13 HHC - HC - Donchuc - Dchuc - t1 PDF

http://hhud.tvu.edu.
vn
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
http://hhud.tvu.edu.vn
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)
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
MC LC
Li gii thiu
M u
Chng1: Cu trc in t ca nguyn t carbon v s to thnh

cc lin kt trong hp cht hu c
ThS. Nguyn Anh Tun
1. Cu trc in t (electron) ca nguyn t carbon
2. S to thnh cc lin kt
Chng 2: Cc hiu ng in t trong ha hu c
11
11
13
22
ThS. Nguyn Anh Tun

1. Hiu ng cm ng
22
2. Hiu ng lin hp (cng hng)

3. Hiu ng siu lin hp (Hyperconjugate effeet)
25
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)
2. Khi nim acid -base theo Lewis (1923)
49
51
3. Hng s cn bng acid base

4. Yu t nh hng n tnh acid -base ca cht hu c
51
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
2. Khi nim v c ch phn ng
Chng 6: Cc phng php ha hc v vt l xc nh cu to hp cht hu c
54
57
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
2. Danh php
3. Phng php iu ch alkan
85
86
4. Tnh cht l hc
5. Tnh cht ha hc
88
89
6. Cht in hnh
93
Chng 8: Cycloalkan
ThS. Th Thy
1. Monocycloalkan
2. Hp cht a vng
95
100
Chng 9: Alken - Hydrocarbon etylenic
102
ThS. Th Thy
1. Cu to ca alken
2. ng phn
3. Danh php
4. Phng php iu ch
5. Tnh cht l hc
6. Tnh cht ha hc
7. Cht in hnh
102
102
104
105
109
110
118
Chng 10: Alkyn - Hydrocarbon acetylenic
120
ThS. Th Thy
1. Cu trc in t
2. Danh php v ng phn
3. Phng php iu ch
4. Tnh cht l hc
5. Tnh cht ha hc
6. Cht in hnh
Chng 11: Aren - Hydrocarbon thm
PGS. TS. ng Vn Tnh
1. Benzen v nhn thm
3. Phng php iu ch
4. Tnh cht l hc
5. Tnh cht ha hc
Chng 12: Hydrocarbon a nhn thm
120
121
121
123
123
127
129
129
132
133
134
135
150
PGSTS. ng Vn Tnh
1. Cu to v danh php
150
2. Biphenyl
3. Biphenylmetan v triphenylmetan
4. Naphtalen
151
153
154
5. Anthracen
6. Phenanthren
155
156
Chng13: H thng lin hp v alkadien
158
PGS. TS. ng Vn Tnh

1. H thng allylic
158
2. Dien
3. H thng lin hp bc cao
161
164
4. Phn ng Diels Alder
165
Chng 14: Dn xut halogen
168
ThS. Trng Ngc Tuyn

1. Danh php
2. ng phn
168
169
3. Phng php iu ch
4. Tnh cht l hc
5. Tnh cht ha hc
169
173
173
Chng 15: Hp cht c kim
181
ThS. Trng Ngc Tuyn

1. Cu to
181
2. Danh php
3.Tnh cht l hc
181
182
4. Phng php iu ch cc hp cht c kim

5. Cc phn ng ca hp cht c kim
182
184
Chng 16: Alcol
189
ThS. Trng Ngc Tuyn
1. Monoalcol
2. Alcol cha no
189
200
3. Alcol vng
4. Polyalcol alcohol a chc
201
201
Chng 17: Phenol
207
ThS. Trng Ngc Tuyn
1. Monophenol
2. Polyphenol
207
215
Chng 18: Ether
219
ThS. Trng Ngc Tuyn
1. Ether mch h
2. Ether vng
219
223
Chng 19: Aldehyd , Ceton v Quinon

ThS. Nguyn Anh Tun
1. Aldehyd v ceton
2. Aldehyd - ceton cha no
224
224
245
3. Aldehyd - ceton a chc

4. Quinon
250
253
Chng 20: Acid carboxylic
257
ThS. Nguyn Anh Tun

1. Cu to
2. Danh php
257
258
3. Phng php iu ch
4. Tnh cht l hc
259
261
5. Tnh cht ha hc
6. Acid carboxylic cha no
262
268
7. Acid a chc polyacid
270
Chng 21: Cc dn xut ca acid carboxylic
273
ThS. Nguyn Anh Tun

1. Ester
2. Anhydrid acid
274
279
3. Ceten
4. Halogenid acid - acyl halogenid
280
281
5. Amid
6. Nitril
283
285
Chng 22: Amin
288
1. Cu to
288
2. Danh php
3. iu ch
289
290
4. Tnh cht l hc
5. Tnh base ca amin
6. Cc phn ng ca amin
292
292
295
7. Amin cha no c mt lin kt i Enamin

8. Amin a chc - polyamin
300
301
Chng 23: Cc hp cht khc cha nit
303

1. Hp cht nitro
2. Isocyanat, carbamat v ure
3. Hp cht diazo v mui diazoni
Chng 24: Hp cht c lu hunh v phosphor
303
306
308
313
ThS. Th Thy
1. Hp cht hu c c lu hunh
2. Hp cht cha phosphor
319
Ti liu tham kho
313
317
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.
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 sp3, sp2 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.
o
C 109 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
2 2 1 1
Carbon c c cu hnh in t C 1S 2S 2px2py
1S22S22p2
1s22s22p2
2 in t n c l px v py. Cn c mt orbital 2pz trng khng c in t
1.2.2. Carbon trng thi kch thch C *
1
1S22S 2px1 2py12pz1
1S22S12p3
11
Carbon hp thu nng lng 60-70 kcal/mol, mt in t 2s2 chuyn ln trng

thi 2p (orbital 2pz).
1s2
2s2
2p2
1s2 2s
2px 2py 2pz
C 1s22s12p3
C 1s22s22p2
Carbon c cu hnh in t 1s22s12p3 l carbon kch thch (1s22s12px2py2pz).

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 sp3
Kiu lai ha th nht gi l lai ho sp3 (cn gi l lai ha t din).
Mt orbital 2s v 3 orbital p t hp vi nhau to thnh 4 orbital lai ha sp3.
SS
t hp
to h2sp v
2s 2p
va 2p
hoa
OrOrbital
bital lailai
ho
sp sp
3
Carbon
a sp
sp3
Carbon lai
lai ho
ho
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 sp3 l 2.
Lai ha sp2.
S t hp orbital 2s vi 2 orbital 2p (2px, 2py) to thnh 3 orbital lai ha sp2
hay cn gi l lai ha tam gic. Trc i xng ca 3 orbital sp2 nm trong mt
mt phng v to nn nhng gc 120. Kh nng xen ph tng i ca orbital
sp2 l 1,99.
12
Pz
120o
S
vva
2p2p
Sttohp
h2s
p 2s
Carbonlai
laihoa
ho 2sp
2
Carbon
2sp
Orbital2p
2pzkhong
khng lai
Orbital
laiho
ho
z
Nh vy trn carbon lai ha sp2 cn c mt in t trn orbital 2pz khng lai

ha. Orbital ny c dng hnh khi s 8 ni .
Lai ha sp
T hp mt orbital s v mt orbital 2px 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 180o 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 t
2p 2p
S
tohp
hp2s2svva
Orbital lai
Orbital
laiho
hoaspsp
2 Orbital 2py v 2pz

2 Orbital
2pyva 2pz
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
Lin kt
Orbital s
Orbital s
Orbital p
Lin kt
Orbital p
Lin kt
Orbital p
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 sp3, sp2, 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 sp3, sp2, 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 Py hoc Pz 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
HH
H-C-C-H
H H
Cac
lien ket
Cc lin kt trong
trongphn
phan
t
t etan etan
H
H
CcCac
lin kt
trong
lien
ket
phn
C C
ethylen
trong t
phan
t etylen H H
Cac
lien
Cc lin
ktket
trong
H
phn
t
acetylen
trong phan t acetylen
Cc lin
kt ket
trong
Cac
lien
phn
t
alcol
ethylic
trong phan t
alccol etylic
C H
c-c
O
H
c-o
o-H
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 Pz 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
LieLin
n kekt
t
trong ethylen
H
H
trong etylen
H
H
Hai lin kt trong acetylen c to thnh do s xen ph cc i v 2 pha

ca cc orbital py v pz tng ng. Cc orbital lin kt nm trong 2 mt phng
thng gc vi nhau.
Lin kt
trong
lie
n keacetyle
t n
Cac
trong phan t acetylen
15
S to thnh lin kt trong h thng alen C=C=C .

H
H
S to thnh lin kt trong h thng lin hp C =CC=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).
CH2=CH_CH=CH_CH=O ; CH2=CH_CH=CH_CH =CH_OCCH3
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 ; CH3_CH3 ; Cl3C_CCl3 ; CH2=CH2 ; HCCH .
Khi hai nguyn t lin kt vi nhau khng ng nht (phn t c dng

A _B) nh H _Cl, CH3_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
kt (phn t c dng A =B hoc A B).
16
m cn xy ra cc lin
Trong cc phn t H2C =O v CH3 _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
). Chiu chuyn dch ca
phn cc ca lin kt ngi ta dng mi tn cong (
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 .
V d: CH3 Cl ; CH3 Cl ; H2C=O ; H2C=O hoc: H2C==O

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.
C__3 H
sp
C__2 H
sp
C__H
sp
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
104,2
C-H
98,8
F-F
36,4
C-F
105,4
Cl-Cl
58,0
C-Cl
78,5
Br-Br
46,1
C-Br
65,9
I-I
36,1
C-I
57,4
N-N
38,4
C-O
84,0
N=N
100,0
C=O
+
171,0
255,8
NN
226,0
C -O
P-P
51,3
C-N
69,7
C-C
83,1
C=N
147,0
C=C
147,2
CN
213,0
CC
194,0
H-F
134,6
Si-Si
42,2
H-Cl
103,2
O-H
110,6
H-Br
87,5
N-H
93,6
H-I
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
Br
OH
CH3
CH3
102
67
51
86,5
83
83
CH3CH2
98
65
52
87,
82
82
(CH3)2CH
89
65
47
84,5
74
82
(CH3)3C
85
61
45
85,
74
60
C6H5
104
71
57
85,
91
103
C6H5CH2
77,5
48
39
85,
63
47
HO-OH ---------------------------------
52 (CH3)2 C N = N C (CH3)2 31
CN
C6H5COO-OCC6H5 -----------------
30
CN
(C6H5)3C N = N C(C6H5)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.
Et
Et
O...H
H
O ...
...
H
...
O
O H
Et
Et
H__C
O ... H O
O H ... O
C__H
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.
OH
C
O.
CH2
..
H .. .
NH2
CH2
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 tos 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 toc l 144C v toc l 241C. ng phn o-nitrophenol (c
lin kt hydro ni toc phn t) c toc l 44C v tos l 114C .
O
N O ...
H
O N
OH ...O N
OH ...O N
Lin kt hydro gia cc phn t p -nitrophenol
OH
...
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-ethylenglycol
Syn-dicloetan
Anti-dicloetan
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 .
NO2
CH 3
Phc to thnh gia

toluen v trinitrobenzen
O2N
NO2
Phn t nhn
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 (HC2=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 C3H8 v phn t n-propylclorid C3H7Cl
H
H
C3 C 2 C1 H
H
n-propan
n-propan
H H
+3 +2 1+
H C C C Cl
3
2
1
H
n-propylclorur
n-propyclorid
Trong phn t n -propylclorid, lin kt C1 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 C1
mang in tch dng nn cp in t lin kt ca lin kt C2 C1 b dch chuyn
v pha carbon C1. Kt qu l lin kt C2 C1 cng b phn cc theo. Nguyn t C2
mang mt phn in tch dng. n lt lin kt C3 C2 cng chu nh hng
nh vy v kt qu nguyn t carbon C3 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)
+I
H
I=0
-I
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 .
+I
CH3
CH2 CH3
CH CH3
CH3
CH3
C CH3
CH3
Trong dy cc nhm mang in tch m, nhm c m in nh hn l

nhm c hiu ng + I ln hn .
-O- < -S- < -Se1.2. 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 sp2 v sp3

-CCR > -CR1=CR2 > -CR2_CR3.
Nhm mang in tch dng c hiu ng -I ln hn nhm c cng cu to

nhng khng mang in tch.
+
-OR2 > -OR
-NR3 > -NR2
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 > -NR2 > -CH3.
-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.
H_COOH
CH3
C
O
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.
CH3
CH3 N:
..
..
H_NH2
CH3 NH2
CH3
Bng 2.1. nh hng hiu ng cm ng n tnh acid base
Lc acid giam khi +I tang

pKa (H2O.25o)
Acid hu c
3,75
4,76
4,87
HCOOH
CH3COOH
CH3CH2COOH
4,82
CH3CH2CH2COOH
(CH3)2CHCOOH
4,86
Lc base tang khi +I tang

Base hu c pKa (H2O.25o)
NH3
CH3NH2
CH3CH2NH2
(CH3)2NH
(CH3)3N
9,10
10,62
10,63
10.77
9,8*
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 CH3 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.
F CH2 C O H
O
pKa 2,58
24
Cl CH2C O H
O
2,85
Br CH2C O H
O
2,9
I CH2 C O H
O
3,16
H CH2 C O H
O
4,76
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.
CH3CH2CH2COOH
pKa
4,82
CH3CH2CHClCOOH
CH3CHClCH2COOH
2,86
4,05
CH2ClCH2CH2COOH
4,42
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
( p- )
-C=C-Cl
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
CH2=C_CH=CH2
CH3
CH2=CH_CH=CH2
1,3-Butadien
2-methyl-1,3-butadien (izopren)
CH2 = CH CH = O
Aldehyd acrylic
CH2 = CH C N
CH2 = CH C = O
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 .
..
..
CH2=CH_Cl
CH2=CH_OCH3
Vinylclorid
Methylvinyl ether
:OH
:NH2
Phenol
Anilin
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
CH2=CH_CH2_CH=CH2 ;
CH2=CH_CH=CH_CH3 ;
CH=CH_CH2_OCH3
Lin hp
Khng 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 .
Benzen
Butadien
phenol
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
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 CH2 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.
CH2
CH CH
CH
CH
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 - NO2, - SO3H...
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
: Cl
:
..
..
C O
..
H
..
C O
..
CH3
..
C O
..
: OR
..
..
..
C O
..
C O
..
:OH
..
: NH
.. 2
..
C O
..
: O.. -
CR = O > CR > CR = CR2

NO2 > 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.
..
..
CH2=CH_OCH3
CH2=CH_Cl
.. :
-NH2 > -OH ; -O- > -OH
Cc nhm c hiu ng + C :
-F > -Cl > -Br > -I

-NR2 > -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:
CH2
CH
CH
CH2
CH2
+
CH
CH
CH2
+
CH2
CH
CH
CH2
CH3
+
CH
CH
CH O
Aldehyd crotonic:
CH3 CH CH
Phenol
+
CH3 CH CH CH
CH O
:OH
+OH
+OH
+OH
OH
-
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 CH3 ca aldehyd crotonic linh ng do
nh hng ca hiu ng lin hp.
H
: CH3 CH CH CH
aldehid
crotonic
Aldehyd
crotonic
Nu ko di mch aldehyd crotonic bng cc nhm vinyl th hydro ca nhm

CH3 vn cn linh ng.
H
: CH2
CH
CH
CH
CH
CH
CH CH
Hiu ng lin hp lm thay i trung tm phn ng:

V d: C hp cht sau:
..
C
CH
NH2
CH
CH
+
NH2
CH
O-
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 NH2 gy hiu ng lin hp + C.
Nhm NH2 c tnh base c kh nng tc dng vi proton H+. Nhng do hiu ng
lin hp, H+ khng tc dng vo nhm amin NH2 m tc dng vo nguyn t oxy
ca nhm carbonyl.
C CH CH
O
+
NH 2 + H+
C CH CH
+
NH 2
OH
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 -NO2 c hiu ng lin hp
- C. Thay 2 nhm CH3 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 CH3 vo v tr orto so vi nhm
NO2 c cht (IV). Cht (IV) c tnh acid yu hn (II). iu chng t 2 nhm
CH3 lm cho nhm NO2 khng c hiu ng lin hp - C nh hng n chc phenol.
OH
OH
OH
OH
CH3
CH3
CH3
I
pKa
9.98
NO2
II
7,16
NO2
III
7,21
CH3
NO2
IV
8,24
S d c iu v trong (III) nhm NO2 khng nm trong cng mt phng

vi vng benzen. Hai nhm CH3 c cn tr khng gian lm cho nhm NO2 b lch
ra khi mt phng ca vng benzen. Hiu ng lin hp ca nhm NO2 khng pht
huy tc dng.
28
CH3
..
..
HO
HO
N O
N O
II
IV
O
CH3
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.
H
C C C
CH3
C C C
H
22lin
ktket
lien
H
3
lin
3 lienkt
ket
H H
H H
H H
CH3
C C C
CH3
C
H
CH3
11lien
lin kt
ket
33lin
ktket
lien
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 C2H5 c hiu ng + I ln hn nhm CH3.
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 CH3 ln hn nh hng siu lin hp ca nhm C2H5 nh hng
n hng cng hp.
H
H C CH CH
CH2
CH3 + HBr
H C CHBr CH2
CH2
CH3
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 CH3 ca aldehyd acetic d dng b ct
t trong mi trng kim to carbanion.
H
H C CH
H
HO -
H
H C CH
O + H2O
Carbanion
Carbanion to thnh c h thng lin hp p - . V vy carbanion ny c th

c cng thc gii hn:
H
H C CH
H
H C CH
Hin tng trn cn th hin trong hp cht ester ethylacetoacetat

CH3COCH2COOC2H5. Lin kt C H ca nhm CH2 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.
CH3 C
O
H
..
C C
H O
OC2H5
+ OH -
C C OC2H5 + H2O
O H O
Carbanion
CH3 C
Carbanion to thnh c h thng lin hp p - do c th c cc cng thc

gii hn.
CH3 C
C C
OC2H5
O
.. : H O
Carbanion
CH3 C
:O
.. :
C
H
OC2H5
Hiu ng siu lin hp tng theo s lng lin kt C _H v tr .

CH3- > CH3CH2- > (CH3)2CH- > (CH3)3C -
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 CH2=CHCH+ v carbanion allylic CH2=CHCH-.
+
CH2=CH_CH2
CH2=CH_CH2
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-C4H8ClCOOH, nguyn t clo cc v tr khc nhau .
b- m-ClC6H4(CH2)nCOOHn = 0,1,2 .
c- m-ClC6H4(CH2)nCOOHn = 0,1,2
4. Vit cng thc gii hn ca sn phm to thnh khi:
a-
NH2 C NH2
NH
+ H+
Guanidin
b-
30
C CH2 C CH2
O
O
+ HO -
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.
CH3 CH2
CH3 CH
CH2 CH3
CH3
iso Butan
n- Butan
CH3
CH3
CH3 CH2
CH2 CH2
n- Pentan
CH3
CH3 CH
CH3
CH2 CH3
iso Pentan
CH3 C
CH3
CH3
neo Pentan
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.
CH3
CH3 CH2
CH3 CH
CH2 CH2 OH
1-Butanol
CH3 C
CH CH3
CH3
OH
2- Butanol
CH3 CH2
2-methyl-2-propanol
CH3 CH
CH CH2
OH
CH CH3
2- Buten
1-Buten
1.3. ng phn nhm chc

C nhm chc khc nhau.
CH3
COOH
HO
CH2
CHO
COOCH3
CH3
CHO
CH2
CH3
CH3
Acid acetic
Aldehyd glycolic
Ester methyl formiat Aldehyd propionic
Aceton
1.4. ng phn lin kt

Cc nguyn t trong phn t c cch lin kt khc nhau
CH3 CH2 CH
CH2 CH2
CH2
CH2 CH2
1- Buten
CH2=CH-CH=CH2
1,3-Butadien
Cyclobutan
CH3-CH-CCH
CH3-CC-CH3
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 CH3COCH2COOC2H5 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
CH3 C CH2 COOOC2H5
CH3 C CH COOOC2H5
OH
Ester ethyl acetoacetat
Dng enol
O
Ester ethyl acetoacetat
Dng ceton
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
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
HH
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.
CH3 CH3
CH3
C
H
C
H
Cis
Cis 2-buten
CH3
C
CH3
Trans
Trans 2-buten
CH3
CH3
C
Mat phang
CH3
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
a
b
acC=Cab
Cau hnh cis
Cau hnh trans
b
a
Cau hnh trans
Cau hnh cis
V d:
H
H
HOOC
cis
COOH
H
HOOC
COOH
Acid maleic
C
C
HOOC cis
CH3
trans
Acid fumaric
HOOC
trans
CH3
H
Acid crotonic
Acid isocrotonic
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
abC=Ccd
a
a>b;c>d
c
Cau hnh E (trans)
Cau hnh Z (cis)
V d:
I
Br
Cl
C
H
C
Br
H
Cl
E
Z
1-Brom-1-Iod-2-Cloethylen
I > Br > Cl > H

34
V th I > Br ; Cl > E
OHC
H3C
OHC
COOH
C
H3C
H
C
COOH > CHO > CH3 > H
C
COOH
CHO > CH3; COOH > H
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
-CH2Cl > -CH2OH > -CH2CH3
CH
OCH3
OH
>
CH
CH2 CH3
CH2 CH3
+ 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 = CH2
CH
CH2
CH = O
Cho nn:
CH
CH3
>
CH
CH2CH3
CH2
>
CH
CH3
CH3
-COOCH3 > -COOH > -CONH2 > -COCH3 > -CHO

-CN > -C6H5 > -CCH > -CH=CH2
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
C6H5
C
H
C6H5
H
C
C6H5
H
Trans-trans
C
H
H
C
C6H5
H
H
Trans-cis
C
C6H5
H
C
C6H5
H
Cis-cis
35
ng phn hnh hc trong cc hp cht vng

CH3
CH3
CH3
CH3
H
H
cis
trans
H
1,3-Dimethylcyclobutan
Cl
Cl
Cl
H
trans
Cl
H
H cis
1,3-Diclocyclohexan
Cc trng hp khc v ng phn hnh hc.

ng phn hnh hc trong h thng ethylen phc tp
CH3
O
CH3
O
Trans
CH3
Cis
CH3
ng phn hnh hc trong hp cht c ni i C=N v N =N

CH3CH2
CH3
C6H5
N
..
CH3CH2
OH
N
..
Z ( syn )
N
..
Z ( syn )
Butanoxim
CH3
C6H5
C6H5
Azobenzen
..
E (anti)
N
..
OH
..
E (anti)
C6H5
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 (tnc) : ng phn trans (E, anti ) c nhit nng
chy cao hn ng phn cis (Z, syn).
Nhit si (ts): 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
C
H
E < Z
b
H
aCH=CHb
a hut, b ay electron
z a
Z > 0
H
C
a
H
E = 0
aHC=CHb
a,b u ht electron
H
C
E > Z
Bng 3.1. Tnh cht vt l ca mt s ng phn hnh hc
Nhiet o nong chay Nhiet o soi

Momen lng cc
Trans (E ) Cis (Z) Trans(E) Cis (Z) Trans(E) Cis (Z)
Hp chat
-50oc
ClCH=CHCl
-80,5oc
48,4oc
68,0oc
PhCH=CHCOOH
60,2oc
134,0oc
p-O2NC6H5CH=CHNO2
CH3CH=CHCl
0D
2,95D
0,5D
7,4D
2,0D
1,7D
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
H
H
a
cis (Z , syn)
H
a
C
a
Quay
H
a
C
H
trans (E , anti)
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.
H
COOH
to
Acid cis butendioic
O
C
O
COOH
+ H2O
C
O
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
Phng truyen song
Vect ien trng
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, KClO3....) 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.
Mat phang anh sang phan cc
Phng truyen song
Anh sang phan cc

Anh sang t nhien
Lang knh Nicon
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
Goc quay
Chat quang hoat
Mat phat phang phan cc

sau khi qua chat quang hoat
Mat phang phan cc
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 [].
to
= 100 __
LC
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).
b
*C
b
c
d
hay
*C
c
d
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 CH3*CH(OH)COOH.

COOH
COOH
COOH
OH
CH3
H
CH3CHOHCOOH
C
H
CH3
OH
hay
C
H
CH3
OH
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
Gng phang
phng
HOOC
COOH
H3C C
C CH3
H
OH
HO
Vt
Vat
nh
Anh
(+ )
(- )
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
CH3 CHOH COOH
COOH
CH3
OH
COOH
COOH
H
CH3
(+ )
(+ )
Cong thc t dien
OH
H3C
HO
HO
(- )
COOH
H
CH3
Cong thc t dien Cong thc chieu Fisher
Cong thc chieu Fisher
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 2n ; n l s nguyn t carbon bt i xng.
V d: Monosachcarid C6H12O6 vi 4 nguyn t carbon bt i xng c
24 = 16 ng phn quang hc . D - Glucose l mt trong 16 i quang .
CH2OH 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
CH3 CHOH CHOH COOH
COOH
COOH
COOH
H
OH
HO
OH
HO
CH3
I
OH
H
HO
CH3
II
COOH
HO
H
OH
CH3
CH3
III
IV
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 2n 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

*
*
HOOC CHOH CHOH
COOH
H
OH
COOH
OH
H
OH
H
COOH
COOH
COOH
I
Acid(+) tartaric
II
Acid(-) tartaric
COOH
OH
H
HO
H
COOH
HO
H
III
COOH
H
HO
mp oi xng
H
HO
COOH
IV
Acid mesotartaric
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:
CH3CHOHCHOHCOOH
HOOCCHOHCHOHCOOH
a>b
1
2
2
2
= ( +a ) + (+b ) =
= ( -a ) + (-b ) =
= ( +a ) + (-b ) =
= ( -a ) + (+b ) =
a=b
(+)
(-)
( +)
( -)
2 oi quang
2 oi quang
1
2
3
4
= ( +a ) + (+b) =
= ( -a ) + (-b ) =
= ( +a ) + (-b) =
= ( -a ) + (+b) =
(+)
(+)
2 oi quang
(0) mot ong pham meso

(0)
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
CH2OH CHOH CHO
CHO
C
CHO
CH2OH
OH
va HO
OH
CH2OH
L ( - ) Aldehid glyceric
Cong thc t dien
HOH2C
HO
CH2OH
D ( + ) Aldehid glyceric
CHO
CHO
II
Cong thc t dien
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
CH2OH_CHOH_CHOH_CHOH_CHOH_CHO
6
1CHO
2
OH
3
H
HO
H 4
H 5
H
OH
OH
6
CH2OH
D(+) - Glucose
1CHO
2
H
3
HO
H
OH
4
HO
H
5
HO
H
6
CH2OH
L(-) - Glucose
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.
*C
*C
a
d
b
d *C
b
*C
II
Gng phang
a,b,c theo chieu quay

cung chieu kim ong ho
Cau hnh R
a,b,c theo chieu quay

ngc chieu kim ong ho
Cau hnh S
V d: Phn t acid lactic c 2 ng phn: acid R- Lactic v acid S Lactic

CH3_CHOH_COOH
o ln cac nhom the OH > COOH > CH3 > H
OH
*C
H3C
OH
OH
C*
COOH
H3C
acid R Lactic
H
COOH
H
HOOC
Gng phang
OH
*C
CH3 HOOC
*C
CH3
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 HOCH2 _ C*HOH _ CHO.
C mt carbon bt i v 4 nhm th chung quanh
C* l HO > CHO > CH2OH > H
HOCH2_CHOH_CHO
Cong thc t dien
*C
H
CH2OH
OH
*C
H
CHO
CHO
CHO
CHO
CH2OH
OH
* OH CH2OH
CH2OH
I
* OH CH2OH
H
oi v tr lan 1
OH
II
CHO
H
oi v tr lan 2
III
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, CH2OH. Ta c OH CHO CH2OH
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
CH3_CH(Ph)_CHOH_CH3
CH3
H
H
CH3
OH
HO
Ph
Ph
R
S
CH3
CH3
HO
CH3
[] = -0,69o
25
H
Ph
Ph
CH3
[] = +30,2o
25
OH
CH3
[] = -30,2o
[] = +0,69o
25
25
CH3
2 ong phan threo
2 ong phan erythro
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.
a
c
C
R"
(CH2)n
R'
Hp chat allen
R'''
Hp chat diphenyl
Hp chat paracyclophan
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:
H
H
H
H
H
H
H
CT t dien
46
H
H
H
H
H
H
CT chieu Fisher
H
H
H
CT phoi canh
H
H H
H
H
CT Newman
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.
a
b
a
C
Dng che khut
Dng xen k
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.
a
b
a
b
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 C1 C2. Ta biu din C2 b che khut bng vng
trn, cn C1 tm vng trn. Ba lin kt xut pht t mi nguyn t carbon to
nn nhng gc 120 trn mt phng giy.
a
b
C
1
CT phoi canh
c a b
b
CT Newman
aa
b
b
cc
CT Newman
Dang xen ke
a
b
C2
c b
CT phoi canh
Dang che khuat
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
Cau dang thuyen
Cau dang ghe
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 C7H14. Bao nhiu ng phn c th c ?
2- Cng thc phn t C5H12. 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 CH2Cl-CHOH-CHOH-CH2Cl.
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:
48
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
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
+
H
HA
Acid lien hp
CH3COOH
CH3OH
NH +
4
+
CH3_O_CH3
H
Proton
Base lien hp
H+
H+
CH3COO
H+
H+
CH3O
..
NH3
..
CH _O_CH
3
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 + B
BH + 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 (H2SO4, HCl, CH3COOH), c phn t acid tch in dng (NH4+, [CH3OCH3]H+),
c phn t base mang in tch m (CH3COO-, CH3O-), c phn t base khng c
in tch (NH3, CH3OCH3) .
Acid ha tan vo nc c s tng tc acid base: Nc l dung mi c tnh base.
CH3COOH + H2O
Acid
Base
H3O+ + CH3COOAcid
Base
Ho tan mui ca acid hu c vo nc, c s tng tc acid -base : Nc l

dung mi c tnh acid.
H2O + CH3COO Base
Acid
CH3COOH + HO Acid
Base
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.
H2SO4 + R_O_H
Acid
Base
+
R_O_H + HSO 4
H
Base
Acid
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.
H3PO4 + CH3 CH=CH2
Acid
Base
+
CH3CH_CH3 +
Acid
H2PO4
Base
Mt s phn ng c xc tc base cng c qu trnh tng tc acid base to

carbanion trung gian.
CH3_CHO + HO Base
Acid
H2O + CH2_CHO
Base (carbanion)
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
CH3
CH2
+
BH
Base rt mnh
Acid rt yu
-
Acid rt yu
Base rt mnh
HO , CH3O l nhng base mnh

H2O, CH3OH 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_NH2 ; R_OH ; NH3 ; HO- ; RO -
Cc cht sau y l acid Lewis:

+
BF3 , AlCl3 , FeCl3 , ZnCl2 , SO3 ,NH4
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 H2O, R2O, NH3 .
..H
N:
H : ..
..H ..F
N :..
B: F
H: ..
..F
..B: F
H F
F
Acid Lewis
Base Lewis
3. Hng s cn bng acid - base

Acid phn ly trong nc. Cc ion b hydrat ha (solvat ha)
HA
H+(nc) + A- (nc)
H+ + A- hay HA( nc )
S solvat ha H + (nc) v A - (nc) c th minh ha:

H2O
+
O
H
+
H3O (H2O)n
OH2
OH2
A-
O
H
H O
A-(H2O)n
H
O
H
51
Bng 4.2. Gi tr pKa ca mt s cht hu c

Hp chat
Acid lien hp
pKa
+ OH
CH3CONH2
CH3 C NH2
+
H3O
+
CH3OH2
+
(CH3CH2)2 OH
+ OH
H2O
CH3OH
(CH3CH2)2 O
CH3COOH
CH3 C OH
+ OH
00
-1.7
-2.2
-3.6
-6.0
CH3 C OC2H5
-6.5
CH3CHO
CH3 C H
+ OH
-8.0
CH3COCl
CH3 C Cl
+
CH3 C NH
CH3COOC2H5
+ OH
CH3CN
-9.0
-10.7
Hng s cn bng ca phn ng:

HA( nc )
Ka =
H+(nc) + A-(nc)
[H+][A-]
[HA]
Ka > 1 thuc nhng acid mnh

Ka < 10-4 thuc nhng acid yu
Gi tr Ka rt b thuc nhng acid rt yu
S dng i lng pKa = -logKa nh gi mnh yu ca acid
pKa cng b th acid cng mnh v ngc li
pKa < -1 thuc acid mnh .
pKa > 3 thuc acid yu.
Tng t ta c hng s cn bng ca base.
B + H2O
Kb =
Kb
BH + + HO-
[ BH +][HO-] v [H2O] = 55,5 M

[B]
S dng i lng pKb = - logKb nh gi mnh ca base.

Kb cng ln th tnh base cng yu
pKb cng ln th tnh base cng mnh v ngc li
52
Bng 4.3. nh hng ca cc hiu ng n tnh acid

Acid
CH3COOH
FCH2COOH
F3CCOOH
ClCH2COOH
Cl2CHCOOH
Ka ,M
pKa
1,8.10-5
2,6.10-3
4,74
2,59
0,59
0,23
1,4.10-3
5,5.10-2
2,86
1,26
0,64
0,23
Cl3CCOOH
BrCH2COOH
1,3.10-3
6,7.10-4
2,90
HOCH2COOH
1,5.10-4
2,9.10-4
3,83
ICH2COOH
CH3OCH2COOH
CH2=CHCH2COOH
HC CCH2COOH
CH3CH2COOH
NCCH2COOH
C6H5CH3COOH
3,18
3,54
4,5.10-5
4,8.10-4
4,35
1,3.10-5
3,4.10-3
4,9.10-5
4,87
3,32
2,46
4,31
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 C2H5OC2H5 l mt base yu, v vy n ch tc dng
vi mt s acid mnh .
..
CH3CH2OCH2CH3 + H+
CH3CH2OCH2CH3
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:
C6H5COOH, C6H5CH2COOH, CH3CH2NO2, C6H5OH, (CH3)3NH+
2- Vit cng thc cc acid lin hp ca cc base sau:
NH3, C6H5NH2, CH3OCH3, CH3COCH3, HCC-, RO3- V sao AlCl3, ZnCl2, NH4+, BF3 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 + IR_Li + H2O
R_H
Tng qut:
R_A + Y
+ LiOH
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
RA+Y
Nhom the Y
R_X
Phan ng halogen hoa
NO2
R_NO2
Phan ng nitro hoa
SO3H
R_SO3H
Phan ng sulfonic hoa.
Halogen X
R'
Ar
R_R'
R_Ar
Phan ng alkyl koa

Phan ng aryl hoa
R'CO
R'CO_R
Phan ng acyl hoa
CHO
R_CHO
Phan ng formyl hoa
N=N_Ar
R_N=N_Ar
R'COO_R
Phan ng azo hoa
R'COO
54
RY+A
San pham the R_Y
Ten phan ng
Phan ng ester hoa
Mt s phn ng th c km theo s loi nc, alcol, amoniac ...cn gi l

phn ng ngng t. V d:
R_CHO
+ CH3COC6H5
R_CH=NR' + H2O
RCOOC2H5 + CH3COC6H5 RCOCH2CO C6H5 + C2H5OH

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 SN
-
R-A + Y
R-Y + A
Y- gi l tc nhn i nhn
V d:
CH3Cl
+ HO-
CH3OH + Cl-
1.1.2. Phn ng th gc t do SR
R-A + R
R-R + A
R l gc t do (nhng gc c mt in t)
V d: SO2Cl2 + C6H5 C6H5Cl + SO2Cl
1.1.3. Phn ng th i in t SE
R _ A + E+
R_E
+ A+
E+ l tc nhn i in t
+
V d: Ar _ H + NO2 Ar _ NO2 + 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
R_CH=CH2 + Br2
H2C=CHCl: Carbon trng thi sp thnh sp2
R_CHBr_CH2Br: Carbon trng thi sp thnh sp3
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 (AdE , AE )

Phn ng cng hp i nhn P (AdN , AN)
Phn ng cng hp gc P (AdR , AR )
1.2.1. Phn ng cng hp i in t (AdE , AE)
R_CH=CH2 + H2O
R_CHOH_CH3
1.2.2. Phn ng cng hp i nhn (AdN , AN )

R_CH=O
+ HCN
R_CH(CN)_OH
1.2.3. Phn ng cng hp gc (AdR , AR )

.
+ Cl
Cl
Cl
+ Cl2
Cl
.
+ Cl
Cl
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_CH2_CH2_OH CH2=CH2 + H2O: Carbon trng thi sp thnh sp2.
Br_CH2_CH2_Br + Zn CH2=CH2 + ZnBr2: Carbon trng thi sp thnh sp2
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
R C CH2 X
-XR
Chuyen v tr
.R. +
+
R C CH2
R C CH2 R
R
R
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
.
A__
.B
A+ + B-
hoac
.B
A__
.
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.
.B
A__
.
.
CH3-CH2
.
.
A + B
.
CH2=CH-CH2
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
CH3CH=CH2
CH3CH_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 .
-CH2CHO + H2O
H_CH2CHO + HO-
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.
CH3CHCH3
CH3CHCH3
CH3
CH3
Cau truc phang cua carbocation

orbital p khong co eletron
CH3
CH3
CH3
CH3CHCH3
:
H
CH3
CH3
Cau truc hnh thap cua carbanion

orbital p vi 2 electron
CH3
Cau truc phang cua goc t do

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: H2C: , Cl2C: , CH2=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 trong
H
orbital sp2
H
Hnh 5.2. Cu trc ca carben H2+C: v lng gc CH2
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: CH3+ < CH3CH2+ < (CH3)2CH+ < (CH3)3C+ do hiu ng +I ca CH3.
CH3+ < C6H5CH2+< (C6H5)2CH+ < (C6H5)3C+ do hiu ng +C ca C6H5

Carbanion bn vng khi c cc nhm ht in t . Hiu ng -I v -C lm
tng bn ca carbanion.
V d: CH3 < (CF3)2CH- < (C6H5)2CH
CH3 CH2CH2- < CH2 = CH CH2 < (CH2=CH)2CH

Cc gc t do km bn v c kh nng phn ng cao. Cc nhm alkyl, aryl
lm tng bn. Gc phenyl C6H5 - c kh nng c hiu ng +C hoc -C
V d: CH3. < CH3CH2. < (CH3)2CH. < (CH3)3C
CH3. < C6H5CH2. < (C6H5)2CH. < (C6H5)3C.

Cc nhm th c hiu ng I , C v H v tr para trong gc p-X-C6H4CH2.
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 .
k = P.Z .e
EA
RT
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 EA 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 EA 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 10oC 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 EA, 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).
A1 Phc chat hoat ong A1
E
Nang lng hoat hoaEA
EA1
B
A2 Phc chat hoat ong A2

EA1
Chat trung gian B
Chat ban au
Tin trnh phn ng
AH
Chat cuoi
Tin trnh phn ng
(a)
(b)
Hnh 5.3. Gin nng lng v tin trnh phn ng
C th xem nng lng hot ha EA 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 EA 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 - T S
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 SN2 v c ch n phn t SN1.
C ch SN2
C ch lng phn t SN2 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: CH3Cl + HO- CH3OH + Cl-
Phng trnh tc phn ng: v = k [CH3Cl] [HO-]

Trng thi chuyn tip:
H
HO -
Cl
HO
H
Tac nhan ai nhan
Chat phan ng
Cl
HO
H + Cl
C
H
San pham cuoi
Trang thai chuyen tiep
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 SN1
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- + (CH3)3C_Br
(CH3)3C_OH + Br-
v = k [(CH3)3C_Br]
Phng trnh tc phn ng:

Giai on chm: (CH3)3C_Br
(CH3)3C+
Br -
Giai on nhanh: (CH3)3C+ + HO - (CH3)3C_OH
61
Phn ng xy ra theo c ch SN1 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 -
CH3
CH3
HO C
HO -
CH3
C+
CH3
CH3
CH3
CH3
CH3
OH
CH3
San pham cuoi
Carbocation
San pham cuoi
Phn ng xy ra theo c ch SN1, 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 (-CH2CHO ...), cc tiu phn c cp in t lin kt (anion
CH3O- ..), hoc cc phn t c cp in t khng lin kt (NH3...)
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 SN1 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 RCH2 _ X phn ng ch yu xy ra theo c ch SN2
RCH2_X
+ HO-
RCH2_OH + X-: c ch SN2.
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)3C X phn ng ch yu xy ra theo c ch SN1
(R)3C_X + HO-
(R)3C_OH + X- c ch SN1
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)2CH_X phn ng xy ra theo c ch SN1 hoc SN1
ph thuc vo cc yu t cu trc hoc dung mi.
(R)2CH _ X
+ HO-
(R)2CH_OH + X- c ch SN1 hoc SN2
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 SN1. Dung mi khng hoc t phn cc lm
cho phn ng u tin xy ra theo c ch SN2.
62
2.3.2. C ch phn ng th i in t SE
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 (+NO2, Br+) hoc phn t
thiu in t (SO3, CO2...). Cht phn ng l nhng hp cht vng c cu trc
thm Ar -H (ph hp vi cng thc Huckel) .
H
E+
Phc
Phc
+ E
Chat trung gian
Chat phan ng
H
San pham
Tien trnh phan ng

trnh
inin
HnhHnh
5-4. 5.4:
CacCc
quaqu
trnh
cuaca
phaphn
n ngng
the th
ai ie
t 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).
H
E+
+ E+
H
+
Phc
E
Phc
H
E
E
+ H+
San pham
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 SR
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
Giai on pht trin mch:
R_H + Cl. R. + HCl

tip tc...............................
Cl. + Cl.
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 Cl2 tn cng t 2 pha ca mt phng
(tng t c ch th SN1) 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 AdE
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 CH3CH=CH2 xy ra nh sau:
H_Br
+ Br-
H+
+ H+
CH3
CH
CH2
CH3
+
CH
CH3
CH2
CH3 + Br +
CH2 + Br -
Cham
H+ l tc nhn i in t E +; Br l Y -.
CH3
+
CH
CH3
+
CH2
CH3
CHBr
CH3
CH2
CH3
CH2
CH3
CH2Br
hoac CH3
CH
H
+
CH2
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:
H
CH3
CH
Br
64
CH2
CH3
CH
H
+
Br Br
CH2
Br -
CH3
CH
H
CH2
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.
RCHY_O-
RCH=O + Y-
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''
O
R C
O
+ Y-
R C
+ 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.
O
R C Cl >
R C
O
O
.. C R'
> R C O.. H > R C O.. R' > R C O

-
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 E2 v c ch n phn t E1.
2.5.1. C ch tch loi E2
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- +
Base manh
H C
Chat phan ng
Y H C
YH + C
C + X-
San pham
65
V d: Phn ng tch loi HBr t ethylbromid di tc dng ca C2H5O l

mt base mnh to thnh ethylen c c ch nh sau:
H
CH3
C2H5O -
Br
CH3
Br
CH3
+
C2H5OH
H
H
C2H5O
+ Br H
iu kin v ha lp th cho c ch E2 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:
CH3
Br
H
H
+ C2H5O -
CH3
Br
CH3
- Br -
- C2H5OH
C H
2.5.2. C ch tch loi E1
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:
H C
H C
Chat phan ng
H C
C+
+ X-
Cham
+ H+
Nhanh
Carbocation
C+
C C
San pham
Carbocation
V d: Tch HBr khi 2-Brom-2,3-dimethylbutan .

CH3CH3
H C C Br
CH3 CH3
- Br -
CH3 CH3
H C C+
- H+
CH3 CH3
CH3
CH3
CH3
CH3
Carbocation
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 CO2 hoc CO32-,
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 CO32-, 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 CO2, H2O, N2, SO2, X2. 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 NH3
hay NH4+ sau dng phng php chun xc nh hm lng NH3 hay NH4+
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
n=
Moi trng 1
Moi trng 2
sin
sin
= C1
C2
C1 va C2 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
< 100 nm
> 286 Kcal
Xa (vng chn khng)
100-200 nm
286 - 143 Kcal
in t
Gn (vng thch anh)
200-300 nm
143 - 82 Kcal
in t
350-800nm
82 - 86 Kcal
in t
Hng ngoi gn
0,8-2,0 m
36 - 14,3 Kcal
Bin dng lin kt
Hng ngoi
2-16,0 m
14,3 - 1,8 Kcal
-nt-
16,0-300 m
1,8 - 0,1 Kcal
-nt-
- Vi sng
cm
10-4 Kcal
Quay
- Tn s radio
mt
10-6 Kcal
Bc x gama, tia X
Dng kch thch
V tia v tr
- Tia t ngoi
- Kh kin
- Hng ngoi
Hng ngoi xa
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
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 = 10-7cm). Cng hp th c biu th bng hp th phn t max
hoc logmax . 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
Etan
H2O
Methanol
Ethylen
Acetylen
1,3-Butadien
v n
Acrolein
thm
Benzen
v n
-n thm
Phenol
max
Bng
hp th
-
135
167
183
7.000
500
165
173
10.000
6.000
150
188
279
1.860
15
217
21.000
210
11.500
*thm
*thm
*thm
60.000
8.000
215
E1
180
200
255
*thm
*thm
2.460
174
E2
208
262
*thm
*thm
6.200
1.450
E2
210
270
Aceton
Toluen
max (nm)
E2
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, NO2.
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, -NH2, - 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:
6
5
4
3
2
1
3
2
1
217 nm
Trang thai c ban

cua butadien
Trang thai kch thch

cua butadien
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:
h (n-)
n
Methyl vinyl ceton
Aceton
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
Ethylenic
Cu to
max
V d
max
Chuyn dch
electron
(nm)
RCH=CHR
CH2=CH2
165
15.00
- *
193
10.00
- *
Acethylenic
RCCR
CHCH
173
6.000
- *
Carbonyl
RR1C=O
CH3COCH3
188
900
- *
279
15
n - *
RCH=O
CH3CHO
290
16
n - *
Carboxyl
RCOOH
CH3COOH
204
60
n - *
Amid
RCONH2
CH3CONH2
208
n - *
Azometin
C=N-
(CH3)2C=N-OH
190
5.000
- *
Nitril
-CN
CH3CN
160
- *
Azo
-N=N-
CH2-N=N
347
4.500
n - *
Nitroso
-N=O
C4H9-N=O
300
100
Nitrat
-ONO2
C2H5ONO2
270
12
n - *
Nitrit
-ONO
C5H11NO
218
1.120
- *
Nitro
-NO2
CH3NO2
271
18.60
n - *
Sulfon
- SO2 -
(CH3)2SO2
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
1
CH3COOH
204
CH3(CH=CH)2COOH
254
Hp cht
C6H6
204
256
C6H5Cl
210
265
C6H5OH
210
270
C6H5NO2
252
280
330
73
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
1.1
1.2
1,3
1,4
1,5
200
250
300
400
350
(nm)
Hnh 6.2: Ph t ngoi ca ceton oxyd mesityl (CH3)2C=CHCOCH3
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 H2O c cc dao ng nh sau:
3756cm-1
1595cm-1
3655cm-1
Dao ong hoa tr

oi xng
Dao ong hoa tr

khong 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 =
74
1
2
m1.m2
m1+m2
l tn s dao ng ca lin kt.

l khi lng rt gn
m1 v m2 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.
1 104
m
cm-1 =
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
Alkan
Tn s cm -1
Cng
2850-3000
1450-1470
1370-1380
Dao ng lin kt
C-H dao ng ho tr
CH2 v CH3 bin dng
720 - 725
3080-3140
1800-1860
1645
990
C=C
910
C-H
3080-3140
=C-H
1750-1800
1650
C=C
890
C-H
3300
C-H
Alken
RCH=CH2
R2C=CH2
=C-H
Alkyn
RCCH
RCCR
2100-2140
CC
600-700
C-H
2190-2260
tf
CC
75
Bng 6.5 (tip)

Hp cht
Cng
Dao ng lin kt
1000-1350
700-850
500-600
200-500
tf
f
f
f
C-F
C-Cl
C-Br
C-I
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
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
Alkyl halogenid
R-F
R-Cl
R-Br
R-I
Alcol
RCH2OH
R2CHOH
R3COH
Tn s cm -1
Hnh 6.4 l ph hng ngoi IR ca phn t 2-methylprophanol

4000
3600
3200 2800 2400 2000 1800
3360
1600
1400
1200
1000
800
600
400
1200
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
1
S proton
S ntron
Spin
Momen t
1/2
2,79267
12
13
1/2
14
0,40357
0,00
16
19
0.00
0,70216
10
1/2
2,6275
31
15
16
1/2
1,1306
32
16
16
0,00
Nu mt ht nhn nh vy nm trong mt t trng ng dng Ho (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 Ho k hiu l spin . nh hng th hai i song vi t trng
ng dng k hiu spin .
Ho
Momen t hat nhan
Momen t hat nhan trong t trng
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 Ho, 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).
Ho
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 Ho (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 Ho 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
Ong ng mau
H o Cc t trng N
...
...
...
...
...
...
S Cc t trng H o
May ghi
Nguon phat song cao tan
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

CH3
CH2
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:
Hhiu dng = Ho - Ho
l hng s che t (hng s chn)
Tn hiu cng hng ch xut hin mt cng t trng bn ngoi Ho
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 (CH3)4Si).
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.
( hoac ppm ) =
60
60.106
.106 = 1,00
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, CH2 v nhm CH3, 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
-CH3
-CH2TMS
-OH
ppm
Hnh 6.9: Ph RMN ca C2H5OH 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:
CH3
CH3CH2CH2CHCH3
+ e-
2e- +
.
CH3
CH3CH2CH2CHCH3
m/e 86
+.
CH3
CH3CH2CH2CHCH3
CH3
+ CHCH
+.
m/e 43
CH3CH2CH2
CH .
CH3CH2CH2CH+ m/e 71
CH3CHCH3
+
CH3CH2
CH3
CH3
m/e 57
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
Cng o
43
100
80
60
40
71
20
57
10
20
30
40
50
86 M+
60
70
80
90
100
m/e
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
toc
tos
nh tnh, nh lng
cac nguyen to
UV
nh tnh nhom chc
IR
RMN
MS
Ket luan ve cau truc

cua chat hu c
81
Chng 7
ALKAN - HYDROCARBON NO
(CnH2n+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
Kh
Thnh phn
t si
C 1 C4
< 20
Ether du ha
C 5 C6
20-60
Xng
C 6 C8
60-200
Ligroin
C7
60-90
Gazolin
C6 C12
85-200
Keroxin
C12 C15
200-300
Du mazut
C16 C23
200-400
Du bi trn
C18 C22
300
Atphan dng phng php hydro ha than nu bng cch nghin nh than
vi du nng c xc tc st v H2 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
CnH2n+2. Cht n gin nht l metan CH4. Cu to mch thng hay phn nhnh.
82
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
n-pentan
metan
H
H
H
H
H
H
H H
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
Metan
Heptan
Etan
Octan
18
Propan
Nonan
35
Butan
10
Decan
75
Pentan
20
Eicozan
366319
Hexan
30
Tricozan
4,11.109
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
Khuat
Cong thc lap the

thong thng
H
H
HH
H
H
Lech
H
Khuat
Cong thc phoi canh
H
Lech
Cong thc Newman
Hnh 7.1: Cch biu din cc cu dng ca etan
Lch
Che khut
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
HH
H
H
HH
H
H
c cc dng lch.
H
H
H
H
HH
H
H
H
H
HH
H
H
H H
H
Kj/mol
11,7
60
120
goc quay
180
300
240
360
Hnh 7.2: Gin ph thuc nng lng v gc quay ca cc cu dng ca etan

H
E H
(Kj/mol)
H H
HH
H
H
HH
H H
H
HH
H H
H
25,5
14,2
3,4
60
120
(goc quay)
180
240
300
360
Hnh 7.3: Gin ph thuc nng lng v gc quay cc cu dng ca n-butan

CH3 k hiu l
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 CH3CH2CH2CH3 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
CnH2n+2 CnH2n+1_
an
yl
Nguyn tc:
Thay v ng ''an'' trong tn gi ca hydrocarbon no bng tip v ng ''yl"
Cc gc bc 1
CH3
CH3CH2
CH3CH2CH2
ethyl
n-propyl
methyl
CH3CH2CH2CH2n-butyl
CH3CH2CH2CH2CH2n-pentyl
CH3 CH CH2
CH3 isobutyl
CH3CHCH2CH2CH3 isopentyl
CH3CH2CH2CH2CH2CH2-
CH3CHCH2CH2CH2CH3
isohexyl
n-hexyl
CH3
CH3CCH2CH3
neopentyl
CH3
CH3CCH2CH2CH3
neohexyl
Cc gc bc hai
CH3CHCH3
isopropyl
CH3
CH3CH2CH-
sec-butyl
Cc gc bc ba
CH3
CH3CCH3
CH3
tert-butyl
CH3CH2CCH3
tert-pentyl
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.
1
CH3_ CH2_ CH_ CH2_ CH_ CH2_ CH2_ CH3

7' 6'
5'
4' 3'
1'
8'
2'
CH2CH3 CH3
CH3_ CH2_ CH_ CH2_ CH2_ CH_ CH2_ CH3
CH2CH3
CH3
CH3_ CH_ CH2_ CH2_ CH2_ CH_ CH_ CH3

1' 2'
4'
3'
5' 6' 7'
8'
CH3 CH3
CH3
CH3
1'
2'
anh so theo nguyen tac tong so nho nhat

3+5 < 4'+6'
3-etyl-5-methyl octan
Nhom methyl quyet nh v tr anh so
3-methyl ,6-ethyl octan
anh so theo nguyen tac tong so nho nhat
2+3+7 < 2'+6'+7'
2,3,7-trimethyl octan
Chon mach chnh la mach dai mhat
3'
CH3 CH2 CH3 C CH2 CH3
va anh so theo quy tac tong so nho nhat

2+3+6+7 < 3+4+5+7
CH3 CH CH CH CH2 CH CH3
6
4
5
3
7
Ma
c
h
nha
n
h
co phan nhanh va anh so
CH 3
CH3 CH CH3
1
2
mach nhanh tai v tr gan vao mach chnh
CH3
2,3,6,7-tetramethyl -5-(1',1'-dimethylpropyl) nonan
CH3 C CH2 CH 3
1'
2'
3'
1',1'-dimethylpropyl
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.
86
CH
CH
R'
+ H2
CH
CH
R'
+ 2H2
Ni
Ni
CH2
CH2
R'
CH2
CH2
R'
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 + Zn2+ + XR-I + HI
R-H + I2
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 + I2
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 + HI
R-I + HOH
R-H + I2
V d:
CH3-CH2-CH2-CH2-OH + 2HI CH3-CH2-CH2-CH3 + H2O + I2
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 PI3 v cht ny khi tc dng vi nc
li ti to HI.
3.1.4. Kh ha acid v dn xut acid
R-CH3 + 2H2O + 3I2
R-COOH + 6HI
Phn ng dng iu ch alkan c mch carbon ln.
Kh ester d hn acid.
3.1.5. Thy phn hp cht c kim
CnH2n+1Br + Mg / ether khan
CnH2n+1MgBr
CnH2n+1MgBr
CnH2n+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:
2CH3-CH2-I + 2Na
CH3-CH2-CH2-CH3 + 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)

CH3CH2COONa
catod
anod
Na+
CH3CH2COO
+e
-e
.
Na
CH3CH2COO
H2O
- CO2
NaOH + H2
CH3CH2 .
CH3CH2CH2CH3
chnh
CH3CH3 + CH2
ph
CH2
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 + Na2CO3
CH3COONa + NaOH CH4 + Na2CO3
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 CH3 v methylen CH2 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 CH4
-161,7
-182,0
Etan
- 88,6
-183.3
Propan C3H8
42,6
-187,7
0,5005
Butan C4H10
- 0,5
-138,3
0,5787
C2 H 6
Pentan C5H12
6,1
-129,8
0,5572
HexanC6H14
68,7
- 95,3
0,6603
Heptan C7H16
98,4
- 90,6
0,6837
Octan C8H18
125,7
- 56,8
0,7026
Nonan C9H20
150,8
- 53,5
0,7177
Decan C10H22
170,4
- 29,7
0,7299
Undecan C11H24
195,8
- 25,6
0,7402
Dodecan C12H26
216,3
- 9,6
0,7487
Tridecan C13H28
235,4
- 5,5
0,7564
Tetradecan C14H30
253,7
5,9
0,7628
Pentadecan C15H32
270,6
10,0
0,7685
Eicosan C20H42
343,0
36,8
0,7886
Triacontan C30H62
449,7
65,8
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
CnH2n+2 + X2
CnH2n+1X + HX
Phn ng xy ra theo c ch gc t do, c xc tc nh sng hoc nhit cao.

F2 > Cl2 > Br2 > I2.
Kh nng phn ng ca halogen sp xp theo
Kh nng phn ng ca C _H bc 3 > C_H bc 2 > C_H bc 1

CH4 + 2F2 C + 4HF
Phn ng clor ha metan xy ra qua cc giai on sau:
Cl2
H = +270kcal
H = -1kcal
. 2Cl
CH4 + Cl
CH3 + HCl
CH3 + Cl2
CH4 + Cl2
CH3Cl + Cl
CH3Cl + HCl
. H = -23kcal
89
Thc t phn ng to thnh hn hp sn phm CH3Cl, CH2Cl2, CHCl3, CCl4

Phn ng s ngng hn khi cc gc t do kt hp vi nhau.
Cl + Cl
Cl2
.
.
; Cl + CH3
CH3Cl
.
.
; CH3+ CH3
CH3CH3
Phn ng clor ha phn t propan to ra nhiu cht:

CH3 CH2 CH3
h + Cl2
CH3 CH2 CH2Cl

+ Cl2
CH3 CHCl CH3

+ Cl2
CH2Cl CH2 CH2Cl + CH3 CHCl CH2Cl
+ Cl2
CH2Cl CHCl CH2Cl
+ CH3 CCl2 CH3

+ Cl2
+ CH3 CCl2 CH2Cl
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 H0 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.
.
Cl + H_CH2CH3
Lien ket phan ly
Cl_H+
o
H = 98 - 103 = - 5 kcal. mol-1
CH2CH3
Lien ket tao thanh
Lien ket tao thanh Lien ket phan ly
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:
CH3
CH3 C CH2 CH3

H
CH3
CH3
+ Cl2
CH2Cl C CH2 CH3 + CH C CH CH Cl

3
2
2
H 30%
H 15%
90
CH3
CH3
+ CH3 C CHCl CH3 + CH3 C CH2 CH3
33%
Cl
22%
Brom ha:
CH3
CH3 C CH2 CH3
CH3
Br2
CH3 C CH2 CH3
HBr
Br
Phn ng iod ha alkan l qu trnh thun nghch:

RH + I2
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 HIO3 tch HI v
phn ng chuyn v pha to iodoalkan.
5.1.2. Phn ng nitro ha - Tc dng vi HNO3
Phn ng nitro ha l phn ng th nguyn t hydro ca alkan bng gc NO2.
nhit thng alkan khng phn ng vi acid nitric. nhit cao (150450C) alkan tc dng vi acid nitric long hoc kh NO2 to thnh dn xut
nitro. Nu dng acid nitric c th alkan b oxy ha.
RH + HO_NO2 ( long )
450o
RNO2 + H2O
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:
CH3_CH2_CH3 + HNO3
CH3_CH2_CH2_NO2 + CH3_CH_CH3 + CH3_CH2_NO2+ CH3_NO2

25%
NO2 40%
10%
25%
1-Nitropropan
Nitroetan
Nitrometan
2-Nitropropan
Phn ng nitro ha xy ra u tin th vo hydro carbon bc cao.

Gc NO2 sinh ra do tc dng ca nhit :
HNO3 + HNO3
to
.
H2O + 2 NO2
Vai tr ca gc NO2 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 H2SO4 m c nhit thng khng tc dng vi alkan. Acid
sulfuric bc khi (c ho tan SO3 - oleum) tc dng vi nhng alkan c mch 6- 8
carbon v to thnh alkansulfoacid.
C6H14
H2SO4
SO3
C6H13SO3H
91
Tc dng vi SO2 v Cl2 - Phn ng sulfoclor ha

Alkan tc dng trc tip vi hn hp SO2 v Cl2 nhit 20 - 30C c
chiu sng bng n t ngoi hoc c peroxyd lm cht khi mo th thu c
alkansulfoclorid.
h
RH + SO2 + Cl2
RSO2Cl + HCl
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.
RSO2Cl + 2NaOH
RSO3Na + H2O + NaCl
Sulfo oxy ha
Khi cho hn hp SO2 v O2 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 + SO2 +
1
O
2 2
RSO 3H
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.
CnH2n+2
CxH2x+2
+ CyH2y
(n = x +y )
Khi cracking n-pentan, phn ng xy ra theo c ch gc.

CH3CH2CH2CH2CH3
.
.
CH3 + CH3
.
.
CH3 + CH3CH2
.
.
CH3CH2 + CH3CH2CH2CH2
.
CH3CH2
92
.
.
CH3 + CH3CH2CH2CH2
.
.
CH
CH
CH
+
CH3CH2
3 2 2
CH3CH3
CH3CH2CH3
CH3CH2CH2CH2CH2CH3
.
CH3CH2CH2
CH3CH3
+ CH3CH=CH2
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 H2SO4 c, KMnO4. 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.
RCH3 +
xuc tac
3
O2
2
to
RCOOH + H2O
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.
CH3_(CH2)nCH3
oxy ho
CH3(CH2)xCOOH
CH3(CH2)yCOOH
n=x+y+2
Khi t chy alkan to CO2 v hi nc ng thi gii phng nng lng.

CnH2n+2 +
3n + 1
2
O2
CH4 + 2 O2
n CO2 + (n+1) H2O + Q

CO2
+ 2 H2O + 885 kj
Chnh v vy cc alkan nh metan, butan, octan ... c dng lm nhin liu.

6. Cht in hnh
Metan CH4
Tng hp metan:
Be2C + 4H2O CH4 + 2Be(OH)2
Al4C3 + 12H2O
CS2 + 2H2S + 8Cu
3CH4 + 3Al(OH)3
CH4 + 4Cu2S
Trong phng th nghim, iu ch metan bng cch nhit phn mui acetat
kim loi kim
CH3COONa + NaOH
CH4 + Na2CO3
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/m3) 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.
CH4 + O2
C + H2 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.
CH4 + H2O
CO + 3H2
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 sp3. 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.
CH3
CH3
Methylcyclopropan Methylcyclobutan
CH3
CH3
2
3
2
3
CH2CH2CH3
CH2CH3
1-Methyl 3-ethylcyclopentan 1-Methyl, 3-(n-propyl) cyclohexan
1.2. ng phn
Monocycloalkan c s ng phn nhiu hn s ng phn ca alkan c s
carbon tng ng. V d: C8H16 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.

CH2CH3
CH3
1
CH3
CH3
CH3
1
3
CH3
CH3
Ethylcyclohexan
1,2-dimethylcyclohexan 1,3-dimethycyclohexan
1,4-dimethycyclohexan
Khc vi cc alkan, cycloalkan c ng phn hnh hc cis - trans

CH3
CH3
CH3
CH3
trans 1,2-dimethylcyclohexan
cis 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:
1 [109o28' 2
(goc lien ket trong vong phang) ]
Bng 8.1: Sc cng Bayer ca mt s cycloalkan
Ho (*)
Cyclopropan
60
+2464'
+12,7
Cyclobutan
90
+964'
+6,8
Hp cht
Cyclopentan
108
+064'
-18,4
Cyclohexan
120
-536'
-29,5
12834
-953'
135
-1286'
Cycloheptan
Cyclooctan
-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 CH2

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).
H
Hnh 8.1
S xen ph cc i b vi phm
v lin kt C-C b un cong
S xen ph cc i
C
H
C
H
S xen ph ca cc orbital sp2

to thnh cyclopropan
1.4.2. Cyclobutan
Cyclobutan c cu dng gy gp - cu dng xp (hnh 8-2)
H
H
H
H
H
H
H
S tng tac gay ra sc cangPitzer
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
H 1 H
H
H
2
H 2 H5
4
H
1
H
3
H
H
4
3
5
1
H 3 H
H
H 4
2
H
S tng tc gy ra sc cng Pitzer
M hnh phn t cyclopentan
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) .
S tng tac gay ra sc cang Pitzer
H
H
H
H
HH
H
H
H H
H
Dang ghe
H
H
H
H
Dang thuyen
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).
Truc oi xng
H
H
H
H
Lien ket axial
H
H
H
H
H
Lien ket equatorial
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).
CH3
a
CH3
e
Axial
(a)-Methylcyclohexan
Equaterial
(e)-Methylcyclohexan
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.
CH3
CH3
CH3
CH3
CH3
Trans1,2
CH3
CH3
CH3
CH3
CH3
Trans1,3
Cis 1,2
CH3
CH3
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.

H
CH3
a
H
CH3
e
Cis a,e H
e
CH3
H
Cis e,a CH3
CH3
a
CH3
a
CH3 e
Cis e,e
Cis a,a
CH3
CH3
CH3
a
e
a
CH3
Cis a,e
CH3
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)
H
CH
a 3
H
e
H
Trans e,e
a
CH3
Trans a,a
CH3
CH3
a
e
CH3
CH3
CH3
a
CH3 e
Trans a,e
e CH3
Trans e,a
a
CH3
CH3
e CH3
e
H
Trans a,a
Trans e,e
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.
2H
HBr
CH3-CH2-CH3 ;
Br2
CH3-CH2-CH2Br;
CH2Br-CH2-CH2Br
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
Cl
6Cl2
Cl
Cl
Cl
Cl
+ 6HCl
Cl
99
Xuc tac
OH
Cyclohexanol
Xuc tac
O2
Pt
+ 3 H2
O
Cyclohexanon
Xuc tac
HOOC (CH2)4 COOH

Acid adipic
Tnh cht c bit ca cc hp cht cycloalkan l c th tham gia phn ng

chuyn v tng hay gim ln ca vng.
CH2CH3
AlCl3
CH3
Ethylcyclobutan
CH3
AlCl3
Methylcyclopentan
Cycloheptan
Methylcyclohexan
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.
_CH2CH2_
Bicyclohexyl
1,2-Bicyclohexyletan
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.
10
9
8
7
1
6
Bicyclo[4.4.0] decan
Bicyclo[4.3.0] nonan
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.
1
6
5
4
Bicyclo[2.2.1] heptan
100
8
7
4
2
3
6
5
8
1
2
Bicyclo[2.2.2] octan
C th c hp cht 3, 4 vng
1
8
7
6
4
1
3
5
10
4
Tetracyclo [2.1.1.0 2,6. 0 3,5] hexan
Tricyclo[3.3.1.0 2,9] decan
Tricyclo[3.3.1. 3,7] decan
Ch : 13,7 ch r mch c 1 carbon v 2 carbon u cu l carbon s 3 v s

7; 0 ch r mch khng c carbon v 2 carbon u cu l carbon s 2 v s 6.
2,6
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.
7
1
4
2
3
1
3
10
8
2
1
5
4
2
3
8
7
10
3
10 11
8
2
Spiro[3.4] octan Spiro[2.4] heptan Spiro[4.5] decan Dispiro[2.1.4.1] decan
12
1
2
Dispiro[2.1.5.2] dodecan
Bi tp
1. V cc ng phn hnh hc c th c ca cc ng phn ca cyclohexan c
CTPT C9H18. 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[5.1.0.03,5]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:
CH3
CH3
101
Chng 9
ALKEN - HYDROCARBON ETYLENIC

(CnH2n)
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 CnH2n.
i vi hp cht vng c mt ni i c cng thc tng qut CnH2n-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 sp2. 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 sp2 ca carbon xen ph vi nhau to thnh lin kt ca HC (hnh 9-1).
Csp2
Hnh 9.1:
Cac nguyen t H ,C cua ethylen

nam tren mot mat phang
C 2
sp
Lien ket tao thanh do

2 carbon lai hoa sp2
o
Lien ket tao thanh

do 2 orbital p t do
o
di lin kt ca HC l 1,076 A , ca C =C l 1,330 A

Gc lin kt HCH l 116, 6o . Gc lin kt H_C=C l 121,7o .
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
Buten
S ng phn
Alkan
S ng phn
C 4 H8
Butan C4H10
Penten C5H10
Pentan C5H12
Hexen C6H12
12
Hexan C6H14
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.
a
b
a
C C
Co ong phan cis-trans
CH3
c
C C
C C
CH3
C C
H
H
CH3
Trans -2-buten
Cis -2-buten
Co ong phan Z-E
CH3
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.
CH3
CH3
H
C C
CH3
Trans -2-buten (74%)
C C
CH3
CH3CH2CH=CH2
1-buten (3%)
Cis-2-buten (23% )
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.
CH3
H
C C
CH2CH2CH3
CH3
H
CH2CH3
Z -3-ethyl-2-hexen
C C
CH2CH3
CH2CH2CH3
E -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''.
CH2=CH2
CH3CH=CH2
Ethylen
CH3CH2CH=CH2
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.
CH3
CH3_CH=CH_CH3
CH3CH=CH2
Dimethylethylen oi xng
Methylethylen
CH3_C=CH2
Dimethylethylen khong oi xng
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
1 CH
CH3CH=CH2
Propen
CH3
4
1
4
3
3
2
_
_
_
CH3 CH=CH CH3 ; CH3 C=CH_CH3
2-Buten
2-Methyl-2-buten
2 CH
CH3
_
_
_
;CH3 CH CH2 CH2_C_CH2_CH3
7
6-Methyl-3-ethyl-3-hepten
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.
Khi a > b va c > d
a
b
C C
c
d
ong phan Z
a
b
C C
d
c
ong phan E
Xc nh ln nhm th theo quy c Cahn -Ingold-Prelog, danh php R,S
104
R- Rectus - bn phi, S - Sinister - bn tri

CH3CH2
CH3
C C
ClCH2CH2
CH2CH3
C C
CH3CH
Cl
Z -3-methyl-3-hexen
CH2Cl
CH3
E -1,4-diclo,2-methyl-3-(2-clorethyl) -2-penten
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
R CH
H
CH3
C CH3
Dung dch KOH / alcol
CH3
_
_
R CH=C CH3 + HX
Dung dch KOH/alcol khi un nng xy ra s cn bng sau:

ROH + OH -
RO- + H2O
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 E1 v E2.
4.1.1. Phn ng tch loi E1 alkylhalogenid
R_CH2_CH_CH3
X
Cham
+
R_CH2_CH_CH3
Nhanh
+
R_CH2_CH_CH3 + X
R_CH=CH_CH3
+
+ H (I)
+
R_CH2_CH=CH2 + H ( II )
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 CH3 vi lin
kt i C =C c s lin kt C -H nhiu hn.
105
H
+
R CH2 CH C H
H
Co 3 lien ket C-H sieu lien hp
+
R_CH2_CH_CH3
H
_
_
R CH=CH C_H
(I)
Co 3 lien ket C-H
H
+
R C CH CH3
H
Co 2 lien ket C-H sieu lien hp
H
_
R C_CH=CH2
H (II)
Ch co 2 lien ket C-H
4.1.2. Phn ng tch loi E2 alkylhalogenid

Phn ng E2 xy ra trong iu kin c base mnh v dung mi km phn cc.
CH3CH2CH2CHBrCH3
EtOK
EtOH
CH3CH2CH=CHCH3+ CH3CH2CH2CH=CH2+ CH3CH2CH2CH(OEt)CH3

41%
25%
20%
Trong c ch E2 c th hnh thnh trng thi chuyn tip sau:

HO ..... H
CH3CH2CH_CHCH
.
. - 3
Br
H ..... OH
_
CH3CH2CH2_CH
. CH2
Br
Trong trng hp tch loi theo c ch E2 (cng nh E1) 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
CH3
_
CH3 CH_CH2_CH=CH_CH3 Co 5 H
CH3
CH3_CH_CH2_CH_CH2_CH3
X
CH3
CH3_CH_CH=CH_CH2_CH3
Co 3 H
Hiu sut olefin thu c ph thuc vo iu kin phn ng .

CH3CH2CBr(CH3)2
EtOK
EtOH
(CH3)3COK
(CH3)3COH
(C2H5)3COK
CH3CH=C(CH3)2 +
71%
CH3
CH3CH2C=CH2
29%
28%
72%
11%
89%
(C2H5)3COH
Tc phn ng E2 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.
H
H
C6H5
C6H5
Br
C6H 5
Br
C6H 5
C6H 5
Base
Br
Br
HBr +
Br
C6H5
C6H5
Br
Br
Br
C6H 5
C6H5
C6H 5
C6H5
Br
(Z) 1-bromo-1,2-diphenyl ethylen
(R,R) 1,2 -dibromo-1,2-diphenyl etan
H
C
Base
HBr +
C6H 5
Br
C6H 5
Meso-1,2 -dibromo-1,2- diphenyl etan
C6H5
C6H 5
Br
C6H5
(E) 1-bromo 1,2-diphenyl ethylen
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 (H2SO4, H3PO4) hoc vi KHSO4 s to alken.
H2SO4
RCH2CH2OH
RCH=CH2
180oC
H2O
Phn ng xy ra qua giai on to ester v c sau s hnh thnh alken

hoc sn phm ph l ether .
RCH2CH2OH
H2SO4
140oC
RCH2CH2OSO3H
RCH2CH2OSO3H
RCH2CH2OSO3H
H2O
RCH=CH2 + H2SO4
RCH2CH2OH
RCH2CH2OCH2CH2R + H2SO4
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:
CH3(CH2)6CH2OH
H3PO4 ,
CH3(CH2)5CH=CH2
CH3(CH2)4CH=CHCH3
C hin tng trn l do s chuyn v ca hydro trong carbocation to thnh.

H
H+ CH (CH ) CH_+CH
CH3(CH2)6CH2OH
3
26
2
- H 2O
+
CH3(CH2)5CH_CH_CH3
H
+
CH3(CH2)4CH_CH_CH2_CH3
..
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 E1.
OH
H2SO4 62%
CH3CH2CH=CHCH3 + H2O
95o
CH3CH2CH2CHCH3
C ch E1
+OH
2
+
+
+
CH3CH2CH2CHCH3 H CH3CH2CH2CHCH3- H2O CH CH CH CHCH -H CH CH CH=CHCH
3 2 2
3
3 2
3
OH
C trng hp xy ra s chuyn v:
CH3 OH
CH3-C__CH-CH3
CH3
CH3
CH3
+
CH3_C_CH_CH3
CH3
+
CH3-C__CH-CH3
+
CH3-C__CH-CH3
H+
to
CH3
CH3
CH3
_
CH2=C CH_CH3
-H+
CH3
CH3
CH3
CH3_C=C_CH3
CH3
4.2.2. pha hi
Alcol di tc dng ca Al2O3 350 - 400C cng to alken theo c ch:
CH3CH2OH
R
Al
+
O
Al2O3
300-400oC
H
OH +
Al
Al
R+
CH2=CH2 + H2O
+ OH
Al
+ alken
Al
+ H2O
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.
Cl Cl
RCH_CHR' + Zn
RCH=CHR' + ZnCl2
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 450C). T
butan, isobutan iu ch c buten v isobutylen.
108
CH3CH2CH2CH3
CrO3
450oC
CH3CH2CH=CH2 + H2
Cc alken cng c to thnh khi nhit phnC, cracking cc hydrocarbon no.

n- C6H14 700-800oC CH + CH =CH + CH CH=CH + San pham khac
4
2
2
3
2
25%
15%
20%
40%
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
Cong thc
CH2=CH2
CH3CH=CH2
CH3CH2CH=CH2
CH3CH=CHCH3
CH3C=CH2
CH3
CH3CH2CH2CH=CH2
CH3CH2CH=CHCH3
CH3CHCH=CH2
CH3
CH3C=CHCH3
CH3
Ten goi
tochay
tosoi
Ty khoi
-103,9
- 47,0
0,566
Propylen
-169,4
-185,2
1-Buten
-130,0
-5,0
0,668
cis 2-Buten
-139,0
-3,5
0,635
isoButylen
-140,0
-6,0
0,566
1-Penten
-138,0
+29,9
0,640
2-Penten
-139,0
+36,4
0,651
3-Methyl-1-buten
-135,0
+25,0
0,648
2-Methyl -2-buten
-124,0
+38,4
0,668
Ethylen
0,609
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=CH2 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
Cl
R
CH=CH2
Cl
=0
Cl
Cl
Cl
C
= 2,95D
Cl
H
C
= 1,97D
CH3
C
CH3
= 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.mol1. 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:
+ X_Y
C=C
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
H2
xuc tac
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 + 2H2O
2Ni + 2AlO2 + 3H2
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.
H2
H H
H H CH2=CH2
C2H4
H_CH2_CH2_H
Be mat xuc tac
S cng hp cis vo lin kt i c th trnh by trong phn ng sau:

H 3C
H 3C
C O OH
H2
Pd
C
C OO H
H OO C
H3C
C
H
C OO H
C H3
H
HO OC
H3 C
H
H
C
C H3
C O OH
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 (AE)

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.
- +
- +
+
X C__C
Cham
C== C
+ Y-
Giai on II
Ion carboni kt hp vi phn cn li ca tc nhn tch in m.
+
X C__C
Nhanh
+ Y-
X C__C
Cc tc nhn phn ng halogen X2 (Cl2, Br2, I2), 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.
C__ C
Br Br
+ Br2
+ HOCl
- +
C__ C
Cl OH
+ H2SO4
C== C
Hp chat dibromo
Hp chat clorhydrin
C__ C
Ester cua acid sulfuric
H OSO3H
+ HCl
+ H2O , H+
C__ C
H Cl
Hp chat monoclor
C__ C
OH
Alcol n chc
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.
CH3
CH3
H
H
H
Cl
CH3
CH3
+
C
H
H
+ Cl
CH3
Cl
CH3
C
C
H
H
H
111
Alken khng i xng tc dng vi proton to thnh carbocation bn vng.

CH3
CH3C=CH2 + HCl
CH3
CH3
+
_
_
_
CH3 C CH3 khong tao thanh CH3 C_CH2
+
H
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
CH3CH2CH=CH2 + HOCl CH3CH2CHOH-CH2Cl (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.
CH3CH2CH = CHCH3 + HBr

2-Penten
+
CH3CH2CH -CH2CH3 Br
+
CH3CH2CH2 -CHCH3 Br
CH3CH2CHBr -CH2CH3
3-Bromopentan
CH3CH2CH2 -CHBrCH3
2-Bromopentan
Cng hp vi nc H2O
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.
CH3
+
CH3C = CH2 + H
Isobuten
CH3
CH3C_ CH3
+
+ H2O
Carbocation
CH3
CH3C_ CH3
+OH
2
CH3
CH3C_ CH3 + H+
OH
t-Butanol
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.
CH3CH = CH2 + HCl
Propylen
CH3CH _ CH3
Cl isopropylclorid
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 CH2 (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 C
H
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 (AE), 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:
+
CH3_CH _ CH3 ( I )
H
H
+
+ _ _
_
_
H C CH C H ( I ) va CH3_CH2 _ CH2 ( II )
H
H
H
+
_
CH3 C _ CH2 ( II )
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
CH3CH=CH2 + HBr
peroxyd
CH2=CHCH2Br + HBr
CH3CH2_CH2Br
peroxyd
BrCH2_CH2CH2B
Cc peroxyd nh dibenzoylperoxyd (C6H5CO)2O2, Peracetic CH3COOOH.

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:
R-O-O-R
R-O . + HBr
Br + CH3CH=CH2
CH3CH_CH2Br + HBr
2R-O .
H = +35 kcal
.
ROH + Br
H = -23 kcal
_
CH3CH CH2Br
H = -5 kcal
.
_
CH3CH2 CH2Br + Br
H = -11 kc
Phn ng kt thc khi cc gc t do kt hp vi nhau
Br. + Br. Br2
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 .
CH3CH_CH2Br (I )
Br + CH3CH=CH2
CH3CHBr_CH2 (II)
CH3
CH
CH3CHBr
CH2Br
CH2
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 Xca tc nhn s kt hp vi carbon ca ni i mang nhm methyl.
CH3CH2_CH=CH_CH3 + HBr
CH3CH2_CH2_CHBr_CH3
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
C==C
X2
X__C__C__X
(X2 = Cl2 , Br2 ..)
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
Br
Br
+
C
+
Br -
+
Br__C__C + Br
Br__C__C_ Br
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.
X
..
:X :
+
C
..
.
:X .
..
:X
C
S tao thanh ion halonium vong
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.
..
:X
X
Br2
CCl4 - 5o
Cyclopenten
Br
+
..:..
Br
Br
H
Br
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 B2H6 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=CH2 + B2H6 2(RCH2CH2)3B
6.3. Phn ng oxy ha
Alken b oxy ha bi cc cht oxy ha khc nhau.
6.3.1. Vi KMnO4
Alken tc dng nhanh vi kali permanganat KMnO4. 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
+ 2KMnO4 +
4H2O
loang
C
OH OH
+ 2MnO2 + 2KOH
Phn ng xy ra theo c ch cng hp cis

H
+ KMnO4
loang
to
O
Mn OO
H
H2O
OH
OH
115
Vi dung dch kali permanganat m c, lin kt i b ct v to hn hp

ceton v acid carboxylic.
R'
C==C
R''
KMnO4
O
C==O + HO_C R
R'
R''
; RCH=CH2
KMnO4
RCOOH + CO 2
6.3.2. Vi ozon (O3 )

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.
C
O
+ H2O
C
O
Molozonid
O3
C
O
Ozonid
C O+
O C
+ H2O2
C th dng phn ng ny xc nh cu trc ca alken.

CH3
CH3
CH2CH3
H
O3
CH3
C
CH3
O
O
C
O
Ozonid
CH2CH3
H
H2O
CH3_C_CH3 + CH3CH2CHO + H2O2
6.3.3. Vi cc peroxyd
Alken b oxy ha bng cc peracid. Sn phm to thnh l cc oxiran (epoxyd)
C6H5
+ CH3COOOH
C
C
H
C6H5
Trans-Stilben
C6H5
H + CH3COOH
C6H5
H
Trans-2,3-diphenyl oxiran
O
COOH
COOH
CH3(CH2)3CH__CH2
+
1-butyl oxiran
CH3(CH2)3CH=CH2 +
1-2-epoxyhexan
Cl
Cl
1-Hexen
Acid 3-cloro benzoic
Acid 3-cloro peroxybenzoic 1-oxydhexen
O
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:
Y + CH2=CH2
S pht trin mch:
Y-CH2CH2 + CH2=CH2
Y-CH2CH2
Y-CH2CH2-CH2CH2
Y-(CH2CH2)n-CH2CH2
S kt thc phn ng:
.
.
Y-(CH2CH2)n-CH2CH2
Y-(CH2CH2)n-CH2CH2
Y-(CH2CH2)n-CH2CH3 + Y-(CH2CH2)n-CH=CH2
Y-(CH2CH2)n-CH2CH2-CH2CH2-(CH2CH2)n-Y
6.4.2. Phn ng polymer ho theo c ch cation

C cc qu trnh
Qu trnh to cation: (CH3)2C=CH2 + H+ (CH3)3C+

Qu trnh pht trin mch polymer.
Qu trnh kt thc
Trong qu trnh trng hp c cc dimer, trimer c to thnh
(CH3)2C=CH2
cham
+
(CH3)3C-CH2-C(CH3)2
CH3
(CH3)3C-CH=C(CH3)2+ (CH3)3C-CH2-C=CH2
20%
80%
6.4.3. Phn ng theo c ch anion

Xc tc to anion thng l cc hp cht c kim.
(CH3)3- Li+ + CH2=CH2 (CH3)3C-CH2-CH2- Li+
Hn hp gm R3Al + TiCl4 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
500-600o
CH3_CH=CH2 + Cl2
CH3C=CH2 + Cl2
Nhiet o phong
ClCH2_CH=CH2 + HCl
ClCH2C=CH2 + HCl
CH3
CH3
Phn ng xy ra theo c ch nh sau:

+
CH3_C_CH2Cl + Cl
CH3
CH3_C=CH2 + Cl_Cl
CH3
+
CH3_C_CH2Cl
-H
CH3
+ Cl
CH2=C_CH2Cl
CH3
Cl
_
CH3 C_CH2Cl
San pham chnh
San pham phu
CH3
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.
CH2=CH2 + Cl2
200-600 o
CH2= CH_Cl + HCl
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.
CH3CH2CH2_CH=CH2 + O2
CH3CH2CH_CH = CH2
O_O_H
7. Cht in hnh
Ethylen CH2=CH2
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 CO2 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
Cl2
CH2
CH2
H2O
KOH
CH2
CH2
CH2
CH2
Cl
OH
ethylen clorhydrin
ethylen oxyd
Ethylen tc dng vi benzen xc tc AlCl3 to ethylbenzen, t ethylbenzen

to styren dng sn xut polystyren v cao su tng hp BuNa -S.
+ CH2
CH2
AlCl3
H2
CH = CH2
CH2CH3
styren
ethylbenzen
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
CH3
a-
C C
CH3
CH2CH3
b-
BrCH2
CH3
C C
CH2C(CH3)3
CH3
; c-
CH3CH2CHCH2
H
H
C C
; d-
CH2 C
CH2CH3
CH2CH2Br
CH2CH2CH(CH3)2
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 KMnO4 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 CH3CH2CHO
b. Aceton v aldehyd propionic CH3CH2CHO
c. Methylisopropylceton CH3COCH(CH3)2 v formaldehyd.
119
Chng 10
ALKYN - HYDROCARBON ACETYLENIC

(CnH2n-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 CnH2n-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.
__C
. .
__C
_
.
. C
C_
Carbon lai hoa sp
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 (1,2A ) ngn hn lin kt C -C.

o
Lin kt C -H (1,06A ) ngn hn lin kt C -H trong ethylen (1,08A ) v trong

o
etan (1,10A ). Hnh di y m t s to thnh lin kt ba:
o
1,20 A
o
1,06 A
H C
C
Csp
sp
H1s Csp
H1s Csp
180 o
o dai va goc lien ket
S tao lien ket trong phan t acetylen
S xen phu cua cac orbital p
Nng lng kin kt:

i vi lin kt ba l 199,6 kcal.mol1, ca lin kt i l 145,8 kcal.mol1 v
ca lin kt n l 82,6 kcal.mol1. 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 >

Csp2 > Csp3. iu gii thch kh nng phn ng cng hp i in t ca lin
kt ba km hn so vi lin kt i.
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
4 3 3 2 1
CH3_CH_C CH
CH
1
5 6 3 7
2 3 4
3-Methyl-1-butyn; CH _C C_CH _CH _CH_CH
3
2
2
3
6-Methyl-2-heptyn
2.2. Danh php hp l - Danh php acetylen

Cc alkyn n gin c xem nh dn xut ca acetylen
CH3CCH
Methyl acetylen
(CH3)2CHCCCH3
Methylisopropylacetylen
F3C_CCH
Trifluoromethyl acetylen
2.3. Tn cc gc
-CCH
Etynyl
CH3-CCH
Propynyl
Etynylcyclopentan ;
Cyclopentylacetylen
C CH
CH3_CC-CH2- 2-Butynyl
C CCH3
Propynylcyclohexan
Methylcyclohexylacetylen
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 T vic -dihalogen -
-C C- + 2HX
CHX-CHX- -C C- + 2HX
Phn ng xy ra qua 2 giai on:

-CB r 2 -CH 2 -
-C H Br-CH Br-
Nhanh
-C X =C H -
Cham
_
-C _ C -
121
S tch loi xy ra khi c mt ca KOH hoc NaOH trong alcol v nhit .

CH3CH2CHBr2
to
CH3_C CH + 2 HBr
Br Br
Br2
C6H5CH=CHC6H5
KOH alcol
KOH alcol
C6H5CH-CHC6H5
to
(77-81%)
1,2-Dibrom-1,2-diphenyletan
ete
Stilben
Br Br
CH3CH_CH2
CH3CH=CH2 + Br2
Propen
C6H5_C C_C6H5 + 2 HBr

(66-69%)
Diphenylacetylen
KOH alcol
CH3_C CH + 2 HBr
Methylacetylen
to
1,2-dibromopropan
Natri amidid NaNH2 l mt base mnh c th s dng tch HX trong

phn ng iu ch cc 1-alkyn.
RCX2-CH3
RCHX-CH2X
RCH2-CHX2
+ 2NaNH2 - NaX
- NH3
+
R_C C _Na + H2O
R_C C_H
NaNH2
R_ C C_ H +
+
R_C C _Na + NH3
NaOH
Phn ng tch HX trong iu kin c mt base mnh v nhit thng c

th xy ra s chuyn v ca ni ba.
KOH alcol t o
CH3CH2_C C_H
1-Butyn
CH3_C C_CH3
2-Butyn
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.
+ RX
H_C C_Na
H_C C_H + Na
CH3_C C_H + Na
Propyn
CH3_C C_Na
H_C C_R + NaX
+ CH3CH2I
CH3_C C_CH2CH3 + NaI

2-Pentyn
C th s dng natri amidid to acetylid trong phn ng alkyl ha acetylen.

H_C C_H + NaNH2
NH3 (lng)
-33oC
H_C C_Na
Natri acetylid
n-C4H9Br
CH3(CH2)3_C C_H
Hexyn-1 (89%)
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
X X
_
R C C_R'
R_C C_R' +
+ 2 Zn
2 ZnX2
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 ca metyl v orbital lai ha ca carbon acetylenic . Mt orbital sp c tnh
cht ca orbital S nhiu hn orbital sp3. 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.
3
CH3CH2CCH (sp3v sp) CH3CH2CH=CH2 (sp3 v sp2) CH3CCCH3

= 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
to si
Hp cht
to nng chy
T khi
Etyn
- 84,0
- 8,9
Propyn
- 23,2
- 102,7
Butyn-1
8,1
- 122,5
Butyn-2
27,0
- 32,3
Pentyn-1
39,3
- 90.0
Pentyn-2
55,5
- 10,0
Hexyn-1
71,0
-132,0
0,7152
Hexyn-2
84,0
- 88,0
0,7317
Hexyn-3
81,0
-105,0
0,7231
Phenylacetylen
143,0
- 43,0
Diphenylacetylen
300,0
- 63,5
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
H2O
Alcol
Acetylen
NH3
Ethylen
Metan
pKa
15,7
16-19
25
35
44
50
123
Lc base
CH3CH2=CH
CH4
CH2=CH2
HC
HC CH
C-
Lc acid
Tnh base ca cc anion khc nhau v nguyn t carbon mang in tch m

cc trng thi lai ha khc nhau.
H
H C
H
Anion methyl
sp3
C C
..
sp2
H
Anion vinyl
H_C C
sp
Anion acetylid
Cc alkyn c ni ba u mch (cc 1- alkyn) cng rt d to carbanion khi

tc dng vi anion amidid trong amoniac lng.
R_C C_H + NH2-
R_C C-
NH3
Cc carbanion RC C-, CH2=CH- v H3C- 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,
AgNO3 trong amoniac u to thnh acetylid hoc alkynylid kim loi.
R_C C_H + AgNO3 + NH3
R_C C_Ag
R_C C_H + CuCl + NH3
+ NH4NO3
R_C C_Cu + NH4Cl
Acetylen cng hp vi aldehyd formic nh l mt tc nhn i nhn.

H_C C_H + 2HCHO
Aldehyd formic
HOCH2_C C_CH2OH
1,4-Butyndiol
Alkyl lithium tch proton khi alkyn.

CH3(CH3)2CCH + n-C4H9Li CH3(CH3)2CCLi + n-C4H10
5.2. Phn ng cng hp
5.2.1. Cng hp vi hydro
Alkyn tc dng vi hydro c xc tc to thnh alkan
R_C C_R' + 2H2
Pt ,( Pd , Ni)
R-CH2CH2-R'
Phn ng thng xy ra 2 giai on. Giai on mt to nhit hn giai on hai.

+ H2
CH2=CH2
H = -41.9 kcal mol-1
H2C=CH2 + H2
CH3_CH3
H = -32,7 kcal mol-1
HCCH
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 PdCaCO3, PdBaSO4-Quinolin.
CH3CH2_C C_CH2CH5
H2
3-Hexyn
C2H5
Pd- BaSO4
Quinolin
C C
C2H5
H
H
cis-3-Hexen
S cng hydro cng c th xy ra khi s dng natri kim loi trong amoniac lng.
Na/NH3(lng)
C4H5C CC4H9
H9C4
NH4OH
H
C C
H
C4H9
Trans- 5-deken
5-Dekyn
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 X2
(halogen), HX, H2O.
+ X2
RC CR'
+ HX
RC CH
RCX CXR'
RCX CH2
+ X2
RCX2 CX2R'
+ HX
RCX2 CH3
Khi cng hp vo ni ba, carbocation dng vinylic R -C+=CH2 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+ CH2=CH+ ;
HC C CH=CH2 + H+
CH2=CH+ + Cl- CH2=CHCl
+
H2C C CH=CH2
+ Cl-
H2C CCl CH=CH2
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 .
R C C H +
1- Alkyn
H2O
C4H9 C C H
1- Hexyn
HgSO4-H2SO4
H2O
OH
R C CH2
Dang enol
HgSO4-H2SO4
O
R C CH3
Ceton
O
C4H9 C CH3
Methylbutylceton
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
ROH
H2C CH OR
Ether vinylic
H2C CH NR2
Vinyl amin
RCOOH
H2C CH OCOR
Ester vinylic
RCONH2
H2C CH NHCOR Amid
R2NH
H C C H
HCN
H2C CH CN
Acrylonitril
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 + H2O
H
CO + ROH
CO + R2NH
H2C
CH
COOH
Acid acrylic
H2C
CH
COOR
Ester acrylat
H2C
CH
CONR2 Amid cua acid acrylic
5.2.5. Phn ng vi diboran B2H6

Alkyn tc dng diboran 0C to cc cht trung gian trivinylboran. Khi c
mt ca acid acetic th to thnh alken dng cis.
+
1B H
2 2 6
3R C C H +
1B H
2 2 6
3 R C C R'
R
H
R
H
C C
C C
R'
3
H
3
3 CH3COOH
B 3 CH3COOH
R
H
R
H
C C
C C
R'
H
H
H
Phn ng cng c th xy ra vi bor dialkyl v theo c ch cng cis

CH3CH2 C C CH2CH3
+
R
B H
R
CH3CH2
CH2CH3
CH2CH3
CH3CH2
C
C
C C
CH3COOH
R
H
H
H
B
0oC
cis 3-Hexen (90%)
R
Lin kt CB trong hp cht vinylboran d b oxy ha bi nc oxy gi

(H2O2) to thnh enol v sau chuyn v thnh aldehyd hoc ceton.
C4H9C CH
1-Hexyn
126
B2H6
H2O2
OH-
C4H9
H
C C
H
OH
C4H9CH2CHO
Hexanal
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.
2 HC CH
3HC CH
Cu(NH3)2Cl
HC C CH=CH2 Vinylacetylen
Carbon ,600oC
Benzen
200 - 300C khi c bt ng lm xc tc, acetylen b trng hp to polyacetylen

cn gi l cht cao phn t Cupren.
n HC CH
200-300oC
Cu
-CH=CH-n Cupren
hay viet (CH)n
6. Cht in hnh
Acetylen C2H2
iu ch
Thy phn carbur calci (t n)
CaC2 + 2H2O
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 CH4 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.
2CH4
HCCH + 3H2
H0298 = 91 kcal/mol
Hn hp kh cha 13% acetylen

+ Cracking oxy ha nhit
6CH4 + 4O2
HCCH + 8H2 + 3CO + CO2 +3H2O
T l CH4 : O2 = 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 H2
km theo hin tng n. Phn ng n to nhiu nhit, H0298 = -54.9 kcal/mol,
nhit kh lc ln ti hng ngn .
127
Acetylen chy trong khng kh cho ngn la sng, to CO2 v nc, nhit
lng ta ra rt ln. Khi dng hn hp C2H2-O2 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:
CH3
CH3
a- CH3_C_CH2_CH2_CH
HC C
CH3
b-
CH3
CH3
_
_
_
CH3 C C C C_CH3
CH3
CH3_CH2
c-
C CH
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 B2H6-H2O2 - 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 SE.
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 C6H6. 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
Kekule
Closs
Ladenburg
Amstrong
Dewar
Thiele
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 (1,35A ). Gc gia cc lin kt CCC v CCH u bng nhau v

c gi tr 120 (hnh11-1 a )
Hnh 11.1:
H
H
.
.
H 120o
. . H
o
1,398A
H
H
Lien ket
H
H1s Csp2 H
2
sp C
H
H
C 2
sp
a
c
b
d
Goc va o dai S xen phu cac orbital
Xen phu cac orbital p t do
Cac orbital p t do
lien ket
va tao lien ket
tao lien ket C-C va C-H tren cac nguyen t carbon
Mi nguyn t carbon to 3 lin kt . Trong c 2 lin kt do s xen ph

ca 2 orbital lai ha sp2 gia carboncarbon bn cnh nhau. Cn mt lin kt
gia CH do xen ph ca orbital lai ha sp2 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.mol1. Nu chuyn ha cyclohexan thnh benzen th ch cn mt
nng lng l 49,3 kcal.mol1.
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.mol1 (hnh 11-2).
Nng lng cng hng

-1
-30 kcal mol
o
H = -24,5
kcal mol
-1
o
H = -26,5
kcal mol -1
o
H = -28,4
kcal mol -1
o
1
H = -49,3 kcal mol -
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.
+
n= 0
Cation cyclopropenyl
2 electron
CH3
n=1
6 electron
Toluen
Cation
Anion
cyclopentadienyl cycloheptatrienyl
.N.
Pyridin
..
N
H
Pyrrol
131
n=2
10 electron
Naphthalen
Anion
cyclononatetraenyl
Dianion
cyclooctatetraen
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).
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
CH2_CH3
CH3
Toluen
CH3
CH_CH
CH2CH2CH3
Ethylbenzen n-Propylbenzen
CH3
CH2CHCH3
Iso-Propylbenzen
Iso-butylbenzen
CH3
C CH3
CH3
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.
CH3
CH3
CH3
1,2-Dimethylbenzen
o-Xylen
CH3
1,3-Dimethylbenzen
m-Xylen
CH3
CH3
CH3
CH3
CH3 CH
1,4-Dimethylbenzen
1-Methyl-4-isopropylbenzen
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.
X
Orto ( o-)
V tr :
1, 2
X
Y
Meta ( m-)
1, 3
Y Para (p- )
1, 4
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
X
1
5
V tr :
2
3
2
3
4
Z 5 4
Z
Asymmetrical (as-)
1, 3 , 4
Vicinal (vic-)
1, 2 , 3
2
3
Symmetrical (s-)
1, 3 , 5
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:
CH3
CH3
o-Tolyl
Phenyl
CH3
p-Tolyl
m-Tolyl
Nu ly 2 nguyn t hydro trn vng benzen ta c gc ha tr 2 v c tn gi:

CH
o-Phenylen
1,2-Phenylen
Benzylyden
Benza
p-Phenylen
1,4-Phenylen
m-Phenylen
1,3-Phenylen
Benzo
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.
CH3
1
2
Toluen
CH3
CH3
o-Xylen
7
6
2
3
8
7
6
5
Naphthalen
10
Antracen
4
2
6
7
8
10
Phenantren
10
5
8
Pyren
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 , to
+ 3 H2
Xuc tac , to
+ H2
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 .
CH3
3 CH CH
Carbon .
600oC.
3 CH3 C CH
Propyn
CH3
CH3
O
CH3
Carbon .
600oC.
CH3
Mesityllen
CH3
CH3
CH3
CH3 O
H2SO4 (16%)
+
CH3
CH3
CH3
3 H2O
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
BrH2C
+ R_ X
+ 2Na
ete
CH2Br
+ 2Na
+ 2 NaX
CH2 CH2
+ 2 NaBr
ete
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).
+
RX
AlCl3
HX
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

Cong thc
C6H6
C6H5CH3
C6H4(CH3)2
C6H5C2H5
C6H5C3H7
C6H5CH(CH3)2
Ten goi
to nong chay
V tr
-
Benzen
Toluen
to soi
T khi
+ 5,51
-95,0
80,10
110,6
1,2
1,3
-29,0
- 53,6
144,4
139,1
0,8641
1,4
+ 13,2
138,4
136,2
0,8610
-94,0
Propylbenzen
-101,6
159,2
0,8669
0,8620
iso-Propylbenzen
-96,9
152,4
0,8618
1,4
-73,5,
176,0
0,8570
o-Xylen
m-Xylen
p-Xylen
Ethylbenzen
CH3C6H4CH(CH3)2 p-Methylisopropyl
benzen
0,8790
0,8669
0,8802
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 + FeBr3 Y+ + FeBr3XTc nhn Y + s tng tc vi nhn benzen ti v tr c mt electron cao nht
Y
+ Y+
Y+
Phc
H
+
H
FeBr3X
hoac
Phc
+ HX + FeBr3
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 FeCl3, FeBr3, AlCl3, SbCl3 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:
H
+ Br-Br + FeBr3
Br
FeBr4
Carbocation trung gian c h lin hp, c mt carbon trng thi lai ha sp3
H
+
Br
Br
Br
Br

xac nh ong hoc
H
Nng lng phn ng
Br. . . Br. . .FeBr3

Br
H. . . Br. . .FeBr3
Trng thi chuyn tip

to sn phm
H
Br
+ FeBr4-
Chat trung gian
Br
+ HBr + FeBr3
+ Br2 + FeBr3
Chat phan ng
San pham
Tien trnh phan ng

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 + FeBr3
Br
Br
+ FeBr4
+ HBr + FeBr3
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 FeCl3 to ra hn hp o -clorotoluen v p - clorotoluen

CH3
FeCl3
CH3
Cl
+ HCl
+ Cl2
CH3
+
FeCl3
HCl
Cl
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.
CH3
CH2Cl
Cl2 , h
Cl2 , h
- HCl
Benzylydenclorid
Benzylclorid
CCl3
Cl2 , h
- HCl
- HCl
Toluen
CHCl2
Benzotriclorid
S to gc t do benzyl cn nng lng thp. Gc benzyl bn nh s lin hp.
CH2 .
CH3
.
+ Cl
CH2
+ HCl H = - 16 kcal.mol-1 ;
CH2
CH2
CH2
Goc t do benzyl
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 NO2. Tc nhn to ra +NO2 thng l hn hp sulfonitric
(HNO3+H2SO4 ). 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.
H2SO4
+ HNO3
NO2
+ H2O
NO2 NO2
+ HNO3
H2SO4
NO2
NO2 NO2
+ HNO3
H2SO4
NO2
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.
CH3
+ HNO3
CH3
H2SO4
NO2
+ H2O
o-Nitrotoluen
CH3
+ HNO3
+ H2O
H2SO4
p-Nitrotoluen
NO2
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:
H
CH3
CH3
H C H
CH3
CH3
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
NO2+ 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.
NO2+ + HSO4 + H3O+
2 H2SO4 + HONO2
O
N+
O
+ N
+ O
- H+
NO2 +
+
H
5.1.3. Phn ng sulfonic ha

Sulfonic ha l phn ng gn nhm sulfonic -SO3H vo phn t cht hu c.
Cc tc nhn sulfonic ha thng l H2SO4 m c, hn hp H2SO4 + SO3
(oleum). Phn ng sulfonic ha c tnh cht thun nghch.
Ar_H +
H2SO4
Ar_SO3H + H2O
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.

SO3H
+ H2O
+ H2SO4
CH3
CH3
+ H2SO4
CH3
SO3H
+
- H2O
Acid benzensulfonic
Acid o-toluensulfonic
SO3H
Hp cht a nhn thm nh naphthalen: s sulfonic ha ph thuc nhiu

n nhit v nng ca acid.
SO3H
< 100o
+ H2O
160o
+ H2SO4
Acid -naphthalensulfonic
SO3H
160o
+ H2O
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
AlCl3 khan (phn ng Friedel -Crafts) hoc FeBr3, FeCl3.
+ Cl HC
C che :
AlCl3 khan
CH
CH3
CH3
CH3
CH
+ 3
+ CH. . . .Cl. . . .AlCl
3
CH3
CH3
CH3
+ HCl
CH3 +
CH. . . .Cl. . . .AlCl3

CH3
CH Cl + AlCl3
CH
+ 3. . . . . .
CH Cl AlCl3
CH3
phc
CH3
CH3
+ AlCl4
CH
CH3
phc
CH
CH3
+ AlCl3+ HCl
CH3
Tc nhn alkyl ha cng c th l alken, alcol khi c H2SO4 hoc H3PO4 lm

xc tc:
+ CH3CH=CH2
H2SO4
CH
CH3
CH3 ;
CH3CH_CH3
+
OH
H2SO4
CH
CH3
CH3
+ H 2O
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
+
CH3CH_CH3 ; CH3CH_CH3 + H+
OH
CH3CH=CH2+ H+
+
CH3CH_CH3+ H2O
CH3CH_CH3
+ OH2
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.
CH2 CH2 CH3
+ HCl
CH CH3
CH3
+ HCl
AlCl3
+ CH3CH2CH2Cl
S chuyn v xy ra
+
CH3CHCH3
CH3CHCH2+
H
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)2O. Xc tc cho phn ng acyl ha thng l AlCl3 khan (phn ng Friedelp
-Crafts) hoc c th dng cc loi xc tc i in t khc nh AlBr3, GaCl3, FeCl3,
SbCl3, SnCl4, BCl2
Sn phm acyl ha l cc ceton:
+ (RCO)2O
AlCl3
O
C-R
+ RCOOH
+ RCOX
RCOX + AlCl3
140
AlCl3
Alk ylphenylcet on
Alk ylphenylceton
+
O AlCl3
O AlCl3
R-C-X
R-C-X
+
O
C-R
+ HX
+ O AlCl3
; R-C-X
R-C
+
O
..
+ ..
R-C O
..
+ AlXCl3
V d:
S Acetyl ha benzen bng acetylclorid hoc anhydrid acetic xy ra theo
phn ng
CH3COCl
Acetylclorid
+ (CH3CO)2O
Anhydrid acetic
O
C-CH3
AlCl3
HCl
Acetophenon ( methyl phenylceton)

O
C-CH3
AlCl3
+
CH3COOH
Phn ng acyl ha thng tin hnh trong dung mi carbondisulfid (CS2)

hoc nitrobenzen. Lng xc tc AlCl3 phi dng nhiu hn v gia sn phm v
xc tc c th to phc cht.
O
C-CH3
O .....AlCl3
C-CH3
AlCl3
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 + AlCl3
CHO
HCl , HCN , AlCl3
CH3
;
CH3
HCl , HCN , AlCl3
CHO
C th gii thch c ch qua cc giai on trung gian:

HC N
ClCH=N_CH=NH.AlCl3
ArH + ClCH=N_CH=NH.AlCl3
- HCl
Ar-CH=N_CH=NH.AlCl3
Ar-CH=N_CH=NH.AlCl3
+ H2O
HC N + HCl
ClCH=NH
Ar-CHO + 2NH3 + HCOOH
Phn ng Gatterman - Koch

Tc nhn phn ng l hn hp CO + HCl + AlCl3 .
CO + HCl , AlCl3
CHO
+ HCl ;
CH3
CO + HCl , AlCl3
CH3
+ HCl
CHO
141
Ar-H (- HCl)
Cl_C_H
O
C che : CO + HCl
Ar-CHO
Phn ng th hydro ca hydrocarbon thm bng nhm _ CH2Cl

Tc nhn phn ng l hn hp HCHO + HCl c ZnCl2 lm xc tc.
CH2Cl
ZnCl2
60o
+ HCHO + HCl
+ H2O
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).
+ 3 H2
CH3
CH3
Ni , 10at
130o
+ 3 H2
Cyclohexan
Ni , to
Methylcyclohexan
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.
CH3
CH3
CH3
CH3
5% Rh/ C , 100o
CH3
+
p sut
CH3
cis- 1,2-Dimethylcyclohexan (90%) Trans- Dimethylcyclohexan (10%)
o-Xylen
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
Br
CHO
H2-PtO2
C2H5OH
OCH3
2-Bromo-5-metoxybenzaldehyd
C6H5
H
C C
H
C6H5
Trans-stilben
142
H2-Pt
C2H5OH
CH2OH
OCH3
Alcol 2-bromo-5-metoxybenzylic
C6H5 CH2 CH2
C6H5
1,2-Diphenyletan
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.
h
+ 3 Cl2
Cl
Cl
Cl
Cl
Cl
Cl
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
Cl
Cl
Cl
. :Cl
Cl
Cl
Cl
Cl
Cl:Cl
Cl Cl
.
Cl
2 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
HNO3, KMnO4, CrO3 u khng oxy ha c vng benzen. Ch nhit cao v
c xc tc V2O5 vng benzen b oxy ha thnh anhydrid maleic.
+ O2
V2 O5
O
C
400-450o
+ O2
O
C
V2 O5
400-450o
O
Anhydrid phtalic
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.
CH3
+ 3 O
CH2 CH2 CH3

+ 6 O
COOH
+ H2O
CH3
CH3
COOH
+ CH3COOH + 2 H2O
+ 6 O
CH CH3
CH3 + 8 O
COOH
+ 2 H2 O
COOH
COOH
+ 2HCOOH+ 2 H2O
Oxy ha o - xylen bng acid nitric long 155C thu c acid o -toluic.
CH3
CH3
HNO3 loang
155o
COOH
CH3
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.
X l nhng nhm th tng hot
Do hiu ng electron
X
+ I , sieu lien hp
CH3, C2H5 ,C3H7
NH2 , NR2 , NHCOR , _O -, OH , OCH3 ,OR , OCOR - I ,+ C

- I ,+ C
F , Cl , Br , I
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
Do hiu ng electron
X l nhng nhm th gim hot
NO2 ,SO3H , COOH CN , CHO , COOR , COR
- I ,- C
COCl , CONH2 , CN , CCl3, CF3 , NH3 , NHR2
- I ,- C
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.
OH
OCH3
+ HBr
OCH3
OH
para ( 96%)
Br
OCH3
Br
+ HBr
+ Br2 FeBr3
+ HNO3
H2SO4
NO2
OH
para
NO2
+ H2O
o-Nitrophenol
o-Bromoanisol ( 4% )
+ H2O
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
CHO
COOH
+ Br2
+ HBr
+ HNO3
Br
acid m-Bromobenzoic
H2SO4
CHO
+ H2O
NO2
m-Nitrobenzaldehyd
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
+
+
H. . Y
Nng lng phn ng
H Y
+
+
Y+
Chat trung gian

Y
Chat phan ng
+ H+
San pham
Tien trnh phan ng
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:
CH3
CH3
+ Y
CH3
+
Y
CH3
CH3
+
CH3
+
H
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.
CH3
H
+
CH3
CH3
+
H
Y
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 + ON
+
+
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
O + O
N
O + O
N
O + O
N
+
+
Y
+
H
O + O
N
H
Y
O + O
N
H
+
Y
O + O
N
H
Y
Trng thi nng lng phc v tr meta thp hn 2 trng thi ortho v para.
O + O
N
H
Y
O + O
N
O + O
N
+
H
Y
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.
Cl
CH3
CH3
Cl
Cl
OCH3
COOH
Br
NO2
NO2
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:
(CH3)2CH < CH3 < CH3CONH- < OCH3 < NH2 < NHR < NR2
Cc nhm ht electron gim dn theo th t

NO2>SO3H>COOH>CN>COCl>CHO>COOR>COR>CONH2>CCl3>NH3>NR2
V d:
CH3
CH3
CH
HNO3
CH3
NO2
H2SO4
;
CH
CH3
CH3
CH3
CH3
HNO3
H2SO4
NHCOCH3
CH3
CH3
NO2
NHCOCH3
NO
HNO3 2
NO H2SO4
2
CH3
NO2
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
CH3
NO2
HNO3
H2SO4
CH3
COOH
NO2
Na2Cr2O7
H2SO4
NO2
NO2
COOH
COOH
NO2
Na2Cr2O7
HNO3
H2SO4
COOH
NO2
+
H2SO4
NO2
NO2
NO2
NO2
Hon hp
Br
Br
Br
Br
Br2
Br
FeBr3
Br
Para ( 86,9%)
Br
Meta (0,1%)
Orto (13%)
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:
CH3
a-
CH2
; b-
; c-
k-
; g- CH
3
148
CH3
d-
CH3
CH(CH3)2
e-
C2H5
l-
hCH3
CH=CH2
; m-
CH3
CH
;
CH=CH
i-
n-
3. Hy gi tn cc cht sau y:
Cl
a-
CH2Cl
; b-
CHCl2
c-
CCl3
d-
Cl
CH3
e-
Br
F
k-
Cl
NO2
CH3
gCH3
; i-
CH2 NO2
; m-
l-
NO2
;
Cl
CH3
CH2Cl
Cl
hCl
CH2
n-
NO2
4. Nhng cht no c to thnh khi un nng hn hp sau y vi AlCl3 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
; b-
a-
NO2
Cl
; c-
; h-
g-
CH3
CH3
NO2
Cl
OH
i-
NO2
NO2
CN
OH
e-
; d-
Cl
Br
OH
CH3
6. Hy xc nh cng thc cu to ca cht C7H7SO3Cl 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.
,
3
,
4
,
5
,
1 1
,
,
5
,
6
HOOC
Biphenyl
NO
, 2 Cl 2
3
4
Cl 6 5
,
Acid 2,6-dicloro- 2 nitro -5'-biphenylcarboxylic
P-terphenyl
Hp cht a vng to thnh do cc vng ngng t vi nhau.

8
7
6
5
8
2
12
3
7
2
6
Naphthacen (Tetracen)
2
3
8
4
7
6
Pyren
Phenantren
Antracen
10
11
10
10
Naphtalen
10
10
11
12
9
8
4
7
11
Srysen
12
150
10
4
8
Coronen
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
Hng un g
H n g sai
S ti a cc nhn khc phi nm cao hn ht v bn phi, trn trc ngang.
Hng sai
Hng ng
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).
2
10
9
8
10
11
12
1
2
9
8
4
7
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:
Naphthalen
1 2
3
10
11
hoac
2
3
4
benzen
Benzen
a
11
12
h gf ed c
Antracen
13
14
10
Naphto[ 1,2-a] pyren
Naphto[ 1,2-a] pyren
14
Pyren
13
12
4
6
Dibenz [a , j] antracen
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)
600-800 o
2H
Nung iodobenzen vi bt ng (phng php Ullman. Fp, 1903)

2
+ 2 Cu
2Cu I
C th iu ch cc biphenyl th bng phn ng th i in t hoc phn ng

chuyn v benzidin.
NH NH
Hydrazobenzen
H+
H 2N
NH 2
Benzidin ; (4,4'-diaminobiphenyl)
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).
45o
Hnh 12.1. Hai mt phng to gc 45o
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
Mat phang gng
NO2 COOH
HOOC
NO2
HOOC
COOH
HOOC
COOH
O2N
HOOC O2N
O2 N
NO2
COOH
O 2N
NO2
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
CH2Cl +
CH2Cl2 +2
- HCl
AlCl3
- 2HCl
CH2
Biphenylmetan
CH
CHCl 3
AlCl 3
+ 3HCl
Triphenylmetan
Cc lin kt C _ H ca di id triphenyl rt linh ng. D b th v d b oxy ha.

Br2
Br
CH
+ HBr
+ H2O
CH2
2O [CrO3]
153
CH
KNH2
.. +
( C6H5 )3 C K + NH3
Br2
( C6H5 )3 C_ Br + HBr
( C6H5 )3 C_ OH
[O ]
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.
2 Ag
C Cl
C.
- AgCl
Triphenylmethyl
(mau vang)
Triphenylmethylclorid
3-Biphenylmethylyden-6-triphenylmethyl1,4-cyclohexadien (khong mau)
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.
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.
'7
'6
'
'
1,424 A
1,365 A
o
1,424 A
o
1,393 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.
HNO3
NO2
NO2
CH3COOH
+
50-70o
- Nitronapthalen
- Nitronapthalen
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).
4 H ( Ni) 150o
6 H ( Ni) 200o
Tetralin
Decalin
( 1,2,3,4-Tetrahydronaphthalen ) ( Bicyclo [4,4,0 ] decan)
4.1.3. Phn ng oxy ha

Oxy ha naphthalen bng oxy khng kh c xc tc V2O5 to thnh anhydrid
phtalic. Crom oxyd oxy ha naphthalen trong mi trng acid acetic to ra 1,4naphtoquinon (1,4-dihydro-1,4-naphthalendion).
O
O2 , V2 O5
C
O
C
O
CrO3 ,CH3 COOH
155
5. Anthracen
Nm1867 Dumas tch c anthracen t nha than . C th tng hp
anthracen t 2-methylbenzophenon theo phn ng:
O
C
+ H2O
CH3
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:
O
O
+O
C
O
Anhydrid ftalic
AlCl3
C
HOOC
O
PPA
[ H]
- H2O
O
Acid-2-benzoylbenzoic
Antraquinon
Tnh thm ca antracen (E =351,5 kj.mol1) 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
3O [HNO3]
- H2O
2 H [Na ,ROH]
9,10-dihydro antracen
Cl2
Cl
Cl
Cl
- HCl
9,10-diclo-9,10-dihydro antracen
O
O
O
O
O
O
Anhydrid cua acid 2,3; 5,6- dibenzodicyclo[2,2,2]octa2,5-dien-7,8-dicarboxylic
156
6. Phenanthren
Nm 1872 Greabe tch phenanthren t nha than . C th tng hp
phenanthren qua cc giai on sau:
NO2
CHO
6H
O2N
6H
- 2H2O
COOH
- 2H2O
COOH
COOH
o- Nitrobenzaldehyd Acid phenyl acetic
+
N2
O2N
- H2O
Acid phenyl-2-nitro crotonic Acid phenyl-2-nitro crotonic
X[Cu]
COOH
- N2
+ CO2
COOH
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.mol1. 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:
2H
CuO/Cr2O3
9,10-Dihydrophenantren
Br2
- HBr
Br
Br
9,10-Dibromo-9,10-dihydrophenantren
Br
9-Bromo phenantren
3O (CrO3)
- H 2O
O
O
9,10-Phenantrequinon
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
CH2 = CH-CH2+
1.1. Cation allylic:
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.
CH3CH = CHCH2OH
0 oC
+ HBr
CH3CH = CH CH2Br
CH3CHOHCH = CH2
0 oC
+ HBr
CH3CHBrCH = CH2
+
3:1
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.
+
CH3CH = CHCH2OH2
+
OH2
CH3CHCH = CH2
-H2O
+
CH3CHCH = CH2
Cation
+Br
CH3CH = CH CH2
Cation
+Br
-H2O
CH3CH = CH CH2Br
CH3CHBrCH = CH2
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.
+
1
+
2
CH2=CHCH2
CH2CH=CH2
Cation allylic
1
+
2
CH2 CH CH2
Cation allylic
CH2
CH
CH2
Cation allylic
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.
CH2=CH-CH2-
Gc:
gi l gc allyl
CH2=CH-CH2-Cl
clorid allyl
CH2=CHCH2OCOCH3
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.
+
CH2=CHCH2
+
CH2CH=CH2
( CH2 CH CH2 )+
..... .
CH 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.
Cp Cp
H
C 2 HS
sp
sp2 C C sp2
Hnh 13.1. Biu din cation allylic di dng orbital
1.2. Phn ng SN2 - S chuyn v allylic

Cc halogenid v alcol allylic u c kh nng to carbocation mt cch d dng
theo c ch SN2 v c s chuyn v ni i. S chuyn v gi l chuyn v allylic.
4
CH3CH=CHCH2OH + HBr
CH3CHBrCH=CH2
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
..............
H2C
CH
CH2
..............
Br
Hnh 13.2. Trng thi chuyn tip ca phn ng gia bromid allyl
vi tc nhn i nhn Nucleophyl theo c ch SN2
H thng allylic cng d xy ra phn ng theo c ch SN1.

4
CH3CH=CHCH2OH +
HBr
CH3CH=CHCH2Br
V carbocation CH3CH=CHCH2+ cng d hnh thnh trong iu kin khng

xy ra s chuyn v allylic theo c ch SN2
C6H5SO2Cl
CH3CH = CHCH2OSO2C6H5
CH3CH = CHCH2OH
Pyridin
2-Buten-1- ol
Cl
CH3CH = CHCH2Cl
1-Clor-2- buten
Phn ng nh vy cng xy ra khi hp cht allylic tc dng vi thuc th

Grignard.
CH2=CH-CH2Br
CH2CH=CH2
MgBr
+ 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 CH2=CH-CH2Thuc th Grignard allylic c iu ch theo phng php thng thng sau:
CH2=CH-CH2-X
+ Mg
eter
CH2=CH-CH2-Mg
Thuc th ny b ng phn ha rt nhanh

3
CH3-CH= CH-CH2-MgX
Nhanh
CH3-CH-CH = CH2
MgX
C th hiu rng in tch m ca anion allylic phn b trn cc nguyn

t carbon lin hp.
CH2 = CH_CH2
CH2 CH CH2 MgX
CH2 _ CH = CH2
+
CH2 CH CH2 MgX
CH2
.... ....
CH CH2
.... CH....CH
CH2
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 OR
C= O
R2C
Ion carboxylat
R2C= C
C= O
R
O-
Ion enolat
CH2 = CH = CH2
1.4. Gc t do allylic:
Gc allylic c n nh nh cng hng
.
CH2 = CH_CH2
.
.... ....
CH2 CH CH2
.
CH2 _ CH = CH2
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 (CH3CH2CH2).
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)
H 2C
CCl4
N Br
H 2C
Br
C
O
H 2C
H 2C
NH
O
83%
N-Bromosuccinimid
Succinimid
C ch
O
H 2C
C
N Br
H 2C
Anh sang
H 2C
H 2C
.
.
N
+ Br
.
Br
+ HBr
O
O
H 2C
C
N Br
H 2C
C
O
H 2C
H 2C
Br
.
N
.
;
Ch : C th minh ha s phn b li mt electron trong gc allyl

+
CH2 = CH _ CH2
CH2 _ CH = CH2 CH = CH _ CH2
Cation allylic
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
162
CH2 _ CH = CH2 CH2 = CH _ CH2

CH2 _ CH = CH2
Goc t do allylic
Anion allylic
C =C_C=C_C
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 sp2.
Cc lin kt C_C v C _H c to thnh do s xen ph ca cc orbital lai
ha sp2 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).
............
............
...................................
Lien ket
H2C
Lien ket
CH
CH
CH2
Csp 2
Csp 2
...................................
............
............
Cp H s
Cp Cp
Hnh 13.3: Cu to ca 1,3-butadien
di lin kt trong 1,3-butadien

Lin kt i C1=C2 v C3=C4 c di l 1,37 ln hn lin kt i bnh thng
(1,34 ). Lin kt n C2_C3 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 C2_C3 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
C
H
C
H
H
C
C
CH
C
H
S-cis
S-trans
2.2. Phn ng cng hp
Quan st phn ng gia phn t brom vi 1,3-butadien

+
CH2 = CH_CH = CH2 + Br2
Hexan
-15o
CH2 = CH_ CH _CH2Br
Br-
CH2 _ CH = CH _ CH2Br
BrCH2_ CH = CH_ CH2Br + CH2 = CH_CHBr_ CH2Br
46%
54%
163
un hn hp thu c 60C th to thnh 90% (E)-1,4-dibromo-2-buten

BrCH2_ CH = CH_ CH2Br (54%)
CH2 = CH_CHBr_ CH2Br
60o
BrCH2
(46%)
C C
90%
H
CH2Br
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
+
CH2=CH_CH=CH 2 + H+
CH2_CH=CH _CH3
CH2=CH_CH_CH3
Cau truc carbocation allyl
CH2 _ CH _ CH_CH3
Cc dien lin hp cng c th cng hp theo c ch i nhn hoc c ch gc.

N
C_ C=C_ C
N
C_ C_ C=C
C=C_ C=C + N
N
.
.
.
. _..C
_
_
C C C..
Cau truc carbo anion allyl
2.3. Dien -1,2 allen

Propadien-1, 2 c gi l allen CH2=C=CH2. 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.
H
.............
C
...............
C
H2C=C=CH2
C
H
................
...............
Csp 2 Csp 2
Csp 2 Csp 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
(CH3)2C
OH
Al2O3
C(CH3)2
420-470o
CH3COOCH2CH2CH2CH2CH2OOCCH3
164
575o
CH2 = C C = CH2
+ 2H2O
CH3 CH3 79-89%

2,3-dimethyl-1,3- butadien
2 CH3COOH + CH2=CHCH2CH=CH2
1,4-pentadien 63-71%
Thay th halogen trn phn t halogenid allyl bng gc vinyl t halogenidvinylmagnesi

CH2=CHCH2Cl + CH2=CHMgBr
ether
CH2=CHCH2CH=CH2 + BrMg
Phn ng Wittig:
+
CH2=CHCH2Cl + P(C6H5)3
C2H5OLi
CH2=CHCH2P(C6H5)3
CH2=CHCH2P(C6H5)3Cl
Allytriphenylphosphin clorid
C6H5CHO
CH2=CHCHP(C6H5) 3
CH2=CHCH =CHC6H5 + (C6H5)3P
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).
nCH2=CH-CH=CH2
n CH2=CH-CH=CH2
(-CH2-CH=CH-CH2-)n
Xuc tac
n CH2=C-CH=CH2
CH2-CH=CH-CH2 n
Xuc tac
CH3
2-Methyl-1,3- butadien (isopren )
n CH2=CH-CH=CH2
1,3-Butadien
CH2-C=CH-CH2 n
CH3
n CH=CH2 Xuc tac

C6H5
Polyisopren
CH2-CH=CH-CH2CH-CH
2n
Cao su Buna S
Styren
C6H5
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
CH2 = CH _ CH = CH_CH=CH2
H+
CH2 = CH _ CH = CH_CH_CH3
+
+ _
+
CH2 CH _ CH _ CH _ CH _ CH3
+
CH2 = CH _ CH _CH=CH_CH2
+
CH2 _CH =CH _ CH=CH_CH3
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:
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
Cc dienophyl thng c hot ha bng cc nhm ht electron (COOH,

COOR, CHO, COR, CN, NO2)
COOCH3
COOCH3
+
Dien
Dienophyl
CHO
4-Methyl cyclohexencarboxylat
CHO
Acrolein
COOC2H5
C
C
COOC2H5
Diethylacetylendicarboxylat
COOC2H5
COOC2H5
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
CH2
HC
CH2
C
H
C
H
Hnh 13.5. Trng thi chuyn tip ca phn ng Diels-Alder
Phn ng xy ra theo c ch lp th cis .

H
COOCH3
+
COOCH3
COOCH3
COOCH3
H
COOCH3
C
C
CH3
COOCH3
COOCH3
CH3
COOCH3
4
3
+
COOCH3
Cyclopentadien
75 - 80oC
Ester methylacrilat
(79-91%)
COOCH3
Ester methyl bicyclo[2,2,1]hepten-5 endo carboxylat
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 CO2 v thy phn trong mi trng
H2SO4 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 D2O trong mi trng base:
O
CH3
CH3
; CH
b. Vit phng trnh phn ng ca 4-methyl-3-penten-2-on vi cc cht sau:

n-C4H9Li; n-C4H9HgBr , CuBr; H2/ Pt ; HCN , (C2H5)3N; Br2 , CCl4
6. Vit cc phng trnh phn ng Diels -Alder ca cyclopentadien vi cc cht sau:
Vinylacetat; Acid acrylic; Ester dimethyl acetylendicarboxylat CH3OOCC
CCOOCH3 (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.
CnH2n+2-2k
CnH2n+2-m-2k Xm
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
CH3_CH2_Cl
Cloroetan
168
Cl_CH2_CH2_F
2-Fluor-1-cloroetan
Br
CH2=C_CH3
2-Bromopropen
Cl C C Cl
dicloroacetylen
Br
Cl
Br
2,3-dibromocyclohexen
Br
F
6-fluoro-2-bromo-1-iodonaphtalen
Clorobenzen
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 ".
6
Cl_CH2_CH2_CH2_CH_CH2_CH2_Cl CH3
Cl
CH3
_
_
_
_
CH2
CH2 CH CH CH2 CH_CH2_CH2_CH3
3 4
2
5
6
7
8
9
CH2 Cl
Br
CH2=C_CH=CH2
CF3
4-cloro-3-bromo-6-methylnonan 2-(trifluoromethyl) -1,3-butadien
1,6-dicloro-3-(2-cloroethyl) hexan
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.
CH3Cl
CH2Br2
CH2=CH_F
Methylclorid
Methylendibromid
Vinylfluorid
CH2=CH_CH2I
Allyliodid
Vn thng gi tn mt s hp cht halogen theo tn quen dng nh cc haloform.

CHCl3
CHBr3
CHI3
Cloroform
Bromoform
Iodoform
2. ng phn
S ng phn ty thuc cu to ca mch carbon v v tr ca halogen.
CH3CH2CHCl2
1,1-dicloropropan
1,1-propylydenclorid
CH3CCl2CH3
2,2-dicloropropan
2,2-propylydenclorid
CH2ClCH2CH2Cl
1,3-dicloropropan
1,3-propylendiclorid
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 + H2O
CH3
CH3 C OH + HCl
CH3
CH3 CH2 CH2 OH +
CH3
CH3 C Cl + H2O
CH3
ZnCl2
HCl
CH3
CH2 CH2 Cl +
H2O
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 ZnCl2. 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.
+
ROH2
ROH + H+
acid lin hp ca alcol
Giai on 2 l giai on chm, giai on xc nh tc phn ng.

C hai kh nng xy ra phn ng:
(1)
+
ROH2
R+ + H2O
R+ + X
RX
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
CH3 CH3
__
CH3 C__C__H
CH3 Br
CH3 CH3
__
CH3 C__C__H
Br CH3
+Br -
+ Br -
CH3 CH3
CH3 CH3
CH3 CH3
CH3 CH3
+
CH3__C__C__H H CH3__C__C__H -H2O CH __C__C__H
__
__C__H
CH
3
3 C
+
+
chuyen v
CH3 OH
CH3 OH2
CH
CH3
3
+
-H+
-H+
-H+
CH3
CH3 CH3
CH3 CH3
CH3__C__CH=CH2 CH __C C_CH CH2 C__C__H
3
3
CH3
CH3
(2)
+ #
[X....R...OH2 ]
+
+ R__OH2
X_R
+ H2O
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 ZnCl2 theo
c ch:
+ ZnCl2
O
H
Cl + CH2
R
RCH2Cl + 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 + PCl3
3RCl + H3PO3
ROH + PCl5
RCl + POCl3 + HCl
Alcol phn ng vi thionylclorid SOCl2 xy ra theo c ch sau:
..
R_OH + SOCl2
O
..
-HCl
R ..
: Cl
..
..
S O
..
..
:O
..
R ..
: Cl
..
..
S O
..
R_Cl + SO2
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
+ N2
3.3.5. iu ch cc dn xut polyhalogen

Cc dihalogen c iu ch bng cch cho aldehyd hoc ceton tc dng vi
phosphopentahalogenid PX5.
Cl
_
R C_R'(H) + POCl3
Cl
R_C_R'(H) + PCl5
O
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
CH3
CH2Cl
Cl2 , h
-HCl
CHCl2
Cl2 , h
-HCl
Benzylclorid
CCl3
Cl2 , h
-HCl
Benzalclorid
Benzotriclorid
Cc haloform c iu ch t ethanol v clor theo s phn ng sau:

Cl2 + H2O
HCl + HClO
H+ + ClO -
HClO
O + 3ClOO
CH3CH2OH + ClO CH3 C
CCl3 C
-Cl , -H2O
H - 3OHH
Ethanol
Cloral
+HO-
CHCl3 + HCOOCloroform
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.
Cl
H
H
Cl
172
H
Cl
H
Cl
H
Cl
Cl
1,2,3,4,5,6-hexaclocyclohexan
e,e,e,a,a,a-hexaclocyclohexan
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.
+
2 Cl
CHO
CCl3
H2SO4
Cl
CH
Cl
+ H2O
CCl3
1,1,1-tricloro-2,2-bis (4,4'-clorophenyl) etan
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
o
di lin kt d (A )
Momen lng cc (D)
CH3F
1,385
1,82
CH3Cl
1,784
1,94
CH3Br
1,929
1,79
CH3I
2,139
1,64
CH3X
C---X
= q.d
q=
e 1e 2
r2
l mt i lng vect
q l lc tng tc gia 2 ht nhn
e1, e2 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
Hp chat
Fluorometan
Clorometan
Bromometan
Iodometan
Cloroetan
1-Cloropropan
2-Cloropropan
Vinylclorid
Allylclorid
Methylenclorid
Cloroform
Carbontetraclorid
Fluorobenzen
Clorobenzen
Bromobenzen
Iodobenzen
Benzylclorid
Benzalclorid
Benzotriclorid
Cong thc cau tao
Nhiet o chay Nhiet o soi
CH3F
-141,8
-78,5
CH3Cl
-97,7
-93,7
-23,7
3,6
-66,5
42,5
-138,7
12,3
-122,8
47,2
CH3CHClCH3
-117,0
35,4
CH2= CHCl
-159,7
-13,8
CH2=CHCH2Cl
-136,4
44,6
CH2Cl2
-96,8
40,2
-63,5
61,2
CCl4
-22,9
-41,9
76,7
84,7
-45,2
131,7
-30,6
156,5
-31,3
188,5
-41,1
179,3
-16,4
205,2
-4,8
220,8
CH3Br
CH3I
CH3CH2Cl
CH3CH2CH2Cl
CHCl3
C6H5_F
C6H5_Cl
C6H5_Br
C6H5_I
C6H5_CH2Cl
C6H5_CHCl2
C6H5_CCl3
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.
CH3CH2CH2Cl
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.
CH3_C = CH2
: Cl
2-Cloropropen
174
CH2 = CH
Cl:
vinyl clorid
..
Br
Bromobenzen
Kh nng phn ng cao l hp cht c cu to allylic.

CH2 = CH_CH2_Cl
Allylclorid
CH2Cl
Benzylclorid
S khc nhau ca 3 loi hp cht trn c cn c vo phn ng thy phn:

RX + HOH
CH3 CH2CH2_Cl + HOH
Cl
CH3 CH2CH2_OH + HCl un nong vi dung dch kiem

OH
+ HOH
CH2 = CH_CH2_Cl + HOH
ROH + HX
+ HCl Kh, un nng 380 v p sut
CH2 = CH_CH2_OH + HCl Rt d b thy phn

CH2OH
CH2Cl + HOH
+ HCl Rt d b thy phn
Kh nng phn ng gim dn theo cu trc ca gc R nh sau:

RCH=CH-CH2_X > ArCH2_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 SN2 hoc n phn t SN1.
[ Y .....R.....X ]
SN2
Y + R _X
SN1
Cham +
R + X ;
R_X
Y_R + X
-Nhanh _
+ Y
R Y
V
k
d[Y-][RX]
dt
d[RX]
dt
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

Amin bac 1
RNH2 + HX
NH3
HO R'O -
Amin bac 2
RNHR' + HX
R'NH2
Amin bac 3
RNHR'2 + HX
R'2NH
Nitril
Alkyn
Alkan
Nitroalkan
CN -
RCN + X R'C CR + XR_R' + MX

RNO2 + X -
R'COO R_X
HS -
R'C C-
R'S -
R'M
HOO -
NO2-
R'OO -
..
RCH(COOR')2 + X (R'OOC)
2 CH
Esteralkyl malonat
SCN -
X - + ROH
Alcol
X - + ROR'
Ether
X - + R'COOR
Ester
X - + RSH
Thioalcol
X - + RSR'
Thioether
X - + ROOH
Hydroperocyd
X - + ROOR'
Perocyd
X - + R_SCN
+ R_NCS
Thiocianat
Isothiocianat
Dn xut halogen tc dng vi cc alcolat hay phenol trong mi trng kim

to thnh ether ROR' hoc ArOR' (phn ng Williamson).
OH
CH3_Br +
OCH3
+ NaBr + H2O
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
CH3
CH3CH2
H
I
Y-
CH3
CH3CH2
( R)
( R)
I-
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.
H13C6
Y- + H
C6H13
H +
I-
CH3
( R)
CH3
( S)
S thay i ca cu hnh carbon qua giai on trng thi chuyn tip

(phc hot ng).
176
H13C6
Y- + H
C6H13
Y...... C ...... I
C
CH3
( S)
CH3
C6H13
+
C
H
CH3
( R)
I-
Minh ha cc trng thi c th c trong qu trnh phn ng SN2 qua hnh 14.1
E
Y + C
X
B
Y C
Thay oi cau hnh
X A
Chat phan ng
+ X
San pham
Tien trnh phan ng
Hnh 14.1: Cc trng thi nng lng ng vi c ch phn ng SN2
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 SN2) hoc mt hn hp racemic (th SN1).
Phn ng gia tert - butylbromid vi alcol ethylic to ether tert - butylethyl
(CH3)3COC2H5 l phn ng th i nhn theo c ch SN1. Phn ng qua giai on
to carbocation (hnh 14-2).
E
+
(CH3)3C + Br - + HOC2H5
(CH3)3CBr + C2H5OH
+
(CH3)3CO
H + BrC2H5
(CH3)3COC2H5 + HBr
Tien trnh phan ng the SN1
Hnh 14.2: Cc trng thi nng lng ng vi c ch phn ng SN1

177
(CH3)3C_ Br
Cham
(CH3)3C+ + Br-
+
(CH3)3C_OCH2CH3
H
(CH3)3C+ + C2H5OH
(CH3)3COCH2CH3 + H+
Gin minh ha tin trnh phn ng th SN1 ng vi cc trng thi nng

lng v s hnh thnh carbocation.
Carbocation (CH3)3C+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_CH2_Cl
- X-
+
R_CH_CH=CH2
+Y -
+
R_CH=CH_CH2
+Y -
R_CH_CH=CH2
Y
R_CH=CH_CH2_Y
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.
OH
NaOH , 300oC
Cl
+ NaCl
NH2
NH3,200oC
Cu2O
+ HCl
Nu trn nhn thm c nhm ht in t th phn ng xy ra d dng hn.

Phn ng th gia clorobenzen v NH3 xy ra theo c ch "tch -cng" hoc ''c
ch aryn"
Cl
NH2
NH2
+NH3
-NH3, - Cl
1,2-dehydrobenzen
(aryn)
+H-
48%
+H52%
NH2
Phn ng th loi ny cng xy ra i vi cc tc nhn i nhn l cyanid CN-
ArCl + CuCN
178
ArCN + CuCl
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
SN2 trnh by trong bng 14.3:
Alkyl halogenid
Tc tng i
CH3-
30,00
CH3CH2-
1,00
(CH3)2CH-
0,02
(CH3) 3C-
Tc SN2 Methyl > gc bc nht > gc bc 2 >> gc bc 3

Tc SN1 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 SN1
Dung mi t phn cc thun li cho phn ng th i nhn theo c ch SN2.
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).
R_X + 2Na + X_R
Ether
R_R + 2NaX
Ether
Ar_X + 2Na + X_R
Ar_R + 2NaX
Phan ng Wurtz.
Phan ng Wurtz - Fittig
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
a- Isobutylen
b- Allyliodid
HBr A ddNaOH
B
Na
2HBr
HI
ddKOH
C
C
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.
R
- +
R M
+
R M
Ty thuc ha tr ca kim lai hp cht c kim c cc lai:

RM ; R2M ; RMX (X l halogen) ; R3M.
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.
O(C2H5) 2 Br
R
R
Mg
O(C2H5) 2
O(C2H5) 2
Mg
R Mg
O(C2H5) 2
Br
Mg R
Br
2. Danh php
2.1. Tn gc hu c + Tn kim loi
CH3) 3CLi
t-Butyllithi
(CH3CH2)2Mg Diethylmagnesi
(CH3)4Si
Tetramethylsilan
(CH3CH2)4Pb Tetraethyl ch
181
(CH3CH2) 3B
Triethylboran
(CH3) 3Al
Trimethyl nhm
CH3Cu
Methylng
(CH3)2Hg
Dimethyl thy ngn
Ch : Cc hp cht ca bo, thic, silic gi tn theo dn xut hydrid ca chng

BH3 boran ; SnH4 Stannan ; SiH4 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.
CH3CH2MgBr
Ethyl magnesi bromid
CH3HgCl
Methyl thu ngn clorid
CH3CH2AlCl2
Ethyl nhm diclorid
3. Tnh cht l hc
Bng 15.1: Tnh cht l hc ca mt s hp cht c kim
tc
ts
Hp cht
tc
ts
CH3CH2Li
Hp cht
95
95,0
(CH3CH2)2Hg
159
(CH3)2Mg
240
CH3CH2HgI
186,0
(CH3)3 Al
130,0
CH3CH2HgCl
193,0
40**
CH3AlCl2
73
97-100*
(CH3)3Ga
-19,0
56
(CH3)4Si
26,5
(CH3)3In
89,0
89**
(CH3CH2)4Si
153,0
(CH3)3Te
38,5
147
(CH3)2Zn
- 42
46,0
(CH3)4Ge
- 88,0
43
(CH3)2Cd
- 4,5
106,0
(CH3)4Sn
- 55,0
78
(CH3)2Hg
96,0
(CH3)4Pb
-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
RMgX
C che :
182
R'X'
R-X
+ Mg
.
R +
X Mg
RR' + XMgX'
.
R + X Mg
R-Mg-X
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:
ether
2CH3CH2CH2Br + 2Na
CH3CH2CH2CH2CH2CH3 + 2NaBr
C ch:
CH3CH2CH2Br + 2 Na
CH3CH2CH2-Na+ + NaBr
CH3CH2CH2- + CH3CH2CH2Br
CH3CH2CH2CH2CH2CH3 + Br-
Phn ng ca hp cht alkyldihalogenid vi Zn hoc Mg thng to hp

cht cha no hoc hp cht vng
BrCH2CH2Br
+ Mg
MgBr2 + CH2=CH2
BrCH2CH2CH2Br + Zn
ZnBr2 +
(80%)
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
Li+
Al
Si
4+
Zn2+
Cd
2+
H+
Sn
Eo, vol
= Li
- 3,045
= Mg
- 2,370
= Al
- 1,660
+ 4e-
= Si
- 0,840
+ 2e-
= Zn
- 0,763
+ 2e- = Cd
- 0,402
+ e-
Mg2+ + 2e3+
Phn ng
+ 3e-
+ e-
= 1/2H2
0,000
4+
+ 4e- = Sn
0,014
+ e-
= Cu
0,522
+ 2e-
= Hg
0,854
Cu
Hg2+
183
Ether
2CH3CH2MgCl + CdCl2
o
E = -0,402
(CH3CH2)2Cd + MgCl2
o
E = -2,370
(CH3)4Si
4CH3MgCl + SiCl4
o
E = -0,840
CH3Li
4MgCl2
o
E = -2,370
CH3Cu
+
CuI
o
E = -0,522
LiI
o
E = -3,045
4.3. Thay kim loi vo lin kt C -H

CH3CH2CH2CCH + n C4H9Li
CH3CH2CH2CCLi + nC4H10
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.
HC CH
ether
CH3CH2MgBr
HC
CMgBr + C2H6
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
6CH2=CH2 + B2H6
2(CH3CH2)3B
Cng hp mt lin kt Al -H vi alkyn.

CH3
CH3CHCH3 2Al
CH3
CH3CHCH3 2AlH + CH3CH2C CH
Diisobytyl nhm hydrid (DIBAl)
C=C
H
CH2CH3
(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.

6CH2=CH2 + B2H6
2(CH3CH2)3B
(CH3)2Hg + 2CH3CH2Li
(CH3CH2)2Hg + 2CH3Li
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
(CH3)3Al + 3H2O
3CH4 + Al(OH)3
Phn ng vi alcol v acid carboxylic

CH3
Li
H3C
CH3
+ CH3OH
H3C
CH3
CH3
CH3
H3C C
Li
+ CH3O Li +
CH3
+ CH3COOH
H3C
CH3
+ CH3COO Li +
CH3
Phn ng vi thiol v amin
RSH, RNH2
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
Cl2 + 2e- = 2Cl- Eo = +1,358 vol
RM + Cl2 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 + O2 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.
Cl
Mg
HCHO
CH OH
2
H2O
ether
(CH3)2CHMgBr + CH3CHO
+
H
ether
(CH3)2CHCHOHCH3
3-Methyl-2- butanol (53-54%)
H2O
C2H5MgBr + (CH3)2CHCH2COCH3
ether
OH
(CH3)2CHCH2CCH2CH3
H2O
CH3
3,5-Dimethyl-3-hexanol
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.
CH3MgBr
O
CH3CH2CCH2CH3
OH
O
CH3CH2MgBr
CH3CH2CCH2CH2CH3
CH3CCH2CH3CH3
O
CH3
CH3CH2CH2MgBr + CH3CCH2CH3
Cc phn ng ph:
O
OH
(CH3)2CHMgBr + (CH3)2CHCCH(CH3)2
(CH3)2CHCHCH(CH3)2 + CH3CH=CH2
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.
O
(CH3)3CLi
t-butyl liti
ether
(CH3)3C-C-C(CH3)3
-70o
di-t-butylceton
H2O
(CH3)3C 3C-OH
S cng hp cc mui natri hoc lithi ca alkyn vi aldehyd hoc ceton.

CH3C
186
CH + NaNH2
CH3C
CNa
CH3COCH3
H2O
CH3C
OH
CC(CH3)
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.
Cl
MgCl
CH3CHCH2 CH3 + Mg
CH3 CHCH2CH3
CO2
COOMgCl
CH3CHCH2 CH3
H2O
H2SO4
COOH
CH3CHCH2CH3
Phn ng xy ra gia carbon dioxyd v hp cht c lithi.

Li
CO2 Li
COOH
H3O+
CO2
Phenyl liti
Acid benzoic
Thuc th Grignard tc dng vi ethyl ortoformiat to acetal. Thy phn

acetal to aldehyd.
C H3
C H3
C H3
Mg
H+
C H(OC 2 H 5 )3
M gB r
Br
CH( OC 2H 5 )2
C H3
C HO
C ch:
- +
Br2MgOC2H5
CH(OC2H5)3 + MgBr2
CH(OC2H5) 2
+
Br 2MgOC2H 5 + C2H 5O-CH-OC2H 5
+
C2H 5O=CH-OC2H 5
RMgBr
RCH(OC2H 5) 2
Phn ng gia hp cht c lithi v epoxyd xy ra theo c ch SN2

O
C6H5CH
-O Li+
CH2 +
C6H5CH
C6H5Li
CH2C6H5
H 2O
OH
C6H5CH CH2C6H5
1,2-diphenyletanol (70-72%)
ng dng tng 2 nguyn t carbon trn mch carbon:

RCl
Mg
Ether
R-MgCl
H2C
CH2
H+
R-CH2-CH2OH
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
CH3Li + CH3Cu
(CH3)2CuLi
C th to hp phc c kim bng phn ng

2CH3CH2CH2Li + CuI
(CH3CH2CH2)2CuLi + LiI
ng dng: S cng hp 1 4 vo cc nguyn t - ethylenic

O
1O
C
4
+ (CH3)2CuLi
R
C
CH3
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 sp3 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: CnH2n +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
CH3 CH CH2OH
CH3
2-Methylpropanol
CH3 CH CH CH2OH
CH3 Cl
2-cloro-3-methylbutanol
CH3
OH
CH2=CH_CH2OH
Propenol
CH C CH CH2OH
CH3
2-Methyl-3-butyn-1-ol
CH3 CH CH CH2OH
CH3 CH2 CH2F
C6H5_CH2OH
Phenylmethanol
CH3 CH CH CH CH3
CH3 CH2 CH2 Br OH
2-isopropyl-4-fluorobutanol
3-bromo-4-methyl-2-heptanol
OH
CH2OH
1-methylcyclopentanol
CH2OH
cis-4-(hydroxymethyl) cyclohexanol
cyclopropyl methanol
189
1.1.2. Danh php thng thng

Gi tn gc hydrocarbon tng ng v thm tip v ng ic
CH3OH
Alcol methylic CH2=CHCH2OH Alcol allylic
CH3CH2OH
Alcol ethylic
CH3CH2CH2CH2OH Alcol butylic
C6H5CH2OH
Alcol benzylic
(CH3)3C_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.
CH3 CH2OH
Methylcarbinol
CH3 CH2 CH CH3

OH
Ethylmethylcarbinol
CH3
CH2=CH_CH2OH
CH3 C OH
CH3
Vinylcarbinol
Trimethylcarbinol
CH3 CH CH2OH
CH3
isopropylcarbinol
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.
CH3CH2CH2CH2OH
CH3
CH3 C OH
CH3
Alcol bac 3
CH3CH2CHCH3
OH
Alcol bac 1
Alcol bac 2
1.2. ng phn
ng phn do mch carbon v do v tr nhm OH
Phn t alcol C4H9OH c cc ng phn.
CH3
CH3 CH2 CH2 CH2OH
n-Butanol
CH3 CH
CH2OH
CH3
Isobutanol
CH3 C
OH
CH3 CH2 CH CH3
CH3
Tert-butanol
OH
Sec-butanol
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.
CH2=CH2 + H2O
300o ,H3PO4
C2H5OH
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).
HO
RX + H2O
ROH + HX
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
H2 [Ni]
R
CH2OH
CHO
H2 [Ni]
R
Alcol bc 1
Aldehyd
R CH R'
R'
OH
Ceton
Alcol bc 2
Nu hp cht carbonyl cha no th ni i cng b hydro ha.

R CH=CH CHO
4H [Ni]
R CH2 CH2 CH2OH
Kh ha bng natri trong alcol

Aldehyd, ceton b kh thnh alcol bc 1 v bc 2.
R C R'
O
2H
[Na-C2H5OH]
R CH R'
OH
Kh ha bng cc hydrid kim loi AlLiH4, NaBH4

Aldehyd
R_CHO
Acid
R_COOH
Ester
Clorid acid
2 H [H4LiAl]
2 H [H4LiAl]
- H 2O
2 H [H4LiAl]
R_COOR'
- ROH
R_COCl
R_CH2OH
Alcol
2 H [H4LiAl]
-HCl
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 CHO
2H [H4LiAl]
R CH=CH CH2OH
Natri bo hydrid NaBH4 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'
4 H [ Na + C2H5OH ]
RCH2OH + R'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 (Cr2O3).
RCOOC4H9
2H2 [CuO+Cr2O3 ]
RCH2OH + C4H9OH
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
HCHO + RMgX
Aldehyd formic
R'CHO + RMgX
Aldehyd
R' C R" + RMgX

O
Ceton
OMgX
+ H 2O
H C R
RCH2OH + HOMgX
H
Alcol bc 1
OMgX
+ H 2O
R' C R
H
R' CH R + HOMgX
OH
Alcol bc 2
OH
OMgX
+ H 2O
R'
C R + HOMgX
R' C R
R"
R"
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
OMgX
OH
+ RMgX OMgX+ H O
+ H2O
2
H C R
RCHO
R C R
R C R + HOMgX
OR' -ROMgX
H
H
Alcol bac 2
HCOOR' + RMgX
Ester alkyl formiat
OMgX
R
R
+ RMgX
+ H2O
+ H2O
R" C R
R" C R
R" C R
R" C R + HOMgX
OR' -ROMgX O
OMg
OH
R"COOR'+ RMgX
Ester
1.3.6. Oxy ha hp cht c magnesi

Oxy ha hp cht c magnesi (thuc th Grignard) v sau thy phn.
RMgX + O2
ROOMgX
+ H2O
ROH + HOMgX
1.3.7. Thy phn ester

Ester b thy phn trong mi trng kim hoc acid to alcol
RCOOR' + H2O
H+hoac HO-
RCOOH + R'OH
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.
CO + H2O
400oC , 200atm
ZnO - Cr2O3
CH3OH H = - 28,4 kcal
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
t osoi 300
alcol bac 1
200
100
n-alcan
0
-100
-200
20
40
60
80 100 120 140 160 180 200
Khoi lng phan t
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 ... O_H ... O_H ... O_H ... O_H ... O_H ... O_H ... O_H ...
H
Bng 16.1. Tnh cht vt l ca mt s alcol

Cong thc
Alcol methylic
Ten theo IUPAC
tochay
tosoi
-97,1
64,7
78,3
CH3CH2OH
Alcol ethylic
Methanol
Ethanol
CH3CH2CH2OH
CH3CHOHCH3
Alcol propylic
1-Propanol
-114,5
-126,1
Alcol isopropylic
2-Propanol
-89,5
82,3
CH3CH2CH2CH2OH
Alcol butylic
1-Butanol
-89,8
117,2
CH3CH2CHOHCH3
Alcol sec-butylic
2-Butanol
-114,7
99,5
(CH3)2CHCH2OH
Alcol isobutylic
3-Methyl-1-propanol
107,9
(CH3)3C_OH
Alcol tert-butylic
2-Methyl-2-propanol
25,5
82,5
CH2=CHCH2OH
Alcol allylic
1-Propenol
-129,0
97,0
C6H5CH2OH
Alcol benzylic
Phenylmethanol
-15,3
205,4
C6H11OH
Alcol cyclohexylic
Cyclohexanol
23,9
161,5
CH3OH
194
Ten thong thng
97,2
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.
H2O + H2O
Ke
+
H3O + HO
+
Ke = [H3O][HO-] = 10 -14
Ke l hng s t phn ly ca nc Ke = [H3O+][ HO -].

Nng ca [H3O+] v [HO-] rt thp v bng 10-7mol/lt.
Hng s t phn ly ca alcol methylic cn thp hn ca nc.
2 CH3OH
Ke
+
CH3OH2 + CH3O -
+
KCH OH = [CH3OH2][CH3O -] = 1,2.10-17
3
Cc ng ng ca alcol methylic gi tr Ke 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:
ROH + H2O
Ka
+
RO - + H3O
Ka =
+
[H3O][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
C2H5OH
C2H5OH
+
+ Na_NH2
Natriamidid
+
+ Na_H
Natri hydrid
2RONa + H2
+
C2H5O_Na + NH3
Natri etoxyd
+
C2H5O_Na + H2
Natri etoxyd
195
Cc phn ng th hin tnh base ca alcol:
..
+..
R _O _ H
_
R _O
.. H + BF3
-BF
H
..+
CH3: O
.. : H + Br -
..
CH3: O
.. : H + HBr
Methyloxoni
Tnh base ca alcol cn th hin qua phn ng vi acid Lewis nh Bo triflo

BF3 hoc km clorid (ZnCl2).
..
+..
R _O _ H
-ZnCl2
_
R _O
.. H + ZnCl2
Ion RO c tn gi l alkoxy. Cc alkoxy l nhng base mnh.

RO-+H2O ROH + HOCH3O-
C 2 H5 O -
(CH3)2CHO-
(CH3)3C_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
Hp chat
pKa
Hp chat
H2O
CH3OH
C2H5OH
(CH3)C_OH
ClCH2CH2OH
14,0
15,5
HCl
-2,2
H2SO4
-5,0
15,9
H3PO4
2,15
18,0
HF
3,18
14,3
H2S
6,97
12,4
HOCl
7,53
10,0
H2O2
11,64
CF3CH2OH
C6H5OH
4 ,8
CH3COOH
pKa
1.5.2. Phn ng loi nc to ether hoc alken

Hai phn t alcol tc dng vi nhau khi c acid mnh nh H2SO4 to ether.
2 R _O _ H
H2SO4
to= 140oC
R _O _R + H2O
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.
R _O - + R'_ I
Ion alcolat
196
R _O _R' + I- Nhanh ;
Ether
ROH + R'I
ROR' + HI Rat cham
Cc alcol di tc dng ca acid sulfuric m c v nhit (>140oC) to alken.

CnH2n+1OH CnH2n + H2O
1.5.3. Phn ng to ester

Alcol tc dng vi acid hu c, anhydrid acid, halogenid acid to thnh
ester hu c.
RCOOH + R'OH
H+
H+
(RCO)2 O + R'OH
Anhydrid acid
RCOCl + R'OH
Clorid acid
Pyridin
RCOOR'
RCOOR'
Ester
+ H2O
+ RCOOH
RCOOR' + HCl.Pyridin
Ester
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 (H2SO4,
H3PO4, acid 4-toluensulfonic), cc base hu c (pyridin).
Hng s cn bng ca phn ng ester ha c tnh theo cng thc:
Kcb =
[RCOOR'][ H2O]
[RCOOH][ R'OH]
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
R C
H
+ OH +R'OH HO
O + H+
R C
R C O R'
+
OH -H
OH -R'OH HO +
..
H2O+
-H2O
+ OH -H+
O
R C
R C O R'
R C
+H2O
OR' + H+
OR'
HO
Theo s trn th H2O 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:

+
R'OH2
R'OH + H+
R C
+
R'
+
R' + H2O
+ OR'
R C
OH
OH
-H+
R C
+H+
OR'
O
+
Giai on to carbocation R + t acid lin hp ca alcol ROH2 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:
R C
O
X
..
HOR'
:OH
O H
R C OR'
+
X
R C OR'
X
R C
+ HX
OR'
X = Cl , Br , R''COO -
Alcol tc dng vi acid v c to ester v c.

HONO (H+) acid nitr
HONO2(H+) acid nitric
R_OH
R_ONO + H2O
Alkylnitrit
R_ONO2 + H2O
Alkyl nitrat
POCl3triclor oxyd phosphor PO(OR) + 3HCl Trialkyl phosphat

3
H2SO4 acid sulfuric
SO3 tri oxyd lu huynh
R_OSO3H + H2O Alkyl hydrosulfat

R_OSO3H
R_OH SO2(OR)2 + H2O

Dialkyl sulfat
Nhiu ester ca acid v c nh acid phosphoric, acid thiophosphoric c s

dng lm thuc tr su.
O CH2 CH3
S P O CH2 CH3
O
NO2
Parathion ( thiophos)
O CH2 CH3
S P O CH2 CH3
O CH2 CH2 S CH2 CH3
Sistoc (mercaptophos)
O CH3
S P O CH3
S CH2 C NHCH3
O
Dimetoat ( phosphamid)
Mui natri alkylsulfat ca cc alcol t C10 _C20 nh natri lauryl sulfat

C12H25OSO3Na 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-C16H33OH 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:
[O]
R_CH2_OH
[O]
R_CHO
- H2O
R_COOH
- H2O
Alcol bc 2 b oxy ha to ceton:

R'
CH OH
R"
R'
C O
R"
+ [O]
+ H2O
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] H
R'
C OH
R"
CH2R'"
R'
C O
R"
+ R'''COOH + H2O
Cc cht oxy ho thng s dng oxy ha alcol l mt s oxyd kim loi nh

ng oxyd (CuO), crom oxyd (CrO3). Trong phng th nghim CrO3 c iu ch t
kali bicromat (K2Cr2O7) 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:
3
CH3
CH3
CH OH + 2CrO3 + 6 H+
CH3
C che
CH3
CH3
CH3
CH3
CH3
C O + 2Cr3+ + 6H2O
CH3
CH OH + CrO3
:O
O CrO3H
CH3
CH3
C O
CH3
CH O CrO3H
+ H3O+ + HCrO3
H3O+ + HCrO3
H2O + H2CrO3
6H+ + 3H2CrO3
CrO3 + Cr3+ + 6H2O
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 KMnO4 th ni i b oxy ha thnh alcol
a chc.
K2Cr2O7 + H2SO4
R_CH=CH_CHO
R_CH=CH_CH2OH
KMnO4
R_CHOHCHOH_CHOH
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.
H
OH
C
H
H
Aldehyd acetic
H
H
Alcol vinylic
OH
H
CH3
2-Propenol
H C C CH3
H
Aceton
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 C C H
H2C CH OOCCH3
Ester vinylacetat
+ CH3COOH
H C C H
+ CH3CH2OH
H2C CH OC2H5
Eter ethyl vinyl
Alcol cha no c nhm OH lin kt vi carbon lai ha sp3 th bn vng.

H2C CH CH2OH
Alcol allylic
Propenol
H C C CH2OH
Alcol propagylic
Propynnol
CH3CH CH CH2OH
Alcol crotonic
2-Butenol
HOCH2 C C CH2OH
1,4-Butyndiol
Alcol cha no propagylic v 1,4-butyndiol c th iu ch t acetylen v

aldehyd formic
H C C H
H C C H
+ HCHO
Cu C C Cu
H C C CH2OH
Cu C C Cu
HOCH2 C C CH2OH
+ 2HCHO
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.
CH3_C=CH_CH2_CH2_CH_CH2_CH2OH
CH3
CH3
CH3
OH
CH3
Geraniol ( 3,7-dimethyl-2,6-octadienol)
Citronelol ( 3,7-dimethyl-6-octenol)
CH3_C=CH_CH2_CH2_C=CH_CH2_CH2_C=CH_CH2 OH
CH3C=CHCH2CH2CCH=CH2
CH3
CH3C=CHCH2CH2C=CHCH2OH
CH3
CH3
Linalol ( 3,7-dimethyl-1,6-octadien-3-ol)
CH3
Pharnezol ( 3,7,1-trimethyl-2,6,9--dodecatrienol)
CH3_CH_CH2_CH2_CH2_CH_CH2_CH2_CH2_C=CH_CH2 OH
2
CH3
CH3
CH3
Phitol ( 3,7,11,15-teramethyl-2--hexadekenol)
200
CH3
3. Alcol vng
Alcol vng c th l no hoc cha no. C cc loi alcol vng thng gp sau y.
CH3
OH
Cyclohexanol
CH2OH
OH
CH(CH3)2
(Menthol)
2-Isopropyl-5-methylcyclohexanol
OH
Cyclohexylcarbinol
2-Cyclohexenol
Cc alcol vng b oxy ha thnh ceton vng.

CH3
CH3
CrO3, H+
O
CH(CH3)2
OH
CH(CH3)2
Menthol
Menthon
Oxy ha cyclohexenol bng dung dch KMnO4 trong mi trng trung tnh
to polyalcol vng.
OH
KMnO4,
OH
pH 7
2-Cyclohexenol
OH
OH
1,2,3-Cyclohexatriol
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.
HO
OH
HO
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
1,2,3,4,5,6-Cyclohexahexanol
OH
OH
OH
OH
OH
(-) - Inositol
(+) - Inositol
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_CH2C(OH)2CH3 ; 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
CH2OHCH2OH ;
CH2OHCHOHCHOHCH2OH
Cc polyalcol ny c tnh cht c bit hn so vi monoalcol.

Nhng polyalcol c cc nhm hydroxyl xa nhau
CH2OHCH2CHOH ;
CH2OHCH2CH2CHOHCH3.
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
Cong thc cau tao
Danh phap thong thng
HOCH2_CH2OH
Danh phap quoc te
Ethylenglycol
1,2-Etandiol
Propylenglycol
1,2-Propandiol
HOCH2 CH2 CH2OH
Trimethylenglycol
1,3-Propandiol
HOCH2 CH2 CH2
Tetramethylenglycol
1,4-Butandiol
CH3 C C CH3
OH OH
Tetramethylethylenglycol
2,3-Dimethyl-2,3butandiol
CH2 CH
OH OH
CH2
OH
Glycerin
1,2,3-Propantriol
CH2 CH
OH OH
CH CH2
OH OH
Erytrit
1,2,3,4-Butantetraol
CH2 CH
OH OH
CH CH CH2
OH OH OH
Pentit
1,2,3,4,5-Pentahydroxy
petan
CH2 CH
OH OH
CH CH CH CH2
OH OH OH OH
Hexit
CH3 CHOH CH2OH

CH2OH
CH3CH3
CH2OH
HOH2C C CH2OH
CH2OH
202
Pentaerytrit
1,2,3,4,5,6-Hexahydroxy
hexan
Tetrahydroxyneopentan
4.3. iu ch polyalcol
Thy phn cc dn xut polyhalogen:
+ 2H2O
CH2Cl CH2Cl
CH2OH CH2OH
+ 3H2O
CH2Cl CHCl CH2Cl
+ 2 HCl
CH2OH CHOH CH2OH
+ 3 HCl
Oxy ha olefin bng dung dch KMnO4:
3 CH2OH_CH2OH + MnO2 + 2KOH
3 CH2=CH2 + 4 H2O + KMnO4
T clohydrin iu ch glycol:
CH2Cl CH2OH + H2O
CH2OH CH2OH
+ HCl
Clohydrin tc dng vi Ca (OH)2 v sau thy phn trong mi trng acid.

O
2 CH2Cl CH2OH + Ca(OH)2

O
CH2
CH2
2 CH2
+ H2O
H+
CH2
+ CaCl2 + 2H2O
CH2OH CH2OH
Kh ha aceton bng in ha hoc tc dng vi magnesi v iod:

2
CH3 2H O
CH3
2
C
C
CH3
CH3
OMgI OMgI
CH3
+ 2 Mg + I2
CH3 C O
CH3
CH3
C
C
CH3
CH3
OH HO
iu ch glycerin t propylen:
Trc tin ngi ta clo ha propylen 500oC thu c allylclorid. Sau cho
allylclorid tc dng vi dung dch clor vi nc th thu c glycerin.
CH2ClCH=CH2 + HCl
CH3CH=CH2 + Cl2
CH2ClCH=CH2 + Cl2 + H2O
CH2ClCHOH_CH2Cl+ HCl
CH2ClCHOH_CH2Cl +2H2O
CH2OH-CHOH-CH2OH + 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.
HCHO + CH3_CHO
HOCH2_CH2_CHO
- H2O
CH2=CH _CHO Acrolein
CH2=CH_CHO + C2H5OH Al( OR)3 CH _CHO +CH2=CH_CH2OH Alcol allylic

3
CH2=CH_CH2OH + H2O2
CH2OH_CHOH_CH2OH
Glycerin
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.
CH2OH_CH2OH + HCl
CH2Cl_CH2OH + H2O
Cc glycol tc dng vi acid hu c c kh nng to 2 loi ester.

HOCH2_CH2_OCOR
RCOOCH2 _CH2_OCOR
Oxy ha glycol to aldehyd hoc ceton.

[O]
CH2OH_CH2OH
- H2O
Ethylenglycol
R CH
OH
R'
C
R''
OH
CH2OH_CHO
[O]
OHC_CHO
- H2O
HIO4
hoac (CH3COO)4Pb
Glyoxal ( aldehyd oxalic)

R C H
O
R'
C
R''
O
Phn ng dehydrat ha glycol (loi nc):

Di tc dng ca acid v c hoc km clorid ZnCl2 ethylenglycol b loi nc
to aldehyd acetic. Phn ng xy ra c s chuyn v anion hydro (H-).
H
..
CH2
..
+
CH2
CH2
+
H OH
OH
Loai nc
CH3
C H
C H
H+
O
Aldehyd acetic
O H
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.
CH3
CH3
OH OH
H+
CH3
CH3 +
C
CH3
- H2O
CH3
CH3
..
CH3
CH3
O H
C
O
Pinacolon
Chuyen v CH3-
Pinacol
CH3
CH3
Glycol b mt nc to ether vng.

OH
OH
CH2
CH2
CH2
CH2
OH
OH
Ethylenglycol
204
H2SO4
CH2
CH2
CH2
CH2
O
Dioxan
2H2O
CH3
H+
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.
CH2OH
2 CHOH
+ Cu( OH) 2
CH2OH
CH2 O
CH
CH2
H
Cu
H
OH
O CH2
O CH
+ 2H2O
HO CH2
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
C7H16O. 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 (CH3)2C(OH)CH2CH2CH2OH.
c. Oxy ha cc alcol n -butylic, sec-butylic bng hn hp kali bicromat v H2SO4.
d. Cho alcol octylic tc dng ln lt vi cc cht POCl3, HNO2, HNO3, SO3.
5. Gii thch c ch phn ng xy ra khi cho acid acetic tc dng vi alcol n-butylic c
xc tc l H2SO4
6. Hon thnh v cn bng cc phn ng oxy ha - kh di y:
a. (CH3CH2CH2)CHOH + CrO3 =
(CH3CH2CH2)C=O + Cr3+
b. CH3CH2CH2CH2CH2OH + H2CrO4 = CH3CH2CH2CH2COOH + Cr3+

c. CH3OH + 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 KMnO4, dung dch HCl.
b. 2-Cyclohexenol tc dng vi dung dch KMnO4 v hn hp kalibicromat v
H2SO4.
c. Cho linalol tc dng vi acid acetic c H2SO4 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 CrO3.
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 CnH2n-7OH
Polyphenol
Ar'(OH)m
CnH2n-6-m(OH)m 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.
OH
OH
Phenol
OH
CH3
m-Cresol
o-Cresol
Hydroxybenzen
Acid Phenic
OH
OH
CH3
o-Hydroxytoluen
2-Methylphenol
m-Hydroxytoluen
3-Methylphenol
CH3
p-Cresol
p-Hydroxytoluen
4-Methylphenol
OH
CH (CH3 )2
OH
CH3
Thimol
3-Hydroxy-p-cymen
5-Methyl-2-Isopropylphenol
1-Hydroxynaphthalen
2-Hydroxynaphthalen
-Naphtol
-Naphtol
207
OH
OH
OH
p-Hydroxydiphenyl (1,4)
10-Phenantrol
1-Phenantrol
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.
Ar_Cl + NaOH
300oC
Ap suat
Ar_OH + NaCl
1.2.2. Nung nng chy acid aren sulfonic vi NaOH

2Ar_SO3H + 2NaOH
300oC
2Ar_OH + Na2SO3 + H2O
1.2.3. Thu phn mui aren diazoni

+
Nhiet o
+
Ar_OH + H3O
Ar_N2 + 2H2O
+ N2
1.2.4. Oxy ho hp cht aryl magnesi halogenid ArMgX
Ar_MgCl+ O2
Ar_OOMgCl
Ar_MgCl
2Ar_OMgCl
2H2O
2Ar_OH+2Mg(OH)Cl
hoc cho hp cht c magnesi tc dng vi ester ca acid boric v sau oxy
ha bng hydro peroxyd H2O2.
Ar_MgCl
+ B ( OR)3
- Mg(OR)Cl
Ar ( OR )2
2H2O
- 2ROH
Ar _B( OH )2
+ H2O2
- H3BO3
Ar _ OH
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(CH3)2
+ O2
Cumen
208
HOOC(CH3)2
OH
H2SO4
Cumen hydroperoxyd
CH3
C CH3
O Aceton
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
Ten chat
toc
Cong thc
C6H5OH
Phenol
o-Cresol
m-Cresol
p-Cresol
Thymol
tos
43
pKa
o-CH3C6H4OH (1,2)
30
181
191
m-CH3C6H4OH (1,3)
p-CH3C6H4OH (1,4)
(CH3) CH(CH3)2C6H3OH (1,5,2)
12
201
10,01
10,17
C10H7OH
35,5
201
51
233
10.
10,2
-Naphtol
-Naphtol
96
C10H7OH
288
122
291,8
o-Clorophenol
ClC6H4OH (1,2)
176
m-Clorophenol
ClC6H4OH (1,3)
29
214
p-Clorophenol
ClC6H4OH (1,4)
37
217
9,39
o-Nitrophenol
O2NC6H4OH (1,2)
44,5
214
7,21
m-Nitrophenol
O2NC6H4OH (1,3)
p-Nitrophenol
O2NC6H4OH (1,4)
2,4-Dinitrophenol
(O2N)2C6H3OH (1,2,,4)
2,4,6- Tribromophenol
Br3C6H3OH (1,2,,4,6)
8
9,11
96
8,0
114
7,16
113
4,
95
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:

ONa
OH
+ Na
ONa
OH
+ [ H] ;
+ NaOH
+ H2O
Phenol c tnh acid yu hn acid carbonic. Phenolat tc dng vi acid carbonic:

OH
ONa
+ NaHCO3
+ CO2 + H2O
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:
C6H5ONa
C6H5O- + Na+
Ion phenolat tn ti cc trng thi trung gian do s cng hng:
-O
Tnh acid ca phenol tng khi trn nhn benzen c cc nhm ht electron
nh Cl, NO2, COOH... (c hiu ng -I,-C). Cc nhm y electron nh CH3 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:
CH3COOH + C6H5OH
CH3COOC6H5 + H2O Ho = + 1,5 kcal.mol-1
CH3COOH + C2H5OH
CH3COOC2H5 + H2O Ho = - 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:
OCOR
OH
+ RCOCl
210
Base
+ HCl
COOH
OH
COOH
OCOCH 3
+
CH 3 COOH
H 3 PO 4
+ ( CH 3 CO ) 2 O
Acid salicylic
Aspirin
Ester ca phenol tham gia phn ng chuyn v Fries to ceton thm khi c
xc tc AlCl3:
OH
C R
O
t = 160o
OCOR
AlCl3
o- Oxyphenylceton
OH
t = 60o
p- Oxyphenylceton
O C CH3
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
OCH2CH=CH2
OH
200oC
CH2CH=CH2
Chuyen v Claisen
o- Allylphenol
Eter allylphenyl
C ch chuyn v Claisen:
O
CH2
O.
CH
.. 2
CH
..
.
... .. ...CH2
CH
CH2
CH2
OH CH
CH2
CH
CH2
H
CH2
1.4.4. Phn ng thay th nhm OH
Nhm OH phenol c th b thay th bi Cl hoc NH2 khi tc dng vi PCl5

hoc NH3 vi xc tc AlCl3:
OH
Cl
PCl5
OH
NO2
-POCl3,-HCl
Phenol
O2N
Clorobenzen
NO2
Acid picric
PCl5
O2N
-POCl3,-HCl
Cl
NO2
NO2
Picrylclorid
211
OH
NH2
NH3 ( AlCl3) ,
+ H2O
- 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:
OCH2OH
O-
O-
OH
+ HO -
O-
+ HCHO
+ H2O
CH2OH
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
+
CH2OH
HCHO + H+
+
OH
+
CH2OH
OH
H
CH2OH - H+
OH
OH
HCHO + R2NH
CH2OH
CH2NR2
- H2O
1.4.6. Phn ng tng hp Kolbe. Tng hp acid salicylic.
Phenolat natri tc dng vi CO2 c p sut v nhit , to natri salicylat.

ONa
+ CO2
OH
p, to
OH
COONa
COONa
OH
COOH
+ H+
C ch phn ng:
..
: O:
+
O
O
C
H
OH
COO
OH
COOH
+ 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.
OH
OH
CHO
+ 3KCl + 2H2O
+ CHCl3 + 3KOH
Aldehyd salicylic
Phn ng xy ra theo c ch to diclorocarben do cloroform tc dng vi KOH.

Cl
..
HO H :C Cl
Cl
+
KCl + H2O + :CCl2
Diclorocarben (CCl2) nh l mt tc nhn i in t tn cng vo phenol v

tr ortho hoc para v sau xy ra s thy phn.
..
: O:
O
+
+ :CCl2
CCl2
CHCl2
+ 2KOH
CHO
+ H 2O
-HO -
-2KCl,-H2O
OH
CHO
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
+
: CCl2
Cl
.
.
Tc nhn i in t
Cl
Cl
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:
HO
+
N N
Base
Muoi diazoni
HO
N N
Phenylazophenol
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
Nitro hoa
OH
HNO3
O2N
OH
H2SO4
O2N
HNO3
H2SO4
2-Nitrophenol
HNO3
O2N
H2SO4
NO2
2,4 Dinitrophenol
OH
NO2
NO2
2,4,6-Trinitrophenol
OH
OH
Halogen hoa
OH
+ Br2
CS2
+ HBr
Br
OH
+ 3Br2 H2O
OH
Br
Br
+ 3HBr
Br
Sulfon ha
OH
OH
HO3S
+ 2H2O
+ H2SO4
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 FeCl3.
Vi dung dch FeCl3 phenol to hp cht C6H5OFeCl2 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.
O.
OH
[O]
- H.
Cromoxyd CrO3 oxy ha phenol to p -benzoquinon. Phn ng xy ra qua

giai on to acid phenylcromic.
214
O_CrO3H
- H2CrO3
O CrO3H
OH
+ CrO3
O H
H
OH
H2CrO4
OH
OH
p- Hydroquinon
O
p- Benzoquinon
-Naphtol b oxy ha to sn phm 4,4'-dihydroxy-1,1'-dinaphtyl. Phn ng

xy ra theo c ch:
O.
OH
-H
OH
H 2
OH
4,4'-Dihydroxy-1,1'-dinaphtyl
Trong trng hp 2,4,6-tri-tert-butylphenol, gc t do 2,4,6-tri-tertbutylphenoxy c mu xanh sinh ra c bn cao. Chng tc dng vi oxy to hp
cht mu vng:
(CH3)3C
OH
C(CH3)3 (CH3)3C
-e
-H+
C(CH3)3
(CH3)3C
O2
O
(CH3)3C
C(CH3)3 (CH3)3C
Mau vang
C(CH3)3 (CH3)3C
C(CH3)3
C(CH3)3
C(CH3)3
Bu Bu
C(CH3)3
C(CH3)3
O
C(CH3)3
Bu
(CH3)3C
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 (tc = 104o)

1,2 -Dihydroxybenzen
OH
OH
Resorcinol (tc = 114o)
OH
OH
Hydroquinon (tc = 169o)
215
HO
OH
OH
OH
OH
OH
OH
Hydroxyhydroquinon (tc = 140o)
1,2,4 -Trihydroxybenzen
HO
OH
Phloroglucinol (tc = 218o)
Pyrogalol (tc = 132o)

Polyphenol c iu ch theo cc phng php c bn trong iu ch

monophenol:
Cl
Cl
OH
H+
NaOH , H2O
OH
CuII, 200oC
SO3H
SO3H
OH
H+,H2O
NaOH
OH
Nong chay
NH2
O
Na2Cr2O7
H2SO4
HO
OH
OH
OH
2[H]
un nong
OH
HO
OH
OH
- CO2
COOH Acid Galic
O2N
COOH
NO2
H2N
COOH
NH2
Sn,HCl
NO2
NH2
OH
HO
H2O , 100oC
OH
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
OH
OH
Ag2O
OH
Na2Cr2O7
MgSO4,ether
Catechol
OH
Hydroquinon
o-Benzoquinon
H2SO4
O
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:
OH
O
+2 H
OH
O
1,3 -Cyclohexandion
Resorcinol
Phloroglucinol cng c kh nng h bin to ceton:

OH
HO
O
O
OH
O
1,3,5 -Cyclohexantrion
Phloroglucinol
Polyphenol to dung dch c mu vi FeCl3. 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:
a- CH3
OH
; b-
OH
c- Cl
OH
; d-
H5C2
e- CH3
OH
Cl
HO
OH
; f-
OH
HO
OH
g - Cl
H5C2
OH
; h - HO
OH
Cl
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
NO2
OH
NO2
OH
OH
;
NO2
OH
CH2OH
NO2
Cl
;
OCH3
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 CHCl3.
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 :
Benzen
218
H2SO4
NaOH
Nung chay
H2O
H+
(CH3)2SO4
NaOH
HNO3
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.
CH3_CH2_O_CH2_CH3
CH3_CH2_O_CH3
CH2=CH_O_CH3
Diethyl ether
Ethylmethyl ether
Methylvinyl ether
Cyclohexylethyl ether
Diethyl oxyd
Ethylmethyl oxyd
Methylvinyl oxyd
Cyclohexylethyl oxyd
CH2 O CH3
O CH2CH3
O_CH3
O CH3
Benzylmethyl ether
Methylphenyl ether
Methyl , naphtyl ether
Diphenyl ether
Benzylmethyl oxyd
Methylphenyl oxyd
Methyl , naphtyl oxyd
Diphenyl oxyd
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:
(CH3)2O
Dimethyl ether
Dimethyl oxyd
Metoxymetan
CH3OCH2CH2CH3
Methylpropyl ether
Methylpropyl oxyd
Metoxypropan
CH3OCH(CH3)2
Methylisopropyl ether
Methylisopropyl oxyd
2-Metoxypropan
C6H5OCH3
Methylphenyl ether
Methylphenyl oxyd
Metoxybenzen
p-CH3C5H4OC2H5
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):
C2H5ONa + ICH3
C2H5OCH3 + NaI
CH2=CHCH2OC2H5 + NaI
CH2=CHCH2ONa + IC2H5
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):
C6H5ONa + ICH3
C6H5OCH3 + NaI.
C6H5OCH3 + CH3OSO2ONa
C6H5ONa + SO2 (OCH3)2

C6H5ONa + p-CH3C6H4_O_SO2_OCH3
Ester Methyl-p- toluensulfonat
C6H5ONa + BrC6H5
C6H5OCH3 + p-CH3C6H4_O_SO2_ONa
Anisol
Natri p- toluensulfonat
C6H5OC6H5 + NaBr.
1.3.2. iu ch ether t alcol

2ROH
ROR + H2O
Phn ng xy ra c xc tc H2SO4 m c (140C) hoc Al2O3 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

to s
Ether
Alcol, phenol
to s
-24oC
CH3OH
66 oC
(C2H5)2O
+35oC
C2H5OH
78oC
C4H9OCH3
70oC
C4H9OH
118oC
C6H5OCH3
155oC
C6H5OH
183oC
(CH3)2O
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 12301270cm-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 (H2SO4, HClO4, HBr)
ether to thnh mui oxoni khng bn:
..
_
C2H5_O
.. C2H5 + HBr
+
H
..
_
C2H5 O
.. _C2H5 + Br Diethyloxoni
Ether tc dng vi acid Lewis (BF3, RMgX) to phc phi tr tng i bn:
..
_
C2H5_O
.. C2H5 + BF3
F
B
..
C2H5_O
.. _C2H5
Botriflorid etherat
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:
..
C2H5_O_C2H5 + H+
H
C2H5_O_C2H5
+
+Br
C2H5_O_H + BrC2H5
SN2
221
H
HSO4
_
(CH3)3C O_C(CH3)3
+
E1
Di-tert-butyloxoni
..
(CH3)3C_O_C(CH3)3 + H+
Di-tert-butyl ether
(CH3)2C=CH2 + HO_C(CH3)3+ H2SO4

(CH3)2C=CH2 + H2O
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:
CH3_CH2_O_CH2_CH3 + O2
CH3_CH_O_CH2_CH3
OOH Hydroperoxyd
Hydroperoxyd s b loi mt phn t alcol etylic v chuyn thnh hp cht

peroxyd polymer, ethyliden peroxyd (-CH(CH3)_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.

OCH3
Gaiacol
OH
OCH3
OCH3
OH
OH
OCH3
CH2 CH CH2
Veratrol
Eugenol
OCH3
CH CH CH3
Isoeugenol
2-Metoxyphenol 1,2-Dimetoxyphenol 4-Allyl-2-metoxyphenol 4-Propenyl-2-metoxyphenol

OCH3
CH2=CHCH2
O
CH2
CH3CH=CH
O
CH2
O
O
CH=CHCH3
Safrol
Isosafrol
Anetol
4-Propenylmetoxybenzen 4-Allyl-1,2-methylendioxybenzen 1,2-Methylendioxy-4-propenylbenzen
222
2. Ether vng
Epoxy
O
Tetrahydrofuran
1,4-Dioxan
Tetrahydropyran
Tetramethylen oxyd Pentamethylen oxyd
Ethylen oxyd
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:
H2 O
HCl
CH2
H2C
H2 C
ClCH2CH2OH
Ethylen clohydrin
CH3OH
O
Ethylen oxyd
HOCH2CH2OH
Ethylen glycol
Base
CH2
O
H2 C
HOCH2CH2OCH3
Methyl xelozol
(HOCH2CH2)2O
Diethylen glycol
CH2
O
CH3O(CH2O)CH2OH
Methylen carbitol
HO_(CH2CH2O)n_H
Carbovac
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:
HO_CH2_CH2_O_(_CH2_CH2_O_)n_CH2_CH2_OH
PEG
Cc ether ca monoalcol bc cao nh octadecylic C18H37OH hoc alcol thm

c mch nhnh di c ng dng lm cht nh ha. Cng thc chung c dng:
C18H37O(CH2CH2O)xCH2CH2OH ;
RC6H4O(CH2CH2O)mCH2CH2OH
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=CHCH2OCH3 ;
O
e-
b- CH3CH2OCH=CH2
O
f-
; c- ( CH3)3CCH2OCH3 ; d- C6H5OCH3
; 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 AN 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:
O
H
O
H
Aldehyd
Aldehyd formic
R1
R2
Ceton
O
Quinon
Ty thuc cu to ca cc gc R, R1, R2 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
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
O
CH3CH2 C H
2
CH3
CH3CH2CH=CH C H
Propanal
CH3CHCH=CH C H
2-Pentenal
4 3
4-Methyl-2-pentenal
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 formic
Formaldehyd
CH3
Aldehyd acetic
Acetaldehyd
C6H5
CH2
Aldehyd benzoic
Benzaldehyd
CH
Aldehyd acrylic
Acrolein
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
tco
tso
H_CHO
Formaldehyd
Metanal
- 92,0
-21,0
CH3_CHO
Acetaldehyd
Etanal
-123,0
20,8
CH3_CH2_CHO
Aldehyd propionic
Propanal
- 81,0
48,8
CH3_CH2_CH2_CHO
Aldehyd butyric
Butanal
- 99,0
74,7
Aldehyd isobutyric
2-Methylpropanal
- 66,9
61,0
CH2=CH_CHO
Acrolein
Propenal
- 87,7
52,5
CHC_CHO
Aldehyd propagylic
Propinal
60,0
CH3 CH CHO
CH3
225
Bng 19.1 (tip)

Cng thc cu to
Tn thng thng
CH3_CH=CH_CHO
Tn quc t
tco
tso
Aldehyd crotonic
2-Butenal
-74,0
104,0
Benzaldehyd
Benzaldehyd
- 56,0
179.5
Aldehydphenylacetic
2-Phenyletanal
-10,0
190.4
Aldehyd cinnamic
3-Phenylpropenal
252.0
CH3COCH3
Aceton
Propanon
- 95,0
56,1
CH3_CH2_CO_CH3
Methylethylceton
Butanon
- 86,4
79,6
C2H5COC2H5
Diethylceton
Pentanon-3
- 42,0
101.7
Pinacolin
3.3-Dimethyl-butanon-2
- 52,5
106,2
CHO
CH2CHO
CH=CHCHO
CH3
CH3 C COCH3
Methyl,tert- Butylceton
CH3
CH3_CO_CH=CH2
Methylvinylceton
O
O
Butenon-3
79,1
Cyclopentanon
- 51,3
130,6
Cyclohexanon
- 31,2
156,7
Cycloheptanon
179,0
COCH3
CO
Methylphenylceton
Acetophenon
19,6
202,3
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.
O
CH3 CH2 CH2 C CH3
5
2-Pentanon
226
O
1
CH2
1
CH CH2 C CH2
2
CH3
CH CH3
6
6-Methyl-1-hepten-4-on
Cyclohexanon
Gi theo danh php ceton

Gi tn 2 gc hydrocarbon lin kt vi nhm carbonyl v thm tn ceton.
Tn cc gc hydrocarbon + Ceton
O
CH3 CH2 C CH3
CH2
Methylethylceton
O CH3
CH C CH CH2
CH2
Divinylceton
CH C CH CH3
Vinylisopropylceton
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).
CH3
CH3
Na2Cr2O7
OH
CH3
+ H2O
H2SO4 -H2O
CH3
CH3
CH3
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 - [(CH3)2CHO]3Al.
R
CH OH +
R'
CH3
C O
[(CH3)2CHO]3Al
C O +
CH OH
CH3
R'
CH3
CH3
Nu oxy ha alcol bc nht RCH2OH 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.
+ O3
CH2Cl2
- 78o
H O
O
O
AcOH
Zn
CHO + HCHO
(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 CO2 (CO)8 v p sut, olefin

tc dng vi hn hp H2 v CO s to thnh aldehyd.
R CH2
CO2 (CO)8
R CH
CH2 + CO + H2
to, p
CH2 CHO
R CH CHO
CH3
1.2.4. Hydrat ha acetylen v alkyn (xem phn hydrocarbon alkyn).

1.2.5. Nhit phn mui ca acid carboxylic (RCOO)nM
Khi nhit phn cc mui calci, bari...ca acid carboxylic nhit khong
300oC s to thnh ceton.
R
to
2RCOO
C O
2-
CO3
Phn ng Perrier
Nn s dng hn hp 2 mui trong c mui ca acid formic s to aldehyd.

RCOONa + HCOONa
to
RCHO + Na2CO3
1.2.6. Tng hp aldehyd theo phn ng Rosenmund (1918)

Hydro ha hp cht acylclorid vi xc tc l palladi trn cht mang BaSO4.
O
R
Pd - H2SO4
+
H2
O
R
HCl
Cl
Aldehyd
Acylclorid
1.2.7. Tng hp aldehyd theo phn ng Stephen (1925)

Kh ha hp cht nitril RC N bng thic clorid SnCl2 trong mi trng acid
thng to thnh aldehyd. Phn ng qua giai on to cht trung gian l aldimin.
R C
Nitril
SnCl2 2HCl
- SnCl4
R CH NH
Aldimin
H2O
H+
O
R
+ NH3
H
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)
O
RO
+ R'MgX
C
H
R'
C
H
- Mg(OR)X
Ester alkylformiat
228
Aldehyd
OR
OR
+ H2O (H+)
+ R'MgX
RO
OR
R'
- Mg(OR)X
OR
H
Aldehyd
Acetal
+ R''MgX
- Mg(OR')X
OR'
Ester
- 2 ROH
Ester alkyl orthoformiat
O
R'
R''
Ceton
Thuc th Grignard tc dng vi nitril cng to thnh ceton.

R
R'MgX
C N
R'
Nitril
C NMgX
+ H2O
- Mg(OH)X
R'
C NH
+ H2O ( H+)
Cetimin
- NH3
R
R'
C O
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.
Cl
AlCl3
5
6
+ HCl
O
Indanon-1
3-Phenylpropanoylclorid
1.2.10. Phn ng Vilsmeier (1927)

Cc alkylformamid tc dng vi aren, phenol, ether...khi c mt ca
tricloroxydphosphor POCl3 xy ra phn ng formyl ha v to thnh aldehyd.
O
+ H
+ POCl3 + 3H2O
N(CH3)2
Dimethylformamid
O
H
+ 3HCl + (CH3)2NH + H3PO4
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 sp2. Nguyn t
carbon v oxy to 1 lin kt v 1 lin kt (Hnh 13-1). di lin kt C =O
o
l 1,22 A
+
o
1,22 A
+
C
120o
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:
Y- +
C O
.. :
.. -
Y C ..O:
H+
Y C OH
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
1+
C
>
2+
>
3+
1+> 2+ >3+
R'
Gemdiol
Aldehyd v ceton tc dng vi nc to thnh gem-diol.
R
C O
R'
R
+ H2O
OH
C
R'
OH
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.
Cl
O
Cl C C
H
Cl
+ H2O
Cl OH
Cl C C OH
Cl H
Cloral
Cl3C CHO. H2O
Cloral hydrat
Formaldehyd b hydrat ho gn nh hon ton, trong dung dch nc n tn

ti di dng gem-diol CH2(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
HCHO
Mc hydrat
99,99%
CH3CHO
58%
CH3COCH3
0%
C6H5 CHO
vt.
Cl3CCHO
100%
F3CCHO
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

R
OH
OH
O
C
+ R'OH
H
Aldehyd
OR'
H
Hemiacetal
Alcol
CH3
+ CH3OH
Acetaldehyd
CH3
OCH3
H
Hemiacetal
Methanol
Ceton tc dng vi alcol theo t l 1: 1 v s mol:

OH
OH
O
R
+ R''OH
R'
Ceton
R'
O
CH3
OR''
Hemicetal
Alcol
C
CH3
CH3
+ CH3OH
CH3
OCH3
Aceton
Methanol
Cng hp 2 mol alcol vi aldehyd hoc ceton s to thnh acetal v cetal.

O
R C H + 2R'OH
Aldehyd
OR'
H+
R C H ; CH3 C H + 2C2H5OH
OR'
Acetal
Alcol
R C H
OC2H5
Acetal
Alcol
Aldehyd
OC2H5
H+
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
Cyclohexanol
56
Ethanol
78
CH3_CHO
2-Propanol
43
(CH3)2CH_CHO
71
23
(CH3)3C_CHO
56
26
11
C6H5_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
O
CH3
OC2H5
C CH3 + HC(OC2H5)3
CH3
OC2H5
Cetal
Ester ethyl ortoformiat
Ceton
C CH3
+ HCOOC2H5
Ester Ethylformiat
Ceton v aldehyd tc dng vi diol to cetal v acetal vng:

R
R
R
C
R'
O +
HO
+
H H
HO
R'
232
Ceton
1,2-diol
+ H2O
R'
Cetal vng
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.
R'
R
HO C H
R
C O +
H+
HO C H
R
O
CH
BrCH
CH3CH2C CLi +
2
2
O
CH3CH2C C CH2CH2
C H
R
Cetal vng
O
CH
CH
CH3CH2C C
2
2
O
H
O
+
H + H 3O
+ H2O
O
R'
1,2-Diol
Ceton
C H
O
H
+ LiBr
CH3CH2C C CH2CH2CHO + HOCH 2CH2CH2OH
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.
CN
O
C
CH3
CH3
+ HCN
H
Acetaldehyd
OH
Acid cyanhydric
Aceton
Cyanohydrin acetaldehyd
CN
O
CH3
CH3
CH3
HCN
C CH3
HO
Cyanohydrin aceton
Acid cyanhydric
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 (NaHSO3)
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.
OH
O
C6H5
H
Benzaldehyd
+ NaHSO3
Natri hydrosulfit
C6H5
CH
SO3Na
Hydrosulfitic benzaldehyd
233
O
CH3
Aceton
CH3
OH
CH3
+ NaHSO3
Natri hydrosulfit
C CH3
SO3Na
Hydrosulfitic Aceton
Hp cht hydrosulfitic thc cht l mui ca acid -hydroxysulfonic

RCH(OH) SO3H. V nguyn t lu hunh c tnh i nhn mnh tc dng vi
nguyn t carbon ca nhm carbonyl theo c ch :
- +
O Na
O
- +
:
S
O
Na
+
R C
OH
R'
Ceton
Natri hydrosulfit
O
OH
C R'
SO3H
C R'
SO3Na
Hydrosulfitic Ceton
Hp cht hydrosulfitic d b thy phn trong mi trng acid to thnh hp

cht carbonyl ban u v SO2. 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
ONa
NH3
-33o
- +
C Na
C C H
Cyclohexanon
C
Ceton
C C H
Etynyl pentamethylen carbinol
O
R
OH
+
H 3O
+ + : Na C
R'
NH3
C H
- 33o
O Na
R
R'
C C H
+
H3O
O H
R
R'
C C H
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)
2 R CH2 CHO
Aldehyd
234
HO-
R CH2 CH CH CHO
OH R
Aldol
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.
O
R CH2 C
CH CHO
R CH2 CH CH CHO
O- R
+H2O
R CH2 CH CH CHO
HO-
OH R
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.
R
CH
CH
OH
CH2
CHO
CH2
CH
CHO + H2O
C
R
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 .
C6H5CHO
Benzaldehyd
HO-
+ CH3CHO
C6H5 CH CH2CHO
to
C6H5 CH
OH
Aldol
Acetaldehyd
CHCHO
Aldehyd cinnamic
Phn ng ngng t aldol xy ra gia acetaldehyd v formaldehyd to thnh

pentaerythrid (c phn ng Cannizaro cho).
O
3H
C
H
C
H
CH2OH
Ca(OH)2
O
+ CH3
HO
CH2
Phn ng aldol
O
H
CH2OH
HCHO,H2O
CH2OH
HO
CH2
- HCOOH
CH2OH
CH2OH
Pentaerythrid
Phn ng Cannizaro cho
Formaldehyd Acetaldehyd
Hai phn t ceton cng xy ra phn ng kiu ngng t aldol nh aldehyd.

2 CH3
O
C CH3
HO -
Aceton
O
OH
CH3 C CH2 C CH3
CH3
4-Hydroxy-4-methylpentanon-2
Phn ng ngng t aldol cng xy ra gia aldehyd v ceton.

OH O
CHO H O
+
Benzaldehyd
- OH
25o
4 gi
25o
Cyclohexanon
10 ngay
O
+ H2O
235
O
C
CH3
CH3
O
Aceton
Benzaldehyd
HO-
CH
CH
C
O
-H2O
CH3
4-Phenyl-3-butenon-2 (Benzalaceton)
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.
CHO
CH = CHCOOH
CH3COONa
+ CH3COOH
+ (CH3CO)2O
Benzaldehyd
Acid cinnamic
C ch: Natri acetat ng vai tr xc tc base to cabanion - tc nhn i nhn.

CH2CO O COCH3
CH3COO - + H CH2CO O COCH3

CH O
CH
O-
CH 2 CO O CO CH 3
CH
OH
C H 2C O
C OC H3
CH
CH 2 CO O CO CH 3
+ CH 3 COOH
CHCO
- H2O
C OC H3
+ H2O
+ CH3COOH
CH
OH
CH
CH 2 CO O CO CH 3
+ CH 3 COO C HC OOH
C H 3C O O H
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 CH3 _CN, CH3_NO2
COOH
CHO
+
COOH
H2C
CH CH
Amin
COOH - H2O
CH CH
COOH
Acid malonic
COOH
+ CO2
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
H O
CN
C C
OH H
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.
-CN
+
C H
O
H
C
O
C N
+
COH
CN
C H
O-
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
H
CHO
+ H
HO
CHO
CH2
Ca(OH)2
HO CH2 CH O + HO CH2
Aldehyd glycolic
CH
O + HO CH2
CH
CH
Aldol hoa
C 6 H1 2 O6
Hexose
Phn ng cng hp vi cc cht c chc amin - NH2

Hp cht c dng tng qut Z -NH2 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
+ NH 2 _ Z
(H) R '
H+
NH
R
C
(H) R '
R
(H) R'
+
C
NH Z
R
C
OH
+
NH Z
(H) R'
NH
H+
+
OH 2
NH Z
(H) R '
- H+
- H2 O
(H) R'
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-NH2 c nhm -NH2 t do c th tc dng
vi phn t c nhm carbonyl v to thnh hp cht azin RCH=NN=CHR'.
RCH=N_NH2 + O=CHR'
RCH=N_N=CHR' + H2O
237
Bng 19-5: Sn phm cng - tch ca Aldehyd -Ceton vi hp cht Z- NH2

RCHO hay RCOR'
Z-NH2
C6H5CHO Benzaldehyd
Sn phm phn ng
NH2OH Hydroxylamin
C6H5CH=N_OH Oxim.
Benzaldoxim
CH3COCH3
NH2OH
(CH3)2C=N-OH Cetoxim
Acetoxim
Aceton
C6H5COCH3
Acetophenon
NH2NH2 Hydrazin
C6H5CHO Benzaldehyd
NH2NH2 Hydrazin
C6H5
C N NH2 Hydrazon
CH3 Acetophenon hydrazon
C6H5CH=N_NH2 Hydrazon
Benzaldehyd hydrazon
C6H5CHO Benzaldehyd
NH2NHCONH2
C6H5CH=N_NHCONH2 Carbazon
Semicarbazid
Benzaldehyd semicarbazon
NH2NHCONH2
Cyclohexanon
Semicarbazid
C N NH C NH2
O
Cyclohexanon semicarbazon
C6H5CHO Benzaldehyd
NH2R Amin bc nht
C6H5CH=N_R
Imin
Benzadehyd imin
C6H5CHO
NH2NHC6H5
C6H5CH=N_NHC6H5 Phenylhydrazon
Benzaldehyd
Phenylhydrazin
Benzaldehyd phenylhydrazon
C6H5CHO
NH NH2
N O2
NH
CHC6H5
NO2
Benzaldehyd
N O2
2,4-Dinitrophenylhydrazin
NO2
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.
C6H5(CH3)C=NOH
CH3CONHC6H5
Acetophenon oxim
Acetanilid
Aldehyd formic tc dng vi amoniac to hexamethylen tetramin.

Hexamethylen tetramin (urotropin) l cht rn c cng thc (CH2)6N4.
6 HCHO + 4 NH3
238
(CH2)6N4 + 6 H2O
N
CH2
CH2
N
CH2
N
CH2 CH2
N
N
N
CH2
( Urotropin )
Hexamethylen tetramin
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.
CH2
+
O
O+
CH2
CH2
O
CH2+
Aldehyd formic
CH2
O
CH2
Trioxymethylen
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 CH2=O
(CH2O)n
n = 10 - 100
Acetaldehyd cng b trng hp nhit thp khi c mt ca acid to

paraldehyd v metaldehyd.
CH3
O
H3C
CH
CH
O
CH
CH O
CH3
H3C
CH
CH
O
O CH
CH3
Paraldehyd
CH3
Metaldehyd
CH3
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.
CH2CH3
CH
(C6H5)3P , C4H9Li 6 5
C C
C6H5CHO + CH3CH2CH2Br
+
H
Ether
H
Z
Benzaldehyd Propylbromid
C6H5
H
H
C
E CH2CH3
1-Phenyl-1-propen
239
C ch phn ng:
C4H9Li
+
(C6H5)3PCH2CH2CH2Br(C6H5)3P=CHCH2CH3 + LiBr + C4H10
Ether
(C6H5)3P+ CH3CH2CH2Br
C6H5
(C6H5)3P=CHCH2CH3 + C6H5CHO
CH2CH3
+ (C6H5)3P
Phn ng Mannich (1917)

L phn ng aminometyl ho. Gn thm nhm (R)2NCH2- 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.
H+
R_CO_CH3 + HCHO + HN(R)2
R_CO_CH2CH2N(R)2 + H2O
C ch phn ng:
OH
H C
O
R C CH3
Methylceton
CH2 NR2
+ HN(R)2
H
Amin
OH
R C CH2
..
+
+ CH2 NR2
H+
- H2O
+
..
CH2 NR2
+
CH2 NR2
+
OH
O
- H+
R C CH2 CH2 NR2
R C CH2 CH2 NR2
Alkylaminoalkylceton
1.4.3. Phn ng kh
Aldehyd hay ceton b kh ha to thnh alcol bc nht v alcol bc hai.
R
[H]
H
Aldehyd
CH2OH
Alcol bac nhat
; R C O
Ceton
[H]
R'
CHOH
R'
Alcol bac hai
Cc tc nhn kh l: Cc hydrid kim loi (LiAlH4, NaBH4), H2 / 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.
CH2 CH CHO
Aldehyd Acrylic
240
+ LiAlH4
H+
Ether
CH2 CH CH2OH + H2 + Li+ + Al3+

Alcol Allylic
O 1) LiAlH
4
2) H+
2- Cyclohexenon
OH
2- Cyclohexenol
1) NaBH4
CH3 CH CH2CH2COOC2H5
2) H+
OH
Ester ethyl-4-hydroxypentanoat
CH3 C CH2CH2COOC2H5
O
Ester ethyl-4-oxopentanoat
1) NaBH4
2) H+
N C CH2CH2CHO
3-Cyanpropionaldehyd
N C CH2CH2CH2OH
4-Hydroxybutyronitril
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.
LiAlH4 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 B2H6 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.
+ 2H2
CH2 CH CHO
Xuc tac
Aldehyd acrylic
O
CH3 CH2 CH2OH

Alcol propylic
OH
+ 2H2
Xuc tac
2- Cyclohexenon
Cyclohexenol
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 1,2diol. y l phng php in ha. Cht kh l in cc kim loi.
2
CH3
C
CH3
Aceton
Na
+ 2H+
CH3
CH3 CH3
C
C
CH3
OH
OH
Pinacon
241
2 C6H5
Na
+ 2H+
C6H5
C
C
C6H5
OH
OH
Hydrobenzoin
Benzaldehyd
C ch kh ha pinacon:
2
CH3
CH3
2 Na-2e
-2 Na+
CH3
CH3
.. C O
.. :
CH3
CH3 CH3
C
- :O
.. :
+ 2H+
C
CH3
:
:O
..
CH3
CH3 CH3
C
HO
C
CH3
OH
Kh ha Clemmensen (1913)
Hn hng km trong mi trng acid HCl m c kh ha aldehyd -ceton
to hydrocarbon tng ng.
R'
R
R'
CH2 + 2 Zn2+ + H2O

R
Hydrocarbon
+ 2Zn + 4H+
Ceton
Aldehid
O
H
+ 2 Zn2+ + H2O
R CH3
Hydrocarbon
+ 2Zn + 4H+
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.
R
Aldehyd
[O]
Acid
O
OH
Cc cht oxy ha l Ag2O, H2O2, KmnO4, CrO3, Cu(OH)2.

CHO
+ Ag2O
THF
H2O
COOH
+ 2 Ag
Phn ng ca aldehyd vi dung dch AgNO3 trong amoniac to Ag kim loi

v acid hu c (phn ng Tollens). Phn ng ca aldehyd vi thuc th Fehling
to oxyd ng Cu2O 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
HNO3
V2O5
Cyclohexanon
HOOC(CH2)4COOH
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
O
H
Ar
Ar
OH
Ar
Alcol thm
Acid
Aldehyd thm
CH2OH
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.
Ar
H
Aldehyd thm
HO -
OH
Acid formic
Ar
CH2OH
Alcol thm
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
..
: O :Ar
C H +
I :OH
..
O
H
O
H
..
:O : -
+ - OH
Ar
C H
:OH
..
.. Ar C + Ar CH2O..:
I : OH
II
..
Ar
II
Ar
C + Ar
I :O
.. : -
..
CH2OH
..
II
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.
R'
R
O +
Ceton
CH3
CH3
CH
OH
[(CH3)2CH_O]3Al R'
R
CH
OH +
Alcol bac hai
CH3
CH3
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).

2R
Aldehyd
(RCH2O)3Al
C
Ester
OCH2R
Nhng phn ng ny c th xem l phn ng chuyn dch hydrid H- t

isopropylat nhm [(CH3)2CHO]3Al, alcolat nhm (RCH2O) 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.
O
CH3
CH3
+ HCl
CH3
+
OH
C CH3 + Cl-
OH
C CH3
Cl
2-Cloropropanol
CH3
Aceton
Trong dung dch alcol, t 1,1-halogenhydrin to thnh -halogeno ether. halogeno ether tch ring c khi hn hp phn ng.
+
H2CCl + CH3OH
H2C
H
+ OCH
OCH3
+ H+
Cl
Clomethylmethylether
H2C
Cl
Tc dng vi PCl5 v PBr3

Aldehyd v Ceton tc dng vi phosphor pentaclorid hoc phosphos tribromid
to gem -dihalogen.
O
CH3CH2
C CH3 + PCl5
Butanon-2
(CH3)2CHCH2CHO+ PCl5
3-Methylbutyraldehyd
Cl
C CH3 + POCl3
Cl
2,2-Diclobutan
CH3CH2
(CH3)2CHCH2CHCl2+ POCl3
1,1-Diclo-3-methylbutan
Phn ng Haloform
Acetaldehyd v metyl ceton tc dng vi Natri hypohalogen NaOX to
haloform.
244
+ 3NaOI
CH3CHO
+ 3NaOI
CI3CHO
CHI3
Acetaldehyd
HCOONa
Iodoform
O
R
+ 3NaOBr
R
CH3
+ 3NaOBr
CHBr3 + RCOONa
CBr3
Bromoform
Methylceton
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 .
O
R C CH3 + Br2
O
R C CH2Br + HBr
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(CH2)nCH=O,

RCH=CH(CH2)nCOR'.
Aldehyd hoc ceton cha no lin hp hoc khng lin hp c cng s nguyn
t carbon l ng phn ca nhau.
CH2=CH-CH2-CH=O
CH3-CH=CH-CH=O
Vinylacetaldehyd
Crotonaldehyd
(ng phn khng lin hp)
CH2
O
C
ong phan cha no ,
H = -6 kcal.mol-1
(ng phn lin hp)

C
C
CH
OH
H
ong phan dang enol
CH
O
C
ong phan cha no ,

(Rat ben)
(Kem ben)
Nguyn t hydro ca nhm methylen (-CH2-) 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 H2O. 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 ,.
2 CH3COCH3
H2SO4
CH3
CH3C=CHCOCH3+ H2O
4-methyl-3- penten-2- on
(mesytyl oxyd)
C ch phn ng:
OH+
CH3COCH3 + H+
OH
_
CH3 C
CH3
CH3
OH
OH
_
_
_
CH3 C CH2 C_CH3
CH3
CH2= C_CH3
+
OH
OH
Hoac: CH _ C_CH _C_CH3
3
2
CH3
OH
OH2
CH3_ C_CH = C_CH3
CH3
246
H2O +
CH3
.. OH
+
OH
- H+
+ H+
CH3
OH
_
_
CH3 C= CH C_CH3
+
CH3
CH3 + H+
O
OH
_
CH3_ C_CH2 C_CH3
CH3
OH
OH
+ H+
CH3_ C_CH = C_CH3
OH
CH3 C CH = C_CH3
CH3
+
_ _
CH2
+ H+
+
OH2
OH
CH3_ C_CH = C_CH3
CH3
OH
_
_
CH3 C= CH C_CH3
CH3
+OH
O
_
_
CH3 C= CH C_CH3
CH3
CH3_ C= CH _C_CH3
CH3
+ 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.
CH3
CH3
CH3
CH3
CH3
Retinol
(Vitamin A1)
CH3
CH3
CH2OH
MnO2
Ether dau hoa
CH3
CHO
CH3
CH3
(80%)
Retinal
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.
C6H5CH=CH_CO_CH3 + Br2
CCl4
C6H5CHBr_CHBr_CO_CH3
(10-20o)
CH2 = CH_CHO + Ag2O
(52-57%)
CH2 = 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
X Y
X Y
C C C O
+ X Y
hay
C C C O
C C C O
Cng hp 1,4
X
C C C O
+ X Y
C C C O
V d: Cng hp 1,2
O
C6H5CH = CH _ C _ C6H5
+ KCN
CH3COOH
CN
C6H5CH _ CH2 _ C _ C6H5

(93-96%)
247
+ HCN
(C2H5)3Al
(85%)
CN
V d: Cng hp 1,4:
+
CH2_CH=CH_O
+
CH2=CH_CH_O
CH2=CH_CH=O
Acrolein (aldehyd acrylic)
CH2=CH_CH=O + CH3SH
CH3S_CH2_CH=CH_OH
Acrolein
Methylmercaptan (Metanthiol)
CH3S_CH2_CH2_CHO
-Methylthiolpropionaldehyd
Cng hp Diels -Alder:

CH2
CH2
CHO
Aldehyd acrylic
CHO
O
2-Formyl-2,3-dihydropyran
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
CH3
H
C=C
C_CH 3
+ CH3MgBr
H3O+
CH3
H
C=C
C(CH 3)2
(80%) OH
2-Methyl trans 3- penten-2- ol
Cng hp1,4
O
_
C6H5CH = CH C_C6H5
+ C6H5MgBr
H3O+
C6H5
C6H5
O
_
_
CH CH2 C_C6H5
1,3,3-triphenyl-1- propanon
Hp cht c lithi c khuynh hng cng hp 1,2:

O
C6H5CH = CH_C_C6H5
+ C6H5Li
H3O+
OH
C6H5CH = CH_C(C6H5)2
75%
Hp cht lithi dialkyl ng (hp phc) thng to ra sn phm cng hp 1,4:

CH3
O
_
CH3C = CH C_CH3
248
+ (CH2 = CH)2CuLi
H3O+
CH3
O
_
_
_
CH2 = CH C CH2 C_CH3
72% CH3
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 LiAlH4 cng vo nhm carbonyl.
O
H2O
Ether
+ LiAlH4
O
+ NaBH4
C2H5OH
OH
(97%)
OH
OH
+
(41%)
(59%)
Kh ho bng hydro c xc tc xy ra ch lin kt i (C=C)

O
O
CH3
+ H2
Pd-C
CH3
(100%)
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.
CH3
CH3 CHO
Citral
+ CH3COCH3
HO CH3
CH3
CH3
O
CH3
CH3
BF3
CH3
CH3
O
CH3
CH3 -Ionon
Aldehyd cinnamic:
L thnh phn ch yu ca tinh du qu.
CH
CH
CHO
Aldehyd cinnamic
Metylvinylceton:
L mt ceton lin hp; th hin tnh cht cha no:
HCl + CH2=CH_CO_CH3
Methylvinylceton
ClCH2_CH2_CO_CH3
-Cloroetylmethylceton
249
Cc ceton lin hp b hydro ha rt chn lc. Vi H2 c xc tc, nhm

carbonyl khng b hydro ha. Khi tc dng vi NaBH4 ch c nhm carbonyl b
kh ha:
CH3_CH2_CO_CH3
H2
Pt
CH2=CH_CO_CH3
Methylvinylceton
NaBH4
CH2=CH2_CHOH_CH3
Cc ceton lin hp c th tham gia phn ng ng vng vi mt s ceton khc:

R
R
Base
HO O
Aldol
O
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
SeO2 hoc oxy ha 1,2-etadiol bng oxy ca khng kh c Cu l xc tc nhit
250-300oC.
Diacetyl (Butadion-2,3: CH3_CO_CO_CH3)
Diacetyl ngng t vi hydroxylamin to diacetyldioxim (dimetylglyoxim).
Dimetylglyoxim tc dng vi ion niken to phc, kh tan, mu .
..
CH3
CH3
H:O:
C
C
N
N
:O :
+ Ni+ +
:O :
N
N
C
C
:O.. : H
CH3
CH3
H
Dimetylglyoxim
CH3
CH3
-:.. : H
:O :
O
C
C
N + N
+ Ni
+
N
N
:O :
C
C
CH3
CH3
:O.. :
H
Phc niken ( mau o )
Dibenzoyl (1,2-Diphenyletandion - Benzyl: C6H5_CO_CO_C6H5)

Oxy ha benzoin thu c dibenzoyl. Dibenzoyl l tinh th mu vng, nhit
nng chy 95oC. Kh ha dibenzoyl trong cc iu kin khc nhau th thu c
cc sn phm khc nhau.
250
4H [ Sn/HCl]
C6H5
- H 2O
C6H
6H [Zn/Hg. HCl]
- 2H 2O
C6H5
C C C6H5
O O
Dibenzoyl
CH2
C
4H2 /Ni
- 2H2O
C6H5
CH2
CO
C6H5 Desoxybenzoin
H
C6H5
CH2
Trans-Stylben
C6H5 1,2-Diphenyletan
Methylglyoxal (2-oxopropanal: CH3-CO-CHO)

Methylglyoxal c iu ch bng cch oxy ha 2-oxopropanol (1hydroxypropanon, hydroxyaceton) bng selen dioxyd.
CH3
C CH2OH
O
2-Oxopropanol
SeO2
CH3
C CHO
O
Methylglyoxal
Methylglyoxal l sn phm trung gian trong chuyn ha carbohydrat.

3.2. Hp cht 1,3-dicarbonyl (-dicarbonyl: R-CO-CH2-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 NaNH2...
CH3
C CH3
O
Aceton
R'O CH3 C CH2 C CH3 + ROH

C OR
O
O
O
Ester alkylacetat
Acetoaceton (petandion,2,4)
CH3
C ch phn ng:
CH3
C CH3
:O :
Aceton
..
:OR
CH3
:O :
CH2
:O :
CH3
R'O -
-R'OH
C CH2
:O :
Carbanion
CH3
CH3
:O..: -
CH2
..
:OR
CH3
C CH2
:O
.. : -
C CH3
:O :
-RO -
CH3
C CH2 C CH3
:O :
:O :
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
R'
R
CH
: O:
R'
C
R"
:O
..
: O:
Dng ceton
R"
CH3
O
. ..:
CH3
CH3
CH2
CH
CH3
.O :
H . . ..
Dng ceton
Dng enol
Acetoaceton
: O:
H ..
Dng enol
1,3-dicarbonyl
:O
..
:O:
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.
CH3
CH2
C
O
CH3
C
- : ..O:
CH
C
O
C
:O:
CH3
CH3
+ Na
CH3
C
:O:
CH3
CH
C
:O:
C
O
Na
CH
CH3
C
O
CH3
CH3
C
:O:
CH
Carbanion
+ 1/2 H2
CH3
C
: O.. : -
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 Cu2+ thnh acetoacetonat ng c cng thc sau:
CH3
CH3
CH2
C
C
: O: + : O :
Cu2+
: O: +
CH3
CH2
CH3
Acetoaceton
CH
: O:
CH3
C
: O:
CH3
CH
CH3
+ 2H+
Cu
: O:
C
C
:O
O:
C
CH3
Acetoacetonat ng
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
CH3
C
- :O
.. :
CH3
CH
C
:O :
CH3
RX
C
:O :
R
-X
C
:O:
CH3
CH
C
: O:
CH3
CH3
CH
C
:O :
CH3
Th vo O
C
:O :
CH
C
:O :
CH3
Th vo C
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.
CH3
O
C
CH2
O
C
HO CH3
to
CH3
O
C
O-
CH3
O
C
CH3
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.
O
O
O
Toluquinon
CH3
O
Antraquinon-9,10
o-Benzoquinon; p-Benzoquinon; 2-Methylbenzoquinon-1,4.
CH3
O
Phthiocol
OH
2-Hydroxy-3-methylnaphthoquinon-1,4
4.2. iu ch
Phng php iu ch quinon l oxy ha cc phenol v amin thm.
OH
NH2
O
Na2Cr2O7
H2SO4
30o
OH
O
Hydroquinon
p-Benzoquinon
OH
Cl
O
Na2Cr2O7
H2SO4
< 30o
Cl
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
OH
CH3
CH3
Na2S2O4 , H2O
Ether
OH
Tnh cht quan trng c minh ha bng phng trnh in ha nh sau:

O
OH
+ 2H+ + 2e
p-Quinon
Hydroquinon
OH
Hydroquinon c s dng lm in cc.

in th ca in cc xc nh theo phng trnh Nernst:
E = Eo+
[Quinon][H+]2
2,303.RT
log
nF
[Hydroquinon]
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, -OCH3, -N(CH3)2, -CH3 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.
O
OH
OH
Quinon
Hydroquinon
OH
O
Quinhydron
OH
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
O
OH
+ HCl
254
OH
Cl
C ch phn ng cng HCl vo quinon.

O
+ OH
OH
+ H+
OH
Cl
-Cl
OH
OH
Cl
Quinon cng hp vi cc dienophyl - Phn ng Diels -Alder.

O
OH
CH3COOH
25o
HCl
CH3COOH
OH
O
Quinon
OH
Butadien
OH
Phn ng acyl ha
Quinon tc dng vi anhydrid acetic to triacetat hydroxyhydroquinon.
O
H+
(CH3CO)2O
- CH3COOH
OH
H
OCOCH3
OCOCH3
OCOCH3
OCOCH3
(CH3CO)2O , H+
- CH3COOH
OCOCH3
OCOCH3
OCOCH3
Cc cht c cu trc quinon thng c mu. Quinon l thnh phn cu to

c bn trong cc cht mu.
HO
HOOC
O
HO
O
COOH
Muscaruphyn
COOH
Lauson
Antraquinon
Vitamin K1 c thnh phn quinon.

O
Vitamin K1
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 C6H5CH2CH2Cl 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. H2/ Ni;
b. Zn/HCl;
c. NaBH4;
d. LiAlH4.
7. Vit phn ng ca Acetophenon vi cc cht sau:

a. PCl5;
b-Cl2/ nh sng;
c- Hn hp Br2, KOH, d-Semicarbazid.
8. Trnh by cc c ch ca cc phn ng sau:

HO- ac
a- Benzaldehyd
b- Acetaldehyd
HO - loang
c- p-Tolualdehyd
KCN
d- Benzaldehyd + Formaldehyd
HO-
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 Ni2+, Cu2+
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.
:O: ..
R C O
.. H
R_COOH
R_CO2H
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 sp2 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)
H
C O
O
H
Acid formic
Lin kt
di
Gc lin kt
gc
C=O
1,202
HC=O
124,1o
CO
1,343
OC=O
124,9o
CH
1,097
HC-O
111,0o
OH
0,972
HO-C
106,3o
trng thi rn, lng v trng thi hi, acid carboxylic tn ti dng dimer.
O ... H O
R C
O H ... O
C R
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 oc
t os
pKa
HCOOH
Acid formic
Acid metanoic
8.4
101
3,75
CH3COOH
Acid acetic
Acid etanoic
16,6
118
4,76
CH3CH2COOH
Acid propionic
Acid propanoic
-21,
141
4,87
CH3(CH2)2COOH
Acid butyric
Acid butanoic
-5
164
4,82
CH3(CH2)3COOH
Acid valeric
Acid pentanoic
-34
186
4,86
CH3(CH2)4COOH
Acid caproic
Acid hexanoic
-3
205
4,88
CH3(CH2)5COOH
Acid nantic
Acid heptanoic
-8
223
4,89
CH3(CH2)6COOH
Acid caprylic
Acid octanoic
17
239
4,90
CH3(CH2)7COOH
Acid pelagonic
Acid nonanoic
15
255
CH3(CH2)8COOH
Acid capric
Acid decanoic
32
270
CH3(CH2)10COOH
Acid lauric
Acid dodecanoic
44
299
CH3(CH2)12COOH
Acid myristic
Acid tetradecanoic
54
251
CH3(CH2)14COOH
Acid palmitic
Acid hexadecanoic
63
267
CH3(CH2)16COOH
Acid stearic
Acid octadecanoic
72
CH=CHCOOH
Acid acrylic
Acid propenoic
12,3
142
Acid metacrylic
Acid
2-methylpropenoic
CH2 C COOH
CH3
258
16
163
CH3
H
C C
CH3(CH2)7
CH 3(C H 2) 7
H
C C
Acid oleic
(CH2)7COOH
Acid E-2-butenoic
71,6
189
4,69
Acid
16.3
45
9.0
144
Z -9-octadekenoic
Acid elaidic
H
(CH 2) 7 COO H
Acid
E - 9-octadekenoic
Acid propiolic
Acid propinoic
Acid cyclopentan
COOH
Acid
cyclopentan
carboxylic
Acid
carboxylic
Acid benzoic
121
249
4,17
COOH
Acid
76,7
265
4,26
135
300
4,44
benzen
Acid phenylacetic
CH2 COOH
C6H5
pKa
COOH
HCCOOH
t os
Danh php
IUPAC
Acid crotonic
C C
t oc
Danh php
thng thng
Cng thc
2-phenyletanoic.
Acid cinnamic
COOH
C C
carboxylic
Acid-E-3phenylpropenoic
H
5
Acid 3-ethyl-4-methyl-hexanoic
Acid -ethyl - -methylcaproic
Acid 2-ethyl-3-methylpetancarboxylic
CH3 CH2 CH CH CH COOH
CH3 CH3 CH3
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
Acid cyclohexan carboxylic
CH3
COOH
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 + 2H2O
R_COOH + NH3
259
Phn ng xy ra khi c xc tc acid hoc base.

CH2CN + 2H2O
+
CH2COOH + NH4 HSO4-
H2SO4
100o, 3 gi
KOH
CH3 CH2 CH2 CH2CN + 2H2O
CH3 CH2 CH2 CH2COOK + NH4OH
3.2. Carboxyl ha hp cht hu c

3.2.1. Hp cht c kim tc dng vi kh CO2 to mui carboxylat
R MgX + CO2
R COOMgX
R Li + CO2
R COOLi
H2O
H2O
R COOH +
HOMgX
R COOH +
LiOH
3.2.2. Hydrocarbon thm tc dng vi phosgen COCl2

Thy phn acylclorid hnh thnh v thu c acid .
Ar H
Cl
Cl
ACl3
- HCl
Ar C
+ H2O
Cl
- HCl
Ar COOH
3.2.3. Natri alcolat tc dng vi carbon oxyd CO

RONa + CO
RCOONa
RCOOH
3.2.4. Carboxyl ho alken

CH2 CH2 + CO
1- Ni(CO)4
2- H2O
CH3 CH2 COOH
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 ROOCCH2COOR v dn xut R'X l nguyn liu c bn
iu ch acid carboxylic. Ester malonic ROOCCH2COOR l nguyn liu ph tr c
bn chuyn dn xut halogen R'X thnh R'CH2COOH.
R'X
R'CH2COOH
Phn ng xy ra nh sau:
Khi c xc tc base, ester malonic chuyn thnh tc nhn i nhn ROOCCHCOOR 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 2H5 O -
ROOCCHCOOR
+ C 2 H 5 OH
ROOCCHCOOR
ROOCCHCOOR + R'X
+X-
R'
H+
ROOCCHCOOR + 2H2O
R'
HOOCCHCOOH
R'
HOOCCHCOOH + 2ROH
R'
Decarboxyl hoa
R'CH2COOH
+ CO2
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.
H+
+ HOH
RCOOR'
RCOOH + R'OH
Thy phn ester trong mi trng kim (phn ng x phng ha) thu c
mui ca acid v alcol.
+ NaOH
RCOOR'
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.
O ... H O
R C
O H ... O
Dang dimer
C R
.
; .. H
R
C
H
...
C
R
O ...
H
O
R
C
...H
C
R
O ...
H
O
R
C
..
O.
Polymer dang thang
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:
max
CH3COOH
197 nm
60
CH3CHO
293 nm
12
Hp cht H
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.
..
OH
R C
..O H Acid
R C
O
O
R C
H
Aldehyd
Nhm carboxyl v gc R c nh hng qua li ln nhau.

C 4 loi phn ng c bn ca acid carboxylic nh sau:
O
1-
R C
Phn ng lm t lin kt OH l cc phn

ng: Phn ly acid, to mui vi kim loi v.v...
O H
O
2-
R C
Y-
262
O H
Phn ng vo nhm carboxyl: a s l nhng

phn ng vi tc nhn i nhn Y, lm t lin
kt COH
3-
Phn ng decarboxyl
O
R C
(tch nhm carboxyl)

O H
4-
Phn ng gc hydrocarbon bao gm nhng

phn ng th v tr v phn ng th vo
gc thm v phn ng cng.
O
R C
O H
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:
CH3COOH + H2O
+
CHCOO - + H3O
Ka =
- +
[CHCOO ][H]
= 1,8.10-5M
[CH3COOH]
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
V tr
Nhom the
CH3
OCH3
OH
Cl
NO2
Para
Meta
4,37
4,47
4,54
3,98
3,43
4,27
Orto
3,91
4,09
4,09
4,08
2,98
3,83
2,94
3,49
2,17
Ion RCOO- gi l ion carboxylat. S phn b mt in t trong ion

o
carboxylat ng u trn 2 nguyn t oxy v di C _O u bng 1,27A
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
+ H2
2 RCOOH + MgO
(RCOO)2Mg + H2O
RCOOH + NaOH
2 RCOOH + Na2CO3
RCOONa
2RCOONa
+ H2 O
+ H2O + CO2
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.
H O
- 2 - H2O
- H2O
H2O
-
H2O
-
H O
2
- -
H2O
-
-- H2O +
-- H O
2
H2O
H O
H2O - 2
- H2O
- H2O
Xa phong
tan trong nc
H2O -
Du m
khng tan trong nc
H2O -
- H2O
-- H O
2
Du m
b tan theo x phng
5.1.3. Tc dng vi diazometan to metylcarboxylat (RCOOCH3)

RCOOH + CH2N2
RCOOCH3 + N2
C ch phn ng:
O
R C O H
O ..
R C O
..:
+
CH2 N N :
CH3 N N:
+
O
.. R C O
..:
+
CH3 N N :
O
R C OCH3
: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.
O
R C O H
O
R C 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.
CH3CH2CH2COOH + NH3
Acid butanoic
CH3CH2CH2CO2 NH4+
Amoni butanoat
Di tc dng ca nhit , amoni butanoat b tch mt phn t nc to

butanamid.
CH3CH2CH2CO2 NH4+
Amoni butanoat
264
185o
CH3CH2CH2CONH2 + H2O
Butanamid
C ch chung:
OR C O H + NH
.. 3
+
O
R C O H
Cong ai nhan
OR C OH
NH3+
O O
+
R C OH2
R C NH2 + H2O
NH2 Tach nc
5.2.2. Tc dng vi LiAlH4 to alcol bc nht.

RCOOH + LiAlH4 RCOOLi + H2 + AlH3
R COOLi
LiAlH4
H
H
H
+
H
LiAlH4
LiAlH4
H3O
R C OLi
R C O
R C OH
R C OLi
H
H
OLi
CH3O
COOH
H4LiAl
H2O
Ether
H2SO4
CH3O
CH3O
CH2OH
CH3O
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.
R COOH + R' OH
H+
R COOR' +
H2O
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:
OH +
H+
R C OH +
Xuc tac acid
OH +
R C OH +
R C OH
..
R' OH
..
Cong ai nhan
OH
R C OH
OH
OH
R C OH
R C OH
HOR'
+
OR'
+ H+
..
: OH
+ OH
+ Tach nc
R C OH2
R C
OR'
OR'
+ H+
OR'
+ OH
O
R C
R C
OR'
OR'
Esther
+ H2O
H+
Xuc tac
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.
+
OH
16
CH3 C OH +
18
CH3 OH
..
18
CH3 C OCH3
Ester co oxy 18
Cong ai nhan
16
+ H2O
Phn ng th nhm OH ca acid bng cc halogen

Acid tc dng vi thionylclorid SOCl2, phosphorpentaclorid PCl5, phosphor
tribromid PBr3 to ra sn phm acylhalogenid RCOX (X= Cl, Br).
O
O
C OH + Cl S Cl
Thionyl clorid
CH3
CH3 C Cl + HCl + SO2

Acetyl clorid
O
C Cl + HCl + POCl3
+ PCl5
C OH
Benzoyl clorid
Phosphor pentaclorid
O
3
C OH
+ PBr3
C Br + H3PO3
Phosphos tribromid
Benzoyl bromid
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 H2 v CO2 hoc H2O v CO ty iu kin phn ng.
Tia t ngoai
HCOOH
H2 + CO2
Os
HCOOH
H2SO4 ac
H2O + CO
Acid acetic kh b decarboxyl. Mui acetat b decarboxyl ha nhit cao:

CH3COONa + NaOH
CH4 + Na2CO3
Dn xut th ca acid acetic c nhm ht in t d b decarboxyl ha nh:

Cl3CCOOH;
V d:
266
O2NCH2COOH; NCCH2COOH; CH3COCH2COOH

CH3COCH2COOH CH3COCH3 + CO2
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.
C6H5CH2COOAg + Br2
CCl4
76oC
C6H5CH2Br
CO2 + AgBr
CO2
C th thay i Ag bng thy ngn.

H
COOH
+ HgO + 2 Br2
Br
+ HgBr2 + H2O
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_CH2_CH2_COOH
Enzym
R_CO_CH2_COOH
Acid
oxo carboxylic
Cht oxy ha l SeO2 to acid -oxocarboxylic
R_CH2_CH2_COOH + SeO2
R_CH2_CO_COOH + H2O + Se
Acid
oxo carboxylic
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 .
R CH2 COOH + Br2
R CHBr COOH
Br2
P
R CBr2 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 .
CH3_CH2_CH2_COOH
Cl2
CH3_CH2_CHCl_COOH 5%
CH3_CHCl_CH2_COOH 64%
CH2Cl_CH2_CH2_COOH 31%
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
HNO3, H2SO4
to
NO2
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
CH2
CH
COOH + Br2
CH2Br
CHBr
COOH
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.
CH3
CH3C = CH_CH2_COOH
acid 4-methyl-3- pentenoic
CH3
CH3CH _ CH = CH_COOH
acid 4-methyl-2- pentenoic
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
CH2 = CH_CH2_Cl
Allylclorid
CuCN
CH2 = CH_CH2_CN
dd HCl
CH2 = CH_CH2_COOH
Acid vinyl acetic (52-62%)
(Acid 3-butenoic)
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
CH3
PBr3
CH3(CH2)9CH _COOH
Br2
CH3
CH3(CH2)9CBr _COBr
CH3OH
(CH3)3COK
(CH3)3COH
CH3
CH3(CH2)9C _COOCH3
Br
Quinolin
160-170o
CH2
CH3
CH3(CH2)9C _COOC(CH3)3 CH3(CH2)8CH = C _COOCH3
ddKOH
ddKOH
H+
H+
CH3
CH3(CH2)8CH = C _COOH
(68-83%)
CH2
CH3(CH2)9C _COOH
Acid 2-methyl-2- dodekenoic
Acid 2- decyl propenoic
Nhn xt:
Cc base (CH3OK; 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 CH2
=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.
CH3CH=CH2 + 3 O2 + 2NH3
450o
Xuc tac
2 CH2=CH_CN + 6 H2O
Cc ester cha no c nhiu trong thin nhin. Cc acid cha no thng gp:
Acid Oleic
CH3(CH2)7CH=CH(CH 2)7COOH
Acid Ricinoleic
CH3(CH2)5CHOHCH 2CH=CH(CH 2)7COOH
Acid Linoleic
CH3(CH2)4CH=CHCH 2CH=CH(CH 2)7COOH
Acid Linolenic
CH3CH2CH=CHCH 2CH=CHCH 2CH=CH(CH 2)7COOH
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.
CH3CH2CH2COOH pKa= 4,82
CH3CH=CHCOOH pKa= 4,6
269
Phn ng to lacton l phn ng ng vng to ester ni phn t.
CH2 CH CH2
CH2 C
CH2
+ H+
OH
CH2
CH2
+
CH3 CH .. C O
HO
CH3 CH
CH2
C O
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
HOOC_COOH
HOOC_CH2_COOH
HOOC_(CH2)2_COOH
HOOC_(CH2)3_COOH
HOOC_(CH2)4_COOH
HOOC_(CH2)5_COOH
HOOC_(CH2)6_COOH
HOOC_(CH2)7_COOH
HOOC_(CH2)8_COOH
HOOC
H
HOOC
H
C C
C C
tco
pKa1
pKa2
Acid Oxalic, Etandioic
189,5
1,27
4,27
Acid Malonic, Propandioic
135,6
2,86
5,70
Acid Succinic, Butandioic
185.
4,21
5,64
Acid Glutaric, Pentandioic
97,5
4,34
5,27
Acid Adipic, Hexandioic
153
4,41
5,28
Acid Pimelic, Heptandioic
104
Acid Suberic, Octandioic
142
Acid Azelaic, Nonandioic
106
Acid Sebacic, Decandioic
134
Acid Maleic z-2-Butendioic
137
1,92
6,23
Acid Fumaric, E-2-Butendioic
287
3,02
4,38
Acid Phtalic,
1,2-Benzendicarboxylic
208
2,58
5,62
Acid Isophtalic,
346
Acid Terephtalic,
300
Tn gi
COOH
H
H
COOH
COOH
COOH
COOH
COOH
COOH
HOOC
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.
KOH
- H2O
COOH
COOH
C2H5OH, H+
- H2O
COOH
KOH
COOK
- H2O
COOK
COOK
COOC2H5
C2H5OH , H+
COOH
- H2O
COOC2H5
COOC2H5
Diethyl ftalat
Acid oxalic v acid malonic d b decarboxyl to acid n chc.
to
HOOC_COOH
HOOC_CH2_COOH
HCOOH + CO2
to
CH3_COOH + CO2
Diacid d to thnh anhydrid vng.

O
CH2
CH2
COOH
CH2
CH2
COOH
C
O
H2O
O
Anhydrid Succinic
Acid Succinic
COOH
O
O
COOH
H2O
O
Anhydrid Ftalic
Acid Ftalic
Bi tp
1. Gi tn cc cht sau theo danh php IUPAC:
a- ClCH2CH2CH2CH2COOH
c- CH3CH2CH(CH3)CH2CHCOOH
b- (CH3)3CCH2CH2CH2COOH
d- CH2=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- (CH3CH2CH2)3CBr
b-HOCH2CH2CH2CH2CH2CH2Br
c- CH3CH2CH2CH2CH=CH2
(CH3CH2CH2)3CCOOH
HOCH2CH2CH2CH2CH2CH2COOH
CH3CH2CH2CH2CH2COOH
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 H2SO4 m c.
c. Phosphor pentaclorid.
b - Thionyl clorid.
d- Phosphor tribromid.
6. Trnh by c ch phn ng ester ha.

CH3COOH + C2H5OH
272
H2SO4
CH3COOC2H5 + H2O
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.
R C
OH
Acid carboxylic
R C
Y
Dan xuat cua acid carboxylic
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
R C
Halogenid acid
Hal
(F , Cl, Br , I)
R C O
R C
R C
Loi dn xut acid
Anhydrid acid
Acid Hydroxamic
NHOH
Azid
Cng thc
R C
R C
R C
Loi dn xut acid
Ester
OR'
Amid
NR2
Hydrazid
NH NH2
R_CN
Nitril
N3
O
R C O OH
Peroxyacid
R
R
C C O
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
o
H
C
O
CH3 Methyl formiat
di lin kt (A )
Gc lin kt ()
C=O.............1,200
H_C=O.........124,95
C(=O)_O.......1,344
O_C=O.........125,87
C(H3)_O.......1,437
H_C_O.........109,78
C(=O)_H.......1,101
CH3_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
O
Goc alkyl cua alcol
R C O R'
Alkylcarboxylat
O
CH3 C O CH2CH3
Ethyl acetat
Ethyl etanoat
CH3 O
CH3 CH C O CH(CH3)2
Isopropyl isobutyrat
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
tco
tso
d20
4
HCOOCH3
Methylforniat
- 99,9
31,5
0,975
HCOOC2H5
Ethylformiat
- 80,5
54,3
0,917
CH3COOCH3
Methylacetat
- 98,1
57,1
0,924
CH3COOC2H5
Ethylacetat
- 83,6
77,1
0,901
CH3COOC3H7n
n-Propyl acetat
- 92,5
101,6
0,887
CH3COOC4H9
Butyl acetat
-76,8
126,5
0,882
CH3COOC5H11
Amylacetat
-78,5
142,6
0,871
CH3CH2CH2COOCH3
Methylbutyrat
-95,5
102,3
0,898
CH3(CH2)14COO(CH2)15CH3
Cetylpalmitat
55,5
0,832
C6H5COOCH3
Methylbenzoat
- 12,5
199,6
1,094
C6H5COOC2H5
Ethylbenzoat
- 34,6
212,6
1,051
C6H5COOC6H5
Phenylbenzoat
70,0
314,0
1,235
Dimethyl oxalat
- 54,0
163,8
1,148
Diethyl oxalat
- 40,6
185,4
1,078
Dimethyl malonat
- 62,0
181,0
1,151
Dimethyl succinat
19,5
192,8
1,120
Dimethyl ftalat
49,5
COOCH3
COOCH3
COOC2H5
COOC2H5
CH2(COOCH3)2
CH2COOCH3
CH2COOCH3
o-C6H4(COOCH3)2
1.3. Phng php iu ch

1.3.1. Phng php ester ha. Xem phn alcol v acid.
RCOOH + R'OH
CH3COOH
H2SO4
+ C2H5OH
RCOOR' + H2O
H2SO4
CH3COOC2H5
+ H2O
Phn ng iu ch ester ethylacetat l phn ng thun nghch c hng s

cn bng:
K=
[CH3COOC2H5][H2O]
= 4
[CH3COOH] [C2H5OH]
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
CH3COOH v C2H5OH 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 H2SO4 m c, HCl khan...
1.3.2. Acyl ha alcol bng anhydrid acid. Xem phn alcol
ROH + (R'CO)2O
RCOOR' + R'COOH.
1.3.3. Acid carboxylic tc dng vi diazometan. Xem phn acid.

RCOOH + CH2N2
RCOOCH3 + N2
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' +
H2O
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
+OH
CH3
CH3 C
+ H+
O C CH3
CH3
+
OH
CH3
CH3 C
CH3
CH3
+C CH
3
CH3
CH3
HO C CH3
CH3
CH3
O C CH3
CH3
OH
CH3 C O : C CH3
H2O
CH3 C
CH3
+C CH
3
CH3
+ H+
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
O
OR'
+ HO -
O
R C
R C
OR'
R C
: OR'
OH
OH
O
R C
R'O -
OH
R'O -
R C
O-
OH
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.
O
R C
O R'
+ R"OH
H+
O
R C
CH2=CH_COOCH3 + C4H9OH
O R" + R'OH
CH3C6H4SO3H
CH2=CH_COOC4H9 + CH3OH
277
1.5.3. Phn ng vi amoniac v mt s dn xut ca amoniac

RCOOR'
Ester
RCO_NH2
NH3
R'OH
R'OH
RCO_NH_NH2 +
R'OH
Amoniac
RCOOR'
Amid
HNR"2
RCO_NR''2
Amin
Amid th
+ H2N_NH2
RCOOR'
Hydrazid
Hydrazin
RCOOR'
RCO_NHOH
+ H2NOH
R'OH
Acid hydroxamic
Hydroxylamin
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 LiAlH4, NaBH4 v hn hp Na + alcol (phn ng Buve Blanc) to ra alcol bc nht.
R COOR'
4[H]
R CH2OH + R'OH
Na+ C2H5OH
CH3(CH2)7CH=CH(CH2)7COOC4H9
CH3(CH2)7CH=CH(CH2)7CH2OH + HOC4H9
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.
O
R C
R'
OC2H5
H CH
COOC2H5
NaOC2H5
O
R C
R'
CH
COOC2H5 + C2H5OH
Cc ester ca acid bo vi glycerin gi l cht bo (lipid).

R1CO
OCH2
R1CO
OCH2
R1CO
OCH2
HOCH
R2CO
OCH
R2CO
OCH
HOCH2
R3CO
OCH2
HOCH2
Monoacylglycerin
Monoglycerid
278
Diacylglycerin
Diglycerid
Triacylglycerin
Triglycerid
R1, R2, R3 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
CH2(CH2)10COOH,
Acid palmitic
CH3(CH2)14COOH
Acid stearic
CH3(CH2)16COOH;
Acid oleic
CH3(CH2)7CH=CH(CH2)7COOH,
Acid linoleic
CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH,
Acid linolenic CH3CH2CH=CHCH2CH=CHCH2CH=CH(CH2)7COOH

Acid stearolic CH3(CH2)7CC(CH2)7COOH,
CH2 O CO(CH2)14CH3
CH2 O COR1
CH O CO(CH2)14CH3
CH O COR2
O
+
CH2 O P OCH2CH2N(CH3)3
OPhospholipid
Lecitin
CH2 O CO(CH2)14CH3
Lipid
Tripalmitatglicerin
2. Anhydrid acid
Hai phn t acid b loi nc to thnh anhydrid acid. Cng thc chung:
O
R C
OH
OH
R C
O
Acid
O
R C
O
R C
O
Anhydrid acid
Anhydrid acid ht nc to thnh acid. ng dng iu ch anhydrid acid.
CH2 C
OH
OH
CH2 C
O
Acid succinic
CH2 C
+ (CH3CO)2O
Anhydrid acetic
CH2 C
O
O
+ 2 CH3COOH
O
Anhydrid succinic
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

Tn gi
tco
t so
(CH3CO)2O
Anhydrid acetic
-73,0
139,6
(C2H5CO)2O
Anhydrid propionic
-45,0
168,0
(C3H7CO)2O
Anhydrid n-butyric
-75,0
198,0
(n-C4H9CO)2O
Anhydrid n-valeric
(n-C17H35CO)2O
Anhydrid stearic.
Cng thc
CH2
CH2
218,0
72,0
O
O
Anhydrid succinic
119,6
261,0
(C6H5CO)2O
Anhydrid benzoic
42,0
360,0
O
C
Anhydrid phtalic
132,0
Anhydrid maleic
53,0
284,0
O
C
CH
O
CH
Anhydrid acid l tc nhn acyl ha.

NH2
NHCOCH3
+ (CH3CO)2O
+ CH3COOH
Acetanilid
3. Ceten (CH2 = C = O)
C th xem ceten l anhydrid acid khi phn t acid b loi mt phn t nc.
CH2 C
H
CH2 C
OH
Ceten
Acid
CH3 CH C
Methylceten
280
CH3
CH3
+ H2O
C C
Dimethylceten
R CH C
Alkylceten
R'
C C
Dialkylceten
Cc phn ng ca ceten
Cc ceten nh l mt tc nhn acyl ha.
..
O
..
CH2 C
CH2
+
C
.. O
..:
H+
CH2
+
C
..
OH
..
B-
CH2 C
..
OH
..
B
..
CH3 C
O..
B
B l nhng cht i nhn nh H2O, alcol, acid, amoniac.

H2O
CH2 C
CH3 C
ROH
CH3 C
RCOOH
CH3 C
R C
NH3
CH3 C
Acid
OH
O
OR
Ester
O
O
Anhydrid acid
O
O
NH2
Amid
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:
.. : O:
..
:O
CH3
..
Cl
.. :
CH3
+
Cl
.. :
Acetyl clorid
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
O
CH3
Cl
di lin kt
Gc lin kt
C=O........ 1,192
C_C=O......127,08o
C_C..........1,499
C_C_Cl......112,66o
C_Cl.........1,789
O=C_Cl......120,26o
C_H..........1,083
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
CH3COCl
Acetyl clorid,
Etanoyl clorid
CH3CH2COF
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 oc
t os
Acetylflorid, Etanoylflorid
CH3COF
20,5
0,993
Acetylclorid, Etanoyl clorid
CH3COCl
52,0
1,104
Acetylbromid, Etanoyl bromid
CH3COBr
76,7
1,520
Cloroacetylclorid
CH2ClCOCl
105,0
1,495
Propionylclorid
CH3CH2COCl
80,0
1,065
n-Butyrylclorid
CH3CH2CH2COCl
102,0
1,028
Isobutyrylclorid
(CH3)2CHCOCl
92,0
1,017
n-Valerylclorid
CH3CH2CH2CH2COCl
128,0
1,016
Isovalerylclorid
(CH3)2CHCH2COCl
113,0
n-Caproylclorid
n-C5H11COCl
153,0
Caprylclorid
CH3(CH2)6COCl
196,0
0,975
Stearylclorid
CH3(CH2)16COCl
215,0
Benzoylclorid
C6H5COCl
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
O
O
R C Cl
+ H2O
R C OH
+ HCl
4.3.2. Tc dng vi hp cht c kim to ceton hoc alcol bc ba

O
R C Cl
R'MgX
O
R C R'
OMgX
R'MgX
R C R'
R'
H2O
OH
R C R'
R'
4.3.3. Hp cht halogenid acid l tc nhn acyl ha to ceton,ester

O
+
R C Cl
O
R'OH +
282
R C Cl
AlCl3
C R
+ HCl
O
R C OR' + HCl
5. Amid
Thay th nhm OH ca acid carboxylic bng nhm NH2 thu c amid.
O
R C OH
Acid
R C NH2
R'
R C N R"
Amid the
R C NHR'
Amid
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 CONH2 cn c gi l carboxamid
O
H C NH2
CH3 C NH2
Formamid
Acetamid
Metanamid
Etanamid
Metan carboxamid
CH3CH2 C NH2
H C N(CH3)2
CH3CH2CH2 C NHCH3
Propionamid
N,N-Dimethylformamid N-Methylbutyramid
Propanamid
N,N-Dimethylmetanamid N-Methylbutanamid
Etancarboxamid
1-Propan-N-methylcaboxamid
CONH2
CONH2
CH2 CH
CONH2
CONH2
Acrylamid
Benzamid
Benzencarboxamid
Cyclohexancarboxamid
3-Cyclopentencarboxamid
Etencarboxamid
Trong bng 21-7 trnh by mt s amid.

Bng 21.7: Tn gi, cng thc ca mt s amid
Tn gi
t oc
Cng thc
n-Valeramid
n-C4H9CONH2
106
n-Caproamid
n-C6H11CONH2
101
Steramid
C17H35CONH2
109
Benzamid
C6H5CONH2
130
Cinnanamid
C6H5CH=CHCONH2
Succinamid
H2NCOCH2CH2CONH2
260
Cc amid th lng c nhit si cao v c lin kt hydro gia cc phn t.

...
O
C NH2
CH3
...
C NH2 ... O
CH3
C NH2 ... O
CH3
Lien ket hydro cua amid
C NH2 ...
Cng thc
tso
CH3_CONH2
221
CH3_CONHCH3
204
CH3_CON(CH3)2
165
CH3
283
Cp in t trn nit lin hp vi lin kt ca nhm C = O nn tnh base

ca nhm NH2 gim.
O
-O
..
+
R C NH2
R C NH2
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.
..
O
..
+ H+
..
R C
..
R C
NH2
..
+
OH
R C
NH2
OH
..
NH2
+
Amid l mt acid yu. Amid tc dng vi natri hoc natri amidid trong ether
to mui.
..
R C
O
..
..
+ Na
..
R C
NH2
..
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.
RCONH2 + H2O
RCOOH + NH3
5.2.3. Phn ng loi nc

Di tc dng ca cc cht ht nc nh P2O5 v nhit , amid b loi nc
to thnh nitril (RC N)
O
(CH3)2CH C NH2
Isobutyramid
P2O5
200 _ 220oC
(CH3)2CH C N + H2O
Isobutyronitril
5.2.4. Khi c nhit cc amid ca diacid d to thnh imid

C
CH2 CONH2
CH2
Succinamid
Succinimid
CH2 CONH2
284
CH2
Nhiet
NH
O
CONH2
Nhiet
O
NH
CONH2
Phtalamid
C
Phtalimid O
5.2.5. Chuyn v Hofmann

Amid tc dng vi hn hp Br2 + NaOH to thnh amin.
O
2R NH2 + CO3 + Br Amin bac nhat
R C NH2 + OBr Amid
C ch phn ng:
O
R C NH2
Amid
O
2NaOH + Br2
O
+ OBr -
..
+ OH
..
R C N
.. Br + H2O
..
R C N
.. Br
..
..
R C N Br
H
R C N Br + OH
NaOBr + NaBr + H2O
..
+ Br -
R C N
.. +
R: C N
.. +
O=C=N_R
Chuyen v
Isocyanat
O=C=N_R + 2OH
Isocyanat
2R NH2 + CO3
Amin bac nhat
V d:
CH3CONH2 + 2NaOH + Br2
CH3NH2
C6H5CONH2 + 2NaOH + Br2
C6H5NH2 + Na2CO3 + NaBr + H2O
C6H5CH2CONH2 +2NaOH+Br2
C6H5CH2NH2 + Na2CO3 + NaBr +H2O
+ Na2CO3 + NaBr + H2O
5.2.6. Kh ha amid bng LiAlH4, NaBH4 to thnh amin

R C
4H [LiAlH4]
NH2
R CH2 NH2
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
CH3_CN
CH3CH2_CN
C6H5_CN
CH2=CH_CN
Etannitril
Propannitril
Propennitril
Acetonitril
Propionitril
Benzonitril
Acrylonitril
Methylcyanid
Ethylcyanid
Phenylcyanid
Vinylcyanid
C N
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 P2O5

R_CONH2
R_CN + H2O
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.
CH3 C N
+ H2O
O
CH3 C NH2
+ H2O
- NH3
O
CH3 C OH
Kh ha nitril
Kh bng LiAlH4, NaBH4 hoc natri trong alcol to thnh amin bc nht
R C N
4H [LiAlHl4]
R CH2 NH2
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.
N
Ar
3 Ar C N
Arylcyanid
286
Ar
N
Ar
2,4,6-Triaryl-1,3,5-Triazin
Bi tp
1. T cc acid sau:
a- CH3CH2CH2CH2CH2COOH
b- (CH3)2CHCH2CH2COOH
c- CH2=CHCH2CH2COOH
d- BrCH2CH2COOH
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. (CH3)2CHCH2CH2COOCH2CH(CH3)2
b. (CH3)3CCH2CH2CON(CH2CH3)2
c. (CH3CH2CH2CO)2O
d C6H5CH2CN
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
NH3
RNH2
R2NH
Nc
H2O
ROH
R2O
R3 N
R l gc alkyl hoc aryl - Ar
1.1. Phn loi amin

Amin bc nht: C mt gc hydrocarbon lin kt vi nguyn t nit: RNH2
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:
R4 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 sp3 v to
thnh 3 lin kt (sp3_s) gia 3 orbital sp3 ca nit vi orbital s ca 3 nguyn t
hydro. Cp in t khng lin kt nm trn orbital sp3 th t. Cc amin cng c
cu to nh th.
..
..
..
..
Amoniac
288
R'
Amin
R''
R
R'
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 sp2.
..
..
N
C2H5
C2H5
CH3
N
H
Ethylmethylamin
CH3
H
C2H5
CH3
..
Ethylmethylamin
Trng thi chuyn tip
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
CH3NH2
(CH3CH2)2NH
Methylamin
Diethylamin
Metanamin
N-Ethyletanamin
CH2CH3
CH2CH3
C6H5
CH3
Diethylmethylamin
N-Methyl,N-Ethyletanamin
CH2CH3
C6H4CH3 p
Ethyl, phenyl,p-tolylamin
N-Ethyl,N-p-Tolylbenzenamin
2.2. Theo danh php IUPAC

Gi tn hydrocarbon tng ng v thm tip v ng amin
Tn hydrocarbon tng ng + amin
NH2
N(CH3)2
NH2
CH3
Benzenamin
N,N-Dimethylbenzenamin
4-Methylbenzenamin
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
CH3NH2
Aminometan
CH2=CHCH2NH2
3-Amino-1-propen
CH3CH2N(CH3)2
C6H5NHCH3
Dimethylaminoetan Methylaminobenzen
289
Ch c tn cc gc:
C6H5NH_
CH3(C2H5)N_
- C10H7NH-
p-CH3C6H4NH-
-Naphtylamino
Phenylamino Methylethylamino p-Toluylamino
S dng tip u ng amino gi tn nhng hp cht c nhm chc amin.

NH2
COOH
NH2
NH2
CH3
SO3H
Acid Sulfanilic
Acid p-Aminobenzensulfonic
p-Toluidin
p-Aminotoluen
Acid p-Aminobenzoic
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.
NH2
NH2
N(CH3)2
Br
m-Bromoanilin
Anilin
N,N-dimethylanilin
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 SN2.
CH3CH2Br + NH3
+ CH3CHNH3Br
+ NaOH
-NaBr -H2O
CH3CH2NH2
Trong thc t thng thu c hn hp cc amin c bc khc nhau.

RX + NH3
-HX
RNH2
RX
-HX
RNHR
RX
-HX
(R)3N
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.
-+
Cl NH2CH2C6H5
NH2
+ C6H5CH2Cl
Anilin
290
Benzylclorid
NHCH2C6H5
NaHCO3
-NaCl -CO2 -H2O
Benzylphenylamoniclorid
Benzylphenylamin
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:
C
C
O
N H
O
Phtalimid
+ NaOH
- H2O
O
N
+ R_X
-X-
C
C
O
NR
H2O
HO -
COO COO -
O
Alkylamin
Alkylphtalimid
Ion phtalimid
R_NH2 +
Ion phtalat
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.
ArNO2 + 3Fe + 6HCl
CH3
ArNH2 + 3FeCl2 +2H2O

CH3
NO2
+ 3H2 / Ni
Ap suat, to
CH(CH3)2
2-Nitro-5-isopropyltoluen
NH2
+ 2H2O
CH(CH3)2
2-Methyl-5-isopropylanilin
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 LiAlH4
trong mi trng ether to amin bc nht.
H2 / xc tc
RC N
hoc LiAlH4
RCH2 NH2
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.
RCHO + NH3
RCH=NH
Aldimin
+ 2H2
RCH=NH + H2O
xc tc
RCH2 NH2
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 (RCONH2)
Kh ha hp cht amid bng LiAlH4 thu c amin.
RC
O
NH2
+ LiAlH4
H O
C N(CH3)2
R CH2NH2 + H2O
+ Al3+ + Li+
+ LiAlH4
N,N-Dimethylcyclohexancarboxamid
+ ...
CH2 N(CH3)2
+ ...
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.
CH3(CH2) 8CONH2 + Cl2 + HO- CH3 (CH2) 8NH2 + CO2 + 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

Tn gi
tc
ts
CH3NH2
Methylamin
- 92,5
- 6,5
10,62
(CH3)2NH
Dimethylamin
- 96,0
7,4
10,77
(CH3) 3N
Trimethylamin
- 124,0
3,5
9,80
CH3CH2NH2
Ethylamin
- 80,6
16,6
10,63
(CH3CH2)2NH
Diethylamin
- 50,0
55,8
10,93
(CH3CH2)3N
Triethylamin
- 11,5
89,5
10,87
CH3CH2CH2NH2
Propylamin
- 83,0
48,7
10,58
C6H5NH2
Anilin, aminobenzen
6,2
184,4
4,58
C6H5NHCH3
N-Methylanilin
- 5,7
196,3
4,85
C6H5N(CH3)2
N,N-Dimethylanilin
o-CH3C6H4NH2
o-Toluidin,
Cng thc
pKa
2,5
192,5
5,06
- 27,7
199,7
4,39
- 43,6
203,2
4,69
43,7
200.4
5,12
185,0
54,0
302,0
50,0
301,0
50,0
306,0
2-Aminotoluen
m-CH3 C6H4NH2
m-Toluidin,
3-Aminotoluen
p-CH3C6H4NH2
p-Toluidin,
4-Aminotoluen
C6H5CH2NH2
Benzylamin
-Aminotoluen
C6H5NH C6H5
Diphenylamin
-Naphtylamin
NH2
1-Aminonaphtalen
NH2
-Naphtylamin
2-Aminonaphtalen
Trong dung dch nc cc amin c cn bng nh sau:

RNH2 + H2O
Kb =
+
Kb
RNH3 + HO -
+
RNH3 + H2O
+
[RNH3][HO -]
[RNH2]
Ka =
Ka RNH + H O +
2
3
+
[RNH2][H3O ]
+
[RNH3]
C mi quan h Ka.Kb = 1O-14 v pKa + pKb = 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
Acid lin hp A
pKb, 25C
pKa, 25C
NH3
4,76
NH4+
9,24
CH3NH2
3,38
CH3NH3+
10,62
CH3CH2NH2
3,36
CH3CH2NH3+
10,64
(CH3)3CNH2
3,32
(CH3)3CNH3+
10,68
(CH3) 2NH
3.27
(CH3)2NH2+
10,73
(CH3CH2)2NH
3,06
(CH3CH2)2NH+
10,94
(CH3)3N
4,21
(CH3)3NH+
9,79
(CH3CH2)3N
3,25
(CH3CH2) 3NH+
10,75
Cc arylamin c tnh base yu hn tnh base ca alkylamin.

Trong dung dch nc c cn bng:
+
NH3
+
NH2
H2O
Ka = 2,5 . 10-5 M.
+
(CH3)2CHNH3 + H2O
+
H3O
pKa= 4,6
+
(CH3)2CHNH2 + H3O
Ka = 2,5 . 10-12 M.
pKa= 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:
..
NH2
+
NH2
+
NH2
+
NH2
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 -C6H4NH3+

pKa, 25C
Nhm th X
Orto
meta
para
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
3,20
2,75
Trifluoromethyl
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 RCONH2.
to
RNH2 + R'COX
R'CONHR
NH2
+ CH3COOH
Anilin
2 CH3NH2
O
CH2 CH C Cl
Acryloylclorid
NH2
C2H5O
p-Phenetidin
p-Etoxyanilin
+ CH3COONa
HCl
to
HX
; X = H , Halogen , RCOO NHCOCH3
+ H2O
Acetanilid (N-phenylacetamid)
O
+
CH2 CH C NHCH3 + CH3NH3Cl
N-Methylacryloamid Methylamin clorhydrat
(CH3CO)2O
NHCOCH3
C2H5O
Phenacetin
p-Etoxyacetanilid
295
6.2. Phn ng vi acid nitr (HNO2)

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 N2. Tng qut nh sau:
- 2H2O
+
RN N Cl RNH2 + O=N_ONa + 2HCl
- NaCl Mui diazoni
Amin bc nht
H2O
ROH + N2 +HCl
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 ( NaNO2 + 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, N2,
alken v alkyl halogen. V d phn ng sau:
CH3(CH2)3NH2
NaNO2
HCl
CH3(CH2)3OH + CH3CH2CHOHCH3+ CH3(CH2)3Cl + CH3CH2CHClCH3

5%
3%
25%
13%
CH3
CH3
CH3
H
+
C C
+ CH3CH2CH=CH2 +
C C
+ N2
H
H
H
CH3
26%
3%
7%
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 N2 v carbocation
CH3(CH2)3NH2 + NaNO2 + 2HCl
+
CH3CH2CH2CH2N
Muoi diazoni
N Cl -
+
CH3CH2CH2CH2N N Cl + 2H2O +NaCl
Butandiazoniclorid
+
CH3CH2CH2CH2 + Cl- + N2
Carbocation
-
Carbocation CH3CH2CH2CH2+ tc dng vi Cl to CH3CH2CH2CH2Cl v tc

dng vi H2O to CH3CH2CH2CH2OH hoc chuyn v to carbocation bc hai
CH3CH2CH+CH3.
+
CH3CH2CH2CH2
+
CH3CH2CHCH3
Carbocation tc dng vi Cl- to CH3CH2CHClCH3 hoc vi H2O to

CH3CH2CHOHCH3 hoc tch loi H+ v to 2-buten dng cis v trans.
296
Cl-
CH3CH2CHClCH3
H2O
CH3CH2CHOHCH3 + H+
+
CH3CH2CHCH3
CH3
H
C C
CH3 CH3
H
+ H+
+
C C
H
CH3
H
Amin thm bc nht tc dng vi acid nitr to mui diazoni t < 5C.
Ar_NH2 + NaNO2 + 2HCl
+
Ar_N
Amin thm bac nhat
Muoi arendiazoniclorid
N Cl -
+ 2H2O + NaCl
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
Ar
R
Ar
N H + O=N_ONa + HCl
N N O + NaCl + H2O
Hp cht nitroso amin
Amin bc hai
N
H + HO_N=O
Piperidin
N
N=O + H2O
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.
(CH3)2N
+ HO_N=O
(CH3)2N
N=O + H2O
p-Nitroso-N,N-dimethylanilin
N,N-Dimethylanilin
6.3. Phn ng vi arylsulfonylclorid to sulfonamid

Amin c bc khc nhau tc dng vi arylsulfonylclorid ArSO2Cl 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).
RNH2
Amin bc nht
ArSO2Cl
Arylsulfonylclorid
ArSO2NHR + HCl
Arylsulfonamid
297
Amin bc hai to sn phm khng tan trong kim.

Ar'
Ar'
N
Ar SO2
H + Ar SO2Cl
+ HCl
AR''
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.
R NH2
Amin
+ X2
Na2CO3,H2O
- HX
+ X2
R NH X
- HX
N-Halogen alkylamin
R N
X
N,N-Dihalogen alkylamin
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.
[O]
RCH2 NH2
H2SO5
Amin
RCH2_NH_OH
N-Alkylhydroxyl amin
RCH=N_OH
Oxim
RCH2_N=O
Nitroso alkan
RCH2_NO2
Nitroalkan
Amin mch thng bc hai b oxy ho to N,N-dialkylhydroxylamin.

R
R
N H
[O]
R
R
N OH
Amin mch thng bc ba b oxy ha to N -oxyd amin
298
R
+
R" N O -
[O]
R" N
R'
H 2 O2
R'
N-oxyd amin bac 3
CH3COOH
Pyridin
+ N O
N-Oxyd pyridin
Amin thm bc nht b oxy ha bng acid permonosulfuric (acid Caro

HOOSO3H) to hp cht nitrosoaren Ar N = O. Anilin b oxy ha bng dung dch
KMnO4 hoc bicromat kali K2Cr2O7 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.
NH2
NH2
Br
Br
+ 3 Br2
+ 3HBr
Br
2,4,6-Tribromanilin
Anilin
Chc amin quyt nh s nh hng vo nhn thm.

NH2
Br
NH2
+ 3 Br2
COOH
Br
Acid m-aminobenzoic
NH2
+ 3HBr
COOH
Acid 3-amino-2,4,6-tribromobenzoic
COOH
Cl
NH2
+ 3 Cl2
Acid antranilic
Br
COOH
+ 3HCl
Cl
Acid 2-amino-3,5-diclorobenzoic
Nitro ha amin thm bc ba cho hiu sut cao trong mi trng acid acetic.
N(CH3)2
HNO3
CH3COOH
N,N-Dimethylanilin
N(CH3)2
NO2
N(CH3)2
+
2-Nitro-N,N-Dimethylanilin
N(CH3)2
NO2
NO2
NO2
2,4-Dinitro-N,N-Dimethylanilin
p dng phn ng Vilsmeier a chc aldehyd vo amin thm bc ba.
299
N(CH3)2
N(CH3)2
1-POCl3
HCON(CH3)2
Dimethylformamid
2-H2O
CHO
p-Dimethylaminobenzaldehyd
DMF
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.
NH2
NHCOCH3
CH3COOH
CH3
Br2
CH3COOH
CH3
4-Methylanilin
NH2
NHCOCH3
Br
HCl
NaOH
Alcol
CH3
Br
CH3
2-Brom-4-methylanilin
6.7. Tch loi nhm amin - Phn ng tch loi Hofmann

Amin n gin RNH2 khng b tch loi chc amin. Chuyn amin v dng
hydroxy amoni bc 4 [(R)4N]+OH. Di tc dng ca nhit , hydroxy amoni bc
4 b nhit phn to amin bc 3 v alken.
+
HO- + H_CH2_CH2_NR3
...
HO H CH2 CH2... NR3
HOH
+ CH2=CH2 + NR3
Phn ng tch loi ny gi l phn ng tch loi Hofmann.

+
N(CH3)3I Ag2O
NH2
CH3I
K2CO3
+
N(CH3)3OH 120o
H2O
+ N(CH3)3 + H2O
Khi tch loi to alken phi theo quy tc Hofmann l tch hydro nhm
CH3 d hn hydro nhm RCH2.
CH3
N(CH3)3 OH
CH2
CH2
+
99%
+ N(CH3)3 + H2O
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_NH2 gi l enamin.
300
Cc enamin thng khng bn v c dng h bin (mesomer) imin C =N

H
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
Cyclohexanon
Pyrolidin
N-(1-cyclohexenyl) pyrolidin
Enamin rt nhy cm trong mi trng acid v d phn hy thnh hp cht

carbonyl v amin.
O
+ H3O
Cc enamin c tc dng lm cho nguyn t carbon v tr C c tnh i nhn.
:NR2
NR2
V vy enamin tc dng vi alkylhalogenid xy ra v tr .
+
N
Br -
N Br H2O
H
H
2-allylcyclohexanon
+ CH2=CHCH2Br
8. Amin a chc Polyamin

Cc amin a chc c nhiu ng dng dng mch thng hay vng.
NH2_CH2_CH2_NH2
Ethylendiamin
NH2
NH2
p-Phenylendiamin
301
NH2
o-Phenylendiamin
NH2
H2N
H N
m-Phenylendiamin
NH2
N H
NH2 NH2
Piperazin
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.
NH2
NH2
N
+ HNO2
o-Phenylendiamin
N + 2H2O
N
H
Benzotriazol
Bi tp
1. Amin c CTPT C5H13N ,
C6H13N
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 C9H15N.
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 (NaNO2+ 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. H2O2
6. Thc hin phn ng chuyn v Hofmann ca cc cht sau:
a. CH3(CH2)7CH2CONH2.
b. C6H5CH2CONH2
c. CH2=CHCH2CH2CONH2
7. Vit cc phn ng trong cc trng hp sau:
a. N,N-dimethyl -2-pentanamin, CH3I, Ag2O, nhit
b. N,N-dimethyl -1-octanamin, CH3I, Ag2O, 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_NO2
Nitro
C6H5NO2
Nitrobenzen
R_N=C=O
Isocyanat
C6H5NCO
Phenylisocyanat
R_NHCOOR
Uretan,carbamat
C6H5NHCOOCH3
Methyl,N-Phenylcarbamat
R_NHCONH_R'
Ure
H2NCONH2
Ure
R_N=NN
Azid
CH3CH2N3
Etylazid
R_N=N_R'
Azo
C6H5N=NC6H5
Azobenzen
+
R N N R'
Azoxy
+
C6H5 N N C6H5
Azoxybenzen
R_NH_NH2
Hydrazin
C6H5NHNH2
Phenylhydrazin
R[NN]+
Diazoni
[C6H5NN]+Cl-
BenzendiazoniClorid
R2C=N2
Diazo
CH2=N2
Diazometan
R_CONH2
Amid
CH3CONH2
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
+
N
..
O
.. : -
+
N
O-
OO
Chc nitro l nhm ht in t, c hiu ng - C v - I

1.2. Nitroalkan (R_NO2)
Nitroalkan c iu ch bng phng php nitro ha alkan theo c ch gc.
CH4 + HNO3
400oC
CH3NO2 + H2
Trong phng th nghim c th iu ch nitroalkan bng phn ng th gia

hp cht alkylhalogen v mui nitrit.
I
CH3(CH2)5CHCH3 + NaNO2
2-Iodooctan
NO2
CH3(CH2)5CHCH3 + NaI
2-Nitrooctan
Hp cht nitroalkan c tnh acid.
CH3NO2
pKa = 10,2
pKa = 7,8
CH3CHCH3
NO2
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:
CH3
+
N
ONitrometan ( acid)
H+ +
CH2
+
N
+
N
+
N
CH2
CH2
OO
OCarbanion , anion nitrometan (Base lien hp)
Anion nitroalkan l tc nhn i nhn (c tnh a nhn), do cc nitro alkan

tc dng vi aldehyd theo kiu aldol ha.
CH3(CH2)7CHO + CH3NO2
Nonanal
HO -
OH
CH3(CH2)7CHCH2NO2
80% 1-Nitro-2-decanol
Cc -hydroxynitro ca hydrocarbon thm b dehydrat (loi nc).

OH
CH CH2 NO2
- H2O
-Hydroxy phenylnitroetan
CHO + CH3NO2 HO

CH CH NO2
Nitrostyren
305
1.3. Nitroaren (Ar_NO2)

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).
NO2
CH3
NO2
NO2
Na2Cr2O7
NO2
H2SO4 45-55oC
COOH
NO2
NO2
Acid Picric
TNT
NO2
- CO2
NO2
NO2
1,3,5-Trinitrobenzen
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.
Ar_NO2 6[H]
Ar_NH2 + 2H2O
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
NO2
2e- + 2H+
- H2O
Nitrobenzen
NO
2e- +
NHOH
2H+
- H2O
Nitrosobenzen
2e- +
2H+
NH2
- H2O
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.
As2O3
NO2
NaOH
Zn
NaOH
H2NNH2
KOH
ON N
+
Azoxybenzen
85%
(C2H5O)3P , H2O2 ,CH3COOH , 65o
N N
Azobenzen
84-86%
Pd/C , H2NNH2, khong kh
NH NH
Hydrazobenzen 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.
CH2OH
CH2OH
HCNHCOCHCl2
HCNHCOCHCl2
HOCH
HCOH
Cloramphenicol
NO2
NO2
Erythro
Threo
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
Acid isocyanic
HO C N
Acid cyanic
Thay th nguyn t oxy bng nguyn t lu hunh thu c acid

thioisocyanic
R_N=C=O
Alkylisocyanat
Ar_N=C=O
RO_CN
ArO_CN
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.
H O H
N C N CH3
NCO
+ CH3NH2
Cyclohexylisocianat
N-Metyl , N'-Cyclohexylure
Khi c mt ca nc, isocyanat to thnh acid carbamic. Acid carbamic

khng bn v phn hy thnh amin tng ng.
R NCO + H2O
N-Alkyl isocyanat
R NCOOH
Acid N-alkyl carbamic
R NH2 + CO2
Alkylamin
2.2. Carbamat - Uretan (H2N_COOR, RNH_COOAr)

Carbamat hay l uretan l ester ca acid carbamic. Acid carbamic c cng
thc cu to H2N_COOH. Cc dn xut ca acid carbamic c cc dng:
307
Thay hydro ca nhm NH2 bng cc gc hydrocarbon

Ar
R
R NH COOH
N COOH
Ar NH COOH
Acid alkylcarbamic
R'
Acid dialkylcarbamic
Acid arylcarbamic
N COOH
Ar'
Acid diarylcarbamic
Thay hydro ca nhm acid bng gc hydrocarbon thu c ester carbamat hay
uretan. C cc loi ester carbamat (uretan):
H2N_COOR alkyl carbamat; H2N_COOAr arylcarbamat.
Isocyanat tc dng vi alcol to ester carbamat
H O
N C OCH3
N C O
+ CH3OH
Cyclohexyl isocyanat
N-Methylcyclohexylcarbamat
Hp cht carbamat (uretan) c nhiu ng dng lm thuc tr su, iu ch

cc polymer hay l polyuretan.
2.3. Ure (H2NCONH2)
C th xem ure (H2NCONH2) nh l amid ca acid carbamic (H2NCOOH)
Ure c cc dn xut alkyl, aryl ure.
R_NHCONH_R'
Ar_NHCONH_Ar'
Thay th oxy ca ure bng S ta c thioure H2NCSNH2.

Thay th oxy ca ure bng nhm NH ta c hp cht guanidin - H2NC (NH)NH2
Cng thc cu to ca guanidin:
H2N
C
NH
H2N
Guanidin c tnh base. Kt hp vi proton to ion guanidin c cng thc gii hn:
H2N
H2N
..
C NH
+ H+
H2N
H2N
..
+
C NH2
+
H2N
H2N
..
..
C NH2
Ion guanidin
Guanidin
..
H2N
H2N
+
..
C NH2
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: R2C=N2.
3.1. Diazometan (CH2=N2)
Cu to in t ca diazometan chng t nguyn t carbon c tnh i nhn.
+
+
CH2 N N :
CH2 N N
..:
Diazometan
CH2=N2
Diazometan
iu ch diazometan t ester ethyl N -methylcarbamat (N-methyluretan).

CH3
C2H5O
NH
+ HNO2
- H2O
Ester ethyl N-methylcarbamat
CH3
C2H5O
N N=O
O
..
HOCH2
- HCO3 - C2H5OH
+
N
N:
Diazometