiu nhn
benzen. Aren cn gi l hydrocarbon thm - hydrocarbon hng phng
1. Benzen v nhn thm
1.1. Cu to benzen
Benzen c cng thc phn t C
6
H
6
. Nm 1825 ln u tin Faraday M. pht
hin benzen trong kh t. Nm 1834 Mitscherlich E. A. iu ch benzen t acid
benzoic thu c t cy Styrax benzoin. Nm 1845 Hofmann tm thy benzen
trong nha than . Benzen c mt s tnh cht c trng gi l " tnh thm ".
gii thch tnh cht c trng cc nh ha hc a ra cc dng cng thc
cu to ca benzen.
1.1.1. Cc dng cng thc c in
Thiele Amstrong Dewar
Ladenburg
Closs
Kekule

Cc cng thc trn khng gii thch y tnh cht ha hc c trng ca
benzen. Cng thc benzen theo Kekule c 3 lin kt i suy ra benzen d tham gia
phn ng cng hp hn phn ng th v benzen khng bn vi tc nhn oxy ha.
Trn thc t benzen d tham gia phn ng th, kh cng hp v rt bn vi cc
cht oxy ha.
Cc cng thc Closs, Ladenburg, Amstrong, Dewar v Thiele u cha tha
mn y cc tnh cht ha -l ca benzen nh di lin kt v kh nng
phn ng.

129
1.1.2. Khi nim hin i v cu to benzen
Bng cc phng php vt hin i: phng php Rnghen, quang ph v
nhiu x in t, cu to ca ben zen c xc nh nh sau:
Benzen c cu to vng phng, 6 nguyn t carbon v 6 nguyn t hydro
u nm trong mt mt phng. Vng benzen hon ton i xng.
Khong cch gia cc nguyn t carbon trong vng u bng nhau 1,398 A

l i lng trung gian gia di lin kt n thun ty v (1,54)

v lin

kt i

(1,35
A
).

Gc gia cc lin kt CCC v CCH u bng nhau v

c gi tr 120 (hnh11-1 a )
o
o

c
Cac orbital p t do
tren cac nguyen t carbon

Goc va o dai
lien ket
S xen phu cac orbital
tao lien ket C-C va C-H
a
Hnh 11.1:
b
Xen phu cac orbital p t do
va tao lien ket

o
1,398A
120
o
. H
H
H
H
H
H
.
.
.
.
.
d
H
1 s

C
sp
2

C
sp
2
Lien ket
H
H
H
H
H
H
sp
2

C

Mi nguyn t carbon to 3 lin kt . Trong c 2 lin kt do s xen ph
ca 2 orbital lai ha sp
2
gia carboncarbon bn cnh nhau. Cn mt lin kt
gia CH do xen ph ca orbital lai ha sp
2
ca carbon v ca orbital s ca hydro
(hnh11.1b).
Trn mi nguyn t carbo cn mt orbital p cha lai ha.
Trc cc orbital ny thng gc vi mt phng ca vng benzen (hnh 11.1c).
Tt c cc orbital ny xen ph ln nhau to thnh mt orbital phn t
chung duy nht (hnh 11.1d). Nh vy cc orbital p trong vng benzen lin hp
vi nhau thnh mt h thng lin hp hon chnh. Do h thng lin hp ny m
khong cch gia cc nguyn t carbon trong vng benzen hon ton ng nht.
Benzen tr nn bn vng, kh tham gia phn ng cng hp, kh b oxy ha v d
tham gia phn ng th. Tnh cht c trng ny ca benzen gi l "tnh thm".
Vy: "Tnh thm " l kh nng ca mt hp cht: D cho phn ng th, kh
cho phn ng cng hp v phn ng oxy ha
C th tng trng cng thc cu to ca benzen nh sau:

130
1.2. Nng lng cng hng ca benzen
Nu dehydro ha cyclohexan to thnh cyclohexatrien phi cn nng
lng 81,4 kcal.mol
1
. Nu chuyn ha cyclohexan thnh benzen th ch cn mt
nng lng l 49,3 kcal.mol
1
.
iu khng nh rng benzen khng phi l cyclohexatrien.
H thng lin hp hon chnh ca benzen l nguyn nhn gim nng lng
trn. Hiu s nng lng ca 2 trng hp trn gi l nng lng cng hng ca
benzen (hay cn gi nng lng thm ha, nng lng lin hp)
=81,4-49,3 =
32,1 kcal.mol
1
(hnh 11-2).
o
o
o
-26,5 kcal mol
-1
-28,4 kcal mol
-1
-24,5 kcal mol
-1
-24,5 kcal mol
-1
H =
H =
H =
-49,3 kcal mol
-
1
H =
o
Nng lng cng hng
-30 kcal mol
-
1

Hnh 11.2: Gin nng lng cng hng ca benzen
1.3. Nhn thm
Benzen l hp cht c tnh thm c bn nht .
Nhng hp cht khc c cu to vng phng, cha no v lin hp c s
electron p to h thng lin hp tha mn v cng thc Huckel 4n+2 u c tnh
thm tng t benzen. Trong cng thc Huckel, n l s t nhin n = 0,1,2, 3...
Nhng phn t hoc ion tha mn cng thc trn gi l nhn thm. Cc ion c th
l carbocation hoc carbanion.
V d: V cc nhn thm vi cc gi tr n khc nhau.
2 electron
n = 0
Cation cyclopropenyl
+

. .
N
H
cycloheptatrienyl cyclopentadienyl
CH
3
_
Toluen
Anion Cation
+
N
. .
Pyridin
Pyrrol
n = 1
6 electron

131
Dianion
Anion
n = 2
10 electron
2
_
_
cyclononatetraenyl cyclooctatetraen
Naphthalen

Cyclooctatetraen khng c tnh thm; khng phi l nhn thm v
cyclooctatetraen ch c 8 electron v khng c cu trc phng (khng lin hp).
2. Danh php v ng phn
Nu thay th mt hay mt s nguyn t hydro trong phn t benzen bng
mt hay mt s gc alkyl th thu c cc ng ng ca benzen. Cc ng ng
benzen c gi tn bng cch gi tn gc alkyl theo th t t n gin n phc
tp c km theo v tr trn nhn thm v cui cng thm ch benzen.
V tr nhnh + tn nhnh + benzen
C
CH
3
CH
3
CH
3
CH
2
_
CH
3
CH
3 CH
2
CH
2
CH
3 CH
2
CHCH
3
CH
3
CH
_
CH
3
CH
3
Toluen
Ethylbenzen
n-Propylbenzen Iso-Propylbenzen Iso-butylbenzen Tert-butylbenzen

Nu cc ng ng c 2 gc alkyl gn vo nhn benzen th 2 nhm ny c
th cc v tr khc nhau. Chng l nhng ng phn ca nhau.
CH
3
CH
3
o-Xylen
1,2-Dimethylbenzen
CH
3
CH
3
CH
3
CH
3
CH
3
CH
CH
3
CH
3
1,3-Dimethylbenzen
1,4-Dimethylbenzen
1-Methyl-4-isopropylbenzen
m-Xylen p-Xylen p-Xymen

Cc tip u ng ortho (o), meta (m), para (p) c dng gi tn cc ng
phn c hai nhm th. Ortho ch 2 v tr cnh nhau. Meta ch 2 v tr trn vng
cch nhau mt nguyn t carbon. Para ch 2 v tr i din nhau.
, , ,
1 1 4 3
2 1 V tr :
Para (p- ) Meta ( m-)
X
Y
X
Y
X
Y
Orto ( o-)

Hp cht c 3 nhm th trn vng: Vicinal (vic-) ch 3 nhm th hon ton
cnh nhau. Asymmetrical ( as-) ch 3 v tr khng i xng. Symmetrical ( s-) ch 3
v tr i xng.
132
5
5
4
4
4
3
3
2
2
2
1
1
5
3
1
,
5 3
,
3
Symmetrical (s-)
, , , ,
1 1 4 3 2 1
V tr :
Asymmetrical (as-)
X
Z Y
X
Y
Z
X
Y
Z
Vicinal (vic-)

Danh php cc gc:
Nu ly bt mt nguyn t hydro ca benzen hoc ng ng s thu c
gc ha tr mt v c tn gi nh sau:
CH
3
Phenyl
CH
3
CH
3
o-Tolyl m-Tolyl
p-Tolyl

Nu ly 2 nguyn t hydro trn vng benzen ta c gc ha tr 2 v c tn gi:
Benzo
C
Benza
1,4-Phenylen 1,3-Phenylen 1,2-Phenylen
Benzylyden
p-Phenylen
m-Phenylen
o-Phenylen
CH

Theo danh php IUPAC cc hydrocarbon thm n gin thng c quy
c gi theo tn thng thng v nh s theo nhng quy tc nht nh.
1
1
10
10 10
9
9
9
8
8
8
8
7
7
7
7
6
6
6
6
5
5
5
5
4
4
4 4
3
3
3
33
2
2
2
2
1
1
1
2
1
Pyren Phenantren Antracen Naphthalen o-Xylen
CH
3
CH
3
Toluen
CH
3

3. Phng php iu ch
Nha than l ngun nguyn liu ch yu v quan trng cung cp cc
hydrocarbon thm. ng dng mt s phng php ha hc iu ch cc
hydrocarbon thm.
3.1. Phng php dehydro ha cc cycloalkan
Cc cycloalkan n vng v a vng nh cyclohexan, decalin (perhydronaphtalen)
khi c xc tc v nhit thch hp c th b dehydro ha v to thnh
hydrocarbon thm tng ng.
Xuc tac , t
o
+ 3 H
2 + H
2
Xuc tac , t
o
;

133
3.2. Phng php trimer ha
Benzen, mesitylen (1,3,5- trimetylbenzen) c th c iu ch t acetylen,
propyn hoc aceton khi c cc xc tc ph hp .
CH CH
C CH CH
3
CH
3
CH
3
CH
3
600
o
C.
Carbon . Carbon .
600
o
C.
;
3
3
Mesityllen
Propyn

+ 3 H
2
O
H
2
SO
4
(16%)
CH
3
CH
3
CH
3
O
CH
3
CH
3
CH
3
CH
3
O
O
CH
3
CH
3

3.3. Phng php Wurtz -Fittig
Phng php ny tng t vi phng php iu ch alkan. Cho kim loi
hot ng tc dng vi dn xut halogen thm v alkyl halogenid.
X
+ R
_
X
R
+ 2 NaX
+ 2Na
ete

ete
CH
2
Br BrH
2
C
+ 2Na
CH
2
CH
2
+ 2 NaBr

3.4. Phng php alkyl ha theo phn ng Friedel - Crafts
y l phng php iu ch cc ng ng ca benzen (Xem tnh cht
ha hc ca hydrocarbon thm).
R
+ RX + HX
AlCl
3

4. Tnh cht l hc
Cc ng ng ca benzen l nhng cht lng, mt s l cht rn. Chng
u c mi c trng.
134
Bng 11: Tnh cht l hc ca mt s hydrocarbon thm
Benzen
Toluen
Ethylbenzen
Propylbenzen
iso-Propylbenzen
p-Methylisopropyl

Ten goi
t
o
soi
-
1,4
1,2
1,3
1
1
1
1,4
V tr
Cong thc
+ 5,51
-95,0
- 53,6
+ 13,2
-94,0
-101,6
-96,9
-73,5,
80,10
110,6
144,4
139,1
138,4
136,2
159,2
176,0
0,8790
0,8669
0,8641
0,8610
0,8669
0,8620
0,8618
0,8570
C
6
H
6
benzen
C
6
H
5
CH
3
C
6
H
4
(CH
3
)
2
C
6
H
5
C
2
H
5
C
6
H
5
C
3
H
7
C
6
H
5
CH(CH
3
)
2
CH
3
C
6
H
4
CH(CH
3
)
2
m-Xylen
o-Xylen
p-Xylen
1
-29,0
152,4
0,8802
t
o
nong chay T khi

5. Tnh cht ha hc
T cu to lin hp ca vng benzen, hydrocarbon thm c cc loi phn ng:
Phn ng th i in t vo nhn benzen.
Phn ng cng vo vng benzen.
Phn ng oxy ho.
5.1. Phn ng th i in t trn vng benzen
C ch chung cc phn ng th i in t xy ra qua 2 giai on ch yu:
Giai on mt l s hnh thnh tc nhn i in t Y
+
.
Giai on hai l s tng tc gia tc nhn i in t vi vng benzen
to phc phc v sn phm ca phn ng th.
Phn ng th tin hnh trong mi trng acid mnh hoc c mt mt cht
xc tc. Acid mnh hoc xc tc c tc dng chuyn ha tc nhn phn ng thnh
dng i in t Y
+
(electrophile).
Y
_
X + FeBr
3

Y
+
+ FeBr
3
X
-

Tc nhn Y
+
s tng tc vi nhn benzen ti v tr c mt electron cao nht
+ Y
+

+
+ HX + FeBr
3
hoac Y
+
FeBr
3
X
-
Phc
Phc
H
Y
H
Y
Phc
(Cation pentadienic)

C cc loi phn ng th i in t vo vng benzen nh sau:
135
5.1.1. Phn ng halogen ha
Tng tc ca halogen nh clor, brom vi benzen khan nhit thng, c
mt xc tc bt st hoc cc acid Lewis nh FeCl
3
, FeBr
3
,

AlCl
3
, SbCl
3
hoc cc
iod, s xy ra phn ng mnh lit v to sn phm l cc dn xut halogen ca
hydrocarbon thm nh clorobenzen, bromobenzen. Phn ng brom ha nh sau:

Br
H
+ Br-Br + FeBr
3
FeBr
4
-
+
+

Carbocation trung gian c h lin hp, c mt carbon trng thi lai ha sp
3
+
H
Br
+
H
Br
+
H
Br
H
Br

E
Tien trnh phan ng
Chat trung gian
xac nh ong hoc
+ Br
2
+ FeBr
3
Br H
H. . . Br. . .FeBr
3
Br
Br. . . Br. . .FeBr
3
H
Chat phan ng San pham
+ FeBr
4
-
Br
+ HBr + FeBr
3
Trng thi chuyn tip
to sn phm

N
n
g

l
n
g

p
h
n
g

Hnh 11.3. Gin thay i nng lng ng vi cc trng thi trong phn ng brom ho
Phn ng brom ha c s chung:
H
Br
+ Br-Br + FeBr
3
FeBr
4
-
+
+ HBr + FeBr
3
+
Br

C th trnh by gin thay i nng lng ng vi cc trng thi hnh
thnh trong phn ng brom ho nh hnh 11-3.

136
Clor ha toluen c xc tc FeCl
3
to ra hn hp o -clorotoluen v p - clorotoluen
CH
3
Cl
+ Cl
2
FeCl
3
CH
3
Cl
CH
3 + HCl
+ HCl
FeCl
3

Phn ng halogen ha vo mch nhnh ca hydrocarbon thm khi c xc tc
l nh sng khng phi l phn ng th i in t m l phn ng halogen ha
xy ra theo c ch th gc.
Clor ha toluen khi c xc tc nh sng to ra cc sn phm benzylclorid,
benzylyden clorid (benzalclorid) v benzotriclorid.
CH
3
CH
2
Cl CHCl
2
CCl
3
Cl
2
, h
- HCl
Toluen
Cl
2
, h
- HCl
Cl
2
, h
- HCl
Benzylclorid Benzylydenclorid Benzotriclorid

S to gc t do benzyl cn nng lng thp. Gc benzyl bn nh s lin hp.
CH
3 CH
2
+ Cl
.
H = - 16 kcal.mol
-1
Goc t do benzyl
+ HCl
.
CH
2
.
CH
2
CH
2
CH
2
.
.
.
;

S to thnh hp cht halogen nhn benzen v mch nhnh l nhng
hp cht hu c c nhiu lnh vc ng dng.
5.1.2. Phn ng nitro ha
Phn ng nitro ha l phn ng thay th nguyn t hydro ca hydrocarbon
bng nhm NO
2
. Tc nhn to ra
+
NO
2
thng l hn hp sulfonitric
(HNO
3
+H
2
SO
4

). Ty trng hp, tc nhn nitro ha c th l acid nitric c hay
long hoc hn hp acid nitric vi anhydrid acetic. Nitro ha benzen, toluen bng
hn hp acid nitric v acid sulfuric xy ra d dng. Sn phm to thnh ty theo
nhit , nng acid.
+ H
2
O
+ HNO
3
NO
2
H
2
SO
4
NO
2
NO
2
NO
2
NO
2
NO
2
NO
2
+ HNO
3
H
2
SO
4
+ HNO
3
H
2
SO
4
;

Tip tc nitro ha mononitrobenzen phi s dng hn hp acid nitric c
nng v nhit cao hn. Sn phm to thnh l meta - dinitrobenzen. a
thm nhm nitro th ba vo phi tin hnh trong iu kin khc nghit hn. L
do l nhm nitro lm gim hot ha, mt electron trn cc v tr ca vng
benzen gim i, s th i in t tip tc vo nitrobenzen s kh khn hn.
137
Toluen b nitro ha s to thnh hn hp sn phm gm o -nitrotoluen v
p - nitrotoluen.
p-Nitrotoluen
+ HNO
3
o-Nitrotoluen
H
2
SO
4
H
2
SO
4
+ HNO
3
+ H
2
O
+ H
2
O
CH
3
NO
2
CH
3
NO
2
CH
3

Nhm methyl trong toluen c tc dng y electron (do siu lin hp v cm
ng) lm cho mt electron trong vng benzen tng ln, c bit cc v tr
ortho v para, v vy s th xy ra u tin ti cc v tr ny. nh hng c th
c minh ha bng cc trng thi cng hng ca toluen nh di y:
C H
H
H
CH
3
CH
3 CH
3 CH
3

Cc sn phm nitro ha hydrocarbon thm lm phong ph thm ngun
nguyn liu sn xut nhiu loi thuc nhum, thuc n ...
C ch phn ng nitro ha
NO
2
+
l tc nhn i in t rt mnh, c cu trc thng. S hnh thnh tc
nhn ny l do s tng tc gia acid nitric v acid sulfuric.
2 H
2
SO
4
+ HONO
2
NO
2
+
+ HSO
4
-
+ H
3
O
+

- H
+
+ H
+
+
-
O
O N
H
N
+
NO
2
+
O
O

5.1.3. Phn ng sulfonic ha
Sulfonic ha l phn ng gn nhm sulfonic -SO
3
H vo phn t cht hu c.
Cc tc nhn sulfonic ha thng l H
2
SO
4

m c, hn hp H
2
SO
4

+ SO
3

(oleum). Phn ng sulfonic ha c tnh cht thun nghch.
Ar
_
H + H
2
SO
4

Ar
_
SO
3
H + H
2
O

Lng nc sinh ra khng nhng lm long nng ca acid m cn gy
nn tnh cht thun nghch ca phn ng.

138
Cc ng ng ca benzen d xy ra phn ng sulfonic ha.
;
+
Acid o-toluensulfonic
Acid benzensulfonic
- H
2
O
+ H
2
SO
4
CH
3
SO
3
H
SO
3
H
CH
3
+ H
2
O
+ H
2
SO
4
CH
3
SO
3
H

Hp cht a nhn thm nh naphthalen: s sulfonic ha ph thuc nhiu
n nhit v nng ca acid.
+ H
2
SO
4
SO
3
H
SO
3
H
+ H
2
O
+ H
2
O
< 100
o
160
o
160
o
Acid
-
naphthalensulfonic
Acid
-
naphthalensulfonic

Acid arenosulfonic l nhng acid mnh v nhit nng chy khng xc
nh. Cc cht hu c dng mui sulfonat d tan trong nc .
5.1.4. Alkyl ho hydrocarbon thm
Thay th nguyn t hydro ca nhn thm bng gc alkyl.
Tc nhn phn ng l alkyl halogenid RX vi xc tc l cc acid Lewis nh
AlCl
3

khan (phn ng Friedel -Crafts) hoc FeBr
3
, FeCl
3
.

CH
CH
3
CH
3
Cl HC
CH
3
CH
3
AlCl
3

khan
+ HCl
+

C che :
+
. . . .
CH Cl AlCl
3
CH
3
CH
3
AlCl
3
. . . . + CH Cl
CH
3
CH
3

phc
phc
+
CH
CH
3
CH
3
CH Cl AlCl
3
CH
3
CH
3
+
. . . . . .
H
CH
3
CH
3
CH
+
CH Cl AlCl
3
CH
3
CH
3
+
. . . . . . . .
+ AlCl
4
-
+ AlCl
3
+

HCl

Tc nhn alkyl ha cng c th l alken, alcol khi c H
2
SO
4

hoc H
3
PO
4
lm
xc tc:
+
H
2
SO
4
CH
3
CH=CH
2 CH
3
CH
3
CH
CH
3
CH
3
CH
CH
3
CH
_
CH
3
OH
+
+ H
2
O
H
2
SO
4
;

Trong nhng phn ng ny tc nhn i in t dng carbocation c hnh
thnh do alken, alcol tc dng vi proton H
+
theo cc phn ng nh sau:
139
+ H
2
O
++
CH
3
CH
_
CH
3
OH
CH
3
CH
_
CH
3
OH
CH
3
CH
_
CH
3
+ H
+
;
OH
2
CH
3
CH
_
CH
3
+
CH
3
CH
_
CH
3
+ H
+
CH
3
CH=CH
2
+

Phn ng alkyl ha kh dng li giai on to monoalkyl. Tip tc phn
ng to di, trialkyl. S c mt ca gc alkyl s hot ha nhn thm v lm
thun li cho phn ng th i in t tip theo.
Sn phm phn ng alkyl ha c th l mch thng hoc mch nhnh v cc
tc nhn i in t hnh thnh c th b chuyn v c carbocation bn vng.
CH
3
CH
2
CH
2
Cl
CH
2
CH
2
CH
3
CH CH
3
CH
3
+ HCl
+ HCl
+
AlCl
3

CH
3
CHCH
3
H
+
CH
3
CHCH
2
+
S chuyn v xy ra

5.1.5. Phn ng acyl ha
Thay th nguyn t hydro ca hydrocarbon thm bng nhm acyl RCO gi
l phn ng acyl ha. Tc nhn acyl ha l halogenid acid RCOX, anhydrid acid
(RCO)
2
O. Xc tc cho phn ng acyl ha thng l AlCl
3
khan (phn ng Friedelp
-Crafts) hoc c th dng cc loi xc tc i in t khc nh AlBr
3
, GaCl
3
, FeCl
3
,
SbCl
3
, SnCl
4
, BCl
2

Sn phm acyl ha l cc ceton:
AlCl
3
+
+
RCOOH
(RCO)
2
O
O
C-R
RCOX
+
O
C-R
+ HX
AlCl
3
AlCl
3
;
Alkylphenylceton
Alkylphenylceton

;
O
O
R-C
-
AlCl
3
R-C-X
+
O R-C
+
..
. .
. .
+
AlXCl
3 +
-
AlCl
3
O
R-C-X
+
-
AlCl
3
O
R-C-X AlCl
3
+
+
RCOX

140
V d:
S Acetyl ha benzen bng acetylclorid hoc anhydrid acetic xy ra theo
phn ng
Anhydrid acetic
Acetophenon ( methyl phenylceton)
Acetylclorid
HCl +
C-CH
3
O
+
CH
3
COCl
C-CH
3
O
(CH
3
CO)
2
O CH
3
COOH + +
AlCl
3
AlCl
3

Phn ng acyl ha thng tin hnh trong dung mi carbondisulfid (CS
2
)
hoc nitrobenzen. Lng xc tc AlCl
3

phi dng nhiu hn v gia sn phm v
xc tc c th to phc cht.
AlCl
3
+
O
C-CH
3
AlCl
3
O
C-CH
3
.....

5.1.6. Mt s phn ng th i in t khc
Phn ng th hydro ca hydrocarbon thm bng nhm chc aldehyd - CHO.
Phn ng Gatterman
Tc nhn phn ng l hn hp HCl + HCN + AlCl
3

CHO
HCl , HCN , AlCl
3
;
CHO
CH
3
CH
3
HCl , HCN , AlCl
3

C th gii thch c ch qua cc giai on trung gian:
ClCH=NH + HC N
HCl N HC
ClCH=N
_
CH=NH.AlCl
3
ClCH=N
_
CH=NH.AlCl
3
Ar-CH=N
_
CH=NH.AlCl
3
ArH +
+ H
2
O
Ar-CHO + 2NH
3
+ HCOOH
- HCl
Ar-CH=N
_
CH=NH.AlCl
3

Phn ng Gatterman - Koch
Tc nhn phn ng l hn hp CO + HCl + AlCl
3
.
CHO
CO + HCl , AlCl
3
;
+ HCl
CHO
CH
3
CH
3
CO + HCl , AlCl
3
+ HCl

141
CO + HCl Cl
_
C
_
H C che :
Ar-CHO
O
Ar-H(- HCl)

Phn ng th hydro ca hydrocarbon thm bng nhm
_
CH
2
Cl
Tc nhn phn ng l hn hp HCHO + HCl c ZnCl
2

lm xc tc.
+ HCHO + HCl
CH
2
Cl
ZnCl
2
60
o
+ H
2
O

5.2. Phn ng cng hp ca hydrocarbon thm
Phn ng cng hp ca hydrocarbon xy ra kh khn hn s cng hp vo
alken v alkyn v nhn benzen l mt h thng lin hp.
5.2.1. Cng hp vi hydro
Khi c xc tc nh Ni, Pt, Pd v nhit , hydrocarbon thm c kh nng
cng hp vi hydro to thnh hp cht vng no (cycloalkan).
Methylcyclohexan Cyclohexan
;
Ni , t
o
+ 3 H
2
+ 3 H
2
CH
3
CH
3
130
o
Ni , 10at
+ 3 H
2

i vi cc cht c 2 nhm th nh dialkylbenzen, s cng hp ch yu to
sn phm cis. Ha lp th ca phn ng ty iu kin v xc tc.
5% Rh/ C , 100
o
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
+
o-Xylen cis- 1,2-Dimethylcyclohexan (90%) Trans- Dimethylcyclohexan (10%)
p sut

Nu trn nhn benzen c cc chc nh aldehyd, ceton hoc ni i th nhm
chc hoc ni i b cng hp trc tin.
Br
OCH
3
CHO
H
2
-PtO
2
Br
OCH
3
CH
2
OH
C
2
H
5
OH
2-Bromo-5-metoxybenzaldehyd Alcol 2-bromo-5-metoxybenzylic

Trans-stilben 1,2-Diphenyletan
CH
2
CH
2
C
6
H
5
C
6
H
5
C C
C
6
H
5
C
6
H
5
H
H
C
2
H
5
OH
H
2
-Pt

142
5.2.2. Phn ng cng halogen
Khi cho clor hoc brom i qua benzen c nhit , nh sng t ngoi, phn
ng cng xy ra.
+ 3 Cl
2
Cl
Cl
Cl
Cl
Cl
Cl
h

Hexaclocyclohexan thu c l mt hn hp cc ng phn lp th.
Phn ng xy ra theo c ch cng hp gc nh sau .
Cl

Cl 2 Cl
.
.
.
h

Cl
Cl
Cl
:
.
Cl

Cl
Cl
.
Cl
.
Cl
Cl
Cl
.
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
.
Cl
Cl
Cl
Cl
Cl
Cl
Cl

Cl

:
Cl

Cl

:
Cl
.
+ Cl
.

5.3. Phn ng oxy ha
Nhn benzen bn vng vi cc tc nhn oxy ha. Cc tc nhn oxy ha nh
HNO
3
, KMnO
4
, CrO
3
u khng oxy ha c vng benzen. Ch nhit cao v
c xc tc V
2
O
5
vng benzen b oxy ha thnh anhydrid maleic.
+ O
2
Anhydrid phtalic
C
O
C
O
O
C
O
C
O
O
V
2
O
5
400-450
o
+ O
2
V
2
O
5
400-450
o
;
Anhydrid maleic

Cc ng ng ca benzen ch b oxy ha mch nhnh. Sn phm to
thnh c th l acid, aldehyd hoc ceton ph thuc vo cht oxy ha.
;
CH
3
+ H
2
O
COOH
CH
3
CH
3
COOH
COOH
+ 6 O
+ 3 O + 2 H
2
O

+ 2 H
2
O
COOH
CH
2
CH
2
CH
3
+ CH
3
COOH
+ 6 O
+ 2HCOOH
+ 2 H
2
O + 8 O
CH
CH
3
CH
3
COOH
;

Oxy ha o - xylen bng acid nitric long 155
C thu c acid o -toluic.

155
o
HNO
3
loang
COOH
CH
3
CH
3
CH
3

143
5.4. S nh hng trong phn ng th i in t
Khi nghin cu phn ng th i in t vo hydrocarbon thm, ngi ta
nhn thy khi trn nhn thm c sn mt hay nhiu nhm th th nhng
nhm th ny c nh hng n kh nng v v tr th tip theo vo nhn thm.
nh hng biu hin nh sau:
Nhm th lm cho phn ng th tip theo d dng hn (nhm th tng hot)
hoc lm cho phn ng tip theo kh khn hn (nhm th h hot).
Nhm th s nh hng cc nhm th mi v nhn thm cc v tr ortho,
meta hoc para ty thuc vo bn cht cu to ca nhm th gy nh
hng.
5.4.1. Nhm th nh hng n kh nng phn ng ca nhn thm
Bn cht ca phn ng th i in t l s tng tc gia h thng electron
lin hp ca nhn thm vi tc nhn i in t mang in tch dng.
Mt electron ca nhn thm tng, kh nng phn ng th i in t d dng.
Mt electron gim th kh nng phn ng th i in t ngc li.
Nhm th y electron gy nh hng cm ng dng (+I), nh hng lin
hp dng (+C) v nh hng siu lin hp lm tng mt electron ca
nhnthm.
F , Cl , Br , I
- I ,+ C
NH
2
,

NR
2
, NHCOR ,
_
O
-
, OH , OCH
3
,OR , OCOR
+ I , sieu lien hp CH
3
, C
2
H
5
,C
3
H
7
X
- I ,+ C
X l nhng nhm th tng hot Do hiu ng electron

Cc nhm th trn l nhm th loi I
Nhm th lm gim mt electron ca nhn thm l nhng nhm th ht
electron c hiu ng - I , - C.
X
+
NO
2
,SO
3
H , COOH CN , CHO , COOR , COR
COCl , CONH
2
, CN , CCl
3
, CF
3
, NH
3
, NHR
2

- I ,- C
+
- I ,- C
X l nhng nhm th gim hot
Do hiu ng electron

Cc nhm th trn l nhm th loi II
5.4.2. S nh hng v quy tc th vo nhn thm
Cc nhm th X tng hot lm cho mt electron cc v tr ortho v para
tng ln. S th i in t tip theo u tin ch yu vo 2 v tr ny.
Cc nhm th X h hot lm cho mt electron ca nhn thm gim nhiu
nht cc v tr ortho v para. Phn ng th i in t tip tc xy ra kh khn
v u tin ch ti v tr meta.
144
Quy tc nh hng - Quy tc Holleman (Holleman Arnold Frederich
1859-1953)
Nu trn nhn benzen c mt nhm th loi I (nhm tng hot) th nhm th
ny nh hng cc nhm th mi vo v tr ortho v para ca vng benzen.
OCH
3
Br
+ HBr
+ HBr
OCH
3
Br
2
FeBr
3
( 96%)
4%
para
o-Bromoanisol ( )
+
OCH
3
Br

OH
NO
2
+
o-Nitrophenol
para
H
2
SO
4
HNO
3
OH
+ H
2
O
+ H
2
O
OH
NO
2

Nu trong nhn benzen c sn mt nhm th loi II (nhm h hot) th
nhm ny s nh hng nhm th mi vo v tr meta trn nhn benzen.
;
COOH
Br
+ HBr
COOH
Br
2
acid m-Bromobenzoic
+

+
m-Nitrobenzaldehyd
H
2
SO
4
HNO
3
CHO
+ H
2
O
CHO
NO
2

5.4.3. L thuyt v s nh hng
Mt electron t nhm th chuyn dch v pha benzen to ra mt h lin
hp mi. Trong h lin hp ny mt electron ti cc v tr ortho v para cao hn
cc v tr khc. iu hon ton ph hp vi cc cu trc gii hn c nng lng
thp. Trng thi nng lng thp dn n cu trc trung gian pentadienyl v sn
phm th m t trn gin hnh 11-4.
H Y
Y
+
H
Y
+
.
.
.
+
+
Y
H
+
H
+
.
.
.
+
+
Y
+
Chat trung gian
Chat phan ng
San pham
Tien trnh phan ng

N
n
g

l
n
g

p
h
n
g

145
Hnh 11.4. Gin nng lng ng vi cc trng thi th i in t vng benzen
Nu trn vng benzen c nhm th loi I th mt electron tng ln. S phn b
li mt electron trn nhn c minh ha qua cc cng thc gii hn nh sau:
. . . .
. . . .
. .
:
OH
+
+
-
-
+
:
OH
OH
OH
OH
-

cc v tr ortho, para c mt electron cao hn v phn ng th i in
t ch yu xy ra y.
Cng c th gii thch s th vo v tr ortho, para bng s n nh bng
trng thi nng lng thp.
Gi thit tc nhn i in t Y
+
tn cng vo c 3 v tr ortho, para v
meta ca toluen v cc cu trc trng thi phc nh sau:
+
CH
3
Y H
CH
3
Y H
+
+
CH
3
Y H
+
+
CH
3
H
Y
CH
3
H
Y
CH
3
H
Y
+
;

Th vo v tr ortho v para th cc cu trc trung gian c carbocation bc ba bn
vng. Nu th vo v tr meta th ch c cc cu trc carbocation bc hai km bn.
+
CH
3
H
Y
CH
3
H
Y
CH
3
H
Y
+
+

Cc phc c n nh nh nhm methyl y electron. S th i in t
xy ra nhanh hn v ch yu u tin v tr ortho v para.
Khi trn vng benzen c nhm th loi II. Mt electron trn nhn thm gim.
Cc cng thc gii hn chng t s gim nhiu nht v tr ortho v para.
+
O
O
N
N
O
O
-
+
N
O
O
-
+
N
O
O
-
+
N
O
O
-
O
O
N

Khi tc nhn i in t Y
+
tc dng vo nitrobenzen, cc phc to thnh
c cu trc trung gian. Trong phc , nhm nitro lm gim mt electron cc
v tr ortho v para.
146
+
+
N
H
Y
O
-
O
N
H
Y
O
-
O
N
H
Y
O
-
O
+
+
N
Y H
O
-
O
N
Y H
O
-
O
+
+
N
Y H
O
-
O
;
+ +
+
+ + +

Trng thi nng lng phc v tr meta thp hn 2 trng thi ortho v para.
+
O
O
-
N
H
Y
O
O
-
N
H
Y
O
O
-
N
H
Y
+ +
+ +
+

5.4.4. S nh hng vo hp cht nhiu nhm th
Hp cht c 2 nhm th
Nhng quy tc sau y c p dng nh hng nhm th th ba vo
nhn thm.
Nhng nhm th tng hot v nh hng ortho, para c nh hng
mnh hn nhng nhm h hot v nh hng meta, ngha l nhm tng
hot ng vai tr quyt nh s nh hng. Hiu ng lp th cng ng
vai tr quan trng trong vic xc nh v tr th ca nhm th ba.
OCH
3
NO
2
Cl
Cl
Cl
CH
3
NO
2
CH
3 COOH
Br

Nu c hai nhm th cng tng hot v nh hng ortho, para th nhm
no tng hot mnh s ng vai tr ch ng .
Cc nhm y electron tng dn theo th t:
(CH
3
)
2
CH < CH
3
< CH
3
CONH- < OCH
3
< NH
2

< NHR < NR
2
Cc nhm ht electron gim dn theo th t
NO
2
>SO
3
H>COOH>CN>COCl>CHO>COOR>COR>CONH
2
>CCl
3
>NH
3
>NR
2
V d:
CH
3
CH
CH
3
CH
3
NHCOCH
3
CH
3 CH
3
NO
2
CH
3
CH
CH
3
CH
3
NO
2
NHCOCH
3
CH
3
NO
2
CH
3
NO
2
NO
2
HNO
3
H
2
SO
4
H
2
SO
4
HNO
3 HNO
3
H
2
SO
4
; ;

Khi tin hnh phn ng th i in t vo nhn thm thng thu c hn
hp sn phm c t l khc nhau.
147
Hon hp
+
Na
2
Cr
2
O
7
H
2
SO
4
HNO
3
H
2
SO
4
H
2
SO
4
Na
2
Cr
2
O
7
H
2
SO
4
HNO
3
COOH
NO
2
NO
2
COOH
NO
2
COOH
NO
2
NO
2
CH
3
NO
2
NO
2

CH
3
NO
2
COOH
NO
2
NO
2

+
+
Br Br
Br
Br
Br
Br
Br
Br
2
FeBr
3
(13%) (0,1%) Para Orto Meta 86,9%
( )

S nh hng trong phn ng th i in t vo nhn thm c tc dng
gip cc nh nghin cu trong lnh vc tng hp hu c iu ch c cc cht
theo mong mun.
Bi tp
1. Hy vit cng thc cu to ca cc hp cht sau:
a- p-xylen; b- o- etyltoluen; c- p-diisopropylbenzen; d- 1,2,3-trimethylbenzen;
e- mesitylen; f- cumen; g- p-xymen; h-p-clorotoluen; i - 1,3,4-tribromobenzen.
2. Hy gi tn cc gc sau y:
; ; ;
;
d-
c-
b- a-
CH
3
CH
3
C
2
H
5
CH
3 CH
2
;
;
;
n- m- l- k-
CH=CH
2
; ;
i-
h-
CH=CH
CH
;
g-
e-
CH
3
CH
3 CH
3
CH(CH
3
)
2

148
3. Hy gi tn cc cht sau y:
CH
3
Br
;
e-
CH
3
Cl
CH
3
g-
CCl
3
CHCl
2
CH
2
Cl
Cl
; ;
;
;
d-
c-
b-
a-
Cl
CH
2
Cl
Cl
Cl
Cl
;
;
i-
h-
CH
2
CH
2
NO
2
CH
3
NO
2
F
NO
2
NO
2
; ;
;
n-
m- l-
k-

4. Nhng cht no c to thnh khi un nng hn hp sau y vi AlCl
3
khan:
a. Butylclorid vi toluen; b-Benzylclorid vi benzen; c-Alcol propylic vi benzen.
d. Propylen vi toluen; e- 1- Buten vi ethylbenzen; g- Cloroform vi benzen.
h. Toluen vi anhydrid acetic; i- Toluen vi carbon oxyd v HCl.
5. Hy ch r v tr th ca nhm th th ba vo cc cht sau:
OH
NO
2
NO
2
NO
2
Cl
Cl
OH
Br
;
; ;
;
d- c- b- a-
e-
OH
CH
3
NO
2
CN
Cl
CH
3
OH
CH
3
;
; ;
i-
h-
g-

6. Hy xc nh cng thc cu to ca cht C
7
H
7
SO
3
Cl bit rng khi oxy ha n
to ra acid benzensulfonic, cn khi halogen ha to ra dn xut monohalogen.
149
Chng 12
HYDROCARBON A NHN THM
Mc tiu hc tp
1. Gi c tn cc hydrocarbon a vng ngng t thm.
2. Trnh by c cc tnh cht ha hc chnh ca hydrocarbon a vng thm
naphtalen, anthracen v phenanthren.
Ni dung
1. Cu to v danh php
C hai loi hp cht a nhn thm.
Hp cht a vng to thnh do cc vng lin kt vi nhau bng lin kt n.
6
,
5
,
4
,
3
2
1
,
1
Biphenyl
6 5
4
3
,
2
,
P-terphenyl
NO
2
Cl
Cl
HOOC
2
, 3
,
4
5
6
1 1
,
2
3
4
,
5
,
6
,
Acid 2,6-dicloro- 2
,
nitro -5'-biphenylcarboxylic

Hp cht a vng to thnh do cc vng ngng t vi nhau.
1
Naphtalen
1
1
1
1 1
1
2
2
2
2
2 2
2
3
3
3
3
3
3
3
4
4
4
4
4
4
4
5
5
5
5
5
5
6 6
5
6
6
6
6
6 10
12
7
7
7
7
7
7
7
8
8
8
8
8
8
8
9
9 9
9
9
9
10
10
10
10
11
11
11
12
12
10
Antracen
Phenantren
Srysen Coronen Pyren
Naphthacen (Tetracen)

Nguyn tc nh s
nh trn chu vi ca hp cht a nhn ngng t theo nguyn tc:
Tng s nhn ln nht phi nm theo mt trc ngang
150
Hng ung
Hng sai

S ti a cc nhn khc phi nm cao hn ht v bn phi, trn trc ngang.
Hng ng
Hng sai

Cch nh s vi nhn cao nht v bn phi v tip tc theo chiu kim ng h
nhng b cnh tip hp cc nhn (khng nh s nhng carbon chung ca cc vng).
1
2
3
4
5
6
9
10
7
8
10
12
11
8
7
9
6
5
4
3
2
1
Hng nh s ng theo chiu kim ng h

i vi cc hp cht a vng ngng t phc tp.
Ngi ta xem chng nh l dn xut ca cc hp cht ngng t n gin c
tn gi theo quy c. gi tn nhng hp cht ny ngi ta nh du cc cnh
bng cc ch a, b, c ...v gi tn nh cc v d sau y:
Naphto[ 1,2-a] pyren
Pyren
Naphthalen
Naphto[ 1,2-a] pyren
hoac
14
13
12
11
10
7 6 5
4
c
b
a
3
3
2
2
1
1
1
2
8
9

Dibenz [a , j] antracen
Benzen
Antracen
j
i
f h
g e d
c
b
a
12
11
13
9
8 7
benzen
10
5
6
4
3
2
14
1

2. Biphenyl
2.1. Tng hp biphenyl
151
Tng hp biphenyl theo cc phng php sau:
Nhit phn benzen nhit cao trong ng st (phng php Berthelot,M, 1867)
2
600-800
o
+ 2H

Nung iodobenzen vi bt ng (phng php Ullman. Fp, 1903)
I
2
+ 2 Cu + 2CuI

C th iu ch cc biphenyl th bng phn ng th i in t hoc phn ng
chuyn v benzidin.
Benzidin ; (4,4'-diaminobiphenyl)
Hydrazobenzen
H
+
NH
2
H
2
N NHNH

2.2. Cu to ca biphenyl
trng thi hi hoc dung dch, hai nhn benzen ca biphenyl trn 2 mt
phng to mt gc 45. S bin dng ny l do 2 cp nguyn t hydro cc v tr
2-2' v 6-6' tng tc vi nhau (hnh 12-1).
45
o

Hnh 12.1. Hai mt phng to gc 45
o
S c mt cc nhm th cc v tr 2-2' v 6-6' s cn tr s quay ca 2 vng
chung quanh lin kt n v dn n cc ng phn quang hc. V d hp cht
acid 6,6'- dinitro 2,2'- biphenyldicarboxylic c tnh quang hot (hnh 12-2).
152
HOOC
NO
2
O
2
N
COOH HOOC
NO
2
O
2
N COOH
COOH
HOOC
NO
2
NO
2
O
2
N COOH
HOOC
Mat phang gng
O
2
N

Hnh 12.2. Cc i gng ca acid 6,6-dinitro-2,2-biphenyldicarboxylic
Biphenyl c nhng tnh cht ha hc ging benzen. Phn ng th i in t
u tin xy ra v tr ortho v para. Nitro ha xy ra v tr para mt cch d
dng. Brom ha thu c 4- bromo biphenyl hoc 4,4'-dibromo biphenyl.
Phn ng th xy ra v tr 4 d hn vo v tr 2. Phn ng acyl ha bng
acetyl clorid xy ra v tr 4 v 4'.
3. Biphenylmetan v triphenylmetan
Cc hp cht ny c iu ch bng phn ng Friedel -Crafts
Biphenylmetan
CH
2
CH
2
Cl +
AlCl
3
- HCl
CH
2
Cl
2
+2
- 2HCl

CHCl
3
+
Triphenylmetan
3
+ 3HCl
CH
AlCl
3

Cc lin kt C
_
H ca di id triphenyl rt linh ng. D b th v d b oxy ha.
Br
2
+ H
2
O

+ HBr
2O [CrO
3
]
CH
2
CH
Br
C
O

153
CH
( C
6
H
5
)
3
C K

KNH
2
( C
6
H
5
)
3
C
_
Br

( C
6
H
5
)
3
C
_
OH

[O]
Br
2
+ NH
3
+ HBr
+
. .

Triphenylclorid trong benzen khi c mt ca khng kh v bc to ra dung dch
mu vng. Khi thm vo dung dch ny mt lng aceton hoc bc hi ht benzen th
thu c mt hydrocarbon khng mu. Gomberg, M xc nh dung dch mu vng
cha gc t do triphenyl. Gc t do ny s to ra mt dimer khng mu.
H
C CC
3-Biphenylmethylyden-6-triphenylmethyl-
1,4-cyclohexadien (khong mau)
2 C Cl C Cl
Triphenylmethylclorid
2 Ag
- AgCl
.
C C
Triphenylmethyl
(mau vang)

Gc t do triphenylmethyl bn hn cc gc t do alkyl v gc triphenylmethyl
tn ti cc cng thc gii hn do s lin hp ca nhn benzen vi electron n c.
CC
.
C
C
C
.
.
.

4. Naphthalen
Naphthalen c nhiu trong nha than hoc trong phn cn li khi nhit
phn du m. Naphthalen c dng kt tinh hnh bn mng. Cng thc cu to ca
naphtalen c xc nh bng tia X. di lin kt c trnh by trn hnh 12-3.
'
'
'
' 8
7
6
5 4
3
2
1
o
o
1,393 A
1,365 A
1,424 A

1,424 A

Hnh 12.3. K hiu cc v tr ca naphthalen di lin kt ca naphthalen
Naphthalen l mt h thng lin hp vi 10 electron . Nng lng cng hng
ca naphthalen (60 kcal. mol
-1
) thp hn nng lng cng hng ca 2 vng
154
benzen. Do naphthalen c kh nng phn ng cao hn benzen. Cc dng cng
thc gii hn ca naphthalen nh sau:

Cc v tr 1, 4 c k hiu l ; v tr 2, 3 k hiu l .
V tr 5, 8 l ' v cc v tr 6, 7 l '.
4.1. Cc phn ng ha hc ca naphthalen
4.1.1. Phn ng th i in t
Naphthalen tham gia cc phn ng halogen ha, nitro ha, sulfonic ha,
alkyl ha v acyl ha theo Friedel -Crafts.
Nitro ha naphthalen to hn hp sn phm 1- v 2-nitronaphthalen.
- Nitronapthalen
- Nitronapthalen
CH
3
COOH
HNO
3
NO
2
NO
2
50-70
o
+

4.1.2. Phn ng cng hp
Hydro cng hp vi naphthalen c xc tc nhit cao to thnh tetralin
(1,2,3,4-tetrahydronaphthalen) v decalin (Bicyclo[ 4,4,0]decan).
Tetralin
( 1,2,3,4-Tetrahydronaphthalen )
Decalin
( Bicyclo [4,4,0 ] decan)
4 H ( Ni) 150
o
6 H ( Ni) 200
o

4.1.3. Phn ng oxy ha
Oxy ha naphthalen bng oxy khng kh c xc tc

V
2
O
5
to thnh anhydrid
phtalic. Crom oxyd oxy ha naphthalen trong mi trng acid acetic to ra 1,4-
naphtoquinon (1,4-dihydro-1,4-naphthalendion).
O
2
, V
2
O
5
C
O
C
O
O
O
O
CrO
3
,CH
3
COOH

155

5. Anthracen
Nm1867 Dumas tch c anthracen t nha than . C th tng hp
anthracen t 2-methylbenzophenon theo phn ng:
CH
3
C
O
+ H
2
O

hoc tng hp theo phng php Friedel - Crafts qua cc giai on hnh thnh
acid 2-benzoylbenzoic, ng vng di tc dng ca acid polyphosphoric (PPA) v
kh ha:
+
Anhydrid ftalic Antraquinon Acid-2-benzoylbenzoic
[ H]
- H
2
O
AlCl
3
C
O
C
O
O
O
O
O
C
HOOC
PPA

Tnh thm ca antracen (E =351,5 kj.mol
1
) km hn naphthalen. V tr 9,
10 ca anthracen c kh nng phn ng cao: cc phn ng oxy ha, kh ha,
halogen ha v phn ng Diels -Alder xy ra v tr 9, 10. Phn ng sulfon ha
xy ra v tr 1 v 2.
O
O
3O [HNO
3
]
- H
2
O

9,10-dihydro antracen
2 H [Na ,ROH]

9,10-diclo-9,10-dihydro antracen
- HCl

Cl
2
Cl
Cl
Cl

Anhydrid cua acid 2,3; 5,6- dibenzodicyclo[2,2,2]octa-
2,5-dien-7,8-dicarboxylic
O
O
O
O
O
O

156
6. Phenanthren
Nm 1872 Greabe tch phenanthren t nha than . C th tng hp
phenanthren qua cc giai on sau:
COOH
CHO
NO
2
- H
2
O
o- Nitrobenzaldehyd Acid phenyl acetic
+
Acid
phenyl-2-nitro crotonic
- 2H
2
O
6 H
- 2H
2
O
O
2
N
COOH
Acid
phenyl-2-nitro crotonic
- 2H
2
O
6 H
- 2H
2
O
O
2
N
COOH

N
2
COOH
[Cu]
- N
2
+
X
-
COOH
+ CO
2

Phenanthren l tinh th hnh kim, khng mu. Nhit nng chy 99,2C.
Phenanthren trong dung mi benzen c mu xanh hunh quang. Phenanthren c
tnh thm. Nng lng cng hng 387,0 kj.mol
1
. Lin kt v tr 9, 10 th hin
tnh cht ca lin kt i -C=C- . Phenanthren tham gia phn ng th i in t.
Phn ng cng hp th hin qua cc phn ng sau:
9,10-Dihydrophenantren
2H
CuO/Cr
2
O
3

Br
Br
Br
9,10-Dibromo-9,10-dihydrophenantren 9-Bromo phenantren
Br
2 - HBr

O
O
- H
2
O
9,10-Phenantrequinon
3O (CrO
3
)

Phenanthren v cc dn xut ca n l nguyn liu quan trng sn xut
thuc nhum. Khung phenanthren c trong cu trc ca nhiu hp cht t nhin
quan trng nh steroid, alcaloid dy morphin.
Bi tp
157
1- Vit cng thc cu to ca cc cht sau:
a- Benzo[c]phenanthren; b- naphto[2,3-a]pyren; c- Perhydrophenanthren.
2- Vit phn ng iu ch cc cht th mt ln ca naphthalen.
a- -Benzoylnaphthalen; b- - Iodonaphthalen; c- -Isopropylnaphthalen.
158
Chng 13
H THNG LIN HP V ALKADIEN
Mc tiu
1. Gii thch c s lin hp ca cc h thng dien.
2. Nu c c ch v ha tnh ca cc dien lin hp
Ni dung
H lin hp l mt h thng lin kt (i, ba) lun phin vi lin kt n,
hay l h cha nguyn t c cp electron p t do lin kt vi nguyn t carbon c
lin kt i.
1. H thng allylic
1.1. Cation allylic: CH
2
= CH-CH
2
+
Khi cho 2-butenol-1 tc dng vi acid bromhydric 0C th to thnh mt
hn hp gm 75% 1-brom-2-buten v 25% 3-brom-1-buten. Mt hn hp nh vy
cng thu c khi cho 3-buten-2-ol tc dng vi HBr trong cng iu kin.

0
o
C
0
o
C
H B r
H B r
+
+
+
3 : 1
C H
3
C H B r C H = C H
2 CH
3
CH= CHCH
2
Br
C H
3
C H O H C H = CH
2
C H
3
C H = C H CH
2
OH

iu c th gii thch l do s to thnh cation trung gian. in tch
dng trn cation ny khng nh v (delocalise) trn 2 nguyn t carbon.
+Br
-
Cation
Cation
-H
2
O
+
+
+
CH
3
CHCH = CH
2
CH
3
CH = CH CH
2
+
+
OH
2
-H
2
O
+Br
-
CH
3
CHCH = CH
2
CH
3
CHBrCH = CH
2
CH
3
CH = CH CH
2
Br
CH
3
CH = CHCH
2
OH
2

Carbocation trung gian t phn ng trn l s cng hng ca 2 cu trc
quan trng. Kiu carbocation n gin thuc loi ny l 2-propenyl hay gi l
cation allylic.
CH
2
CH CH
2
+
Cation allylic
CH
2
=CHCH
2
CH
2
CH=CH
2
+
+
CH
2
CH CH
2
Cation allylic
Cation allylic
+
2
1
+
1
2

159
K hiu tng qut trn c dng m t cu to in t ca cation allylic
Hai cu trc cng hng trong du mc biu hin in tch dng phn b ng
u trn 2 v tr hon ton ging nhau.
Gc: CH
2
=CH-CH
2
- gi l gc allyl
CH
2
=CH-CH
2
-Cl clorid allyl
CH
2
=CHCH
2
OCOCH
3
acetat allyl
c trng quan trng v cu to ca cation allylic l tt c cc nguyn t
u cng trong mt mt phng. Orbital p trng ca carbocation xen ph vi
orbital ca lin kt i. Mt in tch ca lin kt i nh c phn chia
u trn 3 nguyn t carbon. S phn b mt electron nh vy lm cho cation
allyl c nng lng thp hn cation c in tch dng tp trung trn mt carbon.
Trong cation allylic c s phn b li mt elecron thnh mt orbital
phn t bao trm ln c 3 nguyn t carbon.
( CH
2
CH CH
2
)
CH
2
CH=CH
2
CH
2
=CHCH
2
+
+
+
CH
2
CH CH
2
+
..... .....

bn vng ca cation allylic tng t vi bn ca gc alkyl bc 2. Khi
cation tng tc vi mt tc nhn i nhn, phn ng xy ra ti trung tm mang
in tch dng, do mt hn hp sn phm c to thnh. C phn ng xy ra
theo kiu chuyn v allylic.
S
sp
2
p
sp
2
C H
C C
sp
2
p
C C
C
C C
H
H
H
H
H

Hnh 13.1. Biu din cation allylic di dng orbital
1.2. Phn ng S
N2
- S chuyn v allylic

Cc halogenid v alcol allylic u c kh nng to carbocation mt cch d dng
theo c ch S
N2
v c s chuyn v ni i. S chuyn v gi l chuyn v allylic.

1
2 3 4 4 3 2 1
CH
3
CH=CHCH
2
OH + HBr CH
3
CHBrCH=CH
2

iu chng t rng lin kt i c tc dng n nh trng thi chuyn
tip v lm gim mc nng lng hot ha (hnh 13-2).
160
Nu
Br
..............
..............
H
2
C CH CH
2

Hnh 13.2. Trng thi chuyn tip ca phn ng gia bromid allyl
vi tc nhn i nhn Nucleophyl theo c ch S
N2
H thng allylic cng d xy ra phn ng theo c ch S
N1
.
1 2 3 4
4 3 2 1
CH
3
CH=CHCH
2
OH + HBr CH
3
CH=CHCH
2
Br

V carbocation CH
3
CH=CHCH
2
+
cng d hnh thnh trong iu kin khng
xy ra s chuyn v allylic theo c ch S
N2

CH
3
CH = CHCH
2
OH CH
3
CH = CHCH
2
OSO
2
C
6
H
5
CH
3
CH = CHCH
2
Cl
Pyridin
Cl
-
2-Buten-1- ol
1-Clor-2- buten
C
6
H
5
SO
2
Cl

Phn ng nh vy cng xy ra khi hp cht allylic tc dng vi thuc th
Grignard.
CH
2
=CH-CH
2
Br
MgBr CH
2
CH=CH
2
+ MgBr
+
70%

Phn ng theo kiu trn l phng php tt iu ch 1-alken. Phn ng
nh th khng xy ra i vi halogenid alkyl no.
1.3. Anion allylic CH
2
=CH-CH
2
-

Thuc th Grignard allylic c iu ch theo phng php thng thng sau:
CH
2
=CH-CH
2
-X + Mg CH
2
=CH-CH
2
-Mg
eter

Thuc th ny b ng phn ha rt nhanh
CH
3
-CH= CH-CH
2
-MgX
CH
3
-CH-CH = CH
2
MgX
Nhanh 1 2 3
2 1 3
4
4

C th hiu rng in tch m ca anion allylic phn b trn cc nguyn
t carbon lin hp.
-
CH
2
= CH
_
CH
2
CH
2
_
CH = CH
2
-
.... ....
CH
2
CH CH
2
-

+
- -
+
CH
2
CH CH
2
MgX
CH
2
CH CH
2
MgX CH
2
CH CH
2
MgX
.... ....
-

161
Anion allylic bn vng hn anion khng lin hp. Nhng anion bn vng
loi khc c n nh nh s cng hng hoc lin hp c bn cht ngc nhau.
V d:
O = C O
-
R R

-
O C= O
Ion carboxylat

R
R
R
2
C C= O
-
R
2
C= C O
-
Ion enolat

1.4. Gc t do allylic: CH
2
= CH = CH
2

Gc allylic c n nh nh cng hng
.
.... ....
CH
2
CH CH
2
CH
2
= CH
_
CH
2
.
CH
2
_
CH = CH
2
.

Electron t do (n) c phn chia trn 2 carbon lin hp. Gc t do loi
ny bn hn gc t do no tng t (CH
3
CH
2
CH
2
).

Khi brom ha phn t c cha allylic bng N -bromosuccinimid s c qu
trnh phn ng xy ra theo c ch gc t do (Phn ng c xc tc nh sng)
C H
2
C
H
2
C C
NBr
O
O
C H
2
C
H
2
C C
NH
O
O
Br
+
+
CCl
4
N-Bromosuccinimid
Succinimid
83%

C ch
.
Br
.
A nh sa ng
+
O
O
C H
2
C
H
2
C C
N
O
O
C H
2
C
H
2
C C
NBr
.
HBr
+
.
Br +
;

;
.
+
.
+
Br
O
O
C H
2
C
H
2
C C
N
O
C H
2
C
H
2
C C
NBr
.
.

Ch : C th minh ha s phn b li mt electron trong gc allyl
- -
CH
2

_
CH =

CH
2
CH = CH
_
CH
2
+ +
CH
2

_
CH =

CH
2
CH
2
= CH
_
CH
2
Cation allylic Anion allylic Goc t do allylic
. .
CH
2

_
CH =

CH
2
CH
2
= CH
_
CH
2

2. Dien
2.1. Cu to v s bn vng
Dien c ni i cch bit C =C
_
C
_
C=C
Dien c ni i tip cn C =C=C
_
C
_
C
Dien c ni i lin hp C =C
_
C=C
_
C
162
Dien lin hp c 2 lin kt i cch nhau mt lin kt n (cn gi l dien
lun phin, tip cch). Dien lin hp bn vng hn dien khng lin hp v mt
electron phn b u trn cc nguyn t carbon ca h lin hp. Cu trc nh vy
c nng lng thp.
Phn t 1,3-butadien c 4 nguyn t carbon trng thi lai ha sp
2
.
Cc lin kt C
_
C v C
_
H c to thnh do s xen ph ca cc orbital lai
ha sp
2
ca carbon vi nhau hoc vi orbital s ca hydro. Lin kt c to
thnh do cc orbital p t do trn cc nguyn t carbon xen ph vi nhau (trn
hnh 13.3 v s xen ph c minh ha bng ng thng khng lin tc).
. . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
s p
H
C
C
Lien ket
C
p
C
p
CH
2
CH CH H
2
C
Lien ket
C
sp
C
sp
2 2

Hnh 13.3: Cu to ca 1,3-butadien
di lin kt trong 1,3-butadien
Lin kt i C
1
=C
2
v C
3
=C
4
c di l 1,37 ln hn lin kt i bnh thng
(1,34 ). Lin kt n C
2
_
C
3
c di 1,46 ngn hn lin kt n bnh thng (1,54
). iu gii thch rng trong 1,3-butadien cc electron ca cc ni i lin hp
tng tc vi nhau. S tng tc nh hng n di lin kt, nh hng n
bn cng nh kh nng phn ng ca phn t c h lin hp.
V lin kt C
2
_
C
3
trong butadien c mt phn electron nn kh nng quay t
do xung quanh lin kt ny b hn ch. 1,3- butadien c th tn ti 2 dng cu dng
S -trans v S -cis . Dng trans c nng lng thp nn n bn vng hn dng cis.
H
H
H
H
H
H
C
C
C
C
H
H
H
H
C
C C
C H
S-trans
S-cis

2.2. Phn ng cng hp
Quan st phn ng gia phn t brom vi 1,3-butadien
46%
54%
+
-15
o
Hexan
+
+
Br
2
CH
2
= CH
_
CHBr
_
CH
2
Br BrCH
2
_

CH = CH
_
CH
2
Br
CH
2
_
CH = CH
_
CH
2
Br
CH
2
= CH
_
CH
_
CH
2
Br
+
CH
2
= CH
_
CH = CH
2
-
Br

163
un hn hp thu c 60C th to thnh 90% (E)-1,4-dibromo-2-buten
BrCH
2
_

CH = CH
_
CH
2
Br
CH
2
= CH
_
CHBr
_
CH
2
Br
+
(54%)
(46%)
60
o
C C
BrCH
2
CH
2
Br H
H
90%

S d cc dien lin hp to c hn hp sn phm cng hp -1, 4 v sn
phm cng hp -1, 2 v cation trung gian c cu trc carbocation allyl
CH
2
=CH
_
CH=CH
2
+ H
+
CH
2
=CH
_
CH
_
CH
3

+
CH
2
_
CH=CH
_
CH
3

+
CH
2
_
CH
_
CH
_
CH
3

+
Cau truc carbocation allyl Cau truc carbocation allyl Cau truc carbocation allyl

Cc dien lin hp cng c th cng hp theo c ch i nhn hoc c ch gc.
C = C
_
C = C + N
-

N
C
_
C
_
C = C

-
N
C
_
C =

C
_
C

-
N
C
_
C
_
C
_
C

-
.... ....
Cau truc carbo anion allyl

2.3. Dien -1,2 allen
Propadien-1, 2 c gi l allen CH
2
=C=CH
2
. Hai lin kt i tip cn nhau
v di lin kt i b ngn i (1,31 ). y l g tr trung gian gia lin kt
i1,34 (C=C) v lin kt ba 1,20 (CC). Cu trc electron (hnh 13-4) biu
hin 2 h thng lin kt i thng gc vi nhau.
................
...............
...............
.............
C C C
H
H
H
H
H
2
C=C=CH
2
C
sp
C
sp
2 2 C
sp
C
sp
2 2

Hnh 13.4: Cu to orbital ca allen
Tnh cht c trng ca allen l phn t khng ng phng. Hai lin kt
nm trong 2 mt phng thng gc vi nhau. V vy phn t allen th c tnh cht
bt i xng (c tnh quang hot).
2.4. Tng hp cc dien
Phn ln cc dien c iu ch t hp cht c 2 nhm chc.
OH
CH
3
(CH
3
)
2
C C(CH
3
)
2
OH
CH
3
+
79-89%
2,3-dimethyl-1,3- butadien
420-470
o
Al
2
O
3
CH
2
= C C = CH
2 2H
2
O

1,4-pentadien 63-71%
2 CH
3
COOH + CH
2
=CHCH
2
CH=CH
2 CH
3
COOCH
2
CH
2
CH
2
CH
2
CH
2
OOCCH
3
575
o

164
Thay th halogen trn phn t halogenid allyl bng gc vinyl t halogenid-
vinylmagnesi
CH
2
=CHCH
2
Cl + CH
2
=CHMgBr CH
2
=CHCH
2
CH=CH
2
+ BrMg
ether

Phn ng Wittig:
Allytriphenylphosphin clorid
CH
2
=CHCH
2
Cl + P(C
6
H
5
)
3 CH
2
=CHCH
2
P(C
6
H
5
)
3
Cl
+
-
+ -
C
2
H
5
OLi C
6
H
5
CHO
+
CH
2
=CHCH
2
P(C
6
H
5
)
3
CH
2
=CHCHP(C
6
H
5
)
3
CH
2
=CHCH =CHC
6
H
5
+ (C
6
H
5
)
3
P
1-Phenyl-1-3- butadien

2.5. Polymer ha
Cc dien b polymer ha. Polymer ha butadien c xc tc Ziegler -Natta
(Alkyl nhm v titan clorid).
nCH
2
=CH-CH=CH
2

(-CH
2
-CH=CH-CH
2
-)
n
Xuc tac
CH
2
=CH-CH=CH
2
CH
2
-CH=CH-CH
2
n
n

2-Methyl-1,3- butadien (isopren ) Polyisopren
n
n CH
2
-C=CH-CH
2 CH
2
=C-CH=CH
2
Xuc tac
CH
3
CH
3

Cao su Buna S
Styren 1,3-Butadien
+
CH=CH
2
C
6
H
5
Xuc tac
CH
2
=CH-CH=CH
2
n CH-CH
2
C
6
H
5
CH
2
-CH=CH-CH
2
-
n
n

Cao su lu ha
S
S
S

3. H thng lin hp bc cao
H thng trans 1,3,5-Hexatrien
Hp cht c nhiu ni i lin hp bn vng hn cc hp cht no c s
carbon tng ng. S bn vng l do s lin hp , gia cc ni i. Cc ion,
gc t do hoc cc trng thi trung gian c nhiu ni i c n nh nh c s
lin hp v s phn b u mt electron trn cc nguyn t carbon.
165
CH
2
= CH
_
CH
_
CH=CH
_
CH
2

CH
2
_
CH =CH
_
CH=CH
_
CH
3

CH
2
= CH
_
CH = CH
_
CH=CH
2

CH
2
= CH
_
CH = CH
_
CH
_
CH
3

CH
2
_
CH
_
CH
_
CH
_
CH
_
CH
3

H
+
+
+
+
+
+ +
+

4. Phn ng Diels - Alder
H thng dien lin hp cng hp vi mt lin kt kp (ni i hoc ni ba gi
l dienophyl) to hp cht vng 6 cnh c ni i v tr 2, 3 ca hp cht dien
lin hp ban u. Phn ng nh vy l phn ng Diels-Alder. Cc dien lin hp
cu dng cis d xy ra phn ng tng hp Diels -Alder.
Phn ng n gin gia1,3- butadien v ethylen:
+
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2

Cc dienophyl thng c hot ha bng cc nhm ht electron (COOH,
COOR, CHO, COR, CN, NO
2
)
Dienophyl
COOCH
3
+
COOCH
3
Dien
4-Methyl cyclohexencarboxylat

O H
CHO
O CHO
+
Acrolein

COOC
2
H
5
COOC
2
H
5
+
Diethylacetylendicarboxylat
C
C
COOC
2
H
5
COOC
2
H
5
Diethyl 1,4-cyclohexa
1,2-Dien dicarboxylat

C ch phn ng c trnh by trn hnh v 13-5. Bn electron ca h
thng dien lin hp xen ph vi 2 electron ca alken (dienophyl).
166
C
C CH
2
CH
2
H
H
C
C
H
H
H
H

Hnh 13.5. Trng thi chuyn tip ca phn ng Diels-Alder
Phn ng xy ra theo c ch lp th cis .
+
COOCH
3
COOCH
3
H
H
COOCH
3
COOCH
3

+
COOCH
3
COOCH
3
H CH
3
H
CH
3
H
H
C
C
COOCH
3
COOCH
3

(79-91%)
Ester methyl bicyclo[2,2,1]-
hepten-5 endo carboxylat
Ester methylacrilat Cyclopentadien
7
6
5
4
3
2
1
H
COOCH
3
COOCH
3
+
75 - 80
o
C

Bi tp
1. Vit cng thc cc sn phm khc nhau ca phn ng gia
(R)-2-hydroxy (E)-3-hexen v HBr
2. T halogenid allyl hy trnh by phn ng iu ch:
4,4- dimethyl-1- penten v 4-methyl-1-hexen
3. C sn phm no c to thnh khi cho 3-cloro-1-penten tc dng vi Mg
trong dung mi ether. Sau tc dng vi CO
2
v thy phn trong mi trng
H
2
SO
4
long.

167
4. Hy vit phn ng gia N -bromosuccinimid vi cc alken sau:
a- 2-Methyl propen ; b- Cyclopenten ; c- 2-Penten
5. a- Vit cng thc cu to ca cc sn phm to thnh khi cho cc ceton sau tc
dng vi D
2
O trong mi trng base:
O
CH
3
O
CH
3
O
CH
3
O
;
; ;

b. Vit phng trnh phn ng ca 4-methyl-3-penten-2-on vi cc cht sau:
n-C
4
H
9
Li; n-C
4
H
9
HgBr , CuBr; H
2
/ Pt ; HCN , (C
2
H
5
)
3
N; Br
2
, CCl
4

6. Vit cc phng trnh phn ng Diels -Alder ca cyclopentadien vi cc cht sau:
Vinylacetat; Acid acrylic; Ester dimethyl acetylendicarboxylat CH
3
OOCC
CCOOCH
3

(Gi tn cc sn phm to thnh)
168
Chng 14
DN XUT HALOGEN
mc tiu
1. Gi c tn cc alkylhalogenid v arylhalogenid
2. Trnh by v so snh c tnh cht ha hc ca RX v ArX
Ni dung
Nu thay th mt hay nhiu nguyn t hydro ca hydrocarbon bng mt
hay nhiu nguyn t halogen th thu c dn xut halogen.
C
n
H
2n+2-2k

C
n
H
2n+2-m-2k
X
m
C cc loi hp cht halogen sau:
Halogenoalkan, Halogenocycloalkan.
Halogenoalken, Halogenocycloalken.
Halogenoalkyn
Halogenoaren.
Tu thuc s lng nguyn t halogen c trong phn t c th c hp cht
monohalogen v polyhalogen.
Cc halogen hydrocarbon c nhiu ng dng quan trng. Chng c kh nng
phn ng cao v vy hp cht halogen l nguyn liu u trong tng hp hu c.
1. Danh php
1.1. Danh php IUPAC
Gi tn hydrocarbon tng ng v thm tn halogen nh mt tip u ng.
Chn mch chnh l mch di nht cha halogen. nh s sao cho v tr halogen
l b nht. Gi tn theo th t:
S ch v tr v tn halogen + S ch v tr v tn mch chnh
+ Tn hydrocarbon ng vi mch chnh
dicloroacetylen
2-Bromopropen
2-Fluor-1-cloroetan Cloroetan
C C Cl Cl
Br
CH
2
=C
_
CH
3
Cl
_
CH
2
_
CH
2
_
F CH
3
_
CH
2
_
Cl

168
Br
Br
Cl
Br
I
F
1
2
3
2,3-dibromocyclohexen Clorobenzen
6-fluoro-2-bromo-1-iodonaphtalen

Nu phn t c nhiu halogen cng loi th dng cc ch di, tri, tetra...
ch s lng nguyn t halogen. Nu phn t c nhiu halogen khc loi th gi
tn halogen theo th t a, b, c.. hoc theo th t " ln ".
2-(trifluoromethyl) -1,3-butadien
CH
2
=C
_
CH=CH
2
CF
3
4-cloro-3-bromo-6-methylnonan
6 5 4 3 2
1
8 7 9
Br
Cl CH
3
CH
3
CH
2
_
CH
_
CH
_
CH
2
_
CH
_
CH
2
_
CH
2
_
CH
3
3 6
5 4 2 1
1,6-dicloro-3-(2-cloroethyl) hexan
CH
2
CH
2
Cl
Cl
_
CH
2
_
CH
2
_
CH
2
_
CH
_
CH
2
_
CH
2
_
Cl

1.2. Danh php thng thng
Ngi ta xem dn xut halogen l sn phm thay th ca HX (HX RX).
V vy c tn gi:
Tn gc hydrocarbon + tn halogenid.
CH
2
=CH
_
CH
2
I CH
2
=CH
_
F CH
2
Br
2
CH
3
Cl
Methylclorid Methylendibromid Vinylfluorid
Allyliodid

Vn thng gi tn mt s hp cht halogen theo tn quen dng nh cc haloform.
CHCl
3
CHBr
3
CHI
3
Cloroform Bromoform Iodoform
2. ng phn
S ng phn ty thuc cu to ca mch carbon v v tr ca halogen.
1,3-propylendiclorid 2,2-propylydenclorid 1,1-propylydenclorid
CH
3
CH
2
CHCl
2
CH
3
CCl
2
CH
3
CH
2
ClCH
2
CH
2
Cl
1,1-dicloropropan 2,2-dicloropropan
1,3-dicloropropan

3. Phng php iu ch
C th iu ch cc hp cht halogen nh alkylhalogenid, vinylhalogenid,
allylhalogenid, halogenoaren, benzylhalogenid theo cc phn ng ha hc c
phn hydrocarbon. Cn ch rng cc hp cht fluor kh iu ch theo cc
phng php nh iu ch cc hp cht clor, brom v iod.
3.1. Halogen ha alkan (xem phn alkan).
3.2. Cng hp HX vo alken (xem phn alken).
169
3.3. Phn ng gia HX vi alcol
3.3.1. T alcol
Khi alcol tc dng vi HX to thnh dn xut halogen theo s :
ROH + HX RX + H
2
O
CH
3
C
CH
3
CH
3
OH CH
3
C
CH
3
CH
3
Cl + H
2
O + HCl

ZnCl
2
CH
2
CH
2
OH CH
3
CH
2
CH
2
OH CH
3
+ HCl + H
2
O
CH
3
CH
2
CH
2
Cl

Tc phn ng ph thuc vo cu to ca alcol v bn cht ca halogen.
i vi alcol kh nng phn ng gim theo th t sau:
Alcol bc 3 > Alcol bc 2 > Alcol bc 1
i vi cc HX th kh nng phn ng gim theo th t
HI > HBr > HCl.
Phn ng gia HCl vi alcol thng c xc tc l ZnCl
2
. Phn ng to dn
xut halogen t alcol v HX xy ra theo 2 giai on:
Giai on 1 to acid lin hp ca alcol.
acid lin hp ca alcol
+
ROH + H
+

ROH
2

Giai on 2 l giai on chm, giai on xc nh tc phn ng.
C hai kh nng xy ra phn ng:
R
+
+ X
-
R
+
+ H
2
O
ROH
2
+
RX
(1)

Phn ng xy ra theo c ch ny s to thnh hn hp racemic.
Nu phn ng xy ra qua giai on to thnh carbocation R
+
th c kh
nng to alken v mt sn phm ph do s chuyn v. iu c th minh ha
theo phn ng:
170
+Br
-
CH
3
Br
CH
3
CH
3
CH
3
__
C
__
C
__
H
chuyen v
+
CH
3
CH
3
CH
3
CH
3
__
C
__
C
__
H
-H
2
O
+
CH
3
CH
3
CH
3
CH
3
__
C
__
C
__
H
+
H
+
OH
2
CH
3
CH
3
CH
3
CH
3
__
C
__
C
__
H
OH CH
3
CH
3
CH
3
CH
3
__
C
__
C
__
H
OH CH
3
CH
3
CH
3
CH
3
__
C
__
C
__
H
CH
3
CH
3
CH
3
__
C
__
CH=CH
2
-H
+
CH
3
CH
3
CH
3
CH
2

C
__
C
__
H
-H
+
CH
3
CH
3
CH
3
__
C C
_
CH
3
-H
+
Br
+ Br
-
CH
3
CH
3
CH
3
CH
3
__
C
__
C
__
H

+ H
2
O X
_
R
(2)

+
[X....R...OH
2
]
-
+
+ R
__
OH
2
X
-
#

Phn ng xy ra theo c ch th i nhn lng phn t. Sn phm to thnh
c hin tng nghch quay Walden (hin tng thay i cu hnh)
Phn ng xy ra gia alcol bc 1 hoc bc 2 vi HCl c xc tc ZnCl
2
theo
c ch:
+
Cl
-
+

CH
2
O
R
ZnCl
2
H
-
RCH
2
Cl + HOZnCl + Cl
-

3.3.2. Phn ng gia phosphor halogenid hoc thionylclorid vi alcol.
Alcol tc dng vi phosphotriclorid hoc phosphopentaclorid u to
thnh dn xut monohalogen.
3 ROH + PCl
3

3RCl + H
3
PO
3
ROH + PCl
5
RCl + POCl
3
+ HCl
Alcol phn ng vi thionylclorid SOCl
2
xy ra theo c ch sau:
:
:
:
..
..
..
.. ..
..
..
..
..
..
..
..
-HCl
+
+ SO
2
R
_
Cl S O
Cl
S O
Cl
R
R
_
OH + SOCl
2
O
R
O

3.3.3. iu ch dn xut monofluor
Cho dn xut monoclor tc dng vi bc fluorid:
RCl + AgF RF + AgCl
171
3.3.4. iu ch cc hp cht monohalogenoaren
Thc hin phn ng th i in t gia halogen v aren hoc un nng mui
diazoni (phn ng Sandmeyer).
N N X
+
: X
-
+ N
2

3.3.5. iu ch cc dn xut polyhalogen
Cc dihalogen c iu ch bng cch cho aldehyd hoc ceton tc dng vi
phosphopentahalogenid PX
5
.
R
_
C
_
R'(H) + PCl
5
O
R
_
C
_
R'(H) + POCl
3
Cl
Cl

Cc phn ng cng hp halogen vo alken, alkyn u c kh nng to thnh
cc cht di hoc tetrahalogen.
S clor ha toluen c xc tc nh sng thng thu c hn hp mono v
polyclorid
Benzylclorid
-HCl
Cl
2
,

h
CH
2
Cl
CH
3
Benzalclorid
CHCl
2
-HCl
Cl
2
,

h
Benzotriclorid
CCl
3
-HCl
Cl
2
,

h

Cc haloform c iu ch t ethanol v clor theo s phn ng sau:
Cl
2
+ H
2
O HCl + HClO HClO H
+
+ ClO
-
;

Cloroform
+HO
-
- 3OH
-
CCl
3
C
O
H
CH
3
C
O
H
Cloral
CH
3
CH
2
OH

+ ClO
-
+ 3ClO
-
CHCl
3
+ HCOO
-

-Cl
-
,

-H
2
O
Ethanol

Hp cht hexaclocyclohexan iu ch t benzen v clor c xc tc tia t
ngoi xy ra theo c ch gc.
+Cl
.
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
+Cl
.
+Cl
.
.....
.

Hexaclocyclohexan tn ti 8 ng phn lp th. Trong ch c ng phn
c tc dng tr su b.
1,2,3,4,5,6-hexaclocyclohexan
e,e,e,a,a,a-hexaclocyclohexan
Cl
Cl
Cl
Cl
Cl
Cl
H
H
H
H
H
H

172
1,1,1-Tricloro-2,2-bis(4'-clophenyl) etan l hp cht halogen c tc dng dit
cn trng thng gi l DDT. DDT c iu ch t clorobenzen v cloral.
1,1,1-tricloro-2,2-bis (4,4'-clorophenyl) etan
+
2
+ H
2
O
CHO
CCl
3
Cl CH
CCl
3
Cl
Cl
H
2
SO
4

4. Tnh cht l hc
Ngoi mt vi cht trng thi hi nh fluoroetan, clorometan,
bromometan... phn ln cc dn xut halogen l cc cht lng khng mu hoc
cc cht rn. Hp cht halogen khng tan trong nc nhng tan nhiu trong cc
dung mi hu c. Mt s tnh cht vt l ca dn xut halogen c trnh by
trong bng 14-1. Lin kt C
_
X l lin kt phn cc v vy hp cht halogen c
momen lng cc ()
Bng 14.1: Momen lng cc v di lin kt C-X ca mt vi hp cht halogen
CH
3
X C---X
di lin kt d (
o
A
) Momen lng cc (D)
CH
3
F
CH
3
Cl
CH
3
Br
CH
3
I
1,385
1,784
1,929
2,139
1,82
1,94
1,79
1,64
e
1
e
2
r
2
q=

= q.d
l mt i lng vect
q l lc tng tc gia 2 ht nhn
e
1
, e
2
l in tch ca 2 ht nhn.
d l di lin kt
r l khong cch gia hai nhn nguyn t
5. Tnh cht ha hc
5.1. Cu to v kh nng phn ng
Trung tm phn ng ca cc dn xut halogen l lin kt C
_
X. m in
ca halogen ln hn ca carbon. Lin kt C
_
X l lin kt cng ha tr phn cc.
u m ca lin kt lch v pha halogen.
Kh nng phn ng ca cc dn xut halogen ph thuc vo bn cht ca halogen.
Kh nng phn ng tng theo th t RI > RBr > RCl > RF.
Dn xut iod c kh nng phn ng cao v phn cc ca lin kt C
_
I ln
nht so vi cc lin kt C
_
X khc. phn cc ca cc lin kt C
_
X ph thuc
vo m in v kch thc ca nguyn t X. m in ca X cng nh v
kch thc nguyn t X cng ln th lin kt C
_
X cng d phn cc.
173
Bng 14.2: Tnh cht vt l ca mt vi hp cht halogen
Nhiet o soi Nhiet o chay Cong thc cau tao Hp chat
Benzotriclorid
Benzalclorid
Benzylclorid
Iodobenzen
Bromobenzen
Clorobenzen
Fluorobenzen
Carbontetraclorid
Cloroform
Methylenclorid
Allylclorid
Vinylclorid
2-Cloropropan
1-Cloropropan
Cloroetan
Iodometan
Bromometan
Clorometan
220,8
205,2
179,3
188,5
156,5
131,7
84,7
76,7
61,2
40,2
44,6
-13,8
35,4
47,2
12,3
42,5
3,6
-23,7
-4,8
-16,4
-41,1
-31,3
-30,6
CHCl
3

CH
3
I
-45,2
-41,9
-22,9
-63,5
-96,8
-136,4
-159,7
-117,0
-122,8
-138,7
-66,5
-93,7
-97,7
C
6
H
5
_
CCl
3

C
6
H
5
_
CHCl
2

C
6
H
5
_
CH
2
Cl
C
6
H
5
_
I
C
6
H
5
_
Br
C
6
H
5
_
Cl
C
6
H
5
_
F
CCl
4

CH
2
Cl
2

CH
2
=CHCH
2
Cl
CH
2
= CHCl
CH
3
CHClCH
3

CH
3
CH
2
CH
2
Cl
CH
3
CH
2
Cl
CH
3
Br
CH
3
Cl
CH
3
F
-78,5 -141,8
Fluorometan

Kh nng phn ng ca dn xut halogen cn ph thuc vo c im ca
gc hydrocarbon lin kt vi halogen. C th chia thnh 3 loi dn xut halogen
theo kh nng phn ng:
Kh nng phn ng bnh thng l cc dn xut alkyl v cycloalkyl halogenid.

CH
3
CH
2
CH
2
Cl
Cl

Kh nng phn ng thp l cc dn xut cha cc gc hydrocarbon cha no
v gc hydrocarbon thm, trong nguyn t halogen X lin kt trc tip
vi carbon c lin kt i hoc nhn thm. Nguyn nhn kh nng phn ng
thp l do cp in t p trn halogen lin hp vi gc hydrocarbon.
2-Cloropropen Bromobenzen
vinyl clorid
:
..
:
Cl
CH
2
= CH
Cl
CH
3
_
C = CH
2
Cl
Br
CH
3
_
C = CH
2

174
Kh nng phn ng cao l hp cht c cu to allylic.
Benzylclorid
Allylclorid
CH
2
= CH
_
CH
2
_
Cl
CH
2
Cl

S khc nhau ca 3 loi hp cht trn c cn c vo phn ng thy phn:
RX + HOH ROH + HX
+ HOH
CH
3
CH
2
CH
2
_
OH + HCl
CH
3
CH
2
CH
2
_
Cl
un nong vi dung dch kiem
+ HCl OH + HOH Cl
Kh, un nng 380

v p sut
o

+ HCl + HOH CH
2
= CH
_ _ _ _
CH
2
OH CH
2
= CH CH
2
Cl
Rt d b thy phn
CH
2
OH
+ HCl + HOH CH
2
Cl Rt d b thy phn

Kh nng phn ng gim dn theo cu trc ca gc R nh sau:
RCH=CH-CH
2
_
X > ArCH
2
_
X > R
_
X > Ar
_
X > RCH=CH
_
X > RCC
_
X
5.2. Phn ng th i nhn
Cc dn xut halogen tham gia nhiu loi phn ng th khc nhau nh
phn ng thy phn, th amin, to ether....
5.2.1. Phn ng th i nhn ca hp cht alkyl halogenid
Phn ng th xy ra gia alkyl halogenid RX v tc nhn i nhn Y
-
theo
s :
RX + Y
-
RY + X
-

Ty thuc vo cu to ca dn xut halogen, tc nhn i nhn, dung mi
phn ng c th xy ra theo c ch lng phn t S
N2

hoc n phn t S
N1
.
k
dt
d[Y
-
][RX]
V
S
N2
Y
_
R + X
-
[ Y
-
.....R.....X ]
Y
-
+ R
_
X
S
N1
; R
+
+ X
-

R
_
X
Cham Nhanh
k
dt
d[RX]
V
R
_
Y R
+
+ Y
-

Bng phn ng th i nhn, t hp cht halogen to ra nhiu hp cht c
cc nhm chc khc nhau.

175
Phn ng th ca hp cht alkylhalogenid
R
_
X
HO
-
R'O
-
R'COO
-
(R'OOC)
2
CH
HS
-
R'S
-
HOO
-
R'OO
-
SCN
-
X
-
+

ROH
X
-
+

ROR'
X
-
+

R'COOR
X
-
+

RSH
X
-
+

RSR'
X
-
+

ROOH
X
-
+

ROOR'
X
-
+

R
_
SCN + R
_
NCS
Alcol
Ether
Ester
Thioalcol
Thioether
Hydroperocyd
Perocyd
Thiocianat Isothiocianat
NH
3
R'NH
2
R'
2
NH
CN
-
NO
2
-
R'M
R'C
C
-
..
RNH
2
+ HX
RNHR' + HX

RNHR'
2
+ HX

RCN + X
-
RCH(COOR')
2
+ X
-
R
_
R' + MX

RNO
2
+ X
-
R'C
CR X
-
+
Amin bac 1
Amin bac 2
Amin bac 3
Nitril
Alkyn
Alkan
Nitroalkan
Esteralkyl malonat

Dn xut halogen tc dng vi cc alcolat hay phenol trong mi trng kim
to thnh ether ROR' hoc ArOR' (phn ng Williamson).
CH
3
_
Br +
OH OCH
3
+ NaBr + H
2
O
NaOH
Anisol

Ha lp th ca phn ng th i nhn
Nu hp cht halogen c carbon bt i xng th tu thuc hng tn cng
ca tc nhn i nhn m carbon bt i xng c thay i cu hnh hay khng.
Nu hng tn cng ca Y
-
cng hng i ra ca X
-
th khng c s thay
i cu hnh
( R)
( R)
+
Y
Y
-
+
I
-
H
CH
3
CH
2
CH
3
C
I
H
CH
3
CH
2
CH
3
C

Nu hng tn cng ca Y
-
i vo t pha sau hng i ra ca X
-
th c s
thay i cu hnh xy ra.
H
H
I
-
Y
CH
3
CH
3
C
6
H
13
H
13
C
6
C
( S) ( R)
+
Y
-
+
I C

S thay i ca cu hnh carbon qua giai on trng thi chuyn tip
(phc hot ng).
176
C
C
I
+ Y
-
+
( R)
( S)
C
H
13
C
6
C
6
H
13
CH
3
CH
3
Y
I
-
H
H
C
6
H
13
CH
3 H
Y...... ...... I
- -

Minh ha cc trng thi c th c trong qu trnh phn ng S
N2
qua hnh 14.1
C
X
-
Y
-
C X
C Y
Y
-
+

+ X
-
C Y X
C Y
X
A
D
C
B
E
Thay oi cau hnh
San pham
Chat phan ng
E
Tien trnh phan ng

A

Hnh 14.1: Cc trng thi nng lng ng vi c ch phn ng S
N2
V vy cc hp cht to thnh t dn xut halogen quang hot c th l
quang hot vi s thay i cu hnh (th S
N2
) hoc mt hn hp racemic (th S
N1
).
Phn ng gia tert - butylbromid vi alcol ethylic to ether tert - butylethyl
(CH
3
)
3
COC
2
H
5
l phn ng th i nhn theo c ch S
N1
. Phn ng qua giai on
to carbocation (hnh 14-2).
(CH
3
)
3
C
+

+ Br
-
+ HOC
2
H
5

(CH
3
)
3
CBr + C
2
H
5
OH
(CH
3
)
3
CO
C
2
H
5
H
+ Br
-
(CH
3
)
3
COC
2
H
5
+ HBr
E
Tien trnh phan ng the S
N1
+

Hnh 14.2: Cc trng thi nng lng ng vi c ch phn ng S
N1
177
(CH
3
)
3
C
_
Br (CH
3
)
3
C
+
+ Br
-

Cham

(CH
3
)
3
C
+
+ C
2
H
5
OH (CH
3
)
3
C
_
OCH
2
CH
3

H
(CH
3
)
3
COCH
2
CH
3
+ H
+

+

Gin minh ha tin trnh phn ng th S
N1
ng vi cc trng thi nng
lng v s hnh thnh carbocation.
Carbocation (CH
3
)
3
C
+
c cu to phng. Nu dn xut halogen bc 3 c tnh
quang hot th carbocation to thnh b alcol tn cng vo t 2 pha ca mt
phng vi xc sut nh nhau, kt qu l thu uc mt racemic khng quang hot.
5.2.2. Phn ng th i nhn ca hp cht allylhalogenid
Ngoi sn phm th i nhn cn c sn phm th do chuyn v allylic.
R
_
CH=CH
_
CH
2
_
Y
R
_
CH
_
CH=CH
2
Y
+Y
-
+Y
-
- X
-
+
+
R
_
CH
_
CH=CH
2
R
_
CH=CH
_
CH
2
R
_
CH=CH
_
CH
2
_
Cl
Sn phm th c chuyn v Sn phm th S
N1

5.2.3. Phn ng th i nhn ca hp cht halogenoaren
S th xy ra kh khn, i hi nhit cao v p sut.
+ HCl
Cu
2
O
NH
3
,200
o
C
+ NaCl
NaOH , 300
o
C
NH
2
OH
Cl

Nu trn nhn thm c nhm ht in t th phn ng xy ra d dng hn.
Phn ng th gia clorobenzen v NH
3
xy ra theo c ch "tch -cng" hoc ''c
ch aryn"
52%
+ H
-
+ H
-
+NH
3
-
-NH
3
, - Cl
-
NH
2
48%
(aryn)
1,2-dehydrobenzen
NH
2
NH
2
Cl

Phn ng th loi ny cng xy ra i vi cc tc nhn i nhn l cyanid CN
-
ArCl + CuCN ArCN + CuCl

178
5.2.4. nh hng ca c cht v dung mi ln phn ng i nhn.
Cu to gc alkyl v dung mi c nh hng n tc v c ch ca phn
ng th i nhn. nh hng s phn nhnh ca mch carbon ln tc phn ng
S
N2
trnh by trong bng 14.3:
Alkyl halogenid Tc tng i
CH
3
-
CH
3
CH
2
-
(CH
3
)
2
CH-
(CH
3
)
3
C-
30,00
1,00
0,02
0
Tc S
N2
Methyl > gc bc nht > gc bc 2 gc bc 3 > >
Tc S
N1
Methyl < gc bc nht < gc bc 2 < gc bc 3
Dung mi phn cc thun li cho phn ng th i nhn theo c ch S
N1

Dung mi t phn cc thun li cho phn ng th i nhn theo c ch S
N2
.
Phn ng th i nhn ca hp cht halogen b cnh tranh bi phn ng
tch loi.
5.3. Phn ng tch loi (Xem phn iu ch alken)
5.4. Phn ng vi kim loi
5.4.1. Tc dng vi natri
Cc dn xut halogen mch thng cng nh vng thm u tc dng vi
natri kim loi to thnh hydrocarbon (phn ng Wurtz v Wurtz - Fittig).
Phan ng Wurtz. + 2NaX R
_
R
+ 2Na + X
_
R R
_
X
Ether

Ether
Phan ng Wurtz - Fittig + 2NaX Ar
_
R + 2Na + X
_
R Ar
_
X

Phn ng ny cho php iu ch nhng hydrocarbon c s lng carbon ty .
5.4.2. Dn xut halogen tc dng vi nhiu kim loi hot ng khc
Dn xut halogen tc dng vi kim loi to thnh hp cht c kim c nhiu
ng dng v thc t cng nh l thuyt. c bit l phn ng ca hp cht
halogen vi magnesi to thuc th Grignard (xem phn hp cht c kim).
RX + Mg RMgX
Bi tp
1. Vit cng thc cu to cc cht c tn gi sau y:
a. 1,2- Diclobutan; b- 1-Cloro- 2-bromo-3-methylpenten;
c. 3-Cloro-4,4-dimethylpentyn d- Propylbromid;
179
e. Isohexylclorid; f- Vinylfluorid;
g. Allylbromid; h- Ethylidenclorid
i. Tetracloroethylen; j- Trimethylenclobromid;
k. Benzylidenbromid; l- Methylenbromid
2. Trnh by phng php iu ch cc cht sau:
a. 2,2-Diclorobutan t 2,3-diclorobutan; b- sec- Butylbromid t butylbromid.
c. 2,2-Diclopropan t aceton; d- Benzalclorid t aldehyd benzoic.
e. Acid 4-cloro-3-nitrobenzensulfonic t benzen; g- Acid 4-nitrobenzoic t toluen.
3. Trong cc hp cht sau y: ethylclorid, vinylclorid, allylclorid th lin kt C
_
Cl
ca cht no bn vng hn trong phn ng thu phn? Sp xp theo th t tng
dn v gii thch. Phn ng xy ra theo c ch no ?
4. Hy vit phn ng ca cc hp cht di y vi methylat natri:
a. 2-Bromopentan; b- 1-Bromo-4-methylbutan; c- 3-Bromo-2-methyl-2-penten;
d. 1-Bromo-3-methyl-2-buten; e- Isopropyliodid.
5. Vit cc phn ng to cc cht trung gian v cht cui trong cc s phn ng
ddKOH Na 2HBr
A
C
B
b- Allyliodid
ddNaOH HI HBr
A
C B
a- Isobutylen

6. Vit phn ng ca cis-1-iodo-4-methylcyclohexan vi ion iodid. Gii thch c ch.

180
Chng 15
HP CHT C KIM
Mc tiu hc tp
1. c c tn theo danh php cc loi hp cht c kim.
2. Trnh by c ha tnh ca hp cht c Magnesi (thuc thou Grignard.
3. Nu c ng dng ca cc hp cht c kim trong tng hp hu c.
Ni dung
Hp cht c kim l nhng cht hu c c nguyn t kim loi lin kt trc
tip vi nguyn t carbon trong gc hydrocarbon. Khc vi cc cht v c, hp
cht c kim dng kh, dng lng hoc dng rn c nhit nng chy thp. Hp
cht c kim tan c trong dung mi t phn cc nh hydrocarbon v ether.
1. Cu to
Lin kt C - M c tnh cht ion. M l kim loi
Cc kim loi (trong trng hp ny) thiu in t.
-
+
+
-
M M R R M R

Ty thuc ha tr ca kim lai hp cht c kim c cc lai:
RM ; R
2
M ; RMX (X l halogen) ; R
3
M.
Hp cht Grignard (thuc th Grignard): RMgX (X = Cl, Br).
Trong dung mi ether hp cht dialkyl magnesi to lin kt phi tr vi 2
nguyn t oxy ca ether. Trong dung dch ether long (0,1M), thuc th Grignard
tn ti dng monomer. Magnesi phi tr vi 2 phn t dung mi ether. Trong
dung dch m c hn (0,5-1M) thuc th Grignard tn ti dng dimmer.
R
Mg
O(C
2
H
5
)
2
R
O(C
2
H
5
)
2

Mg
O(C
2
H
5
)
2
R
O(C
2
H
5
)
2
Br

R
Mg R
Br
Mg
Br

2. Danh php
2.1. Tn gc hu c + Tn kim loi
CH
3
)
3
CLi t-Butyllithi (CH
3
)
4
Si Tetramethylsilan
(CH
3
CH
2
)
2
Mg Diethylmagnesi (CH
3
CH
2
)
4
Pb Tetraethyl ch
181
(CH
3
CH
2
)
3
B Triethylboran (CH
3
)
3
Al Trimethyl nhm
CH
3
Cu Methylng (CH
3
)
2
Hg Dimethyl thy ngn
Ch : Cc hp cht ca bo, thic, silic gi tn theo dn xut hydrid ca chng
BH
3
boran ; SnH
4
Stannan ; SiH
4
Silan
2.2. c tn nh mui v c
Ha tr ca kim loi khng s dng ht lin kt vi gc hu c m lin
kt vi cc nguyn t khc. Hp cht loi ny xem nh mui v c c gc hu c.
CH
3
CH
2
MgBr Ethyl magnesi bromid
CH
3
HgCl Methyl thu ngn clorid
CH
3
CH
2
AlCl
2
Ethyl nhm diclorid
3. Tnh cht l hc
Bng 15.1: Tnh cht l hc ca mt s hp cht c kim
Hp cht tc ts Hp cht tc ts
CH
3
CH
2
Li 95 95,0 (CH
3
CH
2
)
2
Hg - 159
(CH
3
)
2
Mg 240 - CH
3
CH
2
HgI 186,0 -
(CH
3
)
3
Al 0 130,0 CH
3
CH
2
HgCl 193,0 40**
CH
3
AlCl
2
73 97-100* (CH
3
)
3
Ga -19,0 56
(CH
3
)
4
Si - 26,5 (CH
3
)
3
In 89,0 89**
(CH
3
CH
2
)
4
Si - 153,0 (CH
3
)
3
Te 38,5 147
(CH
3
)
2
Zn - 42 46,0 (CH
3
)
4
Ge - 88,0 43
(CH
3
)
2
Cd - 4,5 106,0 (CH
3
)
4
Sn - 55,0 78
(CH
3
)
2
Hg - 96,0 (CH
3
)
4
Pb -27,5 110
tc = nhit nng chy; ts = nhit si; * mmHg ; ** thng hoa
4. Phng php iu ch cc hp cht c kim
4.1. Phn ng gia alkyl halogenid vi kim loi
Trong phng th nghim s dng iu ch hp cht c lithi v c magnesi.
Dung mi l ether hoc hydrocarbon
RR' + XMgX'
R'X'
RMgX

R-X + Mg R
.
R
.
X Mg + R-Mg-X
C che : X Mg +

182
Trong phng th nghim, thng s dng alkylbromid. iu ch hp cht
c lithi.
Hp cht c Na, K khng iu ch theo phng php ny v c phn ng Wurtz:
2CH
3
CH
2
CH
2
Br + 2Na CH
3
CH
2
CH
2
CH
2
CH
2
CH
3
+ 2NaBr
ether

C ch:
CH
3
CH
2
CH
2
Br + 2 Na CH
3
CH
2
CH
2
-
Na
+
+ NaBr
CH
3
CH
2
CH
2
-

+ CH
3
CH
2
CH
2
Br CH
3
CH
2
CH
2
CH
2
CH
2
CH
3

+ Br
-

Phn ng ca hp cht alkyldihalogenid vi Zn hoc Mg thng to hp
cht cha no hoc hp cht vng
BrCH
2
CH
2
Br + Mg MgBr
2
+ CH
2
=CH
2

(80%)
BrCH
2
CH
2
CH
2
Br + Zn ZnBr
2
+

4.2. Phn ng ca hp cht c kim vi mui
To hp cht c kim mi v mui mi
RM + M'X RM' + MX

Phn ng xy ra theo chiu ty thuc th kh ca 2 ion kim loi
Bng 15.2: Th kh tiu chun
Phn ng Eo, vol
Li+ + e- = Li
Mg
2+
+ 2e- = Mg
Al
3+
+ 3e- = Al
Si
4+
+ 4e- = Si
Zn
2+
+ 2e- = Zn
Cd
2+
+ 2e- = Cd
H
+
+ e- = 1/2H
2
Sn
4+
+ 4e- = Sn
Cu
+
+ e- = Cu
Hg
2+
+ 2e- = Hg
- 3,045
- 2,370
- 1,660
- 0,840
- 0,763
- 0,402
0,000
0,014
0,522
0,854
183
+ +
E
o
= -2,370
(CH
3
CH
2
)
2
Cd
E
o
= -0,402
MgCl
2
CdCl
2
2CH
3
CH
2
MgCl
Ether

4MgCl
2
(CH
3
)
4
Si
+ SiCl
4
+
E
o
= -2,370 E
o
= -0,840
4CH
3
MgCl

LiI CH
3
Cu
+ CuI +
E
o
= -3,045 E
o
= -0,522
CH
3
Li

4.3. Thay kim loi vo lin kt C -H
CH
3
CH
2
CH
2
CCH + n C
4
H
9
Li CH
3
CH
2
CH
2
CCLi + nC
4
H
10

1 - Pentynyl liti
Phn ng acid -base : Pentyn l acid; n-Butyl lithi l base phn ng chuyn
dch v pha phi. Chng t 1-pentyn c tnh acid mnh hn n -butan. y l
phng php chung thay i lin kt C -H thnh C -M (M l kim loi). Thuc
th Grignard c s dng thay kim loi vo alkyn.
+
+ C
2
H
6
CMgBr HC
CH
3
CH
2
MgBr CH HC
Ethyl magnesi bromid
ether
Ethyl magnesi bromid

4.4. Phng php iu ch c th
Hp cht c kim c th iu ch bng cch cng hp vo alken hoc alkyn.
Hydrurboran ha
2(CH
3
CH
2
)
3
B 6CH
2
=CH
2
+ B
2
H
6

Cng hp mt lin kt Al -H vi alkyn.
CH
3
CH
3
CHCH
3

2
Al
CH
2
CH
3 H
H
C=C
CH
3
CHCH
3

2
AlH
+ CH
CH
3
CH
2
C
CH
3
Diisobytyl nhm hydrid (DIBAl)
(E) 1-Butenyl diisobutyl nhm

Hp cht c kim tc dng vi kim loi t do c th to thnh 2 hp cht c kim.
2(CH
3
CH
2
)
3
B 6CH
2
=CH
2
+ B
2
H
6

(CH
3
)
2
Hg + 2CH
3
CH
2
Li (CH
3
CH
2
)
2
Hg + 2CH
3
Li

5. Cc phn ng ca hp cht c kim
5.1. Tc dng vi hp cht c hydro linh ng
Hp cht c kim tc dng vi nhng hp cht c hydro linh ng to hydrocarbon.
184
Trong hp cht c kim, kim loi c in tch dng
Rt d tc dng vi hp cht c hydro linh ng
Thy phn
(CH
3
)
3
Al + 3H
2
O 3CH
4
+ Al(OH)
3

Phn ng vi alcol v acid carboxylic
+ CH
3
O
-
Li
+
H H
3
C
CH
3
CH
3
C + CH
3
OH Li H
3
C
CH
3
CH
3
C

C
CH
3
CH
3
H
3
C Li
+ CH
3
COOH
C
CH
3
CH
3
H
3
C H
+ CH
3
COO
-
Li
+

Phn ng vi thiol v amin RSH, RNH
2

Khng th to c thuc th Grignard t hp cht alkyl halogenid c cha
chc hydroxy hoc chc acid (v c hydro linh ng)
5.2. Phn ng vi halogen
Hp cht c kim tc dng rt mnh vi clor v brom
Cl
2
+ 2e
-
= 2Cl
-
E
o
= +1,358 vol
RM + Cl
2
RCl + M
+
Cl
-.
Phn ng t dng tng hp alkylhalogenid RX. (V iu ch RM t RX).
5.3. Phn ng vi oxy
Hp cht c kim rt nhy cm vi oxy. C th bc chy trong khng kh. Cc
phn ng ca hp chy c kim thng tin hnh trong mi trng tr (kh nit,
kh argon).
Oxy ha thuc th Grignard l phng php iu ch alcol.
RMgX + O
2
ROOMgX
ROOMgX + RMgX 2ROMgX
ROMgX + HCl ROH + XMgCl
Phn ng oxy ha cnh tranh vi phn ng to thuc th Grignard.
Vic iu ch thuc th Grignard thng tin hnh trong mi trng kh tr.

185
5.4. Phn ng vi hp cht carbonyl, dioxydcarbon v epoxyd
Lin kt C -M phn cc c dng C
-_
M
+

nn c kh nng phn ng cao vi
carbon tch in dng ca nhm carbonyl trong aldehyd v ceton.
H
+
H
2
O
HCHO
Mg
CH
2
OH
Cl
ether

H
2
O
H
+
(CH
3
)
2
CHMgBr + CH
3
CHO
(CH
3
)
2
CHCHOHCH
3
(53-54%) 3-Methyl-2- butanol
ether

OH
CH
3
H
2
O
H
+
C
2
H
5
MgBr + (CH
3
)
2
CHCH
2
COCH
3

(CH
3
)
2
CHCH
2
CCH
2
CH
3
3,5-Dimethyl-3-hexanol
ether

ng dng iu ch alcol bc 1, bc 2, bc 3. Phn ng ca thuc th
Grignard vi aldehyd formic to alcol bc 1; vi aldehyd to alcol bc 2 v vi
ceton to alcol bc 3.
CH
3
MgBr + CH
3
CH
2
CCH
2
CH
3
CH
3
CH
2
MgBr + CH
3
CCH
2
CH
3
CH
3
CH
3
CH
2
CH
2
MgBr + CH
3
CCH
2
CH
3
CH
3
CH
2
CCH
2
CH
2
CH
3
OH
CH
3
O
O
O

Cc phn ng ph:
+CH
3
CH=CH
2
O
OH
(CH
3
)
2
CHCHCH(CH
3
)
2
(CH
3
)
2
CHMgBr + (CH
3
)
2
CHCCH(CH
3
)
2

Hp cht c lithi c s dng nhiu hn thuc th Grignard v n hot
ng hn v phn ng xy ra nhit thp. Phn ng kh v s enol ha xy ra
c tm quan trng.
t-butyl liti di-t-butylceton
H
2
O
-70
o
O
(CH
3
)
3
C
3
C-OH (CH
3
)
3
CLi + (CH
3
)
3
C-C-C(CH
3
)
3
ether

S cng hp cc mui natri hoc lithi ca alkyn vi aldehyd hoc ceton.
CH
3
C CH + NaNH
2
CH
3
C CNa
CH
3
COCH
3
H
2
O
CH
3
C CC(CH
3
)
2
OH

186
Thuc th Grignard tc dng d dng vi carbondioxyd. Sn phm trung
gian ca phn ng l mui magnesi ca acid carboxylic. Mui ny tc dng vi
acid v c long to thnh acid carboxylic. y l phng php iu ch acid
carboxylic t cc alkyl halogenur.
H
2
SO
4
H
2
O
COOH COOMgCl
CH
3
CHCH
2
CH
3
CH
3
CHCH
2
CH
3
CO
2
MgCl Cl
CH
3
CHCH
2
CH
3
+ Mg CH
3
CHCH
2
CH
3

Phn ng xy ra gia carbon dioxyd v hp cht c lithi.
Acid benzoic
Phenyl liti
H
3
O
+ CO
2
COOH
CO
2
Li Li

Thuc th Grignard tc dng vi ethyl ortoformiat to acetal. Thy phn
acetal to aldehyd.
CH
3
Br
CH
3
MgBr
CH
3
CH( OC
2
H
5
)
2
CH
3
CHO
H
+
Mg CH(OC
2
H
5
)
3

C ch:
+
-
CH(OC
2
H
5
)
2
Br
2
MgOC
2
H
5
CH(OC
2
H
5
)
3
+ MgBr
2

-
C
2
H
5
O=CH-OC
2
H
5
RCH(OC
2
H
5
)
2
RMgBr
+
Br
2
MgOC
2
H
5
+ C
2
H
5
O-CH-OC
2
H
5
+

Phn ng gia hp cht c lithi v epoxyd xy ra theo c ch S
N2

C
6
H
5
CH CH
2
O
+ C
6
H
5
Li C
6
H
5
CH CH
2
C
6
H
5
-
C
6
H
5
CH CH
2
C
6
H
5
+
(70-72%) 1,2-diphenyletanol
O Li
H
2
O
OH

ng dng tng 2 nguyn t carbon trn mch carbon:
H
2
C CH
2
O
RCl
R-MgCl R-CH
2
-CH
2
OH
Mg
H
+
Ether

187
5.5. Phn ng vi cc hp cht c kim khc
Phn ng vi hp cht c kim to ra mt hp phc c kim khc c nhiu ng
dng trong tng hp hu c
CH
3
Li + CH
3
Cu (CH
3
)
2
CuLi

C th to hp phc c kim bng phn ng
2CH
3
CH
2
CH
2
Li + CuI (CH
3
CH
2
CH
2
)
2
CuLi + LiI

ng dng: S cng hp 1 4 vo cc nguyn t - ethylenic
R
C
C
CH
3
O
O
R
R
R
(CH
3
)
2
CuLi
+
1
4
a

Bi tp
1. Trnh by cu to ca hp cht c kim.
2. Hp cht c kim c cc loi phn ng no? Cho v d.
188
Chng 16
ALCOL
Mc tiu hc tp
1. c c tn cc alcol theo danh php IUPAC v tn thng thng.
2. Trnh by c ha tnh ca alcol v polyalcol.
3. Vit c s chuyn ha tng hp cc alcol.
Ni dung
Alcol l nhng hp cht c nhm hydroxyl - OH gn trc tip vi nguyn t
carbon trng thi lai ha sp
3
ca gc hydrocarbon. C nhiu loi alcol khc nhau:
Alcol no, alcol cha no, alcol vng, alcol thm.
Monoalcol v polyalcol.
Cng thc tng qut ca alcol: C
n
H
2n +2-2k-m
(OH)
m
; n 1; k 0; m 1
1. Monoalcol
1.1. Danh php
1.1.1. Danh php IUPAC
Alcol c tip v ng l ol. Chn mch chnh l mch carbon di nht cha
nhm chc OH. nh s sao cho chc alcol c s b nht.
V tr v tn nhm th + V tr ca OH + tn hydrocarbon tng ng + ol
2-Methylpropanol
CH
3
CH CH
2
OH
CH
3
2-Methyl-3-butyn-1-ol
C CH CH
2
OH
CH
3
CH
Phenylmethanol
C
6
H
5
_
CH
2
OH
2-cloro-3-methylbutanol
CH
3
CH CH
CH
3
CH
2
OH
Cl
2-isopropyl-4-fluorobutanol
CH
3
CH CH
CH
3
CH
2
OH
CH
2
CH
2
F
3-bromo-4-methyl-2-heptanol
CH
3
CH CH
CH
2
CH CH
3
OH CH
2
CH
3
Br
Propenol
CH
2
=CH
_
CH
2
OH

1-methylcyclopentanol
OH
CH
3
CH
2
OH
OH
cis-4-(hydroxymethyl) cyclohexanol
cyclopropyl methanol
CH
2
OH

189
1.1.2. Danh php thng thng
Gi tn gc hydrocarbon tng ng v thm tip v ng ic
CH
3
OH Alcol methylic CH
2
=CHCH
2
OH Alcol allylic
CH
3
CH
2
OH Alcol ethylic C
6
H
5
CH
2
OH Alcol benzylic
CH
3
CH
2
CH
2
CH
2
OH Alcol butylic (CH
3
)
3
C
_
OH Alcol tert-butylic
1.1.3. Danh php carbinol
Alcol methylic c gi l carbinol. Cc alcol n gin khc c xem l
dn xut th hydro ca carbinol.
CH
3
CH
2
OH
Methylcarbinol
CH
3
CH
2
CH
CH
3
OH
Ethylmethylcarbinol Trimethylcarbinol
CH
3
C OH
CH
3
CH
3
Vinylcarbinol
CH
2
=CH
_
CH
2
OH
isopropylcarbinol
CH
3
CH CH
2
OH
CH
3

Danh php ny ch gi cc alcol n gin.
1.1.4. Bc alcol
Chc alcol OH lin kt vi carbon c bc khc nhau ta c alcol bc 1, alcol
bc 2, alcol bc 3.
Alcol bac 1
CH
3
CH
2
CH
2
CH
2
OH
Alcol bac 2
OH
CH
3
CH
2
CHCH
3
Alcol bac 3
CH
3
C OH
CH
3
CH
3

1.2. ng phn
ng phn do mch carbon v do v tr nhm OH
Phn t alcol C
4
H
9
OH c cc ng phn.
n-Butanol
CH
3
CH
2
CH
2
CH
2
OH
Isobutanol
CH
3
CH CH
2
OH
CH
3
Tert-butanol
CH
3
C OH
CH
3
CH
3
Sec-butanol
CH
3
CH
2
CH CH
3
OH

Ph thuc cu to ca alcol c th c ng phn quang hc.
1.3. Phng php iu ch alcol
C nhiu phng php iu ch alcol xut pht t tnh cht ha hc ca cc
hp cht tng ng.
1.3.1. T alken
Hydrat ha alken (xem phn alken).
190
Trong cng nghip alcol ethylic c sn xut theo phng php hydrat ha ethylen.
300
o
,H
3
PO
4
C
2
H
5
OH
CH
2
=CH
2
+ H
2
O

Cc alcol isopropylic, alcol tert-butylic cng c iu ch bng phng
php hydrat ha cc alken tng ng.
1.3.2. Thy phn dn xut halogen (xem phn dn xut halogen).
RX + H
2
O ROH + HX
HO
-

1.3.3. Kh ha cc hp cht aldehyd, ceton
Kh ha hp cht carbonyl to thnh alcol bng cc phng php khc nhau.
Hydro ha hp cht carbonyl c xc tc
;
R CH
2
OH
H
2
[Ni]
R CHO
H
2
[Ni]
R CH
OH
R' R C
O
R'
Aldehyd
Alcol bc 1 Ceton Alcol bc 2

Nu hp cht carbonyl cha no th ni i cng b hydro ha.
R CH=CH CHO
4H[Ni]

R CH
2
CH
2
CH
2
OH

Kh ha bng natri trong alcol
Aldehyd, ceton b kh thnh alcol bc 1 v bc 2.
2 H
R CH R'
OH
R C R'
O

[Na-C
2
H
5
OH]

Kh ha bng cc hydrid kim loi AlLiH4, NaBH
4

Alcol
Clorid acid
Ester
Acid
Aldehyd
- ROH
-HCl
- H
2
O
2 H [H
4
LiAl]
2 H [H
4
LiAl]
2 H [H
4
LiAl]
2 H [H
4
LiAl]
R
_
CH
2
OH
R
_
COCl
R
_
COOR'
R
_
COOH
R
_
CHO

Kh ha bng lithi nhm hydrid tin hnh trong dung mi ether. Cc
aldehyd, ceton, acid, ester v clorid acid u b kh ho to alcol. Trong trng
hp ny nu hp cht cha no th ni i C =C khng b kh ha.
191
R CH=CH CH
2
OH

2H[H
4
LiAl]
R CH=CH CHO

Natri bo hydrid NaBH
4
l tc nhn kh ha c tnh cht chn lc. Ch c
aldehyd, ceton v halogenid acid b kh bng natri bo hydrid. Natri bo hydrid
khng tan trong ether, tan trong alcol methylic v ethylic.
1.3.4. Kh ha ester ca acid carboxylic
Kh ha theo Buve - Blanc
Cht kh l natri v alcol ethylic.
RCOOR' RCH
2
OH + R'OH
4 H [ Na + C
2
H
5
OH]

Hydro ha ester c xc tc
C th kh ha ester bng hydro c xc tc l hn hp ng oxyd (CuO) v
crom oxyd (Cr
2
O
3
).
RCOOC
4
H
9
RCH
2
OH + C
4
H
9
OH
2H
2
[CuO+Cr
2
O
3
]

1.3.5. T hp cht c magnesi RMgX (xem phn hp cht c kim).
Hp cht c magnesi tc dng vi aldehyd, ceton v ester th to thnh cc
alcol bc 1, bc 2 hoc bc 3.
Vi aldehyd, ceton
+ H
2
O
RCH
2
OH + HOMgX H C R
OMgX
H
HCHO + RMgX
R' CH R
OH
+ H
2
O
+ HOMgX
R' C R
OMgX
H
R'CHO + RMgX
+ H
2
O
+ HOMgX R' C R
R"
OH
R' C R
OMgX
R"
+ RMgX R' C R"
O
Ceton
Alcol bc 1
Aldehyd
Aldehyd formic
Alcol bc 2
Alcol bc 3

Vi ester
Ester ca acid formic tc dng vi thuc th Grignard to alcol bc 1. Ester
ca nhng acid khc tc dng vi thuc th Grignard to ceton. Ceton to thnh
li tip tc tc dng vi phn t thuc th Grignard thu c alcol bc ba.
192
Alcol bac 2
-ROMgX
+ H
2
O
R C R
OH
H
R C R
OMgX
H
RCHO
H C R
OMgX
OR'
+ RMgX
HCOOR' + RMgX
+ H
2
O
+ HOMgX
Ester alkyl formiat
-ROMgX
+ H
2
O
R" C R
R
OH
R" C R
R
OMg
R" C R
OMgX
OR'
+ RMgX
R"COOR' + RMgX
R" C R
O
+ H
2
O
+ HOMgX
Ester

1.3.6. Oxy ha hp cht c magnesi
Oxy ha hp cht c magnesi (thuc th Grignard) v sau thy phn.
+ H
2
O
RMgX + O
2
ROOMgX
ROH + HOMgX

1.3.7. Thy phn ester
Ester b thy phn trong mi trng kim hoc acid to alcol
RCOOR'
RCOOH + R'OH
+ H
2
O
H
+
hoa c HO
-

Alcol ethylic, alcol butylic c th iu ch theo phng php ln men.
Trong cng nghip, sn xut alcol methylic bng phn ng hydrat ha
carbon monooxyd vi xc tc thch hp v p sut.
ZnO - Cr
2
O
3
400
o
C , 200atm
CH
3
OH H = - 28,4 kcal CO + H
2
O

1.4. Tnh cht l hc
1.4.1. Nhit si v nhit nng chy
Cc alcol c s carbon thp dng lng, c mi v v c trng. Cc alcol c
s carbon cao dng rn, khng mi. Nhit si tng dn theo phn t lng.
Lin kt hydro nh hng ln n nhit si ca alcol. S lin quan gia
nhit si ca alcol bc 1 v phn t lng trnh by trn hnh 16-1
193
20
40 60 80 100 180 120 140 160 200
-200
-100
0
100
200
300
alcol bac 1
n-alcan
Khoi lng phan t
t

soi
o

Hnh 16.1. Quan h gia nhit si v phn t lng ca alcol bc 1
1.4.2. tan ca alcol
Methanol, ethanol,1-propanol, 2-propanol, 2-methyl-2-propanol tan rt
nhiu trong nc v chng to lin kt hydro vi nc. Cc alcol khc c tan
trong nc gim.
O
_
H
H R
O
_
H O
_
H O
_
H O
_
H O
_
H O
_
H
H
H
O
_
H O
_
H O
_
H
R
R H R
... ... ... ... ... ... ... ... ...

Bng 16.1. Tnh cht vt l ca mt s alcol
CH
3
OH
CH
3
CH
2
OH
CH
3
CH
2
CH
2
OH
CH
3
CH
2
CH
2
CH
2
OH
CH
3
CH
2
CHOHCH
3

CH
2
=CHCH
2
OH
C
6
H
5
CH
2
OH
CH
3
CHOHCH
3

(CH
3
)
2
CHCH
2
OH
(CH
3
)
3
C
_
OH
Alcol methylic
Methanol -97,1 64,7
Alcol ethylic
Alcol propylic
Alcol isopropylic
Alcol butylic
Alcol sec-butylic
Alcol tert-butylic
Alcol isobutylic
Alcol allylic
Alcol benzylic
Ethanol
1-Propanol
2-Propanol
1-Butanol
2-Butanol
3-Methyl-1-propanol
2-Methyl-2-propanol
-114,5
-126,1
-89,5
-114,7
25,5
107,9
82,5
-129,0
-15,3
-89,8
C
6
H
11
OH Alcol cyclohexylic Cyclohexanol 23,9
78,3
97,2
82,3
117,2
99,5
97,0
205,4
161,5
Cong thc
Ten thong thng
Ten theo IUPAC
t
o
chay
t
o
soi
1-Propenol
Phenylmethanol
-

194
1.4.3. Cc c trng v quang ph hng ngoi
trng thi hi cc alcol khng c lin kt hydro, nhm chc OH t do c
vch c trng trn quang ph hng ngoi 3700 cm
-1
.
trng thi dung dch, vch c trng ca nhm OH trn quang ph hng
ngoi c gi tr 3640- 3350 cm
-1
. Di hp th c trng ca nhm OH m
rng ra l do cc alcol trng thi dung dch c lin kt hydro. Lin kt
hydro t to thnh khi dung dch alcol cng long trong cc dung mi khng
phn cc. Dung dch alcol cng m c, lin kt hydro gia cc phn t
alcol cng d hnh thnh.
1.5. Tnh cht ha hc
1.5.1. Tnh acid -base ca alcol
Tnh cht quan trng ca nc l tnh t phn ly.
[H
3
O][HO
-
] = 10
-14
K
e
= K
e
K
e
H
2
O + H
2
O
H
3
O + HO
-
+
;
+

K
e
l hng s t phn ly ca nc K
e
= [H
3
O
+
][ HO
-
].
Nng ca [H
3
O
+
] v [HO
-
] rt thp v bng 10
-7
mol/lt.

Hng s t phn ly ca alcol methylic cn thp hn ca nc.
;
+
CH
3
OH
2
][CH
3
O
-
] = 1,2.10
-17

+
CH
3
OH
2
+ CH
3
O
-
K
CH
3
OH
= [
K
e
2 CH
3
OH

Cc ng ng ca alcol methylic gi tr K
e
cn thp hn.
Tnh acid ca alcol gim dn khi s carbon ca alcol tng ln.
Tnh acid ca alcol trong nc c xc nh theo phng trnh:
+
;
+
H
3
O
+ H
2
O ROH
K
a
Ka =
[H
3
O][RO
-
]
ROH
RO
-
+
[ROH]

Alcol c tnh acid yu hn nc.
Tnh acid: alcol bc 1 > alcol bc 2 > alcol bc 3.
Alcol c tnh base mnh hn tnh base ca nc.
Cc phn ng th hin tnh acid ca alcol:
2ROH+ 2Na 2RONa + H
2

Natri etoxyd

+
Natriamidid
+ NH
3
C
2
H
5
O
_
Na
+ Na
_
NH
2
C
2
H
5
OH

Natri etoxyd

+
Natri hydrid
+ H
2
C
2
H
5
O
_
Na
+ Na
_
H C
2
H
5
OH

195
Cc phn ng th hin tnh base ca alcol:
R
_
O
_
H
-
R
_
O
_
H + BF
3

..
..
BF
3

..
+
;
+
Methyloxoni
H
:
..
..
:
CH
3
O H + Br
-
:
..
..
:
CH
3
O H + HBr

Tnh base ca alcol cn th hin qua phn ng vi acid Lewis nh Bo triflo
BF
3
hoc km clorid (ZnCl
2
).

+
..
ZnCl
2

..
..
R
_
O
_
H + ZnCl
2

-
R
_
O
_
H

Ion RO
c tn gi l alkoxy. Cc alkoxy l nhng base mnh.

RO
-
+H
2
O ROH + HO
-

CH
3
O
-
C
2
H
5
O
-
(CH
3
)
2
CHO
-
(CH
3
)
3
C
_
O
-
Metoxy Etoxy Isopropoxy t-Butoxy.
Ion methylat Ion ethylat Ion isopropylat Ion t-butylat.
Gi tr pKa ca mt s alcol v ca acid c trnh by trong bng 16-2
Bng 16.2. Gi tr pKa ca mt s alcol v acid
pKa pKa Hp chat Hp chat
11,64
6,97
7,53
3,18
-5,0
2,15
-2,2
H
2
O
2
HOCl
H
2
S
HF
H
3
PO
4
H
2
SO
4
HCl
4,8
10,0
12,4
14,3
18,0
15,9
15,5
14,0
CH
3
COOH
C
6
H
5
OH
CF
3
CH
2
OH
ClCH
2
CH
2
OH
(CH
3
)C
_
OH
C
2
H
5
OH
CH
3
OH
H
2
O

1.5.2. Phn ng loi nc to ether hoc alken

Hai phn t alcol tc dng vi nhau khi c acid mnh nh H
2
SO
4
to ether.
t
o
= 140
o
C
R
_
O
_
R + H
2
O
2 R
_
O
_
H
H
2
SO
4

Cc alcolat RO
-
(alkoxy) l nhng tc nhn i nhn mnh tc dng vi alkyl
halogenid to ether. Alcol tc dng vi alkyl halogenid xy ra rt chm.
Ether
ROH + R'I ROR' + HI Rat cham R
_
O
_
R' + I
-
Nhanh ;
Ion alcolat
R
_
O
-
+ R'
_
I

196
Cc alcol di tc dng ca acid sulfuric m c v nhit (>140
o
C) to alken.
C
n
H
2n+1
OH C
n
H
2n
+ H
2
O
1.5.3. Phn ng to ester
Alcol tc dng vi acid hu c, anhydrid acid, halogenid acid to thnh
ester hu c.
H
+
Anhydrid acid
(RCO)
2
O + R'OH
RCOOR' + RCOOH
Ester
RCOOR
'
+ HCl.Pyridin
Clorid acid
RCOCl + R'OH
Ester
Pyridin
H
+
RCOOR' + H
2
O RCOOH + R'OH

Phn ng ester ha l phn ng thun nghch. cho phn ng chuyn dch
v pha to ester ngi ta thng s dng cc cht lm gim nng ca nc,
acid to thnh trong phn ng. Cc cht thng s dng l acid v c (H
2
SO
4
,
H
3
PO
4
, acid 4-toluensulfonic), cc base hu c (pyridin).
Hng s cn bng ca phn ng ester ha c tnh theo cng thc:
[RCOOR'][ H
2
O]
[RCOOH][ R'OH]
K
cb
=

Acid sulfuric m c trong phn ng ester ha ng vai tr cung cp proton
lm xc tc ng thi ng vai tr ht nc lm gim nng ca nc sinh ra
trong qu trnh phn ng. Phn ng c tc nhanh hn v chuyn dch cn bng
v pha to ester.
C ch phn ng ester ha l c ch "cng - tch" c trnh by theo 2 cch:
C ch AAc 2
..
-H
2
O
+
+
+
-H
+
+ H
+
+ H
+
+
-R'OH
+R'OH
+H
2
O
-H
+
C R
H
2
O
O R'
HO
C R
HO
HO
O R'
H
O
C
OR'
R
OH
C
OR'
R
OH
C
OH
R
O
C
OH
R

Theo s trn th H
2
O sinh ra trong phn ng do tch hydro H ca alcol
R'OH v nhm OH ca acid. Phn ng xy ra theo cch nh trn ph hp vi cc
alcol bc 1
Theo c ch ny, nu acid c nh th tc phn ng ph thuc vo cu to
ca alcol. Kh nng phn ng ester ha ca alcol gim dn theo th t sau:
Alcol bc 1 > Alcol bc 2 > Alcol bc 3
197
C ch AAlk 1
Cc alcol bc 3 xy ra theo c ch nh sau:
+ H
+
R'OH
R'OH
2
R' + H
2
O
+
+

O
C
OH
R
OR'
C
OH
R
+
R' +
+
OR'
C
O
R
-H
+
+H
+

Giai on to carbocation R
+
t acid lin hp ca alcol ROH
2
l giai on
xc nh tc phn ng.
+
Cc alcol tc dng vi cc hp cht c cng thc chung RCOX to ester l
qu trnh acyl ha alcol theo c ch:
O
C
X
R
HOR' +
+
O
C
OR'
R C R
O
X
OR'
H
C R
X
OR'
OH
HX +
-
..
X = Cl , Br , R''COO
-
:

Alcol tc dng vi acid v c to ester v c.
Dialkyl sulfat
Alkyl hydrosulfat
Trialkyl phosphat
Alkyl nitrat
Alkylnitrit
R
_
OH
SO
2
(OR)
2
+ H
2
O
R
_
OSO
3
H
R
_
OSO
3
H + H
2
O
PO(OR)
3
+ 3HCl
R
_
ONO
2
+ H
2
O
R
_
ONO + H
2
O
SO
3
tri oxyd lu huynh
H
2
SO
4
acid sulfuric
POCl
3
triclor oxyd phosphor
HONO
2
(H
+
) acid nitric
HONO (H
+
) acid nitr
R
_
OH

Nhiu ester ca acid v c nh acid phosphoric, acid thiophosphoric c s
dng lm thuc tr su.
S P O
O
O
CH
2
CH
3
CH
2
CH
3
NO
2
Parathion ( thiophos)

S P O
O
O
CH
2
CH
3
CH
2
CH
3
CH
2
CH
2
S CH
2
CH
3
Sistoc (mercaptophos)

S P O
O
S
CH
3
CH
3
CH
2
C NHCH
3
O
Dimetoat ( phosphamid)

Mui natri alkylsulfat ca cc alcol t C10
_
C20 nh natri lauryl sulfat
C
12
H
25
OSO
3
Na c s dng lm cc cht nh ha trong dc phm, trong thuc
nh rng v trong mt s cht c tc dng ty ra khc.
Alcol cetylic n-C
16
H
33
OH c trong sp ong.
198
Ty thuc vo v tr ca nhm OH, alcol b oxy ha to ra cc sn phm khc
nhau. Alcol bc 1 b oxy ha thnh aldehyd v sau thnh acid:
R
_
CH
2
_
OH R
_
CHO R
_
COOH
[O]
- H
2
O
[O]
- H
2
O

Alcol bc 2 b oxy ha to ceton:
+ [O] + H
2
O CH OH
R'
R"
C O
R'
R"

V mt l thuyt, trong mi trng kim v trung tnh cc alcol bc ba
khng b oxy ha. Trong mi trng acid mnh alcol bc ba b oxy ha to ceton
v acid c s carbon b hn ru ban u.
+ 3[O] + R'''COOH + H
2
O C OH
R'
R"
CH
2
R'"
C O
R'
R"
H
+

Cc cht oxy ho thng s dng oxy ha alcol l mt s oxyd kim loi nh
ng oxyd (CuO), crom oxyd (CrO
3
). Trong phng th nghim CrO
3
c iu ch t
kali bicromat (K
2
Cr
2
O
7
) v acid sulfuric m c trong dung mi acid acetic. C th
trnh by c ch oxy ha alcol bng crom oxyd theo cc qu trnh sau:
CH OH
CH
3
+ 2CrO
3

+ 6 H
+
+ 2Cr
3+
+ 6H
2
O
3 33
C che
CH OH
CH
3
+ CrO
3
C O
CH
3
+ H
3
O
+
+ HCrO
3

C
CH
3
H
O CrO
3
H
H
O
H
:
-
CrO
3
+ Cr
3+
+ 6H
2
O
6H
+
+ 3H
2
CrO
3

H
2
O

+ H
2
CrO
3

-
H
3
O
+
+ HCrO
3

C O
CH
3
CH
3
CH O
CH
3
CrO
3
H
CH
3
CH
3
CH
3 CH
3
CH
3

Cc alcol cha no b oxy ha bi CrO3 to hp cht carbonyl m lin kt i
khng b oxy ha, nhng oxy ha bng KMnO
4
th ni i b oxy ha thnh alcol
a chc.
R
_
CH=CH
_
CH
2
OH
R
_
CH=CH
_
CHO
K
2
Cr
2
O
7
+ H
2
SO
4
R
_
CHOHCHOH
_
CHOH
KMnO
4

199
2. Alcol cha no
Trong phn t c lin kt i hoc lin kt ba. Nhm chc OH lin kt trc tip
vi carbon c ni i thng khng bn v d chuyn thnh aldehyd hoc ceton.

Aldehyd acetic Alcol vinylic
C C
O
H
H
H
H C C
OH
H
H
H
Aceton 2-Propenol
;
H
O
CH
3
H
H
C C C C
H
H
CH
3
OH

Alcol vinylic khng bn nhng ester v ether ca n th bn vng v c
iu ch bng phn ng cng hp gia acetylen v acid hoc alcol tng ng.
H
2
C CH OOCCH
3
+ CH
3
COOH
C C H H
Ester vinylacetat

Eter ethyl vinyl
H
2
C CH OC
2
H
5
+ CH
3
CH
2
OH C C H H

Alcol cha no c nhm OH lin kt vi carbon lai ha sp
3
th bn vng.
Propenol
H
2
C CH CH
2
OH
Alcol allylic
2-Butenol
Alcol crotonic
CH
3
CH CH CH
2
OH

Propynnol
Alcol propagylic
C C CH
2
OH H

1,4-Butyndiol
C C CH
2
OH HOCH
2

Alcol cha no propagylic v 1,4-butyndiol c th iu ch t acetylen v
aldehyd formic
C C H H + HCHO C C CH
2
OH H
C C Cu Cu

C C H H
+ 2HCHO
C C CH
2
OH HOCH
2
C C Cu Cu

Trong thin nhin tn ti nhiu loi alcol cha no c s carbon cao nh
citronellol, geraniol, linalol, pharnezol, phytol c nhiu ng dng trong cng
nghip hng liu v dc phm.

Citronelol ( 3,7-dimethyl-6-octenol)
CH
3
_
C=CH
_
CH
2
_
CH
2
_
CH
_
CH
2
_
CH
2
OH
Geraniol ( 3,7-dimethyl-2,6-octadienol)
CH
3
C=CHCH
2
CH
2
C=CHCH
2
OH
CH
3
CH
3
CH
3 CH
3

CH
3
C=CHCH
2
CH
2
CCH=CH
2
OH
Linalol ( 3,7-dimethyl-1,6-octadien-3-ol) Pharnezol ( 3,7,1-trimethyl-2,6,9--dodecatrienol)
CH
3
_
C=CH
_
CH
2
_
CH
2
_
C=CH
_
CH
2
_
CH
2
_
C=CH
_
CH
2
OH
CH
3
CH
3
CH
3
CH
3 CH
3

Phitol ( 3,7,11,15-teramethyl-2--hexadekenol)
2
CH
3
_
CH
_
CH
2
_
CH
2
_
CH
2
_
CH
_
CH
2
_
CH
2
_
CH
2
_
C=CH
_
CH
2
OH
CH
3
CH
3
CH
3

200
3. Alcol vng
Alcol vng c th l no hoc cha no. C cc loi alcol vng thng gp sau y.
2-Isopropyl-5-methylcyclohexanol
(Menthol)
OH
CH(CH
3
)
2
CH
3
Cyclohexanol
OH
2-Cyclohexenol
OH
Cyclohexylcarbinol
CH
2
OH

Cc alcol vng b oxy ha thnh ceton vng.
OH
CH(CH
3
)
2
CH
3
Menthol
CrO
3
, H
+

O
CH(CH
3
)
2
CH
3
Menthon

Oxy ha cyclohexenol bng dung dch KMnO
4
trong mi trng trung tnh
to polyalcol vng.
1,2,3-Cyclohexatriol
pH 7
OH
OH
OH
KMnO
4
,
2-Cyclohexenol
OH

Mt s alcol vng c nhiu ng dng. Menthol c trong tinh du bc h c
ng dng nhiu trong y dc. Cyclohexanol l dung mi cn thit ho tan cc
polymer ng dng lm keo dn. Hp cht 1,2,3,4,5,6-cyclohexahexanol c nhiu
ng phn trong ch c ng phn Inositol c ng phn quang hc v c ng
dng trong dc phm.

1,2,3,4,5,6-Cyclohexahexanol
OH
OH
OH
OH
HO
HO
(+) - Inositol
OH
OH
OH
OH
OH OH
(-) - Inositol
OH
OH
OH
OH
OH OH

4. Polyalcol - alcol a chc
Polyalcol l loi hp cht trong phn t c hai hay nhiu nhm chc alcol OH.
4.1. Phn loi polyalcol
C cc loi polyalcol sau:
Cc nhm hydroxyl trn cng mt nguyn t carbon.
R
_
CH
2
C(OH)
2
CH
3 ;
R
_
CH(OH)
2 ;
R
_
C(OH)
3

201
Nhng polyalcol ny khng bn. Chng ch tn ti trong dung dch nc.
Nhng polyalcol c cc nhm alcol lin kt vi cc nguyn t carbon cnh nhau
CH
2
OHCH
2
OH ; CH
2
OHCHOHCHOHCH
2
OH
Cc polyalcol ny c tnh cht c bit hn so vi monoalcol.
Nhng polyalcol c cc nhm hydroxyl xa nhau
CH
2
OHCH
2
CHOH ; CH
2
OHCH
2
CH
2
CHOHCH
3.
Loi polyalcol ny c tnh cht ging monoalcol.
4.2. Danh php polyalcol
Cc polyalcol c gi tn theo danh php thng thng hoc danh php
IUPAC.
Theo danh php IUPAC tn gi cc polyalcol xut pht t tn gi ca
hydrocarbon tng ng thm cc tip v ng diol, triol, tetraol... ch s lng
nhm OH v cc ch s ch v tr cc nhm OH.
Bng 16.3: Tn gi mt s polyalcol
HOCH
2
_
CH
2
OH
HOCH
2
CH
2
CH
2
OH
HOCH
2
CH
2
CH
2
CH
2
OH
CH
2
CH CH
2
OH OH OH
CH
2
CH CH
OH OH OH
CH
2
OH
CH
2
CH CH
OH OH OH
CH
OH
CH
2
OH
CH
2
CH CH
OH OH OH
CH
OH
CH CH
2
OH OH
HOH
2
C C CH
2
OH
CH
2
OH
CH
2
OH
Ethylenglycol
Propylenglycol
Trimethylenglycol
Tetramethylethylenglycol
Tetramethylenglycol
C C
OH OH
CH
3
CH
3
CH
3
CH
3
CH
3
CHOH CH
2
OH
Glycerin
Erytrit
Pentit
Hexit
Pentaerytrit
1,2-Etandiol
1,2-Propandiol
1,3-Propandiol
1,4-Butandiol
2,3-Dimethyl-2,3-
butandiol
1,2,3-Propantriol
1,2,3,4-Butantetraol
1,2,3,4,5-Pentahydroxy
petan
1,2,3,4,5,6-Hexahydroxy
hexan
Tetrahydroxyneopentan
Cong thc cau tao
Danh phap thong thng Danh phap quoc te

202
4.3. iu ch polyalcol
Thy phn cc dn xut polyhalogen:
CH
2
Cl CH
2
Cl CH
2
OH CH
2
OH + 2H
2
O + 2 HCl

CH
2
Cl CHCl CH
2
Cl CH
2
OH CHOH CH
2
OH + 3H
2
O + 3 HCl

Oxy ha olefin bng dung dch KMnO
4
:
3 CH
2
=CH
2
+ 4 H
2
O + KMnO
4
3 CH
2
OH
_
CH
2
OH + MnO
2
+ 2KOH

T clohydrin iu ch glycol:
CH
2
Cl CH
2
OH + H
2
O CH
2
OH CH
2
OH
+ HCl

Clohydrin tc dng vi Ca (OH)
2
v sau thy phn trong mi trng acid.
CH
2
Cl CH
2
OH + Ca(OH)
2
O
CH
2
CH
2
+ CaCl
2
+ 2H
2
O
2
2

CH
2
OH CH
2
OH
+ H
2
O
O
CH
2
CH
2
H
+

Kh ha aceton bng in ha hoc tc dng vi magnesi v iod:
+ 2 Mg + I
2
C O
CH
3
CH
3
C C
CH
3
CH
3
CH
3
CH
3
OMgI OMgI
C C
CH
3
CH
3
CH
3
CH
3
OH HO
2
2H
2
O

iu ch glycerin t propylen:
Trc tin ngi ta clo ha propylen 500
o
C thu c allylclorid. Sau cho
allylclorid tc dng vi dung dch clor vi nc th thu c glycerin.
CH
2
ClCH=CH
2
+ HCl
CH
3
CH=CH
2
+ Cl
2

CH
2
ClCH=CH
2
+ Cl
2
+ H
2
O CH
2
ClCHOH
_
CH
2
Cl+ HCl
CH
2
ClCHOH
_
CH
2
Cl +2H
2
O
CH
2
OH-CHOH-CH
2
OH + 2HCl

Cng c th iu ch glycerin t aldehyd formic v aldehyd acetic bng
phn ng kh theo Oppenauer -Meerwein-Ponndorf to thnh aldehyd allylic.
Sau hydroxyl ha aldehyd ny bng hydro peroxyd.
- H
2
O
Acrolein CH
2
=CH

_
CHO HOCH
2
_
CH
2
_
CHO HCHO + CH
3
_
CHO
Alcol allylic
CH
3
_
CHO +
Al( OR)
3 CH
2
=CH
_
CH
2
OH + C
2
H
5
OH CH
2
=CH
_
CHO
Glycerin CH
2
OH
_
CHOH
_
CH
2
OH CH
2
=CH
_
CH
2
OH + H
2
O
2

203
4.4. Tnh cht l hc v ha hc ca polyalcol
Phn ln cc polyalcol tan c trong nc v c v ngt. Glycerin rt ho
nc, c nht cao. Glycerin c dng lm cht ht m v s dng rng ri
trong hng liu, thc phm v dc phm.
Cc polyalcol c mt s tnh cht ha hc c bn nh sau:
Cc glycol tc dng vi HCl, HBr to thnh clohydrin v bromhydrin.
Chc OH kh tc dng vi HCl v HBr.
CH
2
OH
_
CH
2
OH + HCl CH
2
Cl
_
CH
2
OH + H
2
O
Cc glycol tc dng vi acid hu c c kh nng to 2 loi ester.
HOCH
2
_
CH
2
_
OCOR v RCOOCH
2
_
CH
2
_
OCOR
Oxy ha glycol to aldehyd hoc ceton.
Glyoxal ( aldehyd oxalic)
Ethylenglycol
- H
2
O
- H
2
O
[O] [O]
CH
2
OH
_
CHO OHC
_
CHO CH
2
OH
_
CH
2
OH

CH C
OH OH
R
R''
R'
C
O
R H + C
O
R''
R' HIO
4

hoac (CH
3
COO)
4
Pb

Phn ng dehydrat ha glycol (loi nc):
Di tc dng ca acid v c hoc km clorid ZnCl
2
ethylenglycol b loi nc
to aldehyd acetic. Phn ng xy ra c s chuyn v anion hydro (H
-
).
Aldehyd acetic
Loai nc
+ H
+
CH
3
C
O
H
+
. .
..
CH
2
C
O
H
H
H
H
+
CH
2
CH
2
OH OH
Chuyn v H
-

Phn t pinacol (tetra methylethylenglycol - 2,3-dimetyl-2,3-butadiol)
di tc dng ca acid v c b dehydrat to thnh ceton l pinacolon.
Trong phn ng ny xy ra s chuyn v nhm methyl. S chuyn v ny
gi l s chuyn v pinacol.
Chuye n v CH
3
-
H
+
. .
+
H
+
+
Pinacol
C C
OH OH
CH
3
CH
3
CH
3
CH
3
C C
O
CH
3
CH
3
CH
3
CH
3
H
C C
O
CH
3
CH
3
CH
3
CH
3
- H
2
O
Pinacolon

Glycol b mt nc to ether vng.
Ethylenglycol
H
2
SO
4
+ 2H
2
O
CH
2
CH
2
O
CH
2
CH
2
O
CH
2
CH
2
OH
OH
CH
2
CH
2
OH
OH
Dioxan

204
nh hng ca cc nhm OH lm cho polyalcol c tnh acid mnh hn
monoalcol. Cc polyalcol ha tan c ng hydroxyd (Cu(OH)
2
)

to dung
dch mu xanh.
+ 2H
2
O + Cu( OH)
2
Cu
CH
2
CH
CH
2
O
O
HO
H
CH
2
CH
CH
2
O
O
OH
H
CH
2
OH
2 CHOH
CH
2
OH

Bi tp
Monoalcol
1. Vit cng thc cu to ca nhng cht sau:
a. Alcol tert- butylic ; b- Alcol isoamylic ; c- sec-Butylethylmethylcarbinol;
d. 2-Propanol: e- 2,2-Dimethyl-2-pentanol; f- Alcol cetylic. g- Alcol lauric.
2. Vit cng thc cu to tt c cc ng phn ca alcol c cng thc phn t l
C
7
H
16
O. Gi tn nhng ng phn theo danh php thng thng, danh php
IUPAC v danh php carbinol. ng phn no c tnh quang hot.
3. Nhng alcol no c to thnh khi thy phn bng dung dch kim t cc hp
cht halogen sau:
a. Isobutylbromid; b- sec-butylbromid; c- Ethylenclohydrin; d- 1-Brom2-buten ;
4. Vit phn ng xy ra trong cc trng hp di y:
a. Hydrat ha propylen, trimethylethylen, isobutylen, 2,2-dimethyl-3-hexen.
b. Phn ng loi nc ca hp cht (CH
3
)
2
C(OH)CH
2
CH
2
CH
2
OH.
c. Oxy ha cc alcol n -butylic, sec-butylic bng hn hp kali bicromat v H
2
SO
4
.
d. Cho alcol octylic tc dng ln lt vi cc cht POCl
3
, HNO
2
, HNO
3
, SO
3
.
5. Gii thch c ch phn ng xy ra khi cho acid acetic tc dng vi alcol n-butylic c
xc tc l H
2
SO
4
6. Hon thnh v cn bng cc phn ng oxy ha - kh di y:
a. (CH
3
CH
2
CH
2
)CHOH + CrO
3
= (CH
3
CH
2
CH
2
)C=O + Cr
3+
b. CH
3
CH
2
CH
2
CH
2
CH
2
OH + H
2
CrO
4
= CH
3
CH
2
CH
2
CH
2
COOH + Cr
3+

c. CH
3
OH + CuO = HCHO + Cu
Alcol cha no
7. Vit cng thc cu to cc cht sau:
a- 2,2-Dimethyl-4-hepten-3-ol; b-Alcol allylic; c-Alcol 11-dodekenol; d-Alcol
propagylic

205
8. Vit cc phn ng xy ra trong cc trng hp sau:
a. Alcol allylic tc dng vi dung dch brom, dung dch KMnO
4
, dung dch HCl.
b. 2-Cyclohexenol tc dng vi dung dch KMnO
4
v hn hp kalibicromat v
H
2
SO
4
.
c. Cho linalol tc dng vi acid acetic c H
2
SO
4
lm xc tc.
Alcol vng
a. 2,3- Dimethylcyclohexanol; b- 2,6,6-Trimethylbicyclo[3,1,0]heptanol-3.
10. Vit phn ng oxy ha cyclohexanol bng CrO
3
.
Polyalcol
a-2,3-Dimethyl-2,3-butadiol; b-1,4- Butyndiol; c- 1,2,3-Cyclohexantriol;
d- (+)Inositol.
12. Vit phn ng loi nc trong mi trng acid km theo s chuyn v pinacol
ca hp cht tetraphenylethylenglycol.
13. Gii thch v sao polyalcol c tnh acid mnh hn monoalcol. Cho phn ng
chng minh iu .
14. V sao polyalcol d tan trong nuc hn monoalcol.
206
Chng 17
PHENOL
Mc tiu hc tp
1. Gi c tn cc phenol v polyphenol.
2. Trnh by c cc tnh cht ha hc ca phenol.
Ni dung
Phenol l hp cht c nhm hydroxyl - OH gn trc tip vi nhn benzen.
i din n gin nht ca loi hp cht ny l hydroxybenzen. Phn loi phenol
thng da vo bn cht ca gc hydrocarbon thm v s nhm OH c trong phn
t. Cng thc tng qut ca cc phenol thng gp:
Monophenol Ar-OH hoc C
n
H
2n-7
OH
Polyphenol Ar'(OH)
m
C
n
H
2n-6-m
(OH)
m

>
2 m

1. Monophenol
1.1. Danh php v ng phn
Tn gi phenol thng dng gi theo danh php thng thng.
Xem phenol l dn xut ca hydrocarbon m hydro c thay th bi nhm OH
Gi tn cc phenol khc nh l dn xut ca phenol n gin nht.
Acid Phenic
Hydroxybenzen
Phenol
OH
OH
CH
3
o-Cresol
o-Hydroxytoluen
2-Methylphenol 3-Methylphenol
m-Hydroxytoluen
m-Cresol
OH
CH
3
4-Methylphenol
p-Hydroxytoluen
p-Cresol
OH
CH
3

OH
CH
3
CH (CH
3
)
2
Thimol
5-Methyl-2-Isopropylphenol
3-Hydroxy-p-cymen
1-Hydroxynaphthalen
-Naphtol
OH
2-Hydroxynaphthalen
-Naphtol
OH

207
1-Phenantrol
OH
10-Phenantrol
OH
OH
p-Hydroxydiphenyl (1,4)

ng phn ca phenol ph thuc vo v tr ca nhm OH trn nhn benzen
v ph thuc vo v tr hoc s phn nhnh ca gc hydrocarbon.
1.2. iu ch phenol
1.2.1. Thy phn cc halogeno aren
Halogeno aren b thy phn bng dung dch kim c p sut v nhit
cao.
Ap suat
300
o
C
Ar
_
OH + NaCl Ar
_
Cl + NaOH

1.2.2. Nung nng chy acid aren sulfonic vi NaOH
300
o
C
2Ar
_
OH + Na
2
SO
3

+ H
2
O 2Ar
_
SO
3
H + 2NaOH

1.2.3. Thu phn mui aren diazoni
+
Ar
_
N
2
+ 2H
2
O
Nhiet o +
Ar
_
OH +

H
3
O + N
2

1.2.4. Oxy ho hp cht aryl magnesi halogenid ArMgX
2Ar
_
OH+2Mg(OH)Cl 2Ar
_
OMgCl
Ar
_
MgCl 2H
2
O
Ar
_
OOMgCl Ar
_
MgCl+ O
2

hoc cho hp cht c magnesi tc dng vi ester ca acid boric v sau oxy
ha bng hydro peroxyd H
2
O
2
.

- H
3
BO
3
+ H
2
O
2
Ar
_
MgCl
+ B ( OR)
3
- Mg(OR)Cl
Ar

( OR )
2
Ar
_
B( OH )
2
Ar
_
OH
2H
2
O
- 2ROH

1.2.5. Oxy ha cumen
Trong cng nghip phenol c iu ch bng cch oxy ha cumen. Sau
tc dng vi acid sulfuric thu c phenol v aceton. Phn ng oxy ha xy ra
theo c ch gc.
CH(CH
3
)
2
CH(CH
3
)
2
HOOC(CH
3
)
2
OH
C CH
3
CH
3
O
+ O
2
H
2
SO
4
+
Cumen hydroperoxyd Cumen
Aceton

208
1.3. Tnh cht l hc
S c mt nhm hydroxyl gn trc tip vo nhn benzen quyt nh tnh cht
vt l ca phenol. Do tng tc vi nhn benzen, lin kt O-H b phn cc mnh hn
OH ca alcol. Lin kt hydro trong phenol bn hn lin kt hydro ca alcol.
Phn ln cc phenol u dng rn, kh tan trong nc v t bay hi. Tnh
cht vt l mt s phenol c trnh by trong bng 17-1 :
Bng 17.1: Hng s l hc mt s hp cht phenol
pKa
s c
t
o
t
o
Cong thc Ten chat
4,
7,16
8,0
7,21
9,39
9,11
8
10,17
10,01
10,2
10.
214
217
214
176
291,8
288
233
201
201
191
181
95
113
114
96
44,5
37
29
8
122
96
51
35,5
12
30
43
Br
3
C
6
H
3
OH (1,2,,4,6)
(O
2
N)
2
C
6
H
3
OH (1,2,,4)
O
2
NC
6
H
4
OH (1,4)
O
2
NC
6
H
4
OH (1,3)
O
2
NC
6
H
4
OH (1,2)
ClC
6
H
4
OH (1,4)
ClC
6
H
4
OH (1,3)
ClC
6
H
4
OH (1,2)
p-CH
3
C
6
H
4
OH (1,4)
m-CH
3
C
6
H
4
OH (1,3)
ClC
6
H
4
OH (1,2)
C
10
H
7
OH
C
10
H
7
OH
(CH
3
) CH(CH
3
)
2
C
6
H
3
OH (1,5,2)
o-CH
3
C
6
H
4
OH (1,2)
C
6
H
5
OH
2,4,6- Tribromophenol
2,4-Dinitrophenol
p-Nitrophenol
m-Nitrophenol
o-Nitrophenol
p-Clorophenol
m-Clorophenol
-Naphtol
o-Clorophenol
-Naphtol
Thymol
p-Cresol
m-Cresol
o-Cresol
Phenol

1.4. Tnh cht ha hc ca phenol
Nhm OH gn trc tip vo h thng lin hp ca nhn benzen. Phenol c
cu to nh mt enol CH =C
_
OH bn vng. Tnh cht ca phenol do nhm OH
quyt nh. Phenol c tnh acid. Nhm chc OH phenol l nhm th loi I, phn
ng th xy ra trn nhn benzen to hn hp ng phn ortho v para.
1.4.1. Tnh acid - base
Phenol c tnh acid mnh hn alcol do cp in t trn oxy ca nhm OH
lin hp vi nhn benzen khin hydro ca nhm O
_
H tr nn linh ng. Phenol
c cc trng thi cng thc trung gian sau:
OH OH
OH OH
+
-
+ +
-
-
:

209
Phn ng th hin tnh acid ca phenol:
OH
ONa
+ Na + [ H

]
;

OH
ONa
+ NaOH + H
2
O

Phenol c tnh acid yu hn acid carbonic. Phenolat tc dng vi acid carbonic:
OH
+ NaHCO
3
ONa
+ CO
2

+ H
2
O

Phenolat c tnh base:
Tnh base v tnh i nhn ca phenolat yu hn tnh base v tnh i nhn
ca alcolat RO
-
v cp in t trn oxy ca phenolat lin hp vi nhn benzen lm
gim mt in t trn oxy. Phenolat natri tan trong nc, phn ly thnh ion:
C
6
H
5
ONa C
6
H
5
O
-
+ Na
+

Ion phenolat tn ti cc trng thi trung gian do s cng hng:
O O
O O
-
-
-
-

Tnh acid ca phenol tng khi trn nhn benzen c cc nhm ht electron
nh Cl, NO
2
, COOH... (c hiu ng -I,-C). Cc nhm y electron nh CH
3
lm
gim tnh acid ca phenol.
1.4.2. Phn ng ester ha ca phenol
Phenol tc dng trc tip vi acid hu c to ester vi hiu sut thp. Phn
ng xy ra kh khn hn s ester ha ca alcol. Phn ng ester ha ca phenol l
phn ng thu nhit:
CH
3
COOH + C
6
H
5
OH CH
3
COOC
6
H
5
+ H
2
O H
o
= + 1,5 kcal.mol
-1

CH
3
COOH + C
2
H
5
OH CH
3
COOC
2
H
5
+ H
2
O H
o
= - 4.6 kcal.mol
-1

Phn ng to ester ca phenol d xy ra hn khi phenol tc dng vi cc
clorid acid hoc anhydrid acid c xc tc base hoc acid:
OH
OCOR
+ RCOCl + HCl
Base

210
Acid salicylic
Aspirin
H
3
PO
4
+ CH
3
COOH + ( CH
3
CO )
2
O
OCOCH
3
COOH
OH
COOH

Ester ca phenol tham gia phn ng chuyn v Fries to ceton thm khi c
xc tc AlCl
3
:

OCOR
AlCl
3
OH
C R
O
OH
C O CH
3
o- Oxyphenylceton
p- Oxyphenylceton
t = 60
o
t =160
o

1.4.3. Phn ng to ether ca phenol
Cc phenolat tc dng vi alkyl halogenid to ether (Phn ng Williamson):
ArO
-
+ RX ArOR + X
-
Di tc dng ca nhit , ether cha no allylphenylether tham gia chuyn
v Claisen
o- Allylphenol
Eter allylphenyl
Chuyen v Claisen
200
o
C
OH
CH
2
CH=CH
2
OCH
2
CH=CH
2

C ch chuyn v Claisen:
CH
2
CH
CH
2
O
CH
2
CH
CH
2
OH
CH
2
CH
CH
2
O
H
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
CH
2
CH
CH
2
O
#

1.4.4. Phn ng thay th nhm OH
Nhm OH phenol c th b thay th bi Cl hoc NH
2
khi tc dng vi PCl
5

hoc NH
3
vi xc tc AlCl
3
:
;
Phenol Clorobenzen
-POCl
3
,-HCl
PCl
5
Cl
OH
Picrylclorid Acid picric
-POCl
3
,-HCl
PCl
5
NO
2
NO
2
O
2
N
Cl
OH
NO
2
NO
2
O
2
N

211
OH
NH
3
( AlCl
3
) ,
NH
2
+ H
2
O
- Naphtol - Naphtylamin

1.4.5. Phn ng vi aldehyd
Phenol tc dng vi aldehyd formic trong mi trng base to hn hp
alcol ortho v parahydroxybenzylic:
OH O
-
+ H
2
O + HO
-
O
-
+ HCHO
O
CH
2
OH
O
CH
2
OH
-
-
;

Phn ng xy ra kh iu khin v tc . Cc alcol to thnh tng tc vi
nhau tng t phn ng trng ngng v to thnh polymer gi l bakelit.
Phn ng cng c th xy ra trong mi trng acid. Alcol o-hydroxy
benzylic c to thnh (alcol salicylic). Phenol tc dng vi formaldehyd v amin
bc 2 to hp cht o -aminomethylphenol.
OH
HCHO + H
+
CH
2
OH
CH
2
OH
OH
;
+
OH
CH
2
OH
H
+
CH
2
OH
+
- H
+

- H
2
O
OH
OH
CH
2
NR
2
HCHO + R
2
NH

1.4.6. Phn ng tng hp Kolbe. Tng hp acid salicylic.
Phenolat natri tc dng vi CO
2
c p sut v nhit , to natri salicylat.
p, t
o
COONa
OH
+ CO
2
ONa
;
COONa
OH
COOH
OH
+ H
+

C ch phn ng:
O
+
C
O
O
O
H
O
C
O
:
. .
-
COO
OH
-
COOH
OH
+ H
+
:

Thng p dng phn ng ny sn xut acid salicylic trn quy m cng nghip.
212
1.4.7. Phn ng Reimer -Tieman
Phenol tc dng vi cloroform trong mi trng kim mnh to thnh
hydroxybenzaldehyd. Sn phm phn ng c th l hn hp ng phn ortho
v para.
Aldehyd salicylic
+ 3KCl + 2H
2
O
+ CHCl
3
+ 3KOH
CHO
OH OH

Phn ng xy ra theo c ch to diclorocarben do cloroform tc dng vi KOH.
C Cl
Cl
H
Cl
. .
:
KCl + H
2
O + :CCl
2
+
HO
K

Diclorocarben (CCl
2
) nh l mt tc nhn i in t tn cng vo phenol v
tr ortho hoc para v sau xy ra s thy phn.
+
-
+ :CCl
2

O
CCl
2
H
O
:
. .
:
-
CHO
OH
-HO
-
+ H
2
O
-2KCl,-H
2
O
CHO
O
-
CHCl
2
O
+ 2KOH

Ty theo cu to, diclorocarben c th l tc nhn i in t (c 2 electron u
sp xp trong mt orbital v c mt orbital khng c electron. C in tch dng (+)
trn carbon) hoc cng c th l mt lng gc (trn mi orbital ch c mt electron):

;
.
.
Cl
Cl
+
: CCl
2
.
.
Cl
Cl
Tc nhn i in t Lng gc

1.4.8. Phn ng ghp i vi hp cht diazoni
Phenol tc dng vi mui diazoni trong mi trng kim to hp cht
arylazophenol. y l mt phn ng th i in t vo nhn thm hot ng vi
mt tc nhn i in t km bn l mui diazoni:
Base
Phenylazophenol
Muoi diazoni
+
+ N N HO N N HO

1.4.9. Cc loi phn ng th i in t khc
Phenol tham gia cc phn ng th i in t khc nh nitro ho to cc hp
cht nitrophenol; phn ng halogen ha to hp cht halogenophenol; phn ng
sulfon ha to acid hydroxybenzensulfonic:
213
CS
2
+ HBr
OH
+ Br
2
OH
Br
Halogen hoa
H
2
O
+ 3HBr + 3Br
2
OH
OH
Br
Br
Br
OH OH
O
2
N
OH
NO
2
O
2
N
OH
NO
2
NO
2
O
2
N
HNO
3 HNO
3
HNO
3
H
2
SO
4 H
2
SO
4
H
2
SO
4
Nitro hoa
2-Nitrophenol
2,4 Dinitrophenol 2,4,6-Trinitrophenol

Sulfon ha
+ H
2
SO
4
OH
+ 2H
2
O
OH
HO
3
S

o-Nitrophenol c lin kt hydro ni phn t. p -Nitrophenol ch c lin kt
hydro gia cc phn t vi nhau
1.4.10. Phn ng to mu bi dung dch FeCl
3
.
Vi dung dch FeCl
3
phenol to hp cht C
6
H
5
OFeCl
2
c dung dch mu tm -
; Cresol to dung dch mu xanh v cc phenol khc to dung dch mu vng.
1.4.11. Phn ng oxy ha phenol
Phenol d b ha nu bi oxy khng kh. Nhiu phn ng oxy ha ca
phenol xy ra rt phc tp. Tnh cht ca sn phm ph thuc vo bn cht ca
nhm th. Trong qu trnh oxy ha, hydro ca nhm OH b phn ct v to
thnh gc phenoxyArO
.
OH O
O
O
O
[ O ]
- H
.
.
.
.
.

Cromoxyd CrO
3
oxy ha phenol to p -benzoquinon. Phn ng xy ra qua
giai on to acid phenylcromic.
214
;
H
+ CrO
3

OH
O CrO
3
H

O
OH H
OH
OH O
_
CrO
3
H
H
O
O H O
H
- H
2
CrO
3
H
2
CrO
4
p- Benzoquinon p- Hydroquinon

-Naphtol b oxy ha to sn phm 4,4'-dihydroxy-1,1'-dinaphtyl. Phn ng
xy ra theo c ch:
4,4'-Dihydroxy-1,1'-dinaphtyl
2
-H
.
.
.
OH
OH
O
H
O OH OH O
H

Trong trng hp 2,4,6-tri-tert-butylphenol, gc t do 2,4,6-tri-tert-
butylphenoxy c mu xanh sinh ra c bn cao. Chng tc dng vi oxy to hp
cht mu vng:
-H
+
- e
.
.
.
O
C(CH
3
)
3
C(CH
3
)
3
(CH
3
)
3
C
O
C(CH
3
)
3
C(CH
3
)
3
(CH
3
)
3
C
O
C(CH
3
)
3
C(CH
3
)
3
(CH
3
)
3
C
OH
C(CH
3
)
3
C(CH
3
)
3
(CH
3
)
3
C

O
O O
Bu
(CH
3
)
3
C
(CH
3
)
3
C
O
Bu
C(CH
3
)
3
C(CH
3
)
3
Bu (CH
3
)
3
C
Mau vang
O
2

2. Polyphenol
Polyphenol l hp cht c hai hay nhiu nhm OH gn trc tip trn vng
benzen. Cc polyphenol l cc cht rn.
OH
OH
Catechol (t
c
= 104
o
)
1,2 -Dihydroxybenzen

OH
OH
Resorcinol
(t
c
= 114
o
)

OH
OH
Hydroquinon (t
c
= 169
o
)

215
OH
OH
HO
Pyrogalol (t
c
= 132
o
)
1,2,3 -Trihydroxybenzen

OH
OH
HO
Phloroglucinol (t
c
= 218
o
)

OH
OH
OH
Hydroxyhydroquinon (t
c
= 140
o
)

Polyphenol c iu ch theo cc phng php c bn trong iu ch
monophenol:
H
+
Cu
II
, 200
o
C
NaOH , H
2
O
Cl
Cl
OH
OH

OH
OH
SO
3
H
SO
3
H
NaOH
Nong chay
H
+
,H
2
O

NH
2
O
O
Na
2
Cr
2
O
7
H
2
SO
4
2[H]
OH
OH

OH
OH
HO
COOH
OH
OH
HO
un nong
- CO
2
Acid Galic

H
2
O , 100
o
C Sn,HCl
NH
2 H
2
N
NH
2
COOH
OH
HO
OH
NO
2 O
2
N
NO
2
COOH

Polyphenol t do khng tn ti trong thin nhin. Chng ch tn ti dng
ether hoc ester. C th chng ct polyphenol. Chng d thng hoa v d tan
trong nc, alcol ; khng tan trong hydrocarbon.
Cc phn ng ca polyphenol cng ging phn ng ca monophenol. Kh nng
phn ng ca polyphenol cao hn monophenol. Cc cht catechol, hydroquinon,
pyrogallol d b oxy ha trong mi trng kim. Kh phn ring cc sn phm oxy
ha. Hydroquinon c s dng lm cht hin hnh trong k ngh nh:
216
Catechol o-Benzoquinon
;
MgSO
4
,ether
Ag
2
O
O
O
OH
OH

OH
OH
O
O
Na
2
Cr
2
O
7
H
2
SO
4
Hydroquinon p-Benzoquinon

Resorcinol kh b oxy ha hn. Khi b oxy ha khng to thnh m -quinon.
Sn phm oxy ho resorcinol l mt hn hp phc tp.
Resorcinol c kh nng h bin do s di chuyn hydro ca nhm OH do
resorcinol d b hydro ha bi hn hng natri to thnh 1,3-cyclohexandion:
1,3 -Cyclohexandion
Resorcinol
OH
OH
O
O
O
O
+2 H

Phloroglucinol cng c kh nng h bin to ceton:
1,3,5 -Cyclohexantrion Phloroglucinol
OH
OH
HO
O
O
O

Polyphenol to dung dch c mu vi FeCl
3
. Catechol cho mu xanh.
Resorcinol cho mu tm. Pyrogallol cho mu .
Bi tp
1. Hy vit cng thc cu to cc cht sau y:
a. m-Cresol; b. p-Ethylphenol; c. 2,4- Dinitrophenol;
d. o-Nitrophenol; e. Acid picric; f. Acid 2,4-Phenoldisulfonic
g. Pyrogalol; h. Phloroglucinol; i. Acid galic.
2. Hy gi tn cc cht sau y:
OH CH
3
OH
H
5
C
2
OH Cl
OH
Cl
a-
b-
c-
d-
;
; ;

OH CH
3
OH
OH
H
5
C
2
HO
OH Cl
HO
OH
Cl
HO
e-
f-
g -
h -
;
; ;

217
3. Vit phng trnh iu ch cc phenol:
a. p-Bromophenol, Tribromophenol t benzen.
b. Acid picric t clorobenzen; t acid 2,4-phenoldisulfonic.
c. o-Cresol t o -clotoluen.
4. Hy sp xp cc cht sau y theo th t tng dn tnh acid:
OH OH
NO
2
NO
2
NO
2
OH
NO
2
OH
Cl
OH
OCH
3
CH
2
OH
; ;
;
; ;

5. Vit cc phng trnh phn ng trong cc trng hp sau:
a. Cc cht methyliodid, isoamylbromid, allylbromid tc dng vi kaliphenolat.
b. o-Cresol tc dng vi hn hp KOH v CHCl
3
.
c. p-Cresol tc dng vi aldehyd formic trong mi trng acid.
d. Thc hin s chuyn v Fries ca cc cht ester p -hydroxyphenylacetat,
m-metoxyphenylacetat.
6. B tc v hon thnh cc phn ng theo s :
E
D
C
B A
NaOH
HNO
3
(CH
3
)
2
SO
4
H
+
H
2
O
Nung chay
NaOH
H
2
SO
4
Benzen

218
Chng 18
ETHER
Mc tiu hc tp
1. c c tn cc loi ether.
2. Trnh by c tnh cht ha hc ca ether mch thng, ether vng.
Ni dung
Khi th H ca OH trong ROH, ArOH bng gc R, Ar, ta s c ether.
R O
_
H R O
_
R' R O
_
H R
_
O
_
Ar Ar
_
O
_
H Ar
_
O
_
Ar
Phn loi ether:
Ether mch h
Ether mch vng.
1. Ether mch h
1.1. Cu to
Oxy ca ether lin kt trc tip vi 2 gc R, Ar ging nhau hoc khc nhau.
Diethyl oxyd
Diethyl ether
CH
3
_
CH
2
_
O
_
CH
2
_
CH
3
Ethylmethyl oxyd
Ethylmethyl ether
CH
3
_
CH
2
_
O
_
CH
3
Methylvinyl oxyd
Methylvinyl ether
CH
2
=CH
_
O
_
CH
3
Cyclohexylethyl oxyd
Cyclohexylethyl ether
O CH
2
CH
3

Benzylmethyl oxyd
Benzylmethyl ether
CH
2
O CH
3
Methylphenyl oxyd
Methylphenyl ether
O CH
3
Methyl , naphtyl oxyd
Methyl , naphtyl ether
O
_
CH
3
Diphenyl oxyd
Diphenyl ether
O

1.2. Danh php
Gi tn cc gc alkyl v thm t ether hoc oxyd.
Tn gc hydrocarbon tng ng + ether (hoc oxyd)

219
Cng c th xem ether l dn xut ca hydrocarbon m hydro c thay th
bng nhm alkoxy RO
,
aroxy ArO
:
(CH
3
)
2
O Dimethyl ether Dimethyl oxyd Metoxymetan
CH
3
OCH
2
CH
2
CH
3
Methylpropyl ether Methylpropyl oxyd Metoxypropan
CH
3
OCH(CH
3
)
2
Methylisopropyl ether Methylisopropyl oxyd 2-Metoxypropan
C
6
H
5
OCH
3
Methylphenyl ether Methylphenyl oxyd Metoxybenzen
p-CH
3
C
5
H
4
OC
2
H
5
Ethyl,p-tolyl ether Ethyl,p-tolyl oxyd, p- Etoxytoluen
1.3. Phng php iu ch ether
1.3.1. iu ch ether theo phn ng Williamson
Phng php ph bin hay dng iu ch ether c gc hydrocarbon khc
nhau l cho natri alkoxyd tc dng vi dn xut halogen (Williamson,1850):
C
2
H
5
ONa + ICH
3
C
2
H
5
OCH
3
+ NaI
CH
2
=CHCH
2
ONa + IC
2
H
5
CH
2
=CHCH
2
OC
2
H
5
+ NaI
Phng php Williamson rt thun li iu ch cc ether c gc aryl. Cc
tc nhn alkyl ha l dn xut halogen, alkylsulfat, ester alkyl-p-toluensulfonat
(alkyl tosylat):
C
6
H
5
ONa + ICH
3
C
6
H
5
OCH
3
+ NaI.
C
6
H
5
ONa + SO
2
(OCH
3
)
2
C
6
H
5
OCH
3
+ CH
3
OSO
2
ONa
Anisol Natri p- toluensulfonat
Ester Methyl-p- toluensulfonat
C
6
H
5
OCH
3
+ p-CH
3
C
6
H
4
_
O
_
SO
2
_
ONa C
6
H
5
ONa + p-CH
3
C
6
H
4
_
O
_
SO
2
_
OCH
3

C
6
H
5
ONa + BrC
6
H
5
C
6
H
5
OC
6
H
5
+ NaBr.
1.3.2. iu ch ether t alcol
2ROH ROR + H
2
O
Phn ng xy ra c xc tc H
2
SO
4
m c (140C) hoc Al
2
O
3
nhit
200-300C. Phng php ny c hiu sut cao i vi cc alcol kh to alken.
1.4. Tnh cht l hc
Ether khng c kh nng to lin kt hydro nn nhit si ca ether thp
hn nhit si ca cc alcol tng ng v khng tan trong nc, tan trong dung
mi hu c.
Cc ether thng c mi thm - ''Mi ether''

220
Bng 18: So snh nhit si ca ether vi alcol v phenol
Ether t
o
s
Alcol, phenol t
o
s

(CH
3
)
2
O -24
o
C
(C
2
H
5
)
2
O +35
o
C
C
4
H
9
OCH
3
70
o
C

C
6
H
5
OCH
3
155
o
C
CH
3
OH 66
o
C
C
2
H
5
OH 78
o
C
C
4
H
9
OH 118
o
C
C
6
H
5
OH 183
o
C
Cn c vo ph hng ngoi c th phn bit cc loi ether:
Dialkylether c vch c trng trn quang ph hng ngoi IR ca lin kt
ether vng 1060 - 1150 cm
-1
.
Vch c trng IR ca lin kt ether trong alkylarylether vng 1230-
1270cm
-1
.
1.5. Tnh cht ha hc
Ether c kh nng phn ng km hn alcol v lin kt C
_
O
_
C l lin kt
km phn cc v kh b tch ra. Ether thng c dng lm dung mi trong
tng hp hu c. Khc vi alcol, ether khng c tnh acid v khng c phn ng
vi base.
1.5.1. Phn ng to mui oxoni
Ether c tnh base yu. Khi tc dng vi acid mnh (H
2
SO
4
,

HClO
4
,

HBr)
ether to thnh mui oxoni khng bn:
Diethyloxoni
..
.. ..
..
H
+
C
2
H
5
_
O
_
C
2
H
5
+ Br
-
C
2
H
5
_
O
_
C
2
H
5
+ HBr

Ether tc dng vi acid Lewis (BF
3
, RMgX) to phc phi tr tng i bn:
F
B
F F
Botriflorid etherat
..
..
..
..
C
2
H
5
_
O
_
C
2
H
5 C
2
H
5
_
O
_
C
2
H
5
+ BF
3

Ion dialkyloxoni nhy cm vi phn ng th i nhn v phn ng tch loi
hn phn t ether trung ha. V vy trong mi trng acid mnh ether c th xy
ra phn ng th cho sn phm th v phn ng tch loi to olefin:
S
N2
+Br
-
C
2
H
5
_
O
_
H + BrC
2
H
5
H
C
2
H
5
_
O
_
C
2
H
5
+ H
+
C
2
H
5
_
O
_
C
2
H
5
+
..

221
E
1
Di-tert-butyl ether
(CH
3
)
2
C=CH
2
+

H
2
O

-
+ H
2
SO
4
(CH
3
)
2
C=CH
2
+

HO
_
C(CH
3
)
3
(CH
3
)
3
C
_
O
_
C(CH
3
)
3
HSO
4
H
+
Di-tert-butyloxoni
(CH
3
)
3
C
_
O
_
C(CH
3
)
3
+
H
+
..

1.5.2. Phn ng oxy ha ether
Ether mch h l cht t oxy ha. Ether ethylic tip xc lu ngy vi khng
kh (c bit khi c nh sng) s to hydroperoxyd v peroxyd:
CH
3
_
CH
2
_
O
_
CH
2
_
CH
3
+ O
2
CH
3
_
CH
_
O
_
CH
2
_
CH
3
OOH Hydroperoxyd

Hydroperoxyd s b loi mt phn t alcol etylic v chuyn thnh hp cht
peroxyd polymer, ethyliden peroxyd (-CH(CH
3
)
_
O
_
O
_
)
n
vi n = 4
_
8 v mt s hp
cht cha oxy khc.
Peroxyd polymer l cht lng snh nh du, d gy n khi c va chm v
chng ct.
Khi s dng ether phi kim tra peroxyd bng phn ng vi mui st (II),
titan sulfat (IV).
Peroxyd b ph v khi tinh ch ether vi natri kim loi, mui st (II), mui
mangan (II).
Ether rt nhy cm vi s tn cng ca gc t do. V vy ether khng phi l
dung mi tt cho cc phn ng c c ch gc t do. Cc ether thng dng nh
ether ethylic, dioxan, tetrahydrofuran thng b nhim peroxyd.
Cc ether cha no c gc aryl d tham gia chuyn v Claisen:
Trong thin nhin tn ti nhiu hp cht ether c ng dng trong y dc.
OCH
3
OH
OCH
3
OCH
3
OH
OCH
3
CH
2
CH CH
2
OH
OCH
3
CH CH CH
3
Gaiacol Veratrol
Eugenol Isoeugenol
2-Metoxyphenol 1,2-Dimetoxyphenol 4-Allyl-2-metoxyphenol 4-Propenyl-2-metoxyphenol

4-Propenylmetoxybenzen
Anetol
OCH
3
CH=CHCH
3
4-Allyl-1,2-methylendioxybenzen
Safrol
O
O
CH
2
CH
2
=CHCH
2
1,2-Methylendioxy-4-propenylbenzen
Isosafrol
O
O
CH
2
CH
3
CH=CH

222
2. Ether vng

Tetramethylen oxyd
Tetrahydrofuran
O
O
Tetrahydropyran
Pentamethylen oxyd
Epoxy
Ethylen oxyd
O
1,4-Dioxan
O
O

Ethylen oxyd l ether vng n gin nht. Vng ethylen oxyd d b ph v.
Ethylen oxyd l nguyn liu to nhiu cht hu c c nhiu ng dng quan trng nh
ethylen glycol, diethylen glycol, clohydrin, xelozol v cht cao phn t carbowax:
Carbovac
Methylen carbitol Methyl xelozol
Ethylen clohydrin
Diethylen glycol
Ethylen glycol
Ethylen oxyd
CH
2
H
2
C
O
HO
_
(CH
2
CH
2
O)
n
_
H
Base
ClCH
2
CH
2
OH
HCl
CH
3
O(CH
2
O)CH
2
OH
CH
2
H
2
C
O
HOCH
2
CH
2
OCH
3
CH
3
OH
(HOCH
2
CH
2
)
2
O HOCH
2
CH
2
OH
H
2
O
CH
2
H
2
C
O

Phn ng trng ngng ca ethylen oxyd to thnh cht cao phn t l
polyethylenglycol (PEG) dng lm cht nh ha trong dc phm v k ngh dt:
PEG HO
_
CH
2
_
CH
2
_
O
_
(
_
CH
2
_
CH
2
_
O
_
)
n
_
CH
2
_
CH
2
_
OH
Cc ether ca monoalcol bc cao nh octadecylic C
18
H
37
OH hoc alcol thm
c mch nhnh di c ng dng lm cht nh ha. Cng thc chung c dng:
C
18
H
37
O(CH
2
CH
2
O)
x
CH
2
CH
2
OH ; RC
6
H
4
O(CH
2
CH
2
O)
m
CH
2
CH
2
OH
Bi tp
1. c tn v vit cng thc cu to ca cht to thnh khi cho cc cht di y
tc dng vi acid HBr.
a- CH=CHCH
2
OCH
3
b- CH
3
CH
2
OCH=CH
2
c- (CH
3
)
3
CCH
2
OCH
3
d- C
6
H
5
OCH
3 ;
;
;

; ;
O
O
O
O
O
O
e- f- g-
h- ;
; i-

2. Vit cng thc cu to ca cc cht: Gaiacol, cineol, eugenol, anetol, safrol, PEG

223
Chng 19
ALDEHYD, CETON V QUINON
Mc tiu hc tp
1. Gi c tn cc hp cht carbonyl.
2. Gii thch c c ch A
N
v hot i nhn ca hp cht carbonyl.
3. Nu c cc ha tnh ca aldehyd v ceton ng thi cho bit phng php
ha hc nhn bit chng.
Ni dung
1. Cu to
Aldehyd, ceton, quinon l nhng hp cht cha nhm carbonyl C = O.
Tng qut:
Quinon
Ceton
Aldehyd
Aldehyd formic
R
1
C R
2
O
R C H
O
H C H
O
O O

Ty thuc cu to ca cc gc R, R
1
, R
2
m aldehyd, ceton l nhng hp cht
no, cha no, thm hoc aldehyd vng ceton vng.
Nhm chc CHO trong aldehyd gi l chc aldehyd hay nhm formyl
Nhm carbonyl C = O trong ceton gi l chc ceton hay nhm oxo
Quinon l sn phm oxy ha cc diphenol. Quinon phi l mt h thng lin hp.
C th xem quinon l diceton vng cha no. Chc ceton lin hp vi lin kt i ca
vng. Tn ti 1,2 -hay orto-quinon v 1,4- hay para-quinon. Khng c 1,3-quinon.
O O
1,2-hay orto-Quinon 1,4- hay para- Quinon
O
O

Aldehyd, ceton, quinon thuc loi hp cht carbonyl - cha nhm carbonyl
1. Aldehyd v ceton
1.1. Danh php
1.1.1. Danh php ca aldehyd
224
Theo danh php IUPAC:
Gi tn hydrocarbon tng ng v thm tip v ng al
Tn hydrocarbon tng ng + al
4-Methyl-2-pentenal
2-Pentenal Propanal
5 4 3 3 2 2 1 1 5
4 3
2
1
CH
3
CHCH=CH C H
O
CH
3
CH
3
CH
2
CH=CH C H
O
CH
3
CH
2
C H
O

nh s 1 t carbon ca chc aldehyd.
Tn thng thng:
Gi theo tn thng thng theo acid tng ng.
Aldehyd + Tn acid tng ng hay Tn gc Acyl RCO- + aldehyd
Aldehyd acrylic
Acrolein
Aldehyd benzoic
Benzaldehyd
Aldehyd acetic
Acetaldehyd
Aldehyd formic
Formaldehyd
CH C H
O
CH
2
C
6
H
5
C H
O
CH
3
C H
O
H C H
O

1.1.2. Danh php ca ceton
Theo danh php IUPAC
Gi tn hydrocarbon tng ng v thm tip v ng on
Tn hydrocarbon tng ng + ON
Bng 19.1: Tn gi v tnh cht l hc ca mt s aldehyd v ceton
Cng thc cu to Tn thng thng Tn quc t
t
c
o
t
s
o

H
_
CHO
Formaldehyd Metanal - 92,0 -21,0
CH
3
_
CHO
Acetaldehyd Etanal -123,0 20,8
CH
3
_
CH
2
_
CHO
Aldehyd propionic Propanal - 81,0 48,8
CH
3
_
CH
2
_
CH
2
_
CHO
Aldehyd butyric Butanal - 99,0 74,7
CH
3
CH CHO
CH
3

Aldehyd isobutyric 2-Methylpropanal - 66,9 61,0
CH
2
=CH
_
CHO
Acrolein Propenal - 87,7 52,5
CHC
_
CHO
Aldehyd propagylic Propinal - 60,0
225
Bng 19.1 (tip)
Cng thc cu to Tn thng thng Tn quc t
t
c
o
t
s
o

CH
3
_
CH=CH
_
CHO
Aldehyd crotonic 2-Butenal -74,0 104,0
CHO

Benzaldehyd Benzaldehyd - 56,0 179.5
CH
2
CHO

Aldehydphenylacetic 2-Phenyletanal -10,0 190.4
CH=CHCHO

Aldehyd cinnamic 3-Phenylpropenal - 252.0
CH
3
COCH
3
Aceton Propanon - 95,0 56,1
CH
3
_
CH
2
_
CO
_
CH
3
Methylethylceton Butanon - 86,4 79,6
C
2
H
5
COC
2
H
5
Diethylceton Pentanon-3 - 42,0 101.7
CH
3
C COCH
3
CH
3
CH
3

Pinacolin
Methyl,tert- Butylceton

3.3-Dimethyl-butanon-2

- 52,5

106,2
CH
3
_
CO
_
CH=CH
2
Methylvinylceton Butenon-3 - 79,1
O

- Cyclopentanon - 51,3 130,6
O

- Cyclohexanon - 31,2 156,7
O

- Cycloheptanon - 179,0
COCH
3

Methylphenylceton Acetophenon 19,6 202,3
CO

Diphenylceton Benzophenon 49,0 305,4
Mch chnh l mch di nht cha chc ceton. nh s ch v tr ca chc
ceton. S 1 bt u ti carbon ca mch chnh v gn chc ceton nht.
Cyclohexanon 6-Methyl-1-hepten-4-on
2-Pentanon
5 7 6 4 3 2 1 5 4 3 2 1
O
CH CH
2
C CH
2
CH
2
CH CH
3
CH
3
O
CH
3
CH
2
CH
2
C CH
3
O

226
Gi theo danh php ceton
Gi tn 2 gc hydrocarbon lin kt vi nhm carbonyl v thm tn ceton.
Tn cc gc hydrocarbon + Ceton
Vinylisopropylceton Divinylceton Methylethylceton
CH
2
CH C CH
O
CH
3
CH
3
CH
2
CH C CH
O
CH
2
CH
2
C CH
3
O
CH
3

1.2. iu ch aldehyd v ceton
Aldehyd v ceton u c nhm chc carbonyl C =O, v vy phng php iu
ch aldehyd v ceton gn ging nhau. Tuy vy vn c mt s phng php c th
iu ch aldehyd v ceton.
1.2.1. Oxy ha (hay dehydro ha) alcol. (Xem phn tnh cht ca alcol).
+ H
2
O
H
2
SO
4
-
H
2
O
Na
2
Cr
2
O
7
CH
3
CH
3
O
CH
3
CH
3
CH
3
OH
CH
3

iu ch aldehyd v ceton bng phn ng oxy ha alcol theo phng php
Oppenhauer.
Oxy ha alcol bc 2 bng aceton c xc tc nhm isopropylat - [(CH
3
)
2
CHO]
3
Al.
CH
R'
R
OH C
CH
3
CH
3
O
C
R'
R
O CH
CH
3
OH
CH
3
[(CH
3
)
2
CHO]
3
Al
+
+

Nu oxy ha alcol bc nht RCH
2
OH s to thnh aldehyd RCHO.
1.2.2. Ozon ha alken
Thy phn hp cht ozonid s thu c aldehyd hoc ceton.
Tin hnh phn ng ozon ha trong dung mi diclometan nhit
thp.Sau ph vng ozonid bng acid acetic v km kim loi thu c aldehyd.
- 78
o
CH
2
Cl
2
Zn
AcOH
+ HCHO
CHO
O O
O
H
H
+ O
3
H

(xem li phn tnh cht ha hc ca alken)
1.2.3. Tng hp oxo (hay gi l hydroformyl ha - Phn ng Rouelle).
227
Di tc dng ca xc tc dicobanoctacarbonyl CO
2
(CO)
8
v p sut, olefin
tc dng vi hn hp H
2
v CO s to thnh aldehyd.
t
o
, p
CO
2
(CO)
8
R CH CHO
CH
3
R CH
2
CH
2
CHO
+CO +H
2
R CH CH
2

1.2.4. Hydrat ha acetylen v alkyn (xem phn hydrocarbon alkyn).
1.2.5. Nhit phn mui ca acid carboxylic (RCOO)
n
M
Khi nhit phn cc mui calci, bari...ca acid carboxylic nhit khong
300
o
C s to thnh ceton.
2RCOO
-
t
o
C
R
R
O + CO
3
2
-
Phn ng Perrier
Nn s dng hn hp 2 mui trong c mui ca acid formic s to aldehyd.
RCOONa + HCOONa RCHO + Na
2
CO
3
t
o

1.2.6. Tng hp aldehyd theo phn ng Rosenmund (1918)
Hydro ha hp cht acylclorid vi xc tc l palladi trn cht mang BaSO
4
.
Aldehyd
Acylclorid
+ HCl
R C
O
H
Pd - H
2
SO
4
+ H
2
R C
O
Cl

1.2.7. Tng hp aldehyd theo phn ng Stephen (1925)
Kh ha hp cht nitril RC N bng thic clorid SnCl
2
trong mi trng acid
thng to thnh aldehyd. Phn ng qua giai on to cht trung gian l aldimin.
Nitril Aldimin
+ NH
3
H
+
H
2
O
- SnCl
4
2HCl SnCl
2
R C
O
H
R CH NH
R C N

1.2.8. Phn ng ca ester vi thuc th Grignard
Ty theo cu to ca ester, khi tc dng vi thuc th Grignard to thnh
aldehyd hoc ceton (xem phn hp cht c kim)
- Mg(OR)X
Aldehyd Ester alkylformiat
R' C
O
H
+ R'MgX
RO C
O
H

228
Acetal Ester alkyl orthoformiat
+ H
2
O (H
+
)
- 2 ROH
C
OR
H
OR R' C
OR
H
OR RO
- Mg(OR)X
Aldehyd
R' C
O
H
+ R'MgX

Ceton
Ester
R
C O
R''
- Mg(OR')X
+ R''MgX
R C
O
OR'

Thuc th Grignard tc dng vi nitril cng to thnh ceton.
R C N
R'MgX
R
C
R'
NMgX
R
C
R'
NH
+ H
2
O
-Mg(OH)X
+ H
2
O ( H
+
)
- NH
3
R
C
R'
O
Nitril
Cetimin

1.2.9. Acyl ha vo nhn thm theo phn ng Friedel -Craft
Xem li phn hydrocarbon thm.
Phn ng acyl ha theo Friedel - Crafts c th xy ra trong ni phn t
to ceton vng.
C
O Cl
O
+ HCl
AlCl
3
3-Phenylpropanoylclorid Indanon-1
1 2
3
4
5
6
7

1.2.10. Phn ng Vilsmeier (1927)
Cc alkylformamid tc dng vi aren, phenol, ether...khi c mt ca
tricloroxydphosphor POCl
3
xy ra phn ng formyl ha v to thnh aldehyd.
Dimethylformamid
+ 3H
2
O
+ +
+ H
3
PO
4
+ (CH
3
)
2
NH + 3HCl
POCl
3
C
O
H
H C
N(CH
3
)
2
O
Aldehyd benzoic

1.3. Tnh cht l hc ca aldehyd v ceton
Aldehyd v ceton l nhng cht lng hoc rn. Ch c aldehyd formic l cht
kh. Aldehyd formic, aldehyd acetic, aceton tan v hn trong nc. Aldehyd v
ceton thng c nhit si thp hn alcol tng ng.
Vch c trng trn quang ph hng ngoi ca nhm carbonyl C = O trong
aldehyd v ceton trong khong 1660-1740cm
-1
. Gi tr gim khi c h thng
lin hp.
229
Bng 19.2: Dao ng ha tr ca nhm carbonyl trong aldehyd v ceton
Aldehyd
c=o
, cm
-1

Ceton
c=o,
cm
-1

R
_
CHO
1720......1740
R
_
CO
_
R
1700......1725
Ar
_
CHO
1695......1715.
Ar
_
CO
_
R
1680......1700
R
_
CH=CH
_
CHO
1680......1705
Ar
_
CO
_
Ar
1660......1670

R
_
CO
_
CH=CH
_
R
1665......1685
1.4. Tnh cht ha hc ca aldehyd v ceton
1.4.1. Cu to v kh nng phn ng ca nhm carbonyl C =O
Nguyn t carbon ca nhm carbonyl trng thi lai ha sp
2
. Nguyn t
carbon v oxy to 1 lin kt v 1 lin kt (Hnh 13-1). di lin kt C =O
l 1,22 A
o

-
-
+ +

C O
o
1,22 A
120
o
C O

+

Hnh 19.1: Cu to nhm carbonyl C = O
Nhm carbonyl c tnh cht khng no v phn cc tr thnh trung tm
tn cng ca nhng tc nhn i nhn. Nhm carbonyl hot ha cc nguyn t
hydro v tr ca gc hydrocarbon. V vy xy ra kh nng enol ha trong cc
hp cht carbonyl c nguyn t hydro linh ng.
Ngc li nhm carbonyl s lm gim kh nng phn ng ca nguyn t
hydro trong nhn thm.
Phn ng ca hp cht carbonyl rt phong ph. C 3 loi phn ng chnh:
Phn ng cng hp vo nhm carbonyl.
Phn ng th vo gc hydrocarbon.
Phn ng oxy -ho kh.
1.4.2. Phn ng cng hp i nhn vo nhm carbonyl
Tc nhn i nhn tn cng vo nhm carbonyl theo cc giai on:
C O
:
..
Y
-
Y C O
..
..
:
-
Y C OH
H
+
+

Mi trng acid thch hp thun li cho phn ng cng hp vo nhm carbonyl.
230
Kh nng cng i nhn vo nhm carbonyl ca aldehyd d hn ceton. Ceton
c hai gc hydrocarbon lm gim mt in tch dng trn nguyn t carbon
v c cn tr khng gian s tng tc ca tc nhn i nhn vo nhm carbonyl.
H
C
H
O
R
C
H
O
R
C
R'
O
1 2 3
> >

+

+

+
1
2
3
> >

Gemdiol
Aldehyd v ceton tc dng vi nc to thnh gem-diol.
R
C
R'
O
R
C
R'
OH
OH
+ H
2
O

Gem-diol l nhng cht khng bn. Phn ng cng nc l phn ng thun
nghch. Nu c nhm ht in t ti gc R ca aldehyd v ceton th gem-diol l
cht bn vng.
C C
O
H
Cl
Cl
Cl
+ H
2
O C C
Cl
Cl
Cl OH
OH
H
Cloral
Cloral hydrat
Cl
3
C CHO. H
2
O

Formaldehyd b hydrat ho gn nh hon ton, trong dung dch nc n tn
ti di dng gem-diol CH
2
(OH)
2
.
Mc hydrat ha ca hp cht carbonyl ty thuc vo cu to.
Bng 19.3: Mc hydrat ha ca mt s hp cht carbonyl
Hp cht
carbonyl
Mc hydrat
HCHO 99,99%
CH
3
CHO 58%
CH
3
COCH
3
0%
C
6
H
5
CHO vt.
Cl
3
CCHO 100%
F
3
CCHO 100%
Acetal v cetal
Cng hp mt mol alcol vi aldehyd hoc ceton s to thnh bn acetal
(hemiacetal, Semiacetal) hoc bn cetal (hemicetal, semicetal).

231
Aldehyd tc dng vi mt mol alcol
;
CH
3
C
O
H
+ CH
3
OH CH
3
C OCH
3
OH
H
Acetaldehyd Methanol Hemiacetal Aldehyd Alcol Hemiacetal
R C OR'
OH
H
+ R'OH R C
O
H

Ceton tc dng vi alcol theo t l 1: 1 v s mol:
;
CH
3
C
O
CH
3
+ CH
3
OH CH
3
C CH
3
OH
OCH
3
Aceton Methanol Ceton Alcol Hemicetal
R C R'
OH
OR''
+ R''OH R C
O
R'

Cng hp 2 mol alcol vi aldehyd hoc ceton s to thnh acetal v cetal.
H+
Acetal Alcol Aldehyd
R C H
OC
2
H
5
OC
2
H
5
+ 2C
2
H
5
OH CH
3
C H
O
;
H+
Acetal
Alcol Aldehyd
R C H
OR'
OR'
+ 2R'OH R C H
O

Kh nng to acetal ph thuc vo cu to ca aldehyd v alcol.
Bng 19.4: Mc acetal ha aldehyd vi cc alcol
Aldehyd Mc
Ethanol Cyclohexanol 2-Propanol
CH
3
_
CHO
78 56 43
(CH
3
)
2
CH
_
CHO
71 - 23
(CH
3
)
3
C
_
CHO
56 26 11
C
6
H
5
_
CHO
39 23 13
Ceton khng tc dng trc tip vi alcol to cetal. C th iu ch cetal
bng cch cho ceton tc dng trc tip vi ester ca acid orthoformic H -C(OR)
3
HCOOC
2
H
5
HC(OC
2
H
5
)
3
Ester Ethylformiat Cetal Ester ethyl ortoformiat
+
+
CH
3
C CH
3
O
CH
3
C CH
3
OC
2
H
5
OC
2
H
5
Ceton

Ceton v aldehyd tc dng vi diol to cetal v acetal vng:
+ H
2
O
O C
C O
C
R
H
H
R'
R
R'
H
+
C
C
H HO
R
R
H HO
+ C
R
R'
O
Ceton 1,2-diol
Cetal vng

232
Acetal v cetal l mt loi hp cht quan trng. Cc acetal v cetal vng c
ng dng iu ch nhng aldehyd v ceton cha no khc.
H
+
Cetal vng
Ceton 1,2-Diol
+
+ H
2
O
HO C
R
C
H
R
H HO
R
C
R'
O
O C
C O
H
H
R
R
R
R'
C

O O
BrCH
2
CH
2
H CH
3
CH
2
C CLi CH
3
CH
2
C C
O O
CH
2
CH
2
H
+ LiBr +

+ HOCH
2
CH
2
CH
2
OH
CH
3
CH
2
C C CH
2
CH
2
CHO
+
+ H
3
O CH
3
CH
2
C C
O O
CH
2
CH
2
H

Khi tng hp cc cht hu c, mun bo v nhm carbonyl ngi ta thng
chuyn n v dng acetal hoc cetal.
Cng hp vi acid cyanhydric HCN to -cyanoalcol hay cyanohydrin.
Acid cyanhydric Cyanohydrin acetaldehyd
C
CN
OH
H CH
3
Acetaldehyd
CH
3
C
O
H
+ HCN

Acid cyanhydric Aceton Cyanohydrin aceton
CH
3
C CH
3
HO
CN
+ HCN
CH
3
C
O
CH
3

Phn ng cng hp HCN vi aldehyd hoc ceton phi c xc tc base. Base
lm tng nng tc nhn i nhn
-
CN. Hp cht cyanohydrin c dng
iu ch acid hydroxycarboxylic (hydroxyacid) RCH(OH)CN RCH(OH)COOH.
Cng hp vi natrihydrosulfit (NaHSO
3
)
Aldehyd v ceton (methylceton) tc dng vi dung dch m c
natrihydrosulfit to thnh sn phm cng trng thi tinh th gi l hp cht
hydrosulfitic.
Hydrosulfitic benzaldehyd Natri hydrosulfit Benzaldehyd
C
6
H
5
CH
OH
SO
3
Na
+ NaHSO
3
C
6
H
5
C
O
H

233
Hydrosulfitic Aceton
Natri hydrosulfit
+ NaHSO
3
CH
3
O
C CH
3
Aceton
CH
3
C CH
3
OH
SO
3
Na

Hp cht hydrosulfitic thc cht l mui ca acid -hydroxysulfonic
RCH(OH) SO
3
H. V nguyn t lu hunh c tnh i nhn mnh tc dng vi
nguyn t carbon ca nhm carbonyl theo c ch :
+ -
R C R'
OH
SO
3
Na
- +
:
S O Na
O
OH
Hydrosulfitic Ceton
Natri hydrosulfit
+
R'
O
C R
Ceton
R C R'
O
SO
3
H
Na

Hp cht hydrosulfitic d b thy phn trong mi trng acid to thnh hp
cht carbonyl ban u v SO
2
. V vy phn ng cng hydrosulfitic c dng
tch aldehyd hoc ceton ra khi hn hp.
Aldehyd tc dng vi thuc th Schiff (acid fucsinsulfur) to dung dch c
mu hng. Phn ng vi thuc th Schiff ch c trng cho aldehyd.
Cng hp vi hp cht c kim. (Xem phn hp cht c kim).
Hp cht carbonyl cng hp vi ion acetylid to hp cht etynyl carbinol c
ng dng iu ch alcol loi allylic.
O
H C C Na
-
+
ONa
C C H
OH
C C H
NH
3
-33
o
H
3
O
+
Cyclohexanon Etynyl pentamethylen carbinol

Ceton
R'
O
C R
+
:
Na C C H
-
+
C R R'
C C H
O H
Na O
H C C
R' R C
NH
3
-33
o
H
3
O
+
Etynyl dialkyl carbinol

Phn ng cng hp vi cc hp cht c nhm methylen linh ng.
Phn ng aldol ho:
Cc nguyn t hydro v tr trong gc hydrocarbon ca aldehyd v ceton
rt linh ng. Hai phn t aldehyd trong mi trng base long ngng t vi
nhau to hp cht aldol (hp cht c chc aldehyd v chc alcol)
Aldehyd
Aldol
2
HO
-
R CH
2
CH CH CHO
OH
R
R CH
2
CHO

234
C ch aldol ha:
Lin kt C
_
H v tr so vi nhm carbonyl c hydro linh ng tc dng
vi HO
-
to carbanion RC
-
HCHO. Carbanion ny l tc nhn i nhn cng hp
vo nhm carbonyl ca phn t aldehyd th 2 v to thnh hp cht aldol.
R CH
2
C
O
H
CH CHO
R
-
+ R CH
2
CH
O
R
CHO CH
-
R CH
2
CH
R
CHO CH
OH
+H
2
O
+ HO
-

Trong hp cht aldol cn hydro linh ng v tr , di tc dng ca nhit
, aldol b loi mt phn t nc to aldehyd cha no.
+ H
2
O R CH
2
CH C
R
CHO
R CH
2
CH
OH
CH
R
CHO

Phn ng loi nc t aldol theo c ch trn gi l phn ng croton ha.
Phn ng aldol ha cng xy ra gia 2 phn t aldehyd khc nhau.Trong
mt aldehyd c hydro v phn t kia khng c hydro .
Aldehyd cinnamic
Aldol
Acetaldehyd Benzaldehyd
t
o
C
6
H
5
CH CHCHO C
6
H
5
CH
OH
CH
2
CHO
HO
-
+ CH
3
CHO C
6
H
5
CHO

Phn ng ngng t aldol xy ra gia acetaldehyd v formaldehyd to thnh
pentaerythrid (c phn ng Cannizaro cho).
Acetaldehyd Formaldehyd
Pentaerythrid
- HCOOH
HCHO,H
2
O
HO CH
2
C
CH
2
OH
CH
2
OH
CH
2
OH
HO CH
2
C
CH
2
OH
C
CH
2
OH
O
H
Ca(OH)
2
+ CH
3
C
O
H
3H C
O
H
Phn ng aldol
Phn ng Cannizaro cho

Hai phn t ceton cng xy ra phn ng kiu ngng t aldol nh aldehyd.
2
CH
3
C
CH
3
OH
CH
2
C CH
3
O
CH
3
C CH
3
O
HO
-
Aceton 4-Hydroxy-4-methylpentanon-2

Phn ng ngng t aldol cng xy ra gia aldehyd v ceton.
Cyclohexanon Benzaldehyd
+ H
2
O
25
o
10 ngay
4 gi
25
o
O
OH O
-
OH
+

O
H
CHO

235
Aceton Benzaldehyd (Benzalaceton) 4-Phenyl-3-butenon-2
+
-H
2
O
HO
-
CH CH C CH
3
O
CH
3
C CH
3
O
C
O
H

Phn ng ngng t aldol cng xy ra khi c xc tc acid. C ch xy ra qua
giai on to enol. Khi aldehyd tc dng vi ceton, ceton thng ng vai tr c
hydro linh ng v tr (thnh phn metylen) to carbanion - tc nhn cng
i nhn.
Cc aldehyd - ceton tc dng vi cc dn xut ca acid carboxylic.
Phn ng Perkin:
Phn ng ca aldehyd thm vi anhydrid acetic v natri acetat.
Acid cinnamic Benzaldehyd
+ CH
3
COOH
CH
3
COONa
+ (CH
3
CO)
2
O
CHO
CH = CHCOOH

C ch: Natri acetat ng vai tr xc tc base to cabanion - tc nhn i nhn.
-
CH
2
CO O COCH
3
+ CH
3
COOH
H CH
2
CO O COCH
3
CH
3
COO
-
+

+ CH
3
COO
-
CH CH
2
CO O COCH
3
OH + -
CH
O
CH
2
CO O COCH
3
CHO
-
CH
2
CO O COCH
3
+ CH
3
COOH

+ CH
3
COOH
CH CH
2
CO O COCH
3
OH
+ H
2
O
CH CHCO O COCH
3
- H
2
O
CH CHCOOH

Phn ng Perkin ch xy ra i vi aldehyd thm.
Phn ng Knoevenagel:
Cc aldehyd tc dng theo kiu ngng t croton vi acid malonic, cc hp
cht c hydro linh ng nh CH
3
_
CN, CH
3
_
NO
2

CHO
+
- H
2
O
H
2
C
COOH
COOH
CH CH
COOH
COOH
CH CH COOH
+ CO
2
Amin
Acid malonic Acid Cinnamic

Phn ng ngng t benzoin
Khi c mt KCN lm xc tc, cc aldehyd thm tham gia phn ng c
trng to hp cht mang chc -CH(OH)-CO- gi l phn ng ngng t benzoin.
236
C
O
H
+
C
H
O
-
CN C
OH
H
C
H
O
Benzaldehyd Benzoin

C ch phn ng:
Anion
-
CN cng vo nhm carbonyl ca aldehyd to thnh cyanhydrin.
Cyanhydrin cng vo nhm carbonyl ca phn t aldehyd th hai.
C H
O
CN
-
C H
O
CN
-
C
C N
OH
-
C
O
H
+ +

Cc aldehyd khng thm RCHO khi c mt ca KCN ch tham gia phn ng
aldol ha. Ring i vi aldehyd formic khi c mt Ca (OH)
2
hoc TiOH c th
Acyloin ha, nhng sn phm ny li aldol ha to thnh hexose.
Acyloin ha A
HO CH
2
CH O
Ca(OH)
2
H CHO + H CHO

HO CH
2
CH O HO CH
2
CH O HO CH
2
CH O
C
6
H
1

2
O
6
Aldehyd glycolic Hexose
Aldol hoa
+
+

Phn ng cng hp vi cc cht c chc amin - NH
2

Hp cht c dng tng qut Z -NH
2
trong mi trng acid hoc base thch
hp cng hp i nhn vo nhm carbonyl ca aldehyd v ceton. Sn phm cng
hp thng khng bn, d b loi mt phn t nc v to thnh cc loi hp cht
khc nhau.
R
C O
(H) R'
+ NH
2
_
Z
R
C
(H) R'
NH Z
OH
H
+ R
C
(H) R'
NH Z
OH
2
+
H
+
- H
2
O

+
R
C
(H) R'
NH Z
R
C
(H) R'
NH Z
R
C
(H) R'
NH Z
+
- H
+

Trong bng 19-5 trnh by cc loi hp cht ca phn ng dng ny. Ch in
m l tn ca nhm chc to thnh.
Trong phn t hydrazon RCH=N-NH
2
c nhm -NH
2
t do c th tc dng
vi phn t c nhm carbonyl v to thnh hp cht azin RCH=NN=CHR'.
RCH=N
_
NH
2
+ O=CHR' RCH=N
_
N=CHR' + H
2
O
237
Bng 19-5: Sn phm cng - tch ca Aldehyd -Ceton vi hp cht Z- NH
2

RCHO hay RCOR' Z-NH
2
Sn phm phn ng
C
6
H
5
CHO Benzaldehyd NH
2
OH Hydroxylamin
C
6
H
5
CH=N
_
OH Oxim.
Benzaldoxim
CH
3
COCH
3

Aceton
NH
2
OH (CH
3
)
2
C=N-OH Cetoxim
Acetoxim
C
6
H
5
COCH
3
Acetophenon
NH
2
NH
2
Hydrazin
C
6
H
5
C
CH
3
N NH
2
Acetophenon hydrazon
Hydrazon

C
6
H
5
CHO

Benzaldehyd NH
2
NH
2
Hydrazin
C
6
H
5
CH=N
_
NH
2
Hydrazon
Benzaldehyd hydrazon
C
6
H
5
CHO

Benzaldehyd NH
2
NHCONH
2

Semicarbazid
C
6
H
5
CH=N
_
NHCONH
2
Carbazon

Benzaldehyd semicarbazon

O
Cyclohexanon

NH
2
NHCONH
2

Semicarbazid
C N NH C NH
2
O
Cyclohexanon semicarbazon

C
6
H
5
CHO

Benzaldehyd NH
2
R Amin bc nht
C
6
H
5
CH=N
_
R Imin
Benzadehyd imin
C
6
H
5
CHO

Benzaldehyd
NH
2
NHC
6
H
5

Phenylhydrazin
C
6
H
5
CH=N
_
NHC
6
H
5
Phenylhydrazon

Benzaldehyd phenylhydrazon

C
6
H
5
CHO

Benzaldehyd
NH NH
2
N O
2
N O
2
2,4-Dinitrophenylhydrazin

NH N CHC
6
H
5
NO
2
NO
2
2,4-dinitrophenylhydrazon
Benzaldehyd
Hp cht aldoxim v cetoxim c ng phn hnh hc syn v anti.
Khi c xc tc thch hp cc cetoxim b chuyn v Beckmann to thnh amid th.
C
6
H
5
(CH
3
)C=NOH CH
3
CONHC
6
H
5

Acetophenon oxim Acetanilid
Aldehyd formic tc dng vi amoniac to hexamethylen tetramin.
Hexamethylen tetramin (urotropin) l cht rn c cng thc (CH
2
)
6
N
4
.
6 HCHO + 4 NH
3
(CH
2
)
6
N
4
+ 6 H
2
O
238
Hexamethylen tetramin
( Urotropin )
CH
2
N
CH
2
N
CH
2
N
N
CH
2
CH
2
CH
2
N N
N
N

Phn ng trng hp
Phn ng trng hp ch xy ra mt s aldehyd khng vng u dy ng
ng. Aldehyd formic trng thi kh b trng hp to thnh trimer dng vng.
+
+
+
Trioxymethylen Aldehyd formic
CH
2
O
O
CH
2 CH
2
O
CH
2
O
CH
2
O
O
CH
2

trng thi dung dch 40% trong nc (dd formalin), aldehyd formic b
trng hp thnh polymer khng vng kt ta trng gi l polyoxymethylen hay
paraformaldehyd.
n CH
2
=O (CH
2
O)
n
n = 10 -

100
Acetaldehyd cng b trng hp nhit thp khi c mt ca acid to
paraldehyd v metaldehyd.
Paraldehyd
CH
O
CH
O
CH
O
CH
3
CH
3
H
3
C
Metaldehyd
O CH
O
CH
O CH
O
CH CH
3
CH
3
H
3
C
CH
3

C th thu acetaldehyd bng cch un nng paraldehyd v metaldehyd vi acid.
Phn ng Wittig
Aldehyd tc dng vi alkylhalogenid c xc tc l hn hp triphenylphosphin v
lithi butyl to thnh alken c cu trc lp th xc nh.
1-Phenyl-1-propen
Z
E
Propylbromid Benzaldehyd
Ether
, C
4
H
9
Li (C
6
H
5
)
3
P
+ + C C
H
CH
2
CH
3
C
6
H
5
H
C C
CH
2
CH
3
H
C
6
H
5
H
C
6
H
5
CHO CH
3
CH
2
CH
2
Br

239
C ch phn ng:
CH
3
CH
2
CH
2
Br + (C
6
H
5
)
3
P
C
4
H
9
Li
(C
6
H
5
)
3
PCH
2
CH
2
CH
2
Br
+
-
(C
6
H
5
)
3
P=CHCH
2
CH
3
+ LiBr + C
4
H
10
Ether

C C
CH
2
CH
3
H
C
6
H
5
H
+ (C
6
H
5
)
3
P
(C
6
H
5
)
3
P=CHCH
2
CH
3
+ C
6
H
5
CHO

Phn ng Mannich (1917)
L phn ng aminometyl ho. Gn thm nhm (R)
2
NCH
2
- vo ceton.
Ceton c nguyn t hydro linh ng tc dng vi hn hp aldehyd formic
v amin (bc mt, bc hai) trong mi trng acid to thnh alkylaminoalkylceton.
R
_
CO
_
CH
3
+ HCHO + HN(R)
2
R
_
CO
_
CH
2
CH
2
N(R)
2
+ H
2
O
H
+

C ch phn ng:
H
+
H C
O
H
+ HN(R)
2
CH
2
OH
NR
2
CH
2
NR
2
+ ..
- H
2
O
CH
2
NR
2
+
Amin

..
- H
+
+
+
R C
O
CH
3
OH
CH
2
C R CH
2
NR
2
OH
CH
2
C R CH
2
NR
2
+
O
CH
2
C R CH
2
NR
2
Methylceton
Alkylaminoalkylceton

1.4.3. Phn ng kh
Aldehyd hay ceton b kh ha to thnh alcol bc nht v alcol bc hai.
;
[ H ]
Alcol bac nhat Aldehyd
R CH
2
OH
R C
O
H
R C
O
R'
R CHOH R'
Ceton
Alcol ba c hai
[ H ]

Cc tc nhn kh l: Cc hydrid kim loi (LiAlH
4
, NaBH
4
), H
2
/ xc tc.
Kh ha aldehyd v ceton bng hydrid kim loi:
Hydro trong hp cht hydrid kim loi c in tch m H
-
. C th xem ion
hydrid l tc nhn i nhn tc dng vo nguyn t carbon ca nhm carbonyl
to lin kt C
_
H.
Alcol Allylic
Aldehyd Acrylic
Ether
+ LiAlH
4
H
+
+ Li
+
+ Al
3+
+ H
2
CH
2
CH CH
2
OH CH
2
CH CHO

240
O
1) LiAlH
4
2) H
+
OH
2- Cyclohexenon 2- Cyclohexenol

Ester ethyl-4-hydroxypentanoat Ester ethyl-4-oxopentanoat
1) NaBH
4
CH
3
CH CH
2
CH
2
COOC
2
H
5
OH
CH
3
C CH
2
CH
2
COOC
2
H
5
O
2) H
+

4-Hydroxybutyronitril
3-Cyanpropionaldehyd
C CH
2
CH
2
CHO N C CH
2
CH
2
CH
2
OH N
1) NaBH
4
2) H
+

Cc lithi nhm hydrid, natri bo hydrid l nhng cht kh c tnh chn lc
cao. Cc hydrid kim loi ny ch kh ha chc carbonyl m khng kh ha cc
nhm chc c ni i, ni ba khc nh -HC=CH-, -CC-, -CN, -COOR.
LiAlH
4
phn ng rt mnh v gii phng hydro, thng tin hnh phn ng
trong dung mi ether.
NaBH4 tc dng nh nhng v tin hnh phn ng trong mi trng nc -alcol.
C th s dng cht kh l diboran B
2
H
6
kh nhm carbonyl. Nhng
diboran khng ch kh chc carbonyl m cn kh c lin kt i C =C.
Kh ha bng hydro phn t c xc tc
Aldehyd v Ceton c th b kh ha bng hydro phn t c xc tc kim loi
(Pt, Ni, Pd) to alcol tng ng.
Xuc tac
CH
2
CH CHO CH
3
CH
2
CH
2
OH
+ 2H
2
Aldehyd acrylic Alcol propylic

+ 2H
2
Xuc tac
Cyclohexenol 2- Cyclohexenon
OH
O

Cc lin kt i C =C cng ng thi b kh ha
Kh ha bng kim loi
Kh ha pinacon
Kh ha aldehyd hoc ceton bng kim loi (Na, Mg) to thnh hp cht 1,2-
diol. y l phng php in ha. Cht kh l in cc kim loi.
C
CH
3
CH
3
O CH
3
C C CH
3
OH
CH
3
OH
CH
3
2
Na
+ 2H
+
Aceton Pinacon

241
Hydrobenzoin
Benzaldehyd
+ 2H
+
Na
2 C
6
H
5
C C C
6
H
5
OH OH
H H
C
6
H
5
C
O
H

C ch kh ha pinacon:
CH
3
C C CH
3
HO
CH
3
CH
3
OH
-
-
: : : :
..
..
2
- ..
.
..
:
2 Na-2e
-2 Na
+
+ 2H
+
2
CH
3
C C CH
3
O
CH
3
O
CH
3
C
CH
3
CH
3
O
C
CH
3
CH
3
O

Kh ha Clemmensen (1913)
Hn hng km trong mi trng acid HCl m c kh ha aldehyd -ceton
to hydrocarbon tng ng.
C
R'
O
R
CH
2
R'
R
+ 2Zn + 4H
+ + 2 Zn
2+
+ H
2
O
Ceton
Hydrocarbon

R CH
3
Hydrocarbon
Aldehid
+ 2 Zn
2+
+ H
2
O + 2Zn + 4H
+
R C
O
H

Khi kh ha Clemmensen lin kt i C =C cng b kh theo.
Oxy ha bng cc tc nhn oxy ha v c
Cc aldehyd b oxy ha to thnh acid carboxylic.
Acid
[ O ]
R C
O
OH
R C
O
H
Aldehyd

Cc cht oxy ha l Ag
2
O, H
2
O
2
, KmnO
4
, CrO
3
, Cu(OH)
2
.
CHO
COOH
+ Ag
2
O + 2 Ag
THF
H
2
O

Phn ng ca aldehyd vi dung dch AgNO
3
trong amoniac to Ag kim loi
v acid hu c (phn ng Tollens). Phn ng ca aldehyd vi thuc th Fehling
to oxyd ng Cu
2
O c mu gch. Nhng phn ng ny c dng nh tnh
hp cht c chc aldehyd. Cc ceton ch b oxy ha bng cc cht oxy ha mnh,
mch carbon b ct t to thnh acid.
242
O
HNO
3
V
2
O
5
HOOC(CH
2
)
4
COOH
Cyclohexanon
Acid Adipic

Phn ng Cannizaro
Aldehyd khng c nguyn t hydro v tr , c bit l aldehyd thm, di
tc dng ca hydroxyd kim, kim th m c to thnh alcol v acid (aldehyd
c nguyn t hydro ch tham gia phn ng aldol ha).
+
Ar C
O
H
Alcol thm
+ Ar CH
2
OH
Aldehyd thm
Ar C
O
H
Ar C
O
OH
Acid

Nu hai aldehyd khc nhau u khng c nguyn t hydro v tr , tham
gia phn ng loi ny gi l phn ng Cannizaro cho.
HO
-
+ Ar C
O
H
Alcol thm
+ Ar CH
2
OH
Aldehyd thm
H C
O
H
H C
O
OH
Acid formic

C th xem phn ng Cannizaro l phn ng oxy ha -kh hay l phn ng
chuyn hydrid H
-
t nguyn t carbon ca nhm aldehyd ny n nguyn t
carbon ca chc aldehyd kia. C ch xy ra nh sau:
Ar C
O
H
OH
Ar C
O
H
+
-
OH
: -
:
..
..
:

II II
I
I II
I -
+ +
..
:
: :
..
..
..
:
Ar C
O
O
Ar CH
2
OH Ar CH
2
O Ar C
O
OH
Ar C
O
H
OH
Ar C
O
H
+
:
-
:
..
..
:
-
..
..

Trong phn ng Cannizaro cho, aldehyd formic ng vai tr chuyn hydrid H
-.

Phn ng Meerwein -Pondorf-Oppenauer
un nng aldehyd hay ceton trong dung dch isopropanol c xc tc l
isopropylat nhm th to thnh alcol bc nht hoc alcol bc hai.
Alcol bac hai Ceton
+ +
[(CH
3
)
2
CH
_
O]
3
Al
C
CH
3
O
CH
3
CH
R'
OH
R
CH
CH
3
OH
CH
3
C
R'
O
R

y l phn ng oxy ha - kh c nhiu ng dng trong cc phn ng ca
hp cht t nhin chuyn ha chc aldehyd, ceton thnh alcol.
243
Nu cho aldehyd tc dng vi nhm alcolat th to ester (phn ng Claisen -
Tishenco).
Ester
2
R C
O
OCH
2
R
(RCH
2
O)
3
Al
R C
O
H
Aldehyd

Nhng phn ng ny c th xem l phn ng chuyn dch hydrid H- t
isopropylat nhm [(CH
3
)
2
CHO]
3
Al, alcolat nhm (RCH
2
O) 3Al sang carbon ca
nhm carbonyl trong aldehyd-ceton.
1.4.5. Phn ng th. Phn ng halogen ha
Tc dng vi HCl
Acid HCl cng vi Aldehyd - Ceton to hp cht 1,1-clorhydrin kh tch
ring trng thi tinh khit. y l phn ng thun nghch.
CH
3
C
O
CH
3
CH
3
C CH
3
OH
CH
3
C CH
3
Cl
OH
+ HCl + Cl
-
Aceton
2-Cloropropanol
+

Trong dung dch alcol, t 1,1-halogenhydrin to thnh -halogeno ether. -
halogeno ether tch ring c khi hn hp phn ng.
Clomethylmethylether
+ H
+
H
2
C
OCH
3
Cl
+
H
2
C
OCH
3
Cl
H
+
H
2
CCl + CH
3
OH

Tc dng vi PCl
5
v PBr
3

Aldehyd v Ceton tc dng vi phosphor pentaclorid hoc phosphos tribromid
to gem -dihalogen.
CH
3
CH
2
C
O
CH
3
+ PCl
5
CH
3
CH
2
C CH
3
Cl
Cl
+ POCl
3
2,2-Diclobutan
Butanon-2

1,1-Diclo-3-methylbutan 3-Methylbutyraldehyd
+ + (CH
3
)
2
CHCH
2
CHCl
2
POCl
3
(CH
3
)
2
CHCH
2
CHO PCl
5

Phn ng Haloform
Acetaldehyd v metyl ceton tc dng vi Natri hypohalogen NaOX to
haloform.
244
Bromoform
Methylceton
CHBr
3
+ RCOONa
+ 3NaOBr
R C CBr
3
O
+ 3NaOBr
R C CH
3
O
Iodoform Acetaldehyd
+ 3NaOI + 3NaOI
CHI
3
+ HCOONa CI
3
CHO
CH
3
CHO

ng dng phn ng ny nh tnh acetaldehyd v methylceton. Ngi ta
thng tin hnh phn ng vi hn hp halogen, KOH v KI.
Tc dng vi halogen
Ceton tc dng vi halogen c xc tc nh sng, phn ng th halogen xy
ra i vi hydro v tr .
R C
O
CH
3
+ Br
2
R C
O
CH
2
Br
+ HBr
h

2. Aldehyd - ceton cha no
Aldehyd - ceton cha no c hai loi:
Aldehyd - ceton cha no lin hp: RCH=CHCH=O, RCH=CHCOR'
Aldehyd - ceton cha no khng lin hp: RCH=CH(CH
2
)
n
CH=O,
RCH=CH(CH
2
)
n
COR'.
Aldehyd hoc ceton cha no lin hp hoc khng lin hp c cng s nguyn
t carbon l ng phn ca nhau.
CH
2
=CH-CH
2
-CH=O CH
3
-CH=CH-CH=O
Vinylacetaldehyd Crotonaldehyd H = -6 kcal.mol
-1
(ng phn khng lin hp) (ng phn lin hp)

ong phan cha no ,
CH
2
C
H
O
CH C
H
OH
C C
(Kem ben)
C
H
O
C C H C C
CH

ong phan cha no ,
ong phan dang enol
(Rat ben)

Nguyn t hydro ca nhm methylen (-CH
2
-) trong phn t vinylacetaldehyd
rt linh ng, v n trn carbon v tr so vi nhm carbonyl. Vinylacetaldehyd
c s enol ha. Ion enolat c n nh v c hin tng cng hng. (S enol ha
d xy ra trong mi trng kim).
245

Anion tip nhn proton ca H
2
O. Proton ca nc tng tc trn oxy thu c dng
enol; tng tc vo carbon th to butenal -3, nu xy ra carbon v tr thu c
crotonaldehyd. Trong mi trng base s cn bng chuyn v pha to crotonaldehyd l ch
yu (99,99%). S ngng t aldol ca aldehyd hoc ceton trong mi trng base hoc acid
thng to thnh hp cht aldehyd, ceton cha no ,.

4-methyl-3- penten-2- on
(mesytyl oxyd)
H
2
O
H
2
SO
4
H
2
O
CH
3
+
2 CH
3
COCH
3
CH
3
C=CHCOCH
3

C ch phn ng:

+ H
+
CH
2
C
OH
CH
3
CH
3
C
OH
+
CH
3 + H
+
CH
3
COCH
3

CH
2
= C
_
CH
3
OH
CH
3
_
C
OH
+
+
CH
3
_
C
_
CH
2
OH

_
C
_
CH
3
OH
+
CH
3
.
.
CH
3
CH
3
_
C
_
CH
2
OH

_
C
_
CH
3
O
CH
3
+
H
+

Hoac:
+
OH
CH
3
C
_
CH
3
OH
2
CH
3
_
C
_
CH =
+
H
+
H
+ - H
+
OH
CH
3
C
_
CH
3
OH
CH
3
_
C
_
CH =
CH
3
+
OH

_
C
_
CH
3
OH
CH
3
_
C
_
CH
2
+

+
+
+
OH
CH
3
C
_
CH
3
CH
3
_
C= CH
_
OH
CH
3
C
_
CH
3
CH
3
_
C= CH
_
OH
CH
3
C
_
CH
3
CH
3
_
C
_
CH =
+
H
2
O
+
OH
CH
3
C
_
CH
3
OH
2
CH
3
_
C
_
CH =

246
CH
3
_
C= CH
_
C
_
CH
3
CH
3
OH
+
CH
3
_
C= CH
_
C
_
CH
3
CH
3
O
+
H
+

Aldehyd v ceton cha no , cng c th c iu ch bng cch oxy ha
cc alcol cha no tng ng (trong iu kin lin kt i khng b oxy ha). Cc
alcol cha no c iu ch theo phng php Grignard.
(80%) Retinal
(Vitamin A
1
)
Retinol
Ether dau hoa
CH
3
CHO
CH
3
CH
3
CH
3
CH
3
CH
3
CH
2
OH
CH
3
CH
3
CH
3
CH
3
MnO
2

2.1. Tnh cht ca aldehyd - ceton cha no
Aldehyd - ceton cha no lin hp th hin cc phn ng:
2.1.1. Phn ng cng hp
Aldehyd - ceton cha no , th hin tnh cht ca mt alken (tnh cht ca
lin kt C =C) cng nh tnh cht ca nhm carbonyl.
CCl
4
(52-57%)
C
6
H
5
CH=CH
_
CO
_
CH
3
+ Br
2
C
6
H
5
CHBr
_
CHBr
_
CO
_
CH
3
(52-57%)
(10-20
o
)

CH
2
= CH
_
CHO

+ Ag
2
O CH
2
= CH
_
COOH + 2 Ag

Phn ng cng hp xy ra trn 1 lin kt i (Cng hp 1, 2 thng thng)
hoc 2 u ca h lin hp (Cng hp 1, 4 do lin hp).
Cng hp 1,2
C C C O + X Y C
X
C C O
Y
hay C C C O
X Y

Cng hp 1,4
C C C O + X Y C
X
C C O
Y

V d: Cng hp 1,2
C
6
H
5
CH = CH
_
C
_
C
6
H
5
O
C
6
H
5
CH
_
CH
2

_
C
_
C
6
H
5
O
(93-96%)
KCN
CH
3
COOH
+
CN

247
O
H
O
H
CN
HCN
(C
2
H
5
)
3
Al
(85%)
+

V d: Cng hp 1,4:
Acrolein (aldehyd acrylic)
- +
CH
2
=CH
_
CH
_
O
-
+
CH
2
_
CH=CH
_
O CH
2
=CH
_
CH=O

-Methylthiolpropionaldehyd
Methylmercaptan (Metanthiol)
CH
3
S
_
CH
2
_
CH
2
_
CHO
CH
3
S
_
CH
2
_
CH=CH
_
OH + CH
3
SH
Acrolein
CH
2
=CH
_
CH=O

Cng hp Diels -Alder:
O
CH
2
2-Formyl-2,3-dihydropyran
Aldehyd acrylic
O
CHO
+
CH
2
CHO

Ty thuc iu kin, cc hp cht c kim s c cng hp 1, 2 hoc 1, 4 vi
thuc th Grignard. Yu t lp th l quyt nh chiu hng ca phn ng.
Cng hp1,2
+
H
H
CH
3
C = C
C
_
CH
3
O
CH
3
MgBr
H
H
CH
3
C = C
C(CH
3
)
2
OH
H
3
O
2-Methyl trans 3- penten-2- ol
(80%)
+

Cng hp1,4
+
O
+
C
6
H
5
CH = CH
_
C
_
C
6
H
5
O
CH
_
CH
2
_
C
_
C
6
H
5
C
6
H
5
C
6
H
5
C
6
H
5
MgBr
H
3
O
1,3,3-triphenyl-1- propanon

Hp cht c lithi c khuynh hng cng hp 1,2:
+
75%
OH
H
3
O
C
6
H
5
Li
C
6
H
5
CH = CH
_
C(C
6
H
5
)
2 C
6
H
5
CH = CH
_
C
_
C
6
H
5 +
O

Hp cht lithi dialkyl ng (hp phc) thng to ra sn phm cng hp 1,4:
CH
3
C = CH
_
C
_
CH
3
O
(CH
2
= CH)
2
CuLi
CH
2
= CH
_
C
_
CH
2
_
C
_
CH
3
O CH
3
CH
3
+
+
H
3
O
72%
CH
3

248
2.1.2. Phn ng kh ha
Kh ha hp cht carbonyl cha no , c th xy ra lin kt i (C=C)
hoc vo nhm carbonyl (C=O). Cht kh l LiAlH
4
cng vo nhm carbonyl.
(97%)
H
2
O
OH
H
O
LiAlH
4
Ether
+

+
(59%)
+
C
2
H
5
OH
NaBH
4
O
OH
H
OH
H
(41%)

Kh ho bng hydro c xc tc xy ra ch lin kt i (C=C)
H
2
(100%)
+
CH
3
O
CH
3
H
O
Pd-C

2.2. ng dng ca cc hp cht aldehyd -ceton cha no
Citral:
L mt aldehyd cha no c 2 lin kt i. Gi tn theo danh php IUPAC l
3,7-dimethyl-2,6-octadienal. Citral ngng t vi aceton to -ionon l sn phm
trung gian trong cng nghip tng hp vitamin A.
CHO
CH
3
CH
3 CH
3
CH
3 CH
3
CH
3
CH
3
O
CH
3
CH
3
CH
3
O
CH
3
+ CH
3
COCH
3
HO
-
BF
3
Citral
-Ionon

Aldehyd cinnamic:
L thnh phn ch yu ca tinh du qu.
Aldehyd cinnamic
CH CH CHO

Metylvinylceton:
L mt ceton lin hp; th hin tnh cht cha no:
HCl CH
2
=CH
_
CO
_
CH
3
ClCH
2
_
CH
2
_
CO
_
CH
3
+
Methylvinylceton -Cloroetylmethylceton

249
Cc ceton lin hp b hydro ha rt chn lc. Vi H
2
c xc tc, nhm
carbonyl khng b hydro ha. Khi tc dng vi NaBH
4
ch c nhm carbonyl b
kh ha:
Pt
H
2
CH
3
_
CH
2
_
CO
_
CH
3
NaBH
4
CH
2
=CH
_
CO
_
CH
3
CH
2
=CH
2
_
CHOH
_
CH
3
Methylvinylceton

Cc ceton lin hp c th tham gia phn ng ng vng vi mt s ceton khc:
R
O
O
R
O
O
O
O
R
R
Base
HO
-
Aldol
O
O
R
R
+

3. Aldehyd - ceton a chc
Trong phn ny ch cp nhng hp cht c 2 nhm carbonyl. l nhng
hp cht dialdehyd, diceton v hp cht ceton aldehyd.
3.1. Hp cht 1,2-Dicarbonyl (-1,2-Dicarbonyl)
Glyoxal (Aldehyd oxalic: CHO-CHO)
iu ch glyoxal bng phng php oxy ha paraaldehyd bng selen dioxyd
SeO
2
hoc oxy ha 1,2-etadiol bng oxy ca khng kh c Cu l xc tc nhit
250-300
o
C.
Diacetyl (Butadion-2,3: CH
3
_
CO
_
CO
_
CH
3
)
Diacetyl ngng t vi hydroxylamin to diacetyldioxim (dimetylglyoxim).
Dimetylglyoxim tc dng vi ion niken to phc, kh tan, mu .
+
+
Phc niken ( mau o )
Dimetylglyoxim
H
H
+
N
O
H
C
C
N
O
CH
3
CH
3
-
: : : :
..
: : :
..
:
-
+
O
N
Ni
N
O
H
C
C
N
O
H
O
N
C
C
CH
3
CH
3
CH
3
CH
3
: :
: :
..
: :
:
..
:
+
O
N
H
O
N
C
C
CH
3
CH
3
Ni
+

Dibenzoyl (1,2-Diphenyletandion - Benzyl: C
6
H
5
_
CO
_
CO
_
C
6
H
5
)

Oxy ha benzoin thu c dibenzoyl. Dibenzoyl l tinh th mu vng, nhit
nng chy 95
o
C. Kh ha dibenzoyl trong cc iu kin khc nhau th thu c
cc sn phm khc nhau.
250
C
6
H
5
C C C
6
H
5
O O
C
6
H
5
CH
2
CO C
6
H
5
C
6
H
5
CH
2
CH
2
C
6
H
5
C C
H
C
6
H
5
C
6
H
H
Desoxybenzoin
Trans-Stylben
1,2-Diphenyletan
4H [ Sn/HCl]
6H [Zn/Hg. HCl]
4H
2
/Ni
-H
2
O
-2H
2
O
- 2H
2
O
Dibenzoyl

Methylglyoxal (2-oxopropanal: CH
3
-CO-CHO)
Methylglyoxal c iu ch bng cch oxy ha 2-oxopropanol (1-
hydroxypropanon, hydroxyaceton) bng selen dioxyd.
Methylglyoxal
2-Oxopropanol
SeO
2
CH
3
C CHO
O
CH
3
C CH
2
OH
O

Methylglyoxal l sn phm trung gian trong chuyn ha carbohydrat.
3.2. Hp cht 1,3-dicarbonyl (-dicarbonyl: R-CO-CH
2
-CO-R)
3.2.1. iu ch
Phng php quan trng iu ch hp cht 1,3-dicarbonyl l phn ng
ngng t Claisen. Ceton tc dng vi ester ca acid carboxylic trong iu kin c
mt base hu c nh alcolat natri RO
-
, natri amidid NaNH
2
...
Acetoaceton (petandion,2,4) Ester alkylacetat
Aceton
+
R'O
-
+ ROH CH
3
C CH
2
O O
CH
3
C CH
3
C OR
O
CH
3
C CH
3
O

C ch phn ng:
CH
3
C CH
3
O
-R'OH
R'O
-
+
Aceton
CH
3
C CH
2
O
-
: :
: :
CH
3
C CH
2
O : :
..
-
Carbanion

CH
3
C CH
2
O O
CH
3
C
CH
3
C
O
OR
-RO
:
..
-
CH
2
C CH
3
O
CH
3
C
O
OR
O
CH
3
C CH
2
: : : :
: :
:
: :
: : : :
..
..
-
-

3.2.2. Tnh cht ha hc
Tnh cht h bin
Hp cht 1,3-dicarbonyl c dng h bin (tautomer, mesomer) ceton-enol.
Dng enol c h thng lin hp v c kh nng hnh thnh lin kt hydro ni
phn t. V vy hp cht acetoaceton tn ti ch yu dng enol.
251
:
O O
CH
R
R'
R"
O O
C
R R"
R'
Dng ceton
Dng enol
: : :
:
:
..
.. .
.
.
: O O
CH
2
CH
3
CH
3
O
H
O
CH
CH
3
CH
3
Dng enol
: : :
: :
.. ..
.
.
.
Dng ceton
Acetoaceton 1,3-dicarbonyl
H

Cc phn ng ch yu ca hp cht 1,3-dicarbonyl
Tnh acid:
Hp cht 1,3-dicarbonyl c tnh acid mnh hn cc hp cht 1,2-dicarbonyl
v cc aldehyd, ceton n chc. Nguyn nhn l nguyn t hydro ca lin kt
C - H linh ng hn. Acetoaceton c pKa = 9, 0 ha tan c trong dung dch kim
v tc dng vi natri kim loi gii phng kh hydro v to mt carbanion bn
vng nh s lin hp.
-
C
O O
C
CH
CH
3
CH
3
C
O O
C
CH
2
CH
3
CH
3
Na
+ 1/2 H
2
+ Na

:
C
O O
C
CH
CH
3
CH
3
C
O O
C
CH
CH
3
CH
3
C
O O
C
CH
CH
3
CH
3
:
..
: :
: : : :
: : : :
..
-
-
Carbanion
-

To phc vi ion kim loi:
Hp cht 1,3-dicarbonyl tc dng vi cc mui ca kim loi nng to phc
bn, tan trong cc dung mi hu c nh ether, benzen, cloroform. Acetoaceton to
phc vi Cu
2+
thnh acetoacetonat ng c cng thc sau:
C
O O
C
CH
CH
3
CH
3
C
O O
C
CH
2
CH
3
CH
3
C
O O
C
CH
2
CH
3
CH
3
Cu
2+
+
+
C
O O
C
CH
CH
3
CH
3
Cu
:
:
: :
: :
: : : :
:
: : :
Acetoacetonat ng
Acetoaceton
+ 2H
+

Phn ng th
C th alkyl ha hp cht 1,3-dicarbonyl. Hp cht 1,3-dicarbonyl tc dng
vi dn xut halogen trong mi trng kim. Phn ng xy ra oxy to ether.
Phn ng xy ra carbon to mch nhnh.
252
C
O O
C
CH
CH
3
CH
3
:
C
O O
C
CH
CH
3
CH
3
C
O O
C
CH
CH
3
CH
3
C
O O
C
CH
CH
3
CH
3
-
- :
: : : : : : : :
: :
: :
: :
..
- X
Th vo O
Th vo C
R X
R
R

Ct mch carbon
un nng hp cht 1,3-dicarbonyl vi cc kim mnh, mch carbon b ct
t to thnh mui ca acid v ceton.
C
O O
C
CH
2
CH
3
CH
3
C
O
O
CH
3
-
C
O
CH
3
CH
3
HO
-
+
t
o

4. QUINON
4.1. Danh php
Quinon c cu to nh l cyclohexadiendion. Theo qui c, gi tn hp cht
quinon theo dn xut ca benzen l benzoquinon, dn xut ca toluen l
toluquinon... V vy thut ng quinon c xem l t gc gi tn nhng hp
cht thuc loi ny.
. 2-Hydroxy-3-methylnaphthoquinon-1,4
Phthiocol Antraquinon-9,10
2-Methylbenzoquinon-1,4
Toluquinon
p-Benzoquinon; o-Benzoquinon;
O
O
CH
3
O
O
OH
CH
3
O
O
O
O
O
O

4.2. iu ch
Phng php iu ch quinon l oxy ha cc phenol v amin thm.
OH
NH
2
Cl
OH
OH
O
O
O
O
Cl
Na
2
Cr
2
O
7
H
2
SO
4
Na
2
Cr
2
O
7
H
2
SO
4
30
o
< 30
o
Hydroquinon
p-Benzoquinon 2-Clorobenzoquinon-1,4

4.3. Tnh cht ha hc
4.3.1. Cn bng oxy ha -kh.
Cc hp cht 1, 2 v 1,4-dihydroxybenzen b oxy ha to thnh quinon.
Ngc li, kh ha quinon th to thnh hp cht dihydroxybenzen.
253
Ether
Na
2
S
2
O
4
, H
2
O
CH
3
OH
OH
O
O
CH
3

Tnh cht quan trng c minh ha bng phng trnh in ha nh sau:
+ 2H
+
+ 2e
OH
OH
O
O
p-Quinon
Hydroquinon

Hydroquinon c s dng lm in cc.
in th ca in cc xc nh theo phng trnh Nernst:
+
nF
[Hydroquinon]
[Quinon][H
+
]
2
log
2,303.RT
E = E
o

Qu trnh oxy ha -kh quinon -hydroquinon c nhiu ng dng.
4.3.2. Phc chuyn in tch
Phc chuyn dch in tch c to thnh l s kt hp hai phn t. Mt
phn t cho electron v phn t th hai nhn electron.
Phn t cho in t l phn t c cc nhm -OH, -OCH
3
, -N(CH
3
)
2
, -CH
3
gn
trn nhn benzen.
Phn t nhn in t c cc nhm ht electron nh nhm nitro trong acid
picric, quinon. S thay i mu t cc phn t ban u xc nhn s to phc
chuyn in tch.
Phc chuyn in tch quinhydron c mu xanh lc l mt v d.
OH
OH
O
O
OH
OH
O
O
+
Quinon
Hydroquinon Quinhydron

4.3.3. Cc phn ng ca quinon
Phn ng cng hp
Quinon l hp cht carbonyl cha no, c phn ng c trng ca lin kt i
OH
OH
Cl
O
O
+ HCl

254
C ch phn ng cng HCl vo quinon.
OH
OH
Cl
O
O
+ H
+
O
OH
O
OH
+
+
-
Cl
O
OH
H
Cl

Quinon cng hp vi cc dienophyl - Phn ng Diels -Alder.
Butadien Quinon
CH
3
COOH
25
o
HCl CH
3
COOH
OH
OH
O
O
H
H
+
O
O

Phn ng acyl ha
Quinon tc dng vi anhydrid acetic to triacetat hydroxyhydroquinon.
O
O
- CH
3
COOH
O
OCOCH
3
OCOCH
3
H
OCOCH
3
OH
OCOCH
3
OCOCH
3
OCOCH
3
OCOCH
3
(CH
3
CO)
2
O
H
+
(CH
3
CO)
2
O H
+
- CH
3
COOH
,

Cc cht c cu trc quinon thng c mu. Quinon l thnh phn cu to
c bn trong cc cht mu.
O
O
HO
O
O
HOOC
COOH
HO
COOH
Muscaruphyn Lauson
O
O
Antraquinon

Vitamin K1 c thnh phn quinon.
Vitamin K
1
O
O

255
Bi tp
1. Vit cng thc cu to ca cc hp cht c tn gi sau:
a. 5-Methylhexanal; b. 4-Hydroxy-3-metoxybenzaldehyd; c. Butyroaldehyd;
d. Methylethylceton; e. Methylbenzylceton; f. Acetophenon; g. Benzophenon.
2. T C
6
H
5
CH
2
CH
2
Cl hy tm phng php iu ch phenylacetaldehyd.
3. Chn cc phng php thch hp hy iu ch cc cht sau t cc nguyn liu
cho:
a. iu ch methylethyl ceton t sec -butanol.
b. iu ch methyl n -hexylceton t alcol caprylic.
c. iu ch methyl allylceton t acetaldehyd v allylbromid.
d. iu ch aldehyd cinnamic t acetylen v benzaldehyd.
4. So snh kh nng phn ng ca nhm carbonyl trong cc hp cht sau:
Aceton, diethylceton, acetaldehyd, cloral, diisopropylceton, benzaldehyd, benzophenon
5. Vit phn ng ca benzaldehyd vi cc cht sau:
a. Aceton; b- Hydroxylamin; c- Phenylhydrazin; d- Nitrometan; e-Anilin.
6. Vit phn ng ca citral vi cc cht sau:
a. H
2
/ Ni; b. Zn/HCl; c. NaBH
4;
d. LiAlH
4
.
7. Vit phn ng ca Acetophenon vi cc cht sau:
a. PCl
5
; b-Cl
2
/ nh sng; c- Hn hp Br
2
, KOH, d-Semicarbazid.
8. Trnh by cc c ch ca cc phn ng sau:
a-
HO
-
ac
Benzaldehyd

b-
HO
-
loang
Acetaldehyd

c-
KCN
p-Tolualdehyd

d-
HO
-
Benzaldehyd + Formaldehyd
e-
Benzaldehyd + Anilin

a. o-Benzoquinon; b. p-Benzoquinon;
c. Naphtoquinon-1,4; d. Antraquinon-9,10
10. Trnh by cc phn ng c trng ca aldehyd v ceton lin hp.
11. Ngi ta thng s dng nhng loi hp cht c nhm carbonyl loi no
to phc vi cc ion kim loi Ni
2+
,
Cu
2+
256
Chng 20
ACID CARBOXYLIC
Mc tiu hc tp
1. Gi c tn cc hp cht acid n chc v a chc.
2. Trnh by v so snh c tnh cht ha hc ca acid carboxylic mch thng
v acid carboxylic thm.
Ni dung
1. Cu to
Acid carboxylic l nhng hp cht hu c c nhm chc carboxyl -COOH
C th vit cng thc nhm carboxyl dng cu to khai trin, cu to rt
gn hay dng phn t.
R
_
CO
2
H
R
_
COOH
R
C O H
O :
..
:
..

R c th l hydro, gc hydrocarbon aliphatic R hay gc aryl Ar
Trong 4 orbital ca nguyn t carbon ca nhm carboxyl th 3 orbital
trng thi lai ha sp
2
trong cng mt phng v to lin kt vi gc R, nhm
OH v oxy. Orbital p cn li lin kt vi orbital p ca oxy trong nhm carboxyl to
lin kt . di v gc lin kt ca acid formic c trnh by trong bng 20-1.
Bng 20.1: Cu to ca acid formic (HCOOH)
C O
H
O
H
Acid formic

Lin kt
C=O
CO
CH
OH
di
1,202
1,343
1,097
0,972
Gc lin kt
HC=O
OC=O
HC-O
HO-C
gc
124,1
o
124,9
o
111,0
o
106,3
o
trng thi rn, lng v trng thi hi, acid carboxylic tn ti dng dimer.
R C
O
O H
R C
O
O H
...
...

257
2. Danh php
C 2 loi danh php quan trng. Danh php thng thng v danh php
IUPAC. Danh php thng thng phn nh ngun gc ca acid.
Danh php IUPAC:
Tn Hydrocarbon tng ng + tip v ng OIC
nh s:
nh s trn mch chnh di nht cha chc acid. S 1 bt u t chc acid.
Nu acid c phn nhnh th c tn nhm th v v tr gn vo mch chnh.
Dng cc ch ci , , , xc nh v tr cc nguyn t carbon ca
mch chnh. Ch ci bt u t nguyn t carbon sau nhm acid.
Cng c th xem acid hu c l dn xut ca hydrocarbon. Hydro c thay
th chc acid. Chc acid c tn gi l carboxylic.
Tn hydrocarbon tng ng vi gc R + carboxylic.
Danh php mt s acid trnh by trong bng 20-2.
Bng 20.2: Danh php v tnh cht vt l ca mt s acid.
Cng thc Danh php
thng thng
Danh php
IUPAC
t
o
c t
o
s pKa
HCOOH Acid formic Acid metanoic 8.4 101 3,75
CH
3
COOH Acid acetic Acid etanoic 16,6 118 4,76
CH
3
CH
2
COOH Acid propionic Acid propanoic -21, 141 4,87
CH
3
(CH
2
)
2
COOH Acid butyric Acid butanoic -5 164 4,82
CH
3
(CH
2
)
3
COOH Acid valeric Acid pentanoic -34 186 4,86
CH
3
(CH
2
)
4
COOH Acid caproic Acid hexanoic - 3 205 4,88
CH
3
(CH
2
)
5
COOH Acid nantic Acid heptanoic - 8 223 4,89
CH
3
(CH
2
)
6
COOH Acid caprylic Acid octanoic 17 239 4,90
CH
3
(CH
2
)
7
COOH Acid pelagonic Acid nonanoic 15 255 -
CH
3
(CH
2
)
8
COOH Acid capric Acid decanoic 32 270 -
CH
3
(CH
2
)
10
COOH Acid lauric Acid dodecanoic 44 299 -
CH
3
(CH
2
)
12
COOH Acid myristic Acid tetradecanoic 54 251 -
CH
3
(CH
2
)
14
COOH Acid palmitic Acid hexadecanoic 63 267 -
CH
3
(CH
2
)
16
COOH Acid stearic Acid octadecanoic 72 - -
CH=CHCOOH Acid acrylic Acid propenoic 12,3 142 -
CH
2
C COOH
CH
3

Acid metacrylic Acid
2-methylpropenoic
16 163 -
258
Cng thc Danh php
thng thng
Danh php
IUPAC
t
o
c t
o
s pKa
C C
COOH
CH
3
H
H

Acid crotonic Acid E-2-butenoic 71,6 189 4,69
C C
H
CH
3
(CH
2
)
7
H
(CH
2
)
7
COOH

Acid oleic Acid
Z -9-octadekenoic
16.3 - -
C C
(CH
2
)
7
COOH
CH
3
(CH
2
)
7
H
H

Acid elaidic Acid
E - 9-octadekenoic
45 - -
HCCOOH Acid propiolic Acid propinoic 9.0 144 -
COOH

Acid cyclopentan
carboxylic
Acid cyclopentan
carboxylic
- - -
COOH

Acid benzen
carboxylic
Acid benzoic 121 249 4,17
CH
2
COOH

Acid phenylacetic Acid
2-phenyletanoic.
76,7 265 4,26
C C
COOH
H
H
C
6
H
5

Acid cinnamic Acid-E-3-
phenylpropenoic
135 300 4,44
3-ethyl-4-methyl-hexanoic
-ethyl - -methylcaproic
Acid
2-ethyl-3-methylpetancarboxylic
Acid
Acid
CH
3
CH
2
CH CH CH COOH
CH
3
CH
3
CH
3
1 2 3
4 5
6

Khng phi tt c cc loi acid u c th gi tn theo phng php c tip
v ng oic. V vy c th gi tn theo phng php carboxylic. c bit vi hp
cht vng thng gi theo danh php carboxylic.
COOH
COOH
CH
3
Acid cyclohexan carboxylic Acid 1-methylcyclohexan carboxylic

3. Phng php iu ch
C mt s phng php ch yu sau.
3.1. Thy phn hp cht nitril R
_
CN
Thy phn hp cht nitril to acid v amoniac.
R
_
CN + 2H
2
O R
_
COOH + NH
3

259
Phn ng xy ra khi c xc tc acid hoc base.
CH
2
CN
CH
2
COOH
+ 2H
2
O
NH
4
HSO
4
+
-
+
H
2
SO
4
100
o
3 gi
,

CH
3
CH
2
CH
2
CH
2
CN
CH
3
CH
2
CH
2
CH
2
COOK
2H
2
O
KOH
NH
4
OH
+ +

3.2. Carboxyl ha hp cht hu c
3.2.1. Hp cht c kim tc dng vi kh CO
2
to mui carboxylat
+ R MgX R COOMgX R COOH HOMgX + CO
2
H
2
O

+
R Li
R COOLi R COOH LiOH + CO
2
H
2
O

3.2.2. Hydrocarbon thm tc dng vi phosgen COCl
2

Thy phn acylclorid hnh thnh v thu c acid .
Ar H
C O
Cl
Cl
Ar C
O
Cl
Ar COOH
ACl
3
- HCl
+ H
2
O
- HCl
+

3.2.3. Natri alcolat tc dng vi carbon oxyd CO
RONa + CO RCOONa RCOOH
3.2.4. Carboxyl ho alken
CH
2
CH
2
CH
3
CH
2
COOH
+ CO
2- H
2
O
1- Ni(CO)
4

3.3. Oxy ha alcol bc nht v aldehyd (xem alcol, aldehyd-ceton)
3.4. Tng hp acid t ester malonat - Tng hp malonic
Ester malonic ROOCCH
2
COOR v dn xut R'X l nguyn liu c bn
iu ch acid carboxylic. Ester malonic ROOCCH
2
COOR l nguyn liu ph tr c
bn chuyn dn xut halogen R'X thnh R'CH
2
COOH.
R'CH
2
COOH R'X

Phn ng xy ra nh sau:
Khi c xc tc base, ester malonic chuyn thnh tc nhn i nhn ROOC
-
CHCOOR v sau tc dng vi dn xut halogen. Tip theo l qu trnh thy
phn ester v decarboxyl ha to thnh acid carboxylic.
260
ROOCCH
2
COOR + C
2
H
5
O
-
ROOCCHCOOR
-
+ C
2
H
5
OH

+ X
-
-
ROOCCHCOOR
R'
ROOCCHCOOR + R'X

H
+
+ 2H
2
O
+ 2ROH
HOOCCHCOOH
R'
ROOCCHCOOR
R'

Decarboxyl hoa
+ CO
2
HOOCCHCOOH
R'
R'CH
2
COOH

Vi phng php ny c th iu ch cc acid carboxylic c mch carbon
thng hoc phn nhnh v s carbon ty thuc vo s la chn dn xut halogen.
3.5. Thy phn ester
Thy phn ester trong mi trng acid thu c acid v alcol.
RCOOH + R'OH
H
+
+ HOH RCOOR'

Thy phn ester trong mi trng kim (phn ng x phng ha) thu c
mui ca acid v alcol.
RCOOR' + NaOH RCOONa + R'OH

Trong thc t ng dng phng php ny sn xut x phng t ngun
nguyn liu du thc vt v m ng vt (xem thm phn ester).
3.6. S dng cc phn ng
Thy phn hp cht trihalogen, phn ng Perkin u thu c acid (xem
phn hp cht halogen v phn ng Perkin)
4. Tnh cht l hc
Tnh cht l hc ca acid carboxylic ph thuc rt nhiu vo s cng kt
cc phn t do lin kt hydro gy nn. Lin kt hydro acid carboxylic bn hn
lin kt hydro ca alcol v nhm OH ca acid phn cc mnh hn. Acid
carboxylic tn ti nhng dimer vng ngay c trng thi hi v tn ti dng
polymer mch thng.
;
Dang dimer
Polymer dang thang
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
C
R
O O
H C
R
O O
H
C
R
O O
H
C
R
O O
H
C
R
O O
H
R C
O
O H
R C
O
O H
...
...

261
Tt c cc acid carboxylic l cht lng hoc rn (bng 20-2). Acid thm u
l cht rn. Nhit si ca acid no mch thng khng phn nhnh tng dn
theo trng lng phn t. Cc acid c s carbon chn c nhit nng chy cao
hn acid c s carbon l trc v sau .
Acid c s carbon < 4 tan v hn trong nc. Gc R l gc thn du
(lipophile). Nhm COOH l nhm thn nc (hydrophile).Khi gc R cng tng th
lin kt hydro ca nhm carboxyl vi nc khng lc gi ton b phn t
acid trong nc. Cc acid c s carbon >11 hon ton khng tan trong nc.
Trn quang ph IR dao ng ha tr ca nhm OH trong vng 3000-2500cm
-1

(trong acid khng c lin kt hydro l OH =3550cm
-1
). Vch c trng ca nhm
C =O cng tng t ph ca aldehyd nhng m rng hn.
Trong vng t ngai, nhm carboxyl hp th bc sng ngn hn nhiu so
vi nhm carbonyl.
V d:
Hp cht H
max

CH
3
COOH 197 nm 60
CH
3
CHO 293 nm 12
5. Tnh cht ha hc
Nhm carboxyl l t hp ca 2 nhm carbonyl C =O v nhm hydroxyl
(carboxy) do c tn gi l carboxyl. Hai nhm ny c nh hng ln nhau rt
mnh do s lin hp ca orbital v cp in t khng lin kt ca oxy trong
nhm OH. Kt qu l lin kt OH ca acid yu hn so vi alcol v in tch
dng +ca carbon trong nhm carboxyl t hn so vi aldehyd.
Aldehyd Acid
R C
H
O
R C
O H
O
..
R C
O
OH
..

Nhm carboxyl v gc R c nh hng qua li ln nhau.
C 4 loi phn ng c bn ca acid carboxylic nh sau:
1- R C
O H
O

Phn ng lm t lin kt OH l cc phn
ng: Phn ly acid, to mui vi kim loi v.v...
R C
O H
O
Y
-
2-

Phn ng vo nhm carboxyl: a s l nhng
phn ng vi tc nhn i nhn Y, lm t lin
kt COH
262
R C
O H
O
3-

Phn ng decarboxyl
(tch nhm carboxyl)
R C
O H
O
4-

Phn ng gc hydrocarbon bao gm nhng
phn ng th v tr v phn ng th vo
gc thm v phn ng cng.
5.1. Phn ng lm t lin kt OH
5.1.1. S phn ly acid carboxylic trong dung dch
Xy ra theo cn bng:
CH
3
COOH + H
2
O CHCOO
-
+ H
3
O
+
K
a
=
[CHCOO ][H]
[CH
3
COOH]
-
+
= 1,8.10
-5
M

Gi tr pKa ca mt s acid trnh by trong bng 20.3.
Hng s phn ly ca acid benzoic bin i theo bn cht v v tr cc nhm
th trong vng benzen.
Bng 20.3: Gi tr pKa ca mt s acid benzoic c nhm th
CH
3
OCH
3
OH Cl NO
2
Para
Meta
Orto
4,37
4,27
3,91
4,47
4,09
4,09
4,54
4,08
2,98
3,98
3,83
2,94
3,43
3,49
2,17
Nhom the
V tr

Ion RCOO
-
gi l ion carboxylat. S phn b mt in t trong ion
carboxylat ng u trn 2 nguyn t oxy v di C
_
O u bng 1,27
A

o
5.1.2. Tc dng vi kim loi, oxyd, hydroxyd kim loi, mui acid yu.
Nguyn t hydro ca acid c thay th bng kim loi.
2 RCOOH + Na 2RCOONa + H
2
2 RCOOH + MgO (RCOO)
2
Mg + H
2
O
RCOOH + NaOH RCOONa + H
2
O
2 RCOOH + Na
2
CO
3
2RCOONa + H
2
O + CO
2

Mui ca acid gi l x phng. X phng natri, kali d tan trong nc. Tc
dng ty ra ca x phng l do gc R c s carbon ln l gc thn du, nhm
263
COO
-
l gc thn nc. Cc phn t nc bao quanh nhm COO
-
. Cc gc R c
tc dng bao bc cc cht bn, du m khng tan trong nc. Do cc cht bn
b nc li cun theo x phng.
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
--
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
Xa phong
tan trong nc
+
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
Du m
khng tan trong nc
Du m
b tan theo x phng

5.1.3. Tc dng vi diazometan to metylcarboxylat (RCOOCH
3
)
RCOOH + CH
2
N
2
RCOOCH
3
+ N
2

C ch phn ng:
R C
O
O H CH
2
N N
CH
3
N N
-
+
:
R C
O
O:
..
..
-
+
: +
+

R C
O
O CH
3
N N R C
O
OCH
3
N N
+
-
..
..
: :
: :
+ +

5.2. Phn ng vo nhm carboxyl -Phn ng cng v tch
Nhm carboxyl phn cc. Mt in t tp trung trn nguyn t oxy. in
tch dng trn nguyn t carbon.
R C
O
O H
+
-
R C
O
O H

Phn ng cng hp i nhn vo nguyn t carbon sau xy ra s tch.
5.2.1. Phn ng cng i nhn c xc tc base. Tc dng vi amoniac.
Amoni butanoat Acid butanoic
CH
3
CH
2
CH
2
CO
2
NH
4
CH
3
CH
2
CH
2
COOH + NH
3
+
-

Di tc dng ca nhit , amoni butanoat b tch mt phn t nc to
butanamid.
185
o
H
2
O
Butanamid
CH
3
CH
2
CH
2
CONH
2
+
Amoni butanoat
CH
3
CH
2
CH
2
CO
2
NH
4
+
-

264
C ch chung:
+
Tach nc
Cong ai nhan
R C
O
OH
2
NH
2
-
R C
O
NH
2
+
R C
O
O H R C
O
OH
NH
3
+ NH
3
H
2
O +
-
R C
O
O H
+
-
..

5.2.2. Tc dng vi LiAlH
4
to alcol bc nht.
RCOOH + LiAlH
4
RCOOLi + H
2
+ AlH
3
R COOLi
R C OLi
OLi
H
R C O
H
R C OLi
H
H
R C OH
H
H
LiAlH
4 LiAlH
4
LiAlH
4
H
3
O
+

H
2
SO
4
H
2
O
Ether
H
4
LiAl
CH
3
O
CH
3
O
CH
2
OH
CH
3
O
CH
3
O
COOH

5.2.3. Phn ng cng hp i nhn c xc tc acid - Phn ng ester ha
Acid tc dng vi alcol to ester. Acid v c l xc tc. Alcol l tc nhn i nhn.
+
H
+
+ H
2
O R COOR' R' OH R COOH

Phn ng ester ha l mt phn ng thun nghch. Hn hp trng thi cn
bng c khong 65% ester v nc sinh ra, 35% acid v alcol cha phn ng.
Hiu sut phn ng ester ha ph thuc nng ca cht phn ng hoc
phng php tch ester hay nc ra khi mi trng phn ng (nh lut
Le Chtelier). C ch phn ng nh sau:
H
+
+ R C OH
O
R C OH
OH
+
R C OH
OH
+
R' OH +
..
.. R C OH
OH
HOR'
+
R C OH
OH
OR'
+ H
+
Cong ai nhan
Xuc tac acid

Tach nc
:
..
+ H
2
O
+
+
R C
OH
OR'
R C OH
2
OH
OR'
+ H
+
R C OH
OH
OR'

Xuc tac
Esther
+ H
+
R C
O
OR'
+
R C
OH
OR'

265
Alcol l tc nhn i nhn c chng minh bng phng php s dng alcol
c oxy ng v 18. Ester to thnh c oxy 18, nc c oxy 16 chng t nhm OH
ca acid b tch ra.
Ester co oxy 18
18 16
+ H
2
O
16 18
Cong ai nhan
CH
3
C OCH
3
O
..
+
CH
3
OH +
CH
3
C OH
OH

Phn ng th nhm OH ca acid bng cc halogen
Acid tc dng vi thionylclorid SOCl
2
, phosphorpentaclorid PCl
5
, phosphor
tribromid PBr
3
to ra sn phm acylhalogenid RCOX (X= Cl, Br).
+
CH
3
C OH
O
CH
3
C Cl
O
Cl S Cl
O
+ HCl + SO
2
Acetyl clorid
Thionyl clorid

+
C OH
O
C Cl
O
+ PCl
5
POCl
3
+ HCl
Phosphor pentaclorid Benzoyl clorid

C OH
O
C Br
O
+ PBr
3
+ H
3
PO
3
Phosphos tribromid Benzoyl bromid
3
3

5.3. Phn ng decarboxyl ha (loi nhm carboxyl)
Kh nng decarboxyl ha ph thuc vo cu to ca acid. Acid c nhm ht
in t d b decarboxyl hn.
Acid formic b decarboxyl to H
2
v CO
2
hoc H
2
O v CO ty iu kin phn ng.
HCOOH H
2
+ CO
2
Tia t ngoai
Os

H
2
SO
4
ac
+ CO H
2
O HCOOH

Acid acetic kh b decarboxyl. Mui acetat b decarboxyl ha nhit cao:
CH
3
COONa + NaOH CH
4
+ Na
2
CO
3

Dn xut th ca acid acetic c nhm ht in t d b decarboxyl ha nh:
Cl
3
CCOOH; O
2
NCH
2
COOH; NCCH
2
COOH; CH
3
COCH
2
COOH
V d: CH
3
COCH
2
COOH CH
3
COCH
3
+ CO
2

266
Mui bc ca acid carboxylic d b decarboxyl ha khi c mt ca brom to
dn xut halogen tng ng (Phn ng Hunsdiecker). Phn ng xy ra theo c
ch gc t do.
76
o
C
CCl
4
+ AgBr + CO
2
C
6
H
5
CH
2
Br C
6
H
5
CH
2
COOAg + Br
2

C th thay i Ag bng thy ngn.
+ 2 Br
2
+ CO
2
+ HgBr
2
COOH
H
+ HgO
Br
H
+ H
2
O
2
2

5.4. Phn ng ca gc hydrocarbon
Gc alkyl c th b oxy ha to hp cht acid oxocarboxylic.
Phn ng oxy ha nh xc tc men to acid -oxocarboxylic ng vai tr
quan trng trong chuyn ha cht bo.
R
_
CH
2
_
CH
2
_
COOH R
_
CO
_
CH
2
_
COOH
Acid oxo carboxylic

Enzym

Cht oxy ha l SeO
2
to acid -oxocarboxylic
R
_
CH
2
_
CH
2
_
COOH R
_
CH
2
_
CO
_
COOH
Acid oxo carboxylic
+ SeO
2
+ H
2
O + Se

5.4.2. Phn ng halogen ha gc alkyl
Phn ng th xy ra gc hydrocarbon c cc trng hp sau:
Brom ha c mt ca phosphor. Phn ng th xy ra v tr .
Br
2
P
P
R CBr
2
COOH R CHBr COOH + Br
2
R CH
2
COOH

Phn ng clor ha xy ra theo c ch gc. Phn ng xy ra ch yu v tr
v v mt lng nh sn phm th v tr .
31%
64%
5%
h
Cl
2
CH
2
Cl
_
CH
2
_
CH
2
_
COOH
CH
3
_
CHCl
_
CH
2
_
COOH
CH
3
_
CH
2
_
CHCl
_
COOH
CH
3
_
CH
2
_
CH
2
_
COOH

267
5.4.3. Phn ng th vo gc thm
Phn ng th i in t vo nhn thm ca acid carboxylic xy ra v tr meta.
COOH
COOH
NO
2
HNO
3
H
2
SO
4
t
o
,

Nhm carboxyl lm cho gc thm c hot tnh thp. V vy acid benzoic
khng tham gia phn ng Friedel -Craft.
5.4.4. Cc acid cha no th hin cc phn ng ca lin kt
+ Br
2
CH
2
Br CHBr COOH CH COOH CH
2

6. Acid carboxylic cha no
Acid khng no l nhng acid cha ni i hoc ni ba. Mt s acid cha no
trnh by trong bng 20-2. Acid carboxylic cha no c th lin hp hoc khng lin
hp. Acid carboxylic cha no khng lin hp bn hn acid cha no lin hp.
acid 4-methyl-2- pentenoic
CH
3
CH
_
CH = CH
_
COOH
CH
3
CH
3
C = CH
_
CH
2
_
COOH
acid 4-methyl-3- pentenoic
CH
3

6.1. iu ch
Cc phng php iu ch acid cha no cng ging phng php iu ch
alken v iu ch acid no. Acid carboxylic cha no v cc dn xut ca n c
iu ch t cc hp cht cha no tng t.
6.1.1. T dn xut halogen cha no RX RCOOH
(52-62%)
CuCN
CH
2
= CH
_
CH
2
_
Cl CH
2
= CH
_
CH
2
_
CN
CH
2
= CH
_
CH
2
_
COOH
dd HCl
Acid vinyl acetic
(Acid 3-butenoic)
Allylclorid

6.1.2. Tch loi HX khi ester hoc -halogenoacid
Cc ester hoc acid c halogen v tr c th b tch loi to thnh acid
cha no. Cc tc nhn base c vai tr quan trng trong qu trnh tch loi to
ra cc acid cha no c v tr ni i xc nh. V d di y chng t iu :
268
CH
2
CH
3
(CH
2
)
9
C
_
COOH
CH
3
CH
3
(CH
2
)
8
CH = C
_
COOH
Acid 2- decyl propenoic Acid 2-methyl-2- dodekenoic
(68-83%)
H
+

H
+

ddKOH
ddKOH
(CH
3
)
3
COH
Quinolin
Br
CH
3
OH
160-170
o

(CH
3
)
3
COK
Br
2

CH
3
(CH
2
)
9
C
_
COOC(CH
3
)
3
CH
2
CH
3
(CH
2
)
8
CH = C
_
COOCH
3
CH
3
CH
3
(CH
2
)
9
C
_
COOCH
3
CH
3
CH
3
(CH
2
)
9
CBr
_
COBr
CH
3
PBr
3

CH
3
(CH
2
)
9
CH
_
COOH
CH
3

Nhn xt:
Cc base (CH
3
OK; Quinolin) c tc dng tch loi trc tip to lin kt i.
Acid cha no n gin nht l propenoic (acid acrylic). Nitril tng ng l CH
2

=CH
_
CN (acrylonitril). Chng l nguyn liu quan trng trong cng nghip cht
polymer. iu ch acrylonitril bng cch oxy ha propen c xc tc vi amoniac.
CH
3
CH=CH
2

+ 3 O
2

Xuc tac
+ 2NH
3

2 CH
2
=CH
_
CN + 6 H
2
O
450
o

Cc ester cha no c nhiu trong thin nhin. Cc acid cha no thng gp:
CH
3
(CH
2
)
4
CH=CHCH
2
CH=CH(CH
2
)
7
COOH

Acid Linoleic
CH
3
(CH
2
)
5
CHOHCH
2
CH=CH(CH
2
)
7
COOH

Acid Oleic CH
3
(CH
2
)
7
CH=CH(CH
2
)
7
COOH

Acid Ricinoleic
Acid Linolenic CH
3
CH
2
CH=CHCH
2
CH=CHCH
2
CH=CH(CH
2
)
7
COOH

6.2. Tnh cht ha hc
Th hin tnh cht cha no ca lin kt v tnh cht ca nhm carboxyl.
Acid cha no c mt s tnh cht c trng nh:
Tnh acid mnh hn acid no tng ng.
CH
3
CH
2
CH
2
COOH pKa= 4,82 CH
3
CH=CHCOOH pKa= 4,6
269
Phn ng to lacton l phn ng ng vng to ester ni phn t.
CH
2
CH CH
2
CH
2
C
O
OH
+ H
+
CH
CH
2
CH
2
C
HO
CH
3
O
+
..
CH
CH
2
CH
2
C
O
CH
3
O
Valerolacton Acid allylacetic

Acid , cha no kh to lacton. Vng lacton bn vng khi c vng 5, 6 cnh.
7. Acid a chc - polyacid
Cc diacid c trnh by trong bng 20-4.
Bng 20.4. Cng thc, tn gi v gi tr pKa ca mt s diacid
Cng thc Tn gi
t
c
o

pKa1 pKa2
HOOC
_
COOH
Acid Oxalic, Etandioic 189,5 1,27 4,27
HOOC
_
CH
2
_
COOH
Acid Malonic, Propandioic 135,6 2,86 5,70
HOOC
_
(CH
2
)
2
_
COOH
Acid Succinic, Butandioic 185. 4,21 5,64
HOOC
_
(CH
2
)
3
_
COOH
Acid Glutaric, Pentandioic 97,5 4,34 5,27
HOOC
_
(CH
2
)
4
_
COOH
Acid Adipic, Hexandioic 153 4,41 5,28
HOOC
_
(CH
2
)
5
_
COOH
Acid Pimelic, Heptandioic 104 - -
HOOC
_
(CH
2
)
6
_
COOH
Acid Suberic, Octandioic 142 - -
HOOC
_
(CH
2
)
7
_
COOH
Acid Azelaic, Nonandioic 106 - -
HOOC
_
(CH
2
)
8
_
COOH
Acid Sebacic, Decandioic 134 - -
C C
COOH
H
HOOC
H

Acid Maleic z-2-Butendioic 137 1,92 6,23
C C
H
COOH
HOOC
H

Acid Fumaric, E-2-Butendioic 287 3,02 4,38
COOH
COOH

Acid Phtalic,
1,2-Benzendicarboxylic
208 2,58 5,62
COOH
COOH

Acid Isophtalic,
346 - -
COOH
HOOC

Acid Terephtalic,
300 - -
270
Tnh cht ha hc
Nhm acid nh hng qua li ln nhau.
Tnh acid ca diacid mnh hn monoacid.
Tnh acid ca diacid gim dn khi chc acid cng xa nhau.
Diacid to 2 mui, 2 ester.
Diethyl ftalat
- H
2
O - H
2
O
- H
2
O - H
2
O
, H
+
, H
+
C
2
H
5
OH
C
2
H
5
OH
KOH
KOH
COOC
2
H
5
COOH
COOC
2
H
5
COOC
2
H
5
COOK
COOK
COOH
COOK
COOH
COOH

Acid oxalic v acid malonic d b decarboxyl to acid n chc.
CH
3
_
COOH + CO
2

HOOC
_
CH
2
_
COOH
HCOOH + CO
2
HOOC
_
COOH
t
o
t
o

Diacid d to thnh anhydrid vng.
+ H
2
O
CH
2
CH
2
C
O
C
O
O
CH
2
CH
2
COOH
COOH
Acid Succinic Anhydrid Succinic

+ H
2
O
C
O
C
O
O
COOH
COOH
Acid Ftalic Anhydrid Ftalic

Bi tp
1. Gi tn cc cht sau theo danh php IUPAC:
a- ClCH
2
CH
2
CH
2
CH
2
COOH c- CH
3
CH
2
CH(CH
3
)CH
2
CHCOOH
b- (CH
3
)
3
CCH
2
CH
2
CH
2
COOH d- CH
2
=CHCH=CHCOOH
2. Acid formic c hng s phn ly Ka = 1,77.10-4M. Tnh gi tr pKa. Tnh nng
ca ion formiat trong dung dch acid formic 0,1M.
271
3. Hy thc hin cc chuyn ha sau:
a- (CH
3
CH
2
CH
2
)
3
CBr (CH
3
CH
2
CH
2
)
3
CCOOH
b-HOCH
2
CH
2
CH
2
CH
2
CH
2
CH
2
Br HOCH
2
CH
2
CH
2
CH
2
CH
2
CH
2
COOH
c- CH
3
CH
2
CH
2
CH
2
CH=CH
2

CH
3
CH
2
CH
2
CH
2
CH
2
COOH
4. Vit phng trnh phn ng ca acid 3-methylpentanoic vi cc cht sau:
a. Diazometan trong ether.
b. Tc dng vi NaOH v tip theo vi metyl iodur trong dioxan.
5. Vit phng trnh phn ng ca acid hexanoic vi:
a. Ethanol c mt H
2
SO
4
m c. b - Thionyl clorid.
c. Phosphor pentaclorid. d- Phosphor tribromid.
6. Trnh by c ch phn ng ester ha.
CH
3
COOH + C
2
H
5
OH CH
3
COOC
2
H
5
+ H
2
O
H
2
SO
4

272
Chng 21
CC DN XUT CA ACID CARBOXYLIC
Mc tiu
1. Trnh by c s hnh thnh cc loi dn cht acid carboxylic v nguyn
tc chung gi tn chng.
2. Nu c tnh cht ha hc ca cc dn cht acid carboxylic.
Ni dung
Khi thay th nhm OH ca acid carboxylic bng nhng nhm th khc nhau
thu c cc dn xut nhm chc ca acid carboxylic.

Dan xuat cua acid carboxylic Acid carboxylic
R C
O
Y
R C
O
O H

Trong bng 21-1 trnh by cc loi dn xut ch yu ca acid carboxylic.
Bng 21.1: Mt s dn xut ca acid carboxylic
Cng thc Loi dn xut acid Cng thc Loi dn xut acid
R C
O
Hal
(F , Cl, Br , I)

Halogenid acid
R C
O
OR'

Ester
R C O C R
O O

Anhydrid acid
R C
O
NR
2

Amid
R C
O
NHOH

Acid Hydroxamic
R C
O
NH NH
2

Hydrazid
R C
O
N
3

Azid

R
_
CN

Nitril
R C O OH
O

Peroxyacid
C C O
R
R

Ceten
273
Cng c th xem nitril l dn xut ca acid khi thay th nhm OH v C =O
ca acid bng nguyn t nit -N. Ceten cng c th xem l dn xut ca acid
carboxylic.
Chng ta s nghin cu mt s dn xut quan trng: Ester, halogenid acid,
anhydrid acid, amid, nitril v ceten.
1. Ester
Ester l sn phm th nhm OH ca acid carboxylic -RCOOH bng nhm
alkoxy R'O ca alcol (hay nhm aroxy ArO - ca phenol). Bng 21-3 trnh by
cc ester.
RCOOH RCOOR'
1.1. Cu to
di v gc lin kt ca ester methyl formiat trnh by trong bng 21-2.
Bng 21.2
C O
H
O
CH
3
Methyl formiat

di lin kt (
A
)
o
C=O.............1,200
C(=O)
_
O.......1,344
C(H
3
)
_
O.......1,437
C(=O)
_
H.......1,101

Gc lin kt ()
H
_
C=O.........124,95
O
_
C=O.........125,87
H
_
C
_
O.........109,78
CH
3
_
O
_
C....114,78
1.2. Danh php
C th xem ester nh l mt mui ca acid hu c. Cch gi tn ca ester l
c tn gc alkyl ca alcol v c tn acid tng ng thay ''ic" ca acid bng " at"
Tn gc alkyl ca alcol + Tn ca carboxylat tng ng
R C O R'
O
Goc alkyl cua alcol
Alkylcarboxylat
CH
3
C O CH
2
CH
3
O
CH C O CH(CH
3
)
2
O
CH
3
CH
3
Ethyl acetat Isopropyl isobutyrat
Ethyl etanoat Isopropyl-2-methylpropanoat

Danh php mt s ester trnh by trong bng 21-3

274
Bng 21.3. Danh php v tnh cht l hc ca mt s ester
Cng thc Tn gi
t
c
o
t
s
o

d
20
4

HCOOCH
3
Methylforniat - 99,9 31,5 0,975
HCOOC
2
H
5
Ethylformiat - 80,5 54,3 0,917
CH
3
COOCH
3
Methylacetat - 98,1 57,1 0,924
CH
3
COOC
2
H
5
Ethylacetat - 83,6 77,1 0,901
CH
3
COOC
3
H
7
n n-Propyl acetat - 92,5 101,6 0,887
CH
3
COOC
4
H
9
Butyl acetat -76,8 126,5 0,882
CH
3
COOC
5
H
11
Amylacetat -78,5 142,6 0,871
CH
3
CH
2
CH
2
COOCH
3
Methylbutyrat -95,5 102,3 0,898
CH
3
(CH
2
)
14
COO(CH
2
)
15
CH
3
Cetylpalmitat 55,5 - 0,832
C
6
H
5
COOCH
3
Methylbenzoat - 12,5 199,6 1,094
C
6
H
5
COOC
2
H
5
Ethylbenzoat - 34,6 212,6 1,051
C
6
H
5
COOC
6
H
5
Phenylbenzoat 70,0 314,0 1,235
COOCH
3
COOCH
3

Dimethyl oxalat

- 54,0

163,8

1,148
COOC
2
H
5
COOC
2
H
5

Diethyl oxalat

- 40,6

185,4

1,078
CH
2
(COOCH
3
)
2
Dimethyl malonat - 62,0 181,0 1,151
CH
2
COOCH
3
CH
2
COOCH
3

Dimethyl succinat

19,5

192,8

1,120
o-C
6
H
4
(COOCH
3
)
2
Dimethyl ftalat 49,5 - -
1.3. Phng php iu ch
1.3.1. Phng php ester ha. Xem phn alcol v acid.
RCOOH + R'OH RCOOR' + H
2
O
H
2
SO
4

CH
3
COOH + C
2
H
5
OH
CH
3
COOC
2
H
5
+ H
2
O
H
2
SO
4

Phn ng iu ch ester ethylacetat l phn ng thun nghch c hng s
cn bng:
[CH
3
COOH] [C
2
H
5
OH]
[CH
3
COOC
2
H
5
][H
2
O]
K = = 4

Nh vy c khong 66% c chuyn ha thnh ester. Mun tng hiu sut
ester, tc l chuyn dch cn bng v pha bn phi, ta c th tng nng ca
275
mt trong 2 cht phn ng (alcol hoc acid) hoc tch sn phm (ester hoc nc)
bng cch chng ct. Phn ng ester ha xy ra chm. Hn hp ng phn t ca
CH
3
COOH v C
2
H
5
OH nhit phng cn khong 16 nm mi t ti cn bng.
tng tc phn ng, ngoi vic un nng hn hp, ngi ta cn dng cc cht
xc tc nh H
2
SO
4
m c, HCl khan...
1.3.2. Acyl ha alcol bng anhydrid acid. Xem phn alcol
ROH + (R'CO)
2
O RCOOR' + R'COOH.
1.3.3. Acid carboxylic tc dng vi diazometan. Xem phn acid.
RCOOH + CH
2
N
2
RCOOCH
3
+ N
2

1.3.4. Phn ng Claisen - Tishenco. Xem phn acid
1.3.5. Phn ng gia mui ca acid carboxylic vi dn xut halogen
RCOONa + R'Cl RCOOR' + NaCl
RCOOAg + R'Br RCOOR' + AgBr
1.4. Tnh cht l hc
Ester thng c mi thm. t tan trong nc. Ester c trong cc loi tinh
du, cht bo v sp. Mt s tnh cht vt l ca ester trnh by trong bng 21-3.
1.5. Tnh cht ha hc
1.5.1. Phn ng thy phn
Thy phn trong mi trng acid
+ + RCOOR' H
2
O RCOOH R'OH

C ch phn ng thy phn
Phn ng ester ha l phn ng thun nghch. i vi ester ca alcol bc
nht v bc hai th c ch thy phn l phn ng ngc li ca phn ng
ester ha c trnh by trong phn acid.
i vi ester ca alcol bc ba th c ch thy phn c xc tc acid nh sau:
276
+
CH
3
C O C CH
3
CH
3
CH
3
OH
+ H
+
CH
3
C O
O
C CH
3
CH
3
CH
3
+
C CH
3
CH
3
CH
3
+ CH
3
C O
OH
+
CH
3
C O C CH
3
CH
3
CH
3
OH
:
+ H
+
C CH
3
CH
3
CH
3
HO
+
C CH
3
CH
3
CH
3
H
2
O +

Thy phn trong mi trng base
Cn gi l phn ng x phng ha.
Thy phn ester trong mi trng base to mui carboxylat l phn ng
khng thun nghch. V alcol to thnh c tnh acid yu hn tnh acid ca acid
carboxylic.
RCOOR' + HO
-

RCOO
-
+ R'OH
C ch phn ng thy phn c xc tc base.
R C OR'
O
+ HO
-
R C OR'
O
OH
-

+ R'O
-
-
R C OR'
O
OH
:
R C
O
OH

+ R'O
-
-
R C
O
OH
R C
O
O
+ R'O H

1.5.2. Phn ng chuyn i ester
Khi un ester vi alcol c xc tc acid hoc natri alcolat xy ra phn ng
trao i ester.
H
+
+ R'OH R C O
O
R"
+ R"OH R C O
O
R'

CH
2
=CH
_
COOCH
3
+ C
4
H
9
OH
CH
2
=CH
_
COOC
4
H
9
+ CH
3
OH
CH
3
C
6
H
4
SO
3
H

277
1.5.3. Phn ng vi amoniac v mt s dn xut ca amoniac
RCOOR' + NH
3

Ester Amoniac

RCO
_
NH
2
+ R'OH
Amid
RCOOR' + HNR"
2

Amin
RCO
_
NR''
2
+ R'OH
Amid th
RCOOR' + H
2
N
_
NH
2

Hydrazin
RCO
_
NH
_
NH
2
+ R'OH
Hydrazid
RCOOR' + H
2
NOH
Hydroxylamin
RCO
_
NHOH + R'OH
Acid hydroxamic
1.5.4. Phn ng vi hp cht c kim to alcol bc ba
(Xem cht c kim)
1.5.5. Phn ng kh
Ester b kh bng LiAlH
4
, NaBH
4
v hn hp Na + alcol (phn ng Buve -
Blanc) to ra alcol bc nht.
R COOR' R CH
2
OH + R'OH
4[H]

CH
3
(CH
2
)
7
CH=CH(CH
2
)
7
COOC
4
H
9
CH
3
(CH
2
)
7
CH=CH(CH
2
)
7
CH
2
OH + HOC
4
H
9
Na+ C
2
H
5
OH
Butyl oleat Alcol oleic

1.5.6. Phn ng ca nhm methylen linh ng
Phn ng ngng t Claisen.
Khi c tc dng ca natri kim loi hoc natri alcolat, hai phn t ester c
th ngng t vi nhau to ester ca acid -cetocarboxylic.
NaOC
2
H
5
+ C
2
H
5
OH
R C
O R'
COOC
2
H
5
CH
+
H CH COOC
2
H
5
R'
R C OC
2
H
5
O

Cc ester ca acid bo vi glycerin gi l cht bo (lipid).
R
1
CO OCH
2
OCH
OCH
2
R
2
CO
R
3
CO
Triacylglycerin
Triglycerid Diglycerid
Monoglycerid
Diacylglycerin
Monoacylglycerin
HOCH
2
OCH
2
R
1
CO
HOCH
2
HOCH R
2
CO OCH
OCH
2
R
1
CO

278
R
1
, R
2
, R
3
l cc gc hydrocarbon no hoc cha no, khng phn nhnh c t
11-19 nguyn t carbon. Lipid cng c th l ester ca acid bo v acid
phosphoric. Cc acid bo thng gp nh:
Acid lauric CH
2
(CH
2
)
10
COOH,
Acid palmitic CH
3
(CH
2
)
14
COOH
Acid stearic CH
3
(CH
2
)
16
COOH;
Acid oleic CH
3
(CH
2
)
7
CH=CH(CH
2
)
7
COOH,
Acid linoleic CH
3
(CH
2
)
4
CH=CHCH
2
CH=CH(CH
2
)
7
COOH,
Acid linolenic CH
3
CH
2
CH=CHCH
2
CH=CHCH
2
CH=CH(CH
2
)
7
COOH
Acid stearolic CH
3
(CH
2
)
7
CC(CH
2
)
7
COOH,
CH
2
CH
CH
2
O CO(CH
2
)
14
CH
3
O CO(CH
2
)
14
CH
3
O CO(CH
2
)
14
CH
3
CH
2
CH
O COR
1
O COR
2
CH
2
O P OCH
2
CH
2
N(CH
3
)
3
O
O-
+
Lipid
Phospholipid
Tripalmitatglicerin
Lecitin

2. Anhydrid acid

Hai phn t acid b loi nc to thnh anhydrid acid. Cng thc chung:

R C
O
O H
R C
O
O
O
C R
R C
OH
O
Acid Anhydrid acid

Anhydrid acid ht nc to thnh acid. ng dng iu ch anhydrid acid.
C CH
2
CH
2
C
O
OH
OH
O
C CH
2
CH
2
C
O
O
O + (CH
3
CO)
2
O
+ 2 CH
3
COOH
Acid succinic
Anhydrid succinic Anhydrid acetic
Acid acetic

Trong bng 21-4 trnh by cng thc, tn gi v tnh cht vt l ca mt vi
anhydrid.

279
Bng 21.4. Cng thc, tn gi v tnh cht l hc ca mt s anhydrid acid
Cng thc Tn gi
t
c
o
t
s
o

(CH
3
CO)
2
O Anhydrid acetic -73,0 139,6
(C
2
H
5
CO)
2
O Anhydrid propionic -45,0 168,0
(C
3
H
7
CO)
2
O Anhydrid n-butyric -75,0 198,0
(n-C
4
H
9
CO)
2
O Anhydrid n-valeric - 218,0
(n-C
17
H
35
CO)
2
O Anhydrid stearic. 72,0
C CH
2
CH
2
C
O
O
O

Anhydrid succinic

119,6

261,0
(C
6
H
5
CO)
2
O Anhydrid benzoic 42,0 360,0
C
O
C
O
O

Anhydrid phtalic

132,0

284,0

C CH
CH C
O
O
O

Anhydrid maleic

53,0

-
Anhydrid acid l tc nhn acyl ha.
NH
2 NHCOCH
3
+ CH
3
COOH + (CH
3
CO)
2
O
Acetanilid

3. Ceten (CH
2
= C = O)
C th xem ceten l anhydrid acid khi phn t acid b loi mt phn t nc.
Ceten
Acid
+ H
2
O
CH
2
C O CH
2
C O
OH H

Dialkylceten
Alkylceten Dimethylceten
Methylceten
C C O
R
R'
CH C O R
CH C O CH
3
C C O
CH
3
CH
3
;
;
;

280
Cc phn ng ca ceten
Cc ceten nh l mt tc nhn acyl ha.
..
..
..
..
..
..
CH
3
C
B
O
CH
2
C
OH
B
B
-
H
+
CH
2
C OH
+
+
-
..
..
: CH
2
C O
..
..
CH
2
C O

B
-
l nhng cht i nhn nh H
2
O, alcol, acid, amoniac.
Amid
Anhydrid acid
Ester
Acid
NH
3
RCOOH
ROH
H
2
O
CH
3
C
O
NH
2
R C
O
O
CH
3
C
O
O
CH
3
C
O
OR
CH
3
C
O
OH
CH
2
C O

4. Halogenid acid acyl halogenid
Thay nhm OH ca acid carboxylic bng halogen (X) thu c halogenid acid.
RCOOH RCOX
4.1. Cu to
Nguyn t halogen c cp in t khng lin kt lin hp vi lin kt ca
nhm C=O v vy phn t acyl halogenid c cc trng thi nh sau:
Acetyl clorid
-
+
:
..
: :
..
C
CH
3
Cl
O
:
..
..
..
:
C
CH
3
Cl
O

di lin kt v gc lin kt ca acetyl clorid trnh by trong bng 21-5.
Bng 21.5. di v gc lin kt ca acetyl clorid
Acetyl clorur di lin kt Gc lin kt
C
CH
3
Cl
O

C=O........ 1,192
C
_
C..........1,499
C
_
Cl.........1,789
C
_
H..........1,083
C
_
C=O......127,08
o

C
_
C
_
Cl......112,66
o

O=C
_
Cl......120,26
o

281
4.2. Danh php
c tn acid nhng thay tip v ng ca acid " ic" thnh "yl" hoc
"oic"thnh " oyl" v c tn ca halogen
CH
3
COCl Acetyl clorid, Etanoyl clorid
CH
3
CH
2
COF Propionyl florid, Propanoyl fluorid
Bng 21.6 trnh by cng thc, tn gi v tnh cht l hc ca mt s acyl halogenid
Bng 21.6. Tn gi, cng thc v tnh cht l hc ca acyl halogenid
Tn gi Cng thc t
o
c t
o
s
Acetylflorid, Etanoylflorid CH
3
COF 20,5 0,993
Acetylclorid, Etanoyl clorid CH
3
COCl 52,0 1,104
Acetylbromid, Etanoyl bromid CH
3
COBr 76,7 1,520
Cloroacetylclorid CH
2
ClCOCl 105,0 1,495
Propionylclorid CH
3
CH
2
COCl 80,0 1,065
n-Butyrylclorid CH
3
CH
2
CH
2
COCl 102,0 1,028
Isobutyrylclorid (CH
3
)
2
CHCOCl 92,0 1,017
n-Valerylclorid CH
3
CH
2
CH
2
CH
2
COCl 128,0 1,016
Isovalerylclorid (CH
3
)
2
CHCH
2
COCl 113,0 -
n-Caproylclorid n-C
5
H
11
COCl 153,0 -
Caprylclorid CH
3
(CH
2
)
6
COCl 196,0 0,975
Stearylclorid CH
3
(CH
2
)
16
COCl 215,0 -
Benzoylclorid C
6
H
5
COCl 197,0 1.212
4.3. Mt s tnh cht ha hc thng ng dng
4.3.1. Hp cht halogenid acid rt d thy phn to acid
R C Cl
O
+ H
2
O
R C OH
O
+ HCl

4.3.2. Tc dng vi hp cht c kim to ceton hoc alcol bc ba
R C Cl
O
R C R'
O
R C R'
OMgX
R'
R C R'
OH
R'
R'MgX R'MgX
H
2
O

4.3.3. Hp cht halogenid acid l tc nhn acyl ha to ceton,ester
R C Cl
O
R C
O
+ HCl
AlCl
3
+

R'OH +
R C Cl
O
R C OR' HCl
O
+

282
5. Amid

Thay th nhm OH ca acid carboxylic bng nhm NH
2
thu c amid.

R C OH
O
R C NH
2
O
R C NHR'
O
R C N
O
R'
R"
Acid
Amid
Amid the

5.1. Danh php
c tn acid c s carbon tng ng nhng thay tip v ng " ic" hoc "oic"
bng tip v ng "amid"
Chc CONH
2
cn c gi l carboxamid
Etancarboxamid
Metan carboxamid
H C NH
2
O
CH
3
C NH
2
O
CH
3
CH
2
C NH
2
O
H C N(CH
3
)
2
O
CH
3
CH
2
CH
2
C NHCH
3
O
Formamid
Acetamid Propionamid
N,N-Dimethylformamid
N-Methylbutyramid
Metanamid Etanamid Propanamid
N,N-Dimethylmetanamid N-Methylbutanamid
1-Propan-N-methylcaboxamid

Etencarboxamid 3-Cyclopentencarboxamid Cyclohexancarboxamid Benzencarboxamid
Acrylamid
Benzamid
CH
2
CH CONH
2
CONH
2
CONH
2
CONH
2

Trong bng 21-7 trnh by mt s amid.
Bng 21.7: Tn gi, cng thc ca mt s amid
Tn gi Cng thc t
o
c
n-Valeramid n-C
4
H
9
CONH
2
106
n-Caproamid n-C
6
H
11
CONH
2
101
Steramid C
17
H
35
CONH
2
109
Benzamid C
6
H
5
CONH
2
130
Cinnanamid C
6
H
5
CH=CHCONH
2
-
Succinamid H
2
NCOCH
2
CH
2
CONH
2
260
Cc amid th lng c nhit si cao v c lin kt hydro gia cc phn t.
Lien ket hydro cua amid
C NH
2
O
CH
3
C NH
2
O
CH
3
C NH
2
O
CH
3
C NH
2
O
CH
3
...
... ...
...
...
...

Cng thc
CH
3
_
CONH
2
CH
3
_
CONHCH
3
CH
3
_
CON(CH
3
)
2
t
s
o

221
204
165

283
Cp in t trn nit lin hp vi lin kt ca nhm C = O nn tnh base
ca nhm NH
2
gim.
R C NH
2
O
..
R C NH
2
O
+
-

5.2. Cc phn ng ca amid
5.2.1. Phn ng acid -base
Amid l mt base yu ch tc dng vi nhng acid mnh. S proton ha xy
ra nguyn t oxy.
..
R C
O
NH
2
R C
OH
NH
2
..
..
.. ..
+
R C
OH
NH
2
..
+
+ H
+

Amid l mt acid yu. Amid tc dng vi natri hoc natri amidid trong ether
to mui.
..
R C
O
NH
2
+ Na
R C
O
NHNa
R C
O
NH
R C
O
NH
..
..
..
..
..
..
..
..
-
..
..
..
..
:
-
;

5.2.2. Thy phn amid
Trong mi trng acid hoc base amid thu phn to thnh acid hoc mui.

RCONH
2
+ H
2
O RCOOH + NH
3

5.2.3. Phn ng loi nc
Di tc dng ca cc cht ht nc nh P
2
O
5
v nhit , amid b loi nc
to thnh nitril (RC N)
Isobutyronitril Isobutyramid
+ H
2
O
200
_
220
o
C
P
2
O
5
(CH
3
)
2
CH C N (CH
3
)
2
CH C NH
2
O

5.2.4. Khi c nhit cc amid ca diacid d to thnh imid
CH
2
CH
2
CONH
2
CONH
2
C CH
2
CH
2
C
NH
O
O
Nhie t
Succinamid Succinimid

284
CONH
2
CONH
2
C
NH
C
O
O
Nhiet
Phtalamid
Phtalimid

5.2.5. Chuyn v Hofmann
Amid tc dng vi hn hp Br
2
+ NaOH to thnh amin.
R C NH
2
O
R NH
2
+ CO
3
2-
+ Br
-
+ OBr
-
Amid Amin bac nhat

C ch phn ng: 2NaOH + Br
2
NaOBr + NaBr + H
2
O
R C NH
2
O
+ OBr
-
Amid
R C N
O
Br
H
..
+ OH
-

R C N
O
Br
H
..
+ OH
-
R C N
O
Br
+ H
2
O
..
..

R C N
O
Br
..
..
R C N
O
+ Br
-
..
..
+

Isocyanat
;
O=C=N
_
R
Isocyanat Chuyen v
+
..
..
R C N
O
O=C=N
_
R
-
+ 2OH
:
Amin bac nhat
2-
+ CO
3
R NH
2

V d:
CH
3
CONH
2
+ 2NaOH + Br
2

CH
3
NH
2
+ Na
2
CO
3
+ NaBr + H
2
O

C
6
H
5
CONH
2
+ 2NaOH + Br
2

C
6
H
5
NH
2
+ Na
2
CO
3
+ NaBr + H
2
O

C
6
H
5
CH
2
CONH
2
+2NaOH+Br
2
C
6
H
5
CH
2
NH
2
+ Na
2
CO
3
+ NaBr +H
2
O

5.2.6. Kh ha amid bng LiAlH
4
,
NaBH
4
to thnh amin
R C
O
NH
2
R CH
2
NH
2
4H [LiAlH
4
]

6. Nitril (R-C=N)
Nitril c cu trc R
_
CN v Ar
_
CN
285
6.1. Danh php nitril
Danh php IUPAC: c tn hydrocarbon tng ng v thm nitril.
Danh php thng thng:
Gi tn ca gc acyl c s carbon tng ng v thm nitril.
Gi tn gc hydrocarbon tng ng v thm cyanid
CH
3
_
CN CH
3
CH
2
_
CN C
6
H
5
_
CN CH
2
=CH
_
CN

C N

Etannitril Propannitril - Propennitril -
Acetonitril Propionitril Benzonitril Acrylonitril -
Methylcyanid Ethylcyanid Phenylcyanid Vinylcyanid Cyclopentylcyanid
a s cc hp cht nitril c c cao.

6.2. iu ch nitril
T dn xut halogen v natri cyanid
R
_
X + NaCN

R
_
CN + NaX
T amid v cht ht nc P
2
O
5

R
_
CONH
2
R
_
CN + H
2
O
6.3. Cc phn ng ca nitril
Thy phn nitril
Trong mi trng acid hoc base thy phn nitril to acid hoc mui ca acid.
CH
3
C N CH
3
C NH
2
O
CH
3
C OH
O
+ H
2
O
- NH
3
+ H
2
O

Kh ha nitril
Kh bng LiAlH
4
, NaBH
4
hoc natri trong alcol to thnh amin bc nht
R C N
4H[LiAlHl
4
]
R CH
2
NH
2

Tc dng vi hp cht c kim - RMgX (xem phn hp cht c kim).
Cc arylcyanid - ArCN c th b trimer ho to hp cht d vng triazin.
Arylcyanid
2,4,6-Triaryl-1,3,5-Triazin
3
N N
N Ar
Ar
Ar
Ar C N

286
Bi tp
1. T cc acid sau:
a- CH
3
CH
2
CH
2
CH
2
CH
2
COOH b- (CH
3
)
2
CHCH
2
CH
2
COOH
c- CH
2
=CHCH
2
CH
2
COOH d- BrCH
2
CH
2
COOH
Hy vit cng thc ester, amid, acylclorid, anhydrid v nitril ca acid
tng ng.
Gi tn nhng cht .
2. Gi tn cc hp cht sau:
a. (CH
3
)
2
CHCH
2
CH
2
COOCH
2
CH(CH
3
)
2
b. (CH
3
)
3
CCH
2
CH
2
CON(CH
2
CH
3
)
2
c. (CH
3
CH
2
CH
2
CO)
2
O
d C
6
H
5
CH
2
CN
3. Hy vit phn ng cc giai on thy phn acetamid trong mi trng acid

4. Thc hin s chuyn ha:
Propionamid Ethylamin

Trnh by c ch phn ng .
287
Chng 22
HP CHT AMIN
Mc tiu
1. Gii thch c cu to ca cc amin v gi c tn chng theo danh php
quc t.
2. Nu c ha tnh ca amin mch thng v amin thm ng thi nu c
phng php phn bit cc bc ca amin thng cng nh amin thm.
Ni dung
1. Cu to
Amin l nhng hp cht c cc gc alkyl, gc aryl lin kt trc tip vi
nguyn t nit. C th xem amin l dn xut ca amoniac (cng nh alcol, ether
l dn xut ca nc).
Amoniac NH
3
RNH
2

R
2
NH

R
3
N R l gc alkyl hoc aryl - Ar
Nc H
2
O ROH R
2
O
1.1. Phn loi amin
Amin bc nht: C mt gc hydrocarbon lin kt vi nguyn t nit: RNH
2

Amin bc hai: C hai gc hydrocarbon lin kt vi nguyn t nit: RR 'NH
Amin bc ba: C ba gc hydrocarbon lin kt vi nguyn t nit: RR 'R''N

Ion amoni bc 4: R
4
N
+

1.2. Cu trc khng gian ca amin
Phn t amoniac c cu trc hnh thp. di lin kt N
_
H l 1.008 . Gc
lin kt HNH l 1073. Nguyn t nit trng thi gn nh lai ha sp
3
v to
thnh 3 lin kt (sp
3
_
s) gia 3 orbital sp
3

ca nit vi orbital s ca 3 nguyn t
hydro. Cp in t khng lin kt nm trn orbital sp
3
th t. Cc amin cng c
cu to nh th.
H
N
H
H H
N
H
R
R''
N
R
R' H
N
R'
R
. .
. .
. .
. .
Amoniac
Amin

288
Do cu trc kiu t din, amin vi cc gc R khc nhau c tnh i quang
(chiral). Hai i quang d dng chuyn ha ln nhau. trng thi chuyn tip,
nguyn t nit c trng thi lai ha sp
2
.
N
CH
3
C
2
H
5
H
. .
. .
N
C
2
H
5
H
CH
3
C
2
H
5
N
CH
3
H
. .
. .
Ethylmethylamin Trng thi chuyn tip Ethylmethylamin

Cp in t khng lin kt c vai tr quan trng trong tnh cht ha hc ca
amin: tnh base v tnh i nhn.
2. Danh php
C cc cch gi tn, ty thuc cch s dng thut ng amin.
2.1. Amin l tip v ng (suffixe). Gi tn cc gc hydrocarbon v thm amin
Tn gc hydrocarbon + amin
N-Ethyl,N-p-Tolylbenzenamin N-Methyl,N-Ethyletanamin
N-Ethyletanamin
Metanamin
Methylamin
CH
3
NH
2
Diethylamin
(CH
3
CH
2
)
2
NH
Diethylmethylamin
CH
2
CH
3
N
CH
2
CH
3
CH
3
C
6
H
5
N
CH
2
CH
3
C
6
H
4
CH
3
p
Ethyl, phenyl,p-tolylamin

2.2. Theo danh php IUPAC
Gi tn hydrocarbon tng ng v thm tip v ng amin
Tn hydrocarbon tng ng + amin
4-Methylbenzenamin N,N-Dimethylbenzenamin Benzenamin
CH
3
NH
2
N(CH
3
)
2
NH
2

2.3. Amin l tip u ng (prefixe)
Theo danh php IUPAC. Gi tn hydrocarbon tng ng, thm tip u
ng amino.
Amino + Tn hydrocarbon tng ng
CH
3
NH
2

CH
2
=CHCH
2
NH
2
CH
3
CH
2
N(CH
3
)
2

C
6
H
5
NHCH
3
Aminometan 3-Amino-1-propen Dimethylaminoetan Methylaminobenzen

289
Ch c tn cc gc:
C
6
H
5
NH
_
CH
3
(C
2
H
5
)N
_

p-CH
3
C
6
H
4
NH- - C
10
H
7
NH-
Phenylamino Methylethylamino p-Toluylamino -Naphtylamino
S dng tip u ng amino gi tn nhng hp cht c nhm chc amin.
p-Toluidin
Acid Sulfanilic
Acid p-Aminobenzensulfonic
p-Aminotoluen Acid p-Aminobenzoic
NH
2
COOH
NH
2
CH
3
NH
2
SO
3
H

2.4. Danh php cc amin thm
Theo danh php IUPAC, quy c aminobenzen l anilin. Cc amin thm n
gin c c tn theo anilin.
N,N-dimethylanilin m-Bromoanilin
Anilin
NH
2
NH
2
Br
N(CH
3
)
2

3. iu ch
3.1. Alkyl ha trc tip amoniac v cc amin khc
Phn ng gia amoniac v alkylhalogenid bc nht to thnh amin bc
nht. Phn ng xy ra theo c ch S
N2
.
-H
2
O -NaBr
+ NaOH - +
CH
3
CH
2
NH
2 CH
3
CHNH
3
Br
CH
3
CH
2
Br + NH
3

Trong thc t thng thu c hn hp cc amin c bc khc nhau.
RX + NH
3
RNH
2
RX
RNHR (R)
3
N
RX
-HX
-HX
-HX

Cc amin bc nht tc dng vi alkylhalogenid thu c amin bc hai. Tnh
cht i nhn ca amin thm yu hn amin mch thng. Anilin tc dng vi alkyl
halogenid ch yu thu c amin bc hai.
NH
2
NH
2
CH
2
C
6
H
5
+ C
6
H
5
CH
2
Cl
NaHCO
3
Cl
+
-
NHCH
2
C
6
H
5
-NaCl -CO
2
-H
2
O
Anilin Benzylclorid Benzylphenylamoniclorid Benzylphenylamin

290
3.2. Tng hp Gabriel. Alkyl ha khng trc tip
Xut pht t phtalimid, alkylhalogenid s thu c alkylamin bc nht.
Phn ng xy ra nh sau:
Ion phtalat Alkylamin Alkylphtalimid Ion phtalimid Phtalimid
C
N
C
H
O
O
- H
2
O
+ NaOH
- X
-
C
NR
C
O
O
+ R
_
X
-
C
N
C
O
O
HO
-
H
2
O
R
_
NH
2
-
-
+
COO
COO

Ion phtalimid l mt tc nhn i nhn, tc dng vi alkylhalogenid (RX) to
alkylphtalimid. Alkylphtalimid b thy phn to alkyl amin bc nht.
3.3. Kh ha hp cht nitro
Kh ha hp cht nitro to hp cht amin. Cht kh thng dng l kim
loi trong mi trng acid, hoc hydro phn t c xc tc.
ArNO
2

+ 3Fe + 6HCl ArNH
2

+ 3FeCl
2
+2H
2
O
2-Nitro-5-isopropyltoluen 2-Methyl-5-isopropylanilin
+ 2H
2
O
,
t
o
Ap suat
+ 3H
2
/ Ni
NH
2
CH
3
CH(CH
3
)
2
NO
2
CH
3
CH(CH
3
)
2

y l phng php thng s dng iu ch cc amin thm.
3.4. Kh ha hp cht nitril (RC N)
Kh ha hp cht nitril bng hydro phn t c xc tc hoc bng LiAlH
4

trong mi trng ether to amin bc nht.
RC N
H
2
/ xc tc
hoc LiAlH
4
RCH
2
NH
2

3.5. Kh ha hp cht imin (RCH =NH)
Xut pht t aldehyd hoc ceton v amoniac thu c hp cht imin. Trong
trng hp ny imin l hp cht khng bn d b kh ho v to thnh amin. Kh
ha imin bng hydro phn t c xc tc.
RCH=NH + H
2
O + NH
3
RCHO

xc tc
RCH=NH + 2H
2
RCH
2
NH
2
Aldimin
Amin bc nht

291
Xut pht t ceton v amoniac thu c cetimin (cetoimin). Kh ha
cetimin thu c amin bc hai.
3.6. Kh ha hp cht amid (RCONH
2
)
Kh ha hp cht amid bng LiAlH
4
thu c amin.
+ H
2
O + Al
3+
+ Li
+ + LiAlH
4
R CH
2
NH
2
R C
O
NH
2
+
. . .

+ LiAlH
4
C N(CH
3
)
2
O
H
CH
2
N(CH
3
)
2
H
N,N-Dimethylcyclohexancarboxamid N,N-Dimethylcyclohexylmetanamin
. . .
+

3.7. Phng php chuyn v Hofmann
Cc amid tc dng vi halogen trong mi trng kim to amin. Phn ng
qua giai on chuyn v Hofmann.
CH
3
(CH
2
)
8
CONH
2

+ Cl
2
+ HO
-
CH
3
(CH
2
)
8
NH
2
+ CO
2
+ HCl + Cl
-
Decanamid Nonanamin
C ch chuyn v Hofmann (xem phn amid).
4. Tnh cht l hc
Cc amin aliphatic l nhng cht khng mu, tan trong nc. Cc amin c t 3
nguyn t carbon dng lng. tan trong nc gim khi phn t lng tng.
Cc amin thm l cht lng hoc rn khng mu. B ha nu v en dn khi
tip xc vi khng kh.
Cc amin thm u c mi kh chu. Cc amin bc nht, bc hai c lin kt
hydro gia cc phn t. V vy nhit si ca amin cao hn cc hydrocarbon
tng ng.
Tnh cht vt l ca amin c trnh by trong bng 22-1.
Amin bc nht c nhit si cao hn amin bc hai v bc ba c cng trng
lng phn t. Nguyn nhn l amin bc nht d to lin kt hydro gia cc phn t.
5. Tnh base ca amin
Vi s hin din ca cp in t khng lin kt trn nguyn t nit, amin
c xem l nhng base Lewis nh alcol, ether. Nhng m in ca nit nh
hn oxy do amin c tnh base mnh hn alcol v ether.

292
Bng 22.1: Tnh cht l hc ca cc amin
Cng thc Tn gi tc ts pKa
CH
3
NH
2
Methylamin - 92,5 - 6,5 10,62
(CH
3
)
2
NH Dimethylamin - 96,0 7,4 10,77
(CH
3
)
3
N Trimethylamin - 124,0 3,5 9,80
CH
3
CH
2
NH
2
Ethylamin - 80,6 16,6 10,63
(CH
3
CH
2
)
2
NH Diethylamin - 50,0 55,8 10,93
(CH
3
CH
2
)
3
N Triethylamin - 11,5 89,5 10,87
CH
3
CH
2
CH
2
NH
2
Propylamin - 83,0 48,7 10,58
C
6
H
5
NH
2
Anilin, aminobenzen 6,2 184,4 4,58
C
6
H
5
NHCH
3
N-Methylanilin - 5,7 196,3 4,85
C
6
H
5
N(CH
3
)
2
N,N-Dimethylanilin 2,5 192,5 5,06
o-CH
3
C
6
H
4
NH
2
o-Toluidin,
2-Aminotoluen
- 27,7 199,7 4,39
m-CH
3
C
6
H
4
NH
2
m-Toluidin,
3-Aminotoluen
- 43,6 203,2 4,69
p-CH
3
C
6
H
4
NH
2
p-Toluidin,
4-Aminotoluen
43,7 200.4 5,12
C
6
H
5
CH
2
NH
2
Benzylamin
-Aminotoluen
185,0 -
C
6
H
5
NH C
6
H
5
Diphenylamin 54,0 302,0 -
NH
2

-Naphtylamin
1-Aminonaphtalen

50,0

301,0

-
NH
2

-Naphtylamin
2-Aminonaphtalen

50,0

306,0

-

Trong dung dch nc cc amin c cn bng nh sau:
RNH
2
+ H
2
O RNH
3
+ HO
-

RNH
3
+ H
2
O RNH
2
+ H
3
O
+

K
b K
a
+ +
;

+
K
b
=
[RNH
3
][HO
-
]
[RNH
2
]

+
+
K
a
=
[RNH
2
][H
3
O ]
[RNH
3
]

C mi quan h Ka.Kb = 1O
-14

v pKa

+ pK
b
= 14
Gi tr pKb ca mt s amin v gi tr pKa ca cc ion amoni tng ng
(acid lin hp) c trnh by trong bng 22-2.
293
Bng 22.2: Tnh base ca mt s amin
Amin pK
b
,
25C Acid lin hp A pK
a
,
25C
NH
3
4,76
NH
4
+

9,24
CH
3
NH
2
3,38
CH
3
NH
3
+

10,62
CH
3
CH
2
NH
2
3,36
CH
3
CH
2
NH
3
+

10,64
(CH
3
)
3
CNH
2
3,32
(CH
3
)
3
CNH
3
+

10,68
(CH
3
)
2
NH 3.27
(CH
3
)
2
NH
2
+

10,73
(CH
3
CH
2
)
2
NH 3,06
(CH
3
CH
2
)
2
NH
+

10,94
(CH
3
)
3
N 4,21
(CH
3
)
3
NH
+

9,79
(CH
3
CH
2
)
3
N 3,25
(CH
3
CH
2
)
3
NH
+

10,75
Cc arylamin c tnh base yu hn tnh base ca alkylamin.
Trong dung dch nc c cn bng:
+
+ H
3
O
NH
2
+ H
2
O
NH
3
+

K
a
= 2,5 . 10
-5
M. pK
a
= 4,6
+
+
(CH
3
)
2
CHNH
3
+ H
2
O (CH
3
)
2
CHNH
2
+ H
3
O

K
a
= 2,5 . 10
-12
M. pK
a
= 11,60
Tnh base ca anilin gim so vi amin mch thng l do hiu ng ht in
t ca nhm phenyl v hiu ng lin hp - C ca nhm amin. Cp in t khng
lin kt trn nit phn b vo nhn benzen theo cc cng thc gii hn sau:
NH
2
NH
2
NH
2 NH
2
+ +
+
-
-
-
..

Tnh base ca amin ph thuc cc nhm th v hiu ng khng gian.
Cc nhm th y in t lm tng tnh base. Cc nhm th ht in t lm
gim tnh base. Hiu ng khng gian c nh hng ng k n tnh base.

294
Bng 22.3: Gi tr pKa ca cc ion anilinium X -C
6
H
4
NH
3
+

pK
a
,
25C
Nhm th X Orto meta para
H 4,60 4,60 4,60
Benzoyl - - 2,17
Bromo 2,53 3,58 3,86
Cloro 2,65 3,52 3,98
Cyano 0,95 2,75 1,74
Fluoro 3.20 3,57 4,65
Iodo 2,60 3,60 3,78
Methoxy 4,52 4,23 5,34
Methyl 4,44 4,72 5,10
Nitro -0,26 2,47 1,00
Trifluoromethyl - 3,20 2,75
6. Cc phn ng ca amin
Cp in t khng lin kt trn nit lm cho amin c tnh base v tnh i
nhn. V vy amin c phn ng th i nhn vi mt s cc cht c trung tm i
in t.
6.1. Phn ng to amid
Amin phn ng vi acid hu c v cc dn xut ca acid nh acylhalogenur
RCOX to amid RCONH
2
.

RNH
2
R'COX X = H , Halogen , RCOO R'CONHR + HX
t
o
+ ;
-

(N-phenylacetamid) Acetanilid
Anilin
t
o
+ CH
3
COOH
+ H
2
O
NHCOCH
3
NH
2

Methylamin clorhydrat N-Methylacryloamid
Acryloylclorid
-
+
+
+
CH
2
CH C NHCH
3
O
CH
3
NH
3
Cl
2 CH
3
NH
2
CH
2
CH C Cl
O

p-Etoxyacetanilid p-Etoxyanilin
Phenacetin
p-Phenetidin
HCl
(CH
3
CO)
2
O
+ CH
3
COONa
NHCOCH
3
C
2
H
5
O
NH
2
C
2
H
5
O

295
6.2. Phn ng vi acid nitr (HNO
2
)
Acid nitr phn ng vi amin mch thng v amin thm c cc bc khc
nhau thng to ra cc sn phm khc nhau.
6.2.1. Vi amin bc nht
Acid nitr phn ng vi amin bc nht mch thng to mui diazoni khng
bn, phn hy thnh alcol v N
2
. Tng qut nh sau:
NCl
+
-
+ N
2
RN
RNH
2
+ O=N
_
ONa + 2HCl
ROH
- 2H
2
O
- NaCl
+HCl
+ H
2
O
Amin bc nht
Mui diazoni
Alcol

y l phn ng c bn ng dng nh lng nit trong cc acid amin.
Acid nitr kh tn ti iu kin bnh thng. c c acid nitr phi s
dng hn hp mui nitrit v acid ( NaNO
2
+ HCl).
Trong thc t, amin bc nht mch thng tc dng vi acid nitr to hp
cht mui diazoni khng bn phn hy thnh hn hp cc sn phm alcol, N
2
,
alken v alkyl halogen. V d phn ng sau:
7%
3%
26%
3%
5%
13% 25%
CH
3
(CH
2
)
3
NH
2
NaNO
2
HCl
CH
3
(CH
2
)
3
OH CH
3
CH
2
CHOHCH
3
CH
3
(CH
2
)
3
Cl CH
3
CH
2
CHClCH
3
CH
3
CH
2
CH=CH
2
C C
CH
3
CH
3
H
C C
CH
3
H
CH
3
H H
N
2
+ + +
+
+
+
+

C th gii thch cc c ch phn ng to thnh cc cht nh sau:
Hp cht mui diazoni to thnh khng bn, phn hy thnh N
2
v carbocation
Butandiazoniclorid
+NaCl + 2H
2
O
- +
Cl N CH
3
CH
2
CH
2
CH
2
N + NaNO
2
+ 2HCl CH
3
(CH
2
)
3
NH
2

+
CH
3
CH
2
CH
2
CH
2
N N Cl
+
-
CH
3
CH
2
CH
2
CH
2
+ N
2
+ Cl
-
Muoi diazoni Carbocation

Carbocation CH
3
CH
2
CH
2
CH
2
+
tc dng vi Cl
-
to CH
3
CH
2
CH
2
CH
2
Cl v tc
dng vi H
2
O to CH
3
CH
2
CH
2
CH
2
OH hoc chuyn v to carbocation bc hai
CH
3
CH
2
CH
+
CH
3
.

+
CH
3
CH
2
CH
2
CH
2
CH
3
CH
2
CHCH
3
+

Carbocation tc dng vi Cl
-
to CH
3
CH
2
CHClCH
3
hoc vi H
2
O to
CH
3
CH
2
CHOHCH
3
hoc tch loi H
+
v to 2-buten dng cis v trans.
296
+
H
C C
CH
3
H
CH
3
H
C C
CH
3
CH
3
H
CH
3
CH
2
CHCH
3
+
CH
3
CH
2
CHClCH
3
CH
3
CH
2
CHOHCH
3
Cl
-
H
2
O
+ H
+
+ H
+

Amin thm bc nht tc dng vi acid nitr to mui diazoni t

< 5C.
Muoi arendiazoniclorid Amin thm bac nhat
Ar
_
N Ar
_
NH
2
+ NaCl + 2H
2
O
-
+
Cl N + NaNO
2
+ 2HCl

Mui diazoni ca amin thm c nhiu ng dng (xem phn mui diazoni).
6.2.2. Amin bc hai
Cc amin bc hai tc dng vi acid nitr to hp cht N-nitroso amin c
mu vng
Amin bc hai
N
Ar
R
H + O=N
_
ONa + HCl + H
2
O
Hp cht nitroso amin
+ NaCl N
Ar
R
N O

N
H
+ H
2
O
+ HO
_
N=O
N
N=O
Piperidin N-Nitrosopiperidin

6.2.3. Amin bc ba
Amin bc ba kh xy ra phn ng vi acid nitr. Cc alkylamin bc ba hu
nh khng phn ng. Vi cc arylamin bc ba phn ng xy ra khng phi ti
nit ca amin m xy ra phn ng th nhm chc nitroso vo v tr para so vi
chc amin.
p-Nitroso-N,N-dimethylanilin N,N-Dimethylanilin
(CH
3
)
2
N N=O (CH
3
)
2
N H + HO
_
N=O + H
2
O

6.3. Phn ng vi arylsulfonylclorid to sulfonamid
Amin c bc khc nhau tc dng vi arylsulfonylclorid ArSO
2
Cl to thnh
sn phm c kh nng tan khc nhau trong dung dch kim.
Amin bc nht to sn phm tan trong kim (NaOH, KOH).
RNH
2

+ ArSO
2
Cl ArSO
2
NHR + HCl
Amin bc nht Arylsulfonylclorid Arylsulfonamid
297
Amin bc hai to sn phm khng tan trong kim.
+ HCl Ar SO
2
N
Ar'
AR''
+ Ar SO
2
Cl N
Ar'
R
H

Amin bc hai
Arylsulfonamid I ha tan c vo dung dch NaOH v cn c mt hydro c
tnh acid gn trn nit. Arylsulfonat II khng tan trong dung dch NaOH v
khng c hydro ny.
Amin bc ba khng tc dng vi arylsulfonylclorid
S dng phn ng ny phn bit cc amin c bc khc nhau v to cc
loi sulfamid khc nhau c nhiu ng dng trong dc phm.
6.4. Phn ng vi halogen. To N -Halogen amin
Trong mi trng kim long, amin bc nht v amin bc hai tc dng vi
halogen to N -halogen amin.
N,N-Dihalogen alkylamin N-Halogen alkylamin
Amin
- HX
+ X
2
R N
X
X
R NH X
- HX
Na
2
CO
3
,H
2
O
+ X
2
R NH
2

6.5. Phn ng oxy ha
Qu trnh oxy ho ph thuc vo cu to ca amin v cht oxy ho.
Amin mch thng bc nht b oxy ha to hn hp cc cht: oxim, nitrosoalkan,
N-alkylhydroxylamin v nitroalkan.
H
2
SO
5
[ O ]
Nitroalkan
Nitroso alkan
Oxim
N-Alkylhydroxyl amin
RCH
2
_
NO
2
RCH
2
_
N=O
RCH=N
_
OH
RCH
2
_
NH
_
OH
Amin
RCH
2
NH
2

Amin mch thng bc hai b oxy ho to N,N-dialkylhydroxylamin.
[ O ]
R
N
R
OH
R
N
R
H

Amin mch thng bc ba b oxy ha to N -oxyd amin
298
N
R
R'
R" N O
R
R'
R"
+
-
N-oxyd amin bac 3
[ O ]
N-Oxyd pyridin Pyridin
+ -
N O
CH
3
COOH
H
2
O
2
N

Amin thm bc nht b oxy ha bng acid permonosulfuric (acid Caro
HOOSO
3
H) to hp cht nitrosoaren Ar N = O. Anilin b oxy ha bng dung dch
KMnO
4
hoc bicromat kali K
2
Cr
2
O
7
to hp cht 1,4-benzoquinon hoc cht mu
"en anilin".
6.6. Phn ng th i in t vo nhn thm
Chc amin l nhm th loi I. Amin thm c phn ng th vo nhn thm.
2,4,6-Tribromanilin
Anilin
+ 3 Br
2
+ 3HBr
NH
2
Br
Br
Br
NH
2

Chc amin quyt nh s nh hng vo nhn thm.
NH
2
COOH
NH
2
Br
Br
Br
COOH
+ 3HBr
+ 3 Br
2
Acid m-aminobenzoic Acid 3-amino-2,4,6-tribromobenzoic

Acid 2-amino-3,5-diclorobenzoic
Acid antranilic
+ 3 Cl
2
+ 3HCl
NH
2
COOH
Cl
Cl
NH
2
COOH

Nitro ha amin thm bc ba cho hiu sut cao trong mi trng acid acetic.
2,4-Dinitro-N,N-Dimethylanilin 2-Nitro-N,N-Dimethylanilin N,N-Dimethylanilin
+ +
N(CH
3
)
2
NO
2
NO
2
N(CH
3
)
2
NO
2
N(CH
3
)
2
NO
2
CH
3
COOH
HNO
3
N(CH
3
)
2

p dng phn ng Vilsmeier a chc aldehyd vo amin thm bc ba.
299
DMF
Dimethylformamid
p-Dimethylaminobenzaldehyd
+
N(CH
3
)
2
CHO
2-H
2
O
1-POCl
3
HCON(CH
3
)
2
N(CH
3
)
2

Khi thc hin phn ng th i in t vo amin thm, ngi ta thng phi
bo v chc amin bng s acyl ha nhm amin.
2-Brom-4-methylanilin
4-Methylanilin
CH
3
COOH
NaOH
Alcol
HCl
Br
2
CH
3
COOH
NH
2
CH
3
Br
NHCOCH
3
CH
3
Br
NHCOCH
3
CH
3
NH
2
CH
3

6.7. Tch loi nhm amin - Phn ng tch loi Hofmann
Amin n gin RNH
2
khng b tch loi chc amin. Chuyn amin v dng
hydroxy amoni bc 4 [(R)
4
N]
+
OH
. Di tc dng ca nhit , hydroxy amoni bc

4 b nhit phn to amin bc 3 v alken.
HO
-
+ H
_
CH
2
_
CH
2
_
NR
3
HO

+ CH
2
=CH
2
+ NR
3
H CH
2
CH
2
NR
3
... ...
+
HOH

Phn ng tch loi ny gi l phn ng tch loi Hofmann.
+
NH
2
N(CH
3
)
3
I N(CH
3
)
3
OH
+ N(CH
3
)
3
+ H
2
O
CH
3
I
K
2
CO
3
Ag
2
O
H
2
O
-
120
o
+
-

Khi tch loi to alken phi theo quy tc Hofmann l tch hydro nhm
CH
3
d hn hydro nhm RCH
2
.

CH
3
N(CH
3
)
3 OH
+
-
CH
2 CH
2
+ N(CH
3
)
3
+ H
2
O
99% 1%
+

6.8. Mt s phn ng khc ca amin
Amin bc nht tc dng vi sulfur carbon to acid dithiocarbamid th
nguyn t nit RNH -C(S)
_
SH, dn xut th ca thiour, th nguyn t nit
RNH
_
C(S)
_
NHR.
7. Amin cha no c mt lin kt i - Enamin
Chc amin gn trc tip vi carbon c lin kt i
_
C=C
_
NH
2
gi l enamin.
300
Cc enamin thng khng bn v c dng h bin (mesomer) imin C =N

N
H
N

Enamin Imin
Khi nguyn t nit ca enamin l amin bc ba th enamin bn (khng c s
h bin). Enamin bc ba c th iu ch:
+
O
N
H
Pyrolidin N-(1-cyclohexenyl) pyrolidin
N
Cyclohexanon

Enamin rt nhy cm trong mi trng acid v d phn hy thnh hp cht
carbonyl v amin.
+
O
N
H H
N
+ H
3
O +

Cc enamin c tc dng lm cho nguyn t carbon v tr C c tnh i nhn.
NR
2
+
NR
2
-
:

V vy enamin tc dng vi alkylhalogenid xy ra v tr .
+
N
N
H H
+
+ CH
2
=CHCH
2
Br
N
Br
-
O
+
Br
-
H
2
O
2-allylcyclohexanon

8. Amin a chc Polyamin
Cc amin a chc c nhiu ng dng dng mch thng hay vng.
NH
2
_
CH
2
_
CH
2
_
NH
2

Ethylendiamin

NH
2
NH
2
p-Phenylendiamin

301
NH
2
NH
2

o-Phenylendiamin

N N H H

Piperazin

NH
2
H
2
N

m-Phenylendiamin

NH
2
NH
2

1,8-Diaminonaphthalen

Cc polyamin th hin cc tnh cht c trng ca amin.
o-Phenylendiamin tc dng vi acid nitr to hp cht vng benzotriazol.
N
N
N
H
NH
2
NH
2
+ HNO
2
+ 2H
2
O
Benzotriazol
o-Phenylendiamin

Bi tp
1. Amin c CTPT C
5
H
13
N , C
6
H
13
N
a. Vit cng thc cu to ca cc amin.
b. Gi tn cc amin theo danh php thng thng v IUPAC (amin l tip
v ng, tip u ng).
2. Amin thm c CTPT C
9
H
15
N.
a. Vit CTCT cc amin thm.
b. Gi tn cc amin .
3. Hy iu ch cc amin theo phng php Gabriel.
a. iu ch n -butylamin t n -butylbromid.
b. iu ch benzylamin t toluen.
4. Vit phng trnh phn ng ca cc cht sau y vi acid nitr (NaNO
2
+ HCl).
a. n-pentylamin, o-toluidin, -naphtylamin.
b. ethylisopropylamin, N-ethylanilin. N-methylcyclohexylamin.
c. N-methyl, N-ethyl-p-toluidin.
5. C cc cht sau: Anilin, p-aminophenol, 2-cyclohexenamin.
Cho cc cht ln lt tc dng vi cc cht sau:
a. Acid acetic
b. Acroleylclorid
c. Benzensulfonylclorid.
d. Acetylbromid.
302
e. H
2
O
2

6. Thc hin phn ng chuyn v Hofmann ca cc cht sau:
a. CH
3
(CH
2
)
7
CH
2
CONH
2
.
b. C
6
H
5
CH
2
CONH
2

c. CH
2
=CHCH
2
CH
2
CONH
2
7. Vit cc phn ng trong cc trng hp sau:
a. N,N-dimethyl -2-pentanamin, CH
3
I, Ag
2
O, nhit
b. N,N-dimethyl -1-octanamin, CH
3
I, Ag
2
O, nhit
303
Chng 23
CC HP CHT KHC CHA NIT
Mc tiu
1. Gii thch c s hnh thnh cc loi hp cht nitro, isocyanat, ur, diazo.
2. Nu c mt s ha tnh ch yu ca chng.
3. Nu c mt s ng dng ca dn cht nitro trong tng hp hu c.
Ni dung
Ngoi hp cht amin cn c mt s nhm chc khc cha nit c trnh
by trong bng 23-1.
Bng 23. Cc nhm chc cha nit
Cu to Nhm chc V d
R
_
NO
2
Nitro C
6
H
5
NO
2
Nitrobenzen
R
_
N=C=O
Isocyanat C
6
H
5
NCO Phenylisocyanat
R
_
NHCOOR
Uretan,carbamat C
6
H
5
NHCOOCH
3
Methyl,N-Phenylcarbamat
R
_
NHCONH
_
R'
Ure H
2
NCONH
2
Ure
R
_
N=NN
Azid CH
3
CH
2
N
3
Etylazid
R
_
N=N
_
R'
Azo C
6
H
5
N=NC
6
H
5
Azobenzen
-
+
R N N R'
O

Azoxy
C
6
H
5
N N C
6
H
5
O
-
+

Azoxybenzen
R
_
NH
_
NH
2
Hydrazin C
6
H
5
NHNH
2
Phenylhydrazin
R[NN]
+

Diazoni
[C
6
H
5
NN]
+
Cl
-

BenzendiazoniClorid
R
2
C=N
2
Diazo CH
2
=N
2
Diazometan
R
_
CONH
2
Amid CH
3
CONH
2
Acetamid
1. Hp cht nitro
Hp cht nitro aliphatic tng i t gp. Hp cht nitro ca hydrocarbon
thm c nhiu ng dng lm nguyn liu iu ch amin.

304
1.1. Cu to chc nitro
N
O
O
+
- :
..
..
N
O
O
N
O
O
-
+ +
-

Chc nitro l nhm ht in t, c hiu ng - C v - I
1.2. Nitroalkan (R
_
NO
2
)
Nitroalkan c iu ch bng phng php nitro ha alkan theo c ch gc.
400
o
C
CH
4
+ HNO
3
CH
3
NO
2
+ H
2

Trong phng th nghim c th iu ch nitroalkan bng phn ng th gia
hp cht alkylhalogen v mui nitrit.
2-Nitrooctan 2-Iodooctan
+ NaI CH
3
(CH
2
)
5
CHCH
3
NO
2
+ NaNO
2
CH
3
(CH
2
)
5
CHCH
3
I

Hp cht nitroalkan c tnh acid.
CH
3
NO
2
CH
3
CHCH
3
NO
2
pKa = 10,2 pKa = 7,8

Cng nh acid carboxylic v ceton, hp cht nitroalkan c tnh acid yu.
Base lin hp ca nitroalkan l nhng cht bn v c cng thc gii hn nh sau:
( acid)
(Base lien hp)
Nitrometan
Carbanion , anion nitrometan
-
+
-
-
-
+ +
-
-
+
H
+
+
CH
2
N
O
O
CH
2
N
O
O
CH
2
N
O
O
-
CH
3
N
O
O

Anion nitroalkan l tc nhn i nhn (c tnh a nhn), do cc nitro alkan
tc dng vi aldehyd theo kiu aldol ha.
Nonanal 1-Nitro-2-decanol 80%
+
OH
CH
3
(CH
2
)
7
CHCH
2
NO
2
CH
3
(CH
2
)
7
CHO CH
3
NO
2
HO
-

Cc -hydroxynitro ca hydrocarbon thm b dehydrat (loi nc).
HO
-
-Hydroxy phenylnitroetan
Nitrostyren
- H
2
O
CH CH NO
2
CH CH
2
NO
2
CHO +
OH
CH
3
NO
2

305
1.3. Nitroaren (Ar
_
NO
2
)
1.3.1. iu ch nitroaren
Phn ng th i in t l phng php c bn iu ch hp cht
nitroaren. Trinitrobenzen c iu ch t trinitrotoluen (TNT).
1,3,5-Trinitrobenzen
Acid Picric
TNT
CH
3
NO
2
NO
2
NO
2
COOH
NO
2
NO
2
NO
2
NO
2
NO
2
NO
2
Na
2
Cr
2
O
7
H
2
SO
4
45-55
o
C - CO
2

1.3.2. Cc phn ng ca nitroaren
Nhm nitro bn vng vi cc acid, cc cht oxy ha v cc tc nhn i in
t. Phn ng quan trng ca hp cht nitroaren l phn ng kh to amin.
+ 2H
2
O
6[H]
Ar
_
NH
2
Ar
_
NO
2

Phn ng kh ha nitroaren qua nhiu giai on, to nhiu sn phm trung
gian v ph thuc mi trng phn ng.
Trong mi trng acid
NO
2
NO
NHOH NH
2
2e
-
+ 2H
+

- H
2
O
2e
-
+ 2H
+

2e
-
+ 2H
+

- H
2
O
- H
2
O
Nitrobenzen Nitrosobenzen Phenylhydroxylamin Anilin

Trong mi trng trung tnh
Kh ha trong mi trng trung tnh to thnh arylhydroxylamin l ch yu.
Trong mi trng kim.
Kh ha trong mi trng kim to thnh cc sn phm trung gian.
Pd/C , H
2
NNH
2
, khong kh
(C
2
H
5
O)
3
P , H
2
O
2
,CH
3
COOH , 65
o
NO
2
N N
O
N N
NH NH
Azoxybenzen
Azobenzen
Hydrazobenzen
As
2
O
3
NaOH
Zn
H
2
NNH
2
KOH
NaOH
+
-
85%
84-86%
80%

Cc sn phm trung gian ny trong mi trng acid u to thnh anilin.
306
Dn xut nitroaren c ng dng trong dc phm l chloramphenicol.
Chloramphenicol c 2 nguyn t carbon bt i xng cu hnh threo v erythro.
Cloramphenicol
Erythro Threo
NO
2
HCOH
HCNHCOCHCl
2
CH
2
OH
NO
2
HOCH
HCNHCOCHCl
2
CH
2
OH

2. Isocyanat, carbamat v ure
2.1. Isocyanat (R
_
N=C=O, Ar
_
N=C=O)
Isocyanat l mui (ester) ca acid isocyanic H
_
N=C=O. ng phn ca acid
isocyanic l acid cyanic H -O-CN.
H N=C=O
HO C N
Acid isocyanic
Acid cyanic

Thay th nguyn t oxy bng nguyn t lu hunh thu c acid
thioisocyanic
R
_
N=C=O Ar
_
N=C=O RO
_
CN ArO
_
CN
Alkylisocyanat Arylisocyanat Alkylcyanat Arylcyanat
Isocyanat l sn phm trung gian trong phn ng iu ch amin (chuyn v
Hofmann). Isocyanat tc dng vi amin to ure.
N-Metyl , N'-Cyclohexylure Cyclohexylisocianat
N C N CH
3
O H H
+ CH
3
NH
2
NCO

Khi c mt ca nc, isocyanat to thnh acid carbamic. Acid carbamic
khng bn v phn hy thnh amin tng ng.
Alkylamin Acid N-alkyl carbamic N-Alkyl isocyanat
R NCOOH
+ H
2
O
R NCO
+ CO
2
R NH
2

2.2. Carbamat - Uretan (H
2
N
_
COOR, RNH
_
COOAr)
Carbamat hay l uretan l ester ca acid carbamic. Acid carbamic c cng
thc cu to H
2
N
_
COOH. Cc dn xut ca acid carbamic c cc dng:
307
Thay hydro ca nhm NH
2
bng cc gc hydrocarbon
Acid diarylcarbamic Acid arylcarbamic Acid dialkylcarbamic Acid alkylcarbamic
N COOH
Ar
Ar'
Ar NH COOH
N COOH
R
R'
R NH COOH

Thay hydro ca nhm acid bng gc hydrocarbon thu c ester carbamat hay
uretan. C cc loi ester carbamat (uretan):
H
2
N
_
COOR alkyl carbamat; H
2
N
_
COOAr arylcarbamat.
Isocyanat tc dng vi alcol to ester carbamat
N-Methylcyclohexylcarbamat Cyclohexyl isocyanat
+ CH
3
OH
N C OCH
3
O H
N C O

Hp cht carbamat (uretan) c nhiu ng dng lm thuc tr su, iu ch
cc polymer hay l polyuretan.
2.3. Ure (H
2
NCONH
2
)
C th xem ure (H
2
NCONH
2
) nh l amid ca acid carbamic (H
2
NCOOH)
Ure c cc dn xut alkyl, aryl ure.
R
_
NHCONH
_
R' Ar
_
NHCONH
_
Ar'
Thay th oxy ca ure bng S ta c thioure H
2
NCSNH
2
.
Thay th oxy ca ure bng nhm NH ta c hp cht guanidin - H
2
NC (NH)NH
2

Cng thc cu to ca guanidin:
C NH
H
2
N
H
2
N

Guanidin c tnh base. Kt hp vi proton to ion guanidin c cng thc gii hn:
+ H
+
H
2
N
C NH
2
H
2
N
H
2
N
C NH
2
H
2
N
H
2
N
C NH
2
H
2
N
H
2
N
C NH
H
2
N
+
..
..
.. ..
..
..
+
+
Guanidin
Ion guanidin

C th xem cc acid isocyanic, acid carbamic, ure... l dn xut ca acid
carbonic; Hydro hoc nhm OH ca acid carbonic c thay th bi cc nhm th
tng ng.
308
3. Hp cht diazo v mui diazoni
Hp cht diazo c cng thc tng qut: R
2
C=N
2
.

3.1. Diazometan (CH
2
=N
2
)
Cu to in t ca diazometan chng t nguyn t carbon c tnh i nhn.
:
..
CH
2
=N
2
CH
2
N N
CH
2
N N
+
-
+
-
:
Diazometan
Diazometan

iu ch diazometan t ester ethyl N -methylcarbamat (N-methyluretan).
Diazometan N-nitroso-N-methyluretan Ester ethyl N-methylcarbamat
- C
2
H
5
OH - HCO
3
HO
-
- H
2
O
+ HNO
2
:
+
..
-
CH
2
N N
CH
3
N
C C
2
H
5
O
O
N=O
CH
3
NH
C C
2
H
5
O
O

Cng c th iu ch diazometan t aldoxim v cloramin. Mui natri ca
formaldoxim tc dng vi cloramin to thnh diazometan.
..
+
: CH
2
=N-ONa + NH
2
Cl + NaCl + H
2
O CH
2
N N

Diazometan l tc nhn methyl ha.
R C OH
O
+ CH
2
N
2
R C OCH
3
O
+ N
2

Diazometan c dng tng mt nguyn t carbon trn mch nhnh.
O
O
O
CH
2
N N
O
CH
2
+
-
:
..
..
..
..
:
:
+
-
+ CH
2
N
2
- N
2
- +
Cyclohexanon
Cycloheptanon

+ CH
2
N
2
+ N
2
CH
2
C Cl
O
CH
2
C CHN
2
O
CH
2
C CH
2
Cl
O
+ HCl
83-85%

3.2. -Diazoceton (RCOCH=NN)
..
C CH N N
O
C CH N N
O
+
-
-
+
: :
Diazoacetophenon

309
3.3. Hp cht mui diazoni [Ar
_
NN]
+

Hp cht mui diazoni ca hydrcarbon thm bn vng nhit thp < 5C.
Mui diazoni c nhiu ng dng trong iu ch cc nhm chc khc nhau.
Cu to in t ca mui diazoni:
N N
-
+
:
..
N N
.. +
+
:
N N
+

3.3.1. Danh php mui diazoni
Tn hydrocarbon (hay tn gc hydrocarbon)+ diazoni + halogenid (sulfat)
C
6
H
5
N
2
Cl: Benzendiazoniclorid hay Phenyldiazoniclorid
p-CH
3
C
6
H
4
N
2
Br: p-Toluendiazonibromid hay p-Tolyldiazonibromid
3.3.2. Cc phn ng ca mui diazoni
C th chia cc phn ng ca hp cht mui diazoni thnh hai loi:
Phn ng gii phng phn t N
2
.

Phn ng ngng t khng gii phng phn t N
2
.
a. Phn ng gii phng phn t N
2

Phn ng thy phn khi c nhit .
Dung dch mui diazoni, kh c nhit , to thnh phenol v kh N
2
.
NH
2
Br
CH
3
+
-
+ N
2
N
2
Br
CH
3
HSO
4
+ H
2
O
Br
CH
3
OH

Phn ng xy ra theo c ch th i nhn SN
1
.
ArN
2
+

Ar
+
+ N
2
Ar
+
+ H
2
O

Ar
_
OH
2
+
+ ArOH + H
+

Cation aryl c kh nng tng tc vi cc cht i nhn v to thnh cc dn
xut ca hydrocarbon thm.
Phn ng Sandmeyer. iu ch ArCl, ArBr, ArCN
Hp cht mui aryldiazoni tc dng vi cc cht CuCl, CuBr, CuCN to ra
cc dn xut hydrocarbon thm tng ng gi l phn ng Sandmeyer.
310
CuCl
Cl
-
HCl
NaNO
2
CH
3
Cl
N
2
CH
3
+ N
2
+
NH
2
CH
3

Br
-
HBr
CuBr NaNO
2
Cl
Br
N
2
Cl
+ N
2
+
NH
2
Cl

p-Toluidin p-Tolunitril
0-5
o
5
o
HCl
CuCN
Cl
-
NaNO
2
CH
3
CN
N
2
CH
3
+ N
2
+
NH
2
CH
3

Qua cc phn ng trn chng t mui ng (I) c vai tr xc tc.
Benzosulfocyanid
Benzonitril
Nitrobenzen
Bromobenzen
- N
2
- N
2
- N
2
SCN
-
, Cu
2
(SCN)
2
,
CN
-
, CuCN ,
NO
2
, CuCl ,
- N
2
Br
-
, CuBr ,
+
:
SCN
CN
NO
2
Br
N N

Hp cht nitril thu c l nguyn liu iu ch acid thm, amin thm.
Phn ng th nhm diazoni bng nguyn t hydro.
Acid hypophosphor H
3
PO
2
kh ha mui aryldiazoni thnh aren.
N N:
+
X
-
H
3
PO
2
, H
2
O ( Cu
+
)
-N
2
- HX -H
3
PO
4

Phn ng trn c ngha trong tng hp cc cht hu c:
Khng th brom ha trc tip acid benzoic thu c acid 2,4,6-
tribromobenzoic. V vy phi qua chc amin nh hng brom vo v tr thch
hp sau loi chc amin qua mui diazoni.
311
NH
2
COOH
Br
Br
Br
N
2
COOH
Br
Br
Br
COOH
Br
Br
Br
NaNO
2
H
2
SO
4 HSO
4
+ -
- 5
o
c
H
3
PO
2
- 5
o
c

b. Phn ng ngng t khng gii phng phn t N
2
Ion aryldiazoni [ArNN]
+
l tc nhn i in t, d tc dng vi cc cht c
tnh i nhn nh phenol v amin thm.
Ngng t vi amin thm
p-Aminoazobenzen
NH
2
N N
+
+
..
..
..
N N
N N NH
2 +

Trc tin ion phenyldiazoni tng tc vo nguyn t oxy ca phenol hoc
nguyn t nit ca anilin, sau c s chuyn v v to sn phm.
Phn ng ngng t ca aryldiazoni l c s iu ch cc cht mu.
+ H
+
4-Dimethylaminoazobenzen
N(CH
3
)
2
N N
+
+
..
..
..
N N
N N N(CH
3
)
2 +

4-Dimetylaminoazobenzen chnh l heliantin cht ch th mu ng dng
trong ha phn tch. Cc cht mu rt ph thuc vo pH.
Ngng t vi cc phenol
4-Hydroxyazobenzen
OH N N
+
+
..
..
..
N N N N N N
OH
+

-naphtol Pham vang -naphtol
+ H
+
+
+
N NaO
3
S N
HO
HO
N NaO
3
S N

c. S dng mui diazoni trong tng hp cc cht hu c.
iu ch p -nitrobenzaldehyd t benzaldehyd qua nhiu giai on nh sau:
Chc aldehyd (formyl) nh hng meta. Khng th nitro ha trc tip
benzaldehyd c p -Nitrobenzaldehyd m ch thu c m -Nitrobenzaldehyd.
312
H
2
O NaOH
CHO
H
2
SO
4
HNO
3
CHO
NHCOCH
3
NO
2
CHO
NH
2
NO
2
CHO
NO
2
+ H
2
O
HCl NaNO
2
H
2
O
H
2
SO
4
HNO
3
H
3
PO
2
CH
3
COOH
Fe , HCl
CHO
NO
2
CHO
N
2
NO
2
CHO
NHCOCH
3
CHO
NH
2

Chc nitro chuyn ha thnh amin. Thay th chc amin bng cc chc khc
qua giai on diazo ha. V d:
CHO
CHO
F
CHO
N
2
CHO
CHO
SH
CHO
I
CHO
CN
1-HNO
3
,H
2
SO
4
2-Fe, HCl,H
2
O
3-NaNO
2
,H
2
SO
4
, H
2
O
+

Bi tp
1. Gi tn cc cht c CTCT sau:

a- Cl NO
2
NO
2
CH
3
NO
2
NH
2
NCO NH
2
NCO NH
2
C
2
H
5
_
NCO
;
;
;
; b-

OH N N NH
2 N N NH
2
Cl
-
+
OCH
3
NH NH NH
2
NHOH CH
3
;
;
c-
d-

2. T benzen hy thc hin cc phn ng c phn ng Sandmeyer iu ch cc
cht: clorobenzen, bromobenzen, acid benzoic, benzylamin, o-aminophenol.
313
Chng 24
HP CHT C LU HUNH V PHOSPHOR
Mc tiu
1. c c tn cc hp cht c S v P.
2. Nu c mt s tnh cht ha hc v ng dng ca chng trong tng hp
hu c.
Ni dung
1. Hp cht hu c c lu hunh
Cc loi hp cht cha lu hunh trnh by trong bng 24-1
Bng 24.1: Cc loi hp cht c lu hunh
Loi hp cht Cng thc Loi hp cht Cng thc
Thiol , Mercaptan RSH , ArSH Metanthiol, Methylmercaptan CH
3
SH
Sulfid RSR , ArSR Diethylsulfid C
2
H
5
SC
2
H
5

Sulfoxyd
R S R
O

Dimethylsulfoxyd
CH
3
S CH
3
O

Acid sulfenic RSOH Acid1-propen sulfenic
CH
3
_
CH=CHSOH
Acid sulfinic RSO
2
H Metansulfinic CH
3
SO
2
H
Acid sulfonic RSO
3
H Metansulfonic CH
3
SO
3
H
Sulfohalogenid
Sulffonylhalogenid
RSO
2
Hal Benzensulfoclorid
Benzensulfonylclorid
C
6
H
5
SO
2
Cl
Sulfinylhalogenid RSOHal Metansufinylclorid CH
3
SOCl
1.1 .Thiol v sulfid
Thiol c Thioalcol R
_
SH v Thiophenol Ar
_
SH
Nhm chc SH gi l chc Thiol hoc mercaptan
Danh php
Gi tn hydrocarbon tng ng v thm thiol.
Gi tn gc hydrocarbon tng ng thm mercaptan
i vi Thiophenol: C th gi Thio + tn ca phenol c s carbon tng ng
hoc Mercaptoaren.
314

V d:
CH
3
CH
2
SH Etanthiol Ethylmercaptan .
HSCH
2
CH
2
SH 1,2-Etandithiol 1,2- Ethylendimercaptan
C
6
H
5
SH Thiophenol Mercaptobenzen
CH
3
SH

2- Thiocresol .
2-Mercaptotoluen
CH
2
SH

Phenylmetanthiol
Benzylmercaptan
di lin kt v gc lin kt trong metanthiol c trnh by di y:
C S
H
H
H
H
Metanthiol

di lin kt (A
o
)
C
_
H ................1,10.
S
_
H .................1,33
C
_
S .................1,82.
Gc lin kt ()
H
_
S
_
H ...........110,2
H
_
S
_
S ...........108
C
_
S
_
H ...........100,3
Sulfid c cng thc R
_
S
_
R'. C th xem hp cht sulfid nh l hp cht
ether, trong nguyn t oxy c thay th bi nguyn t lu hunh.
Danh php: Gi tn cc gc hydrocarbon tng ng v thm sulfur.
CH
3
CH
2
_
S
_
CH
2
CH
3

Diethylsulfid .
C
6
H
5
CH
2
_
S
_
CH
2
CH
3

Ethylbenzylsulfid.
p-CH
3
C
6
H
4
_
S
_
C
6
H
5

Phenyl p-tolylsulfid
di lin kt v gc lin kt ca dimethylsulfid trnh by di y:
Dimethylsulfid
C S
H
H
C
H
H
H
H

di lin kt (A
o
)
C
_
H................1,09.
C
_
S ..............1,80

Gc lin kt ()
H
_
S
_
H ...........109,5
H
_
S
_
S ........... 106.7
C
_
S
_
H ........... 98,9
Cc hp cht thiol v sulfid c nhiu ng dng trong y dc, cng nghip v
nng nghip. Trong ha hc cc hp cht thiol c nhiu ng dng trong tng hp
hu c.
1.2. Acid sulfonic
Acid sulfonic cha nhm chc -SO
3
H .
C cc loi acid sulfonic R
_
SO
3
H , Ar
_
SO
3
H

315
1.2.1. Danh php
c tn hydrocarbon tng ng v thm "sulfonic "
S OH
O
O
CH
3
CH
2
CH
2
S OH
O
O
Acid 1- Propansulfonic Acid Benzensulfonic

1.2.2. iu ch acid sulfonic
Bng phng php sulfon ha hydrocarbon tng ng.
iu ch cc dn xut ca acid sulfonic cng ging nh iu ch dn xut
ca acid carborcylic.
V d: Ar
_
SO
3
H + PCl
5

Ar
_
SO
2
Cl + POCl
3

+ HCl
Ar
_
SO
2
Cl + NH
3

Ar
_
SO
2
_
NH
2
+ HCl
Ar
_
SO
2
Cl + ROH

Ar
_
SO
2
_
OR + HCl
1.2.3. Acid sulfonic v cc dn xut
Bng 24.2: Danh php, tnh cht vt l ca acid sulfonic v dn xut
Cng thc Tn gi tc ts
CH
3
-SO
3
H Acid Metansulfonic 20,0 167
CH
3
CH
2
-SO
3
H Acid Etansulfonic - 17,0 -
SO
3
H

Acid Benzensulfonic 44,0 -
SO
3
H CH
3

Acid p-Toluensulfonic 106.5 -
SO
3
H
CH
3

Acid o-Toluensulfonic

67,5

-
SO
3
H

Acid -Naphthalensulfonic

91,0

-
SO
3
H

Acid -Naphthalensulfonic

102,0

-
CH
3
SO
2
Cl Metansulfonylclorid - 160
316
Bng 24.2 (tip)
Cng thc Tn gi tc ts
SO
2
Cl

Benzensulfonylclorid 14,5 246
SO
2
Cl CH
3

p-Toluensulfonylclorid 69,0 -
SO
2
Cl

-Naphthalensulfonylclorid

68,0

-
SO
2
Cl

-Naphthalensulfonylclorid

76,0

-
SO
2
NH
2

Benzensulfonamid; Benzensulfamid 156,0 -
SO
2
NH
2

-Naphthalensulfonamid ;
-Naphthalensulfamid

-

-
SO
2
OCH
3
CH
3

Ester methyl p-toluensulfonat 28 -
SO
2
OC
2
H
5

Ester ethyl -naphthalensulfonat

-

-
Cc phn ng ca hp cht sulfonic c ng dng trong tng hp ha dc.
Tng hp cc loi sulfamid trn c s phn ng:
Ar
_
SO
2
_
Cl + H
2
N
_
R' Ar
_
SO
2
_
NH
_
R' + HCl
S phong ph ca cc hp cht sulfamid l do gc Ar khc nhau. R'cng
khc nhau v c nhiu loi khung hydrocarbon khc nhau.
Trong sulfamid nguyn t hydro trong NH, NH
2
c th thay th cc nguyn t
khc lm tng kh nng ng dng ca sulfamid trong nhiu lnh vc khc nhau.
Cloramin T v Dicloramin T c tc dng st trng:
317
-HCl
-HCl
-2NaOH
+ NH
3
2 NaOCl
- H
2
O
NaOCl ( HO
-
)
Dicloramin T
Cloramin T
CH
3
SO
2
NCl
2
CH
3
SO
2
NCl Na
CH
3
SO
2
NH
2
CH
3
SO
2
Cl
+ HOSO
2
Cl
CH
3

Acid o-Toluensulfonic l nguyn liu iu ch saccharin (ng ha hc) :
Saccharin
-H
2
O
-H
2
O
3[O],KMnO
4
- HCl -POCl
3
PCl
5 CO
NH
SO
2
COOH
SO
2
NH
2
CH
3
SO
2
NH
2
CH
3
SO
2
Cl
-HCl
+ NH
3
CH
3
SO
3
H

Saccharin l imid ca acid 2-carboxybenzensulfonic hoc imid ca acid
o-sulfobenzoic. Saccharin c ngt gp 550 ln ngt ca ng saccharose.
2. Hp cht cha phosphor
Cc hp cht hu c cha phosphor nh l dn xut ca cc hp cht sau:
Phosphin PH
3

Phosphoran PH
5
.
Acid phosphinic (H
3
PO
2
)

HOH
2
P=O

Acid phosphonic (H
3
PO
3
)

(HO)
2
HP=O
Acid phosphor (H
3
PO
3
)

(HO)
3
P
Acid phosphoric (H
3
PO
4
) (HO)
3
P=O
Acid pyrophosphoric (H
4
P
2
O
7
)

(HO)
2
P(O)
_
O
_
(O)P(OH)
2

Ngi ta chia hp cht hu c cha phosphor thnh 2 nhm:
Hp cht c nguyn t phosphor lin kt trc tip vi nguyn t carbon P
_
C .
Cc hp cht nguyn t phosphor khng lin kt trc tip vi carbon P
_
O
_
C
2.1. Phosphin
Ging hp cht amin, phosphin c 3 loi:
Monoalkyl RPH
2
Dialkyl R
2
PH Trialkylphosphin R
3
P
CH
3
CH
2
PH
2
(CH
3
CH
2
CH
2
CH
2
)
2
PH

(C
6
H
5
)
3
P

Ethylphosphin Di n-butylphosphin Triphenylphosphin .

C th iu ch triphenylphosphin t hp cht c magnesi.
6C
6
H
5
MgBr + 2PCl
3

2(C
6
H
5
)
3
P + 3MgCl
2

+ 3MgBr
2
318
2.2. Cc alkyl ca acid cha phosphor
2.2.1. Acid dialkylphosphinic
Acid Dialkylphosphinic
R P O
OH
R'
Acid Diethylphosphinic
Diethylphosphin
2[ O]
CH
3
CH
2
P
H
CH
2
CH
3
CH
3
CH
2
P O
OH
CH
2
CH
3

2.2.2. Acid Alkylphosphonic
Acid Alkylphosphonic
R P O
OH
OH
Acid Ethylphosphonic
Ethylphosphin
3[ O]
CH
3
CH
2
P
H
H
CH
3
CH
2
P O
OH
OH

2.3. Cc ester ca acid cha phosphor
2.3.1. Ester ca acid phosphonic

Ester dialkyl alkylphosphonat
Ester dialkyl cua acid alkylphosphonic
R P O
OR'
OR''
Ester diethyl ethylphosphonat
Ester diethyl cua acid ethylphosphonic
CH
3
CH
2
P O
OCH
2
CH
3
OCH
2
CH
3

2.3.2. Ester ca acid phosphor
P OCH
2
CH
3
OCH
2
CH
3
OH
P OR
OR'
OH
Ester diethylphosphit Ester Dialkylphosphit Ester trialkylphosphit
P OR
OR'
OR''
P OCH
2
CH
3
OCH
2
CH
3
OCH
2
CH
3
Ester Triethylphosphit

2.3.3. Ester ca acid phosphoric

Ester Trialkylphosphat
RO P O
OR'
OR''
Ester Triethylphosphat
CH
3
CH
2
O P O
OCH
2
CH
3
OCH
2
CH
3

2.3.4. Ester ca acid pyrophosphoric

Ester Tetraalkylpyrophosphat
RO P O
OR'
O
P OR''
O
OR'''
Ester Tetraethylpyrophosphat
C
2
H
5
O P O
C
2
H
5
O
O
P OC
2
H
5
O
OC
2
H
5

319
Ti liu tham kho
1. E.Angeletcu - Nhng vn l thuyt ca Ho hu c - Rumani -
Bucarest, 1969.
2. Clayden, Greeves, Warren, Wothers - Organic chemistry - Oxford, 2001
3. I.L.Finar - Organic chemistry, 1969
4. Boyd Harrisson - Organic chemystry, 1999
5. Jerry March - Advanced organic chemistry - Wiley, 1992
6. C.D. Neninetscu - Ho hc hu c - Nga - Matxcva, 1963
7. Trn Quc Sn - C s l thuyt Ho hu c - Nh xut bn Gio dc, 1974
8. Phan Tng Sn, Trn Quc Sn, ng Nh Ti, C s Ho hc hu c -
H Ni, 1976 - 1978.
9. Streitwieser, Heathcock - Introduction la chimie organique, 1995
10. L Vn Thi - Ho hc lp th hu c - B Vn ho Gio dc v Thanh
nin, 1974
11. http:// www.uis.edu - University off lllnois
12. http:// www.ouc.bc.ca/chem

320

HHC HC Donchuc Dchuc t1

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

HHC HC Donchuc Dchuc t1

Uploaded by

Copyright:

Available Formats

B Y t

Cac lien ket

Cc lin kt trong phn

H Cac lien ket

v nguyn t carbon mang mt phn in tch dng

) l nhng anion m in tch m (2 in t) tp trung

) l nhng tiu phn c cha 1 in t t do (khng cp

hot ho ca trng thi chuyn tip cng m s

tc l bit c tin trnh v c ch phn ng xy ra.

tn cng vo carbon v 2 pha ca mt phng vi kh nng nh nhau. V vy

trong phn th i nhn c th l anion (HO-, Cl-,

l mt base mnh ng thi HO

cng l mt tc nhn i nhn mnh.

l mt base rt yu nhng n l mt tc nhn i nhn mnh.

) to thnh ion mang

Trang thai chuyen tiep

Momen t hat nhan trong t trng

vi lin kt CH xy ra chm hn. Nh vy chng t rng hot

sinh ra do tc dng ca nhit :

trong phn ng nitro ha ging vai tr X

tc dng vi propylen, phn cation H

ca tc nhn s kt hp vi carbon ca ni i mang nhm methyl.

2 orbital p t do cua carbon orbital s cua hydro

C to cc cht trung gian trivinylboran. Khi c

C khi c bt ng lm xc tc, acetylen b trng hp to polyacetylen

C thu c acid o -toluic.

c tn gi l alkoxy. Cc alkoxy l nhng base mnh.

Valerolacton Acid allylacetic

Acid Succinic Anhydrid Succinic

. Di tc dng ca nhit , hydroxy amoni bc

You might also like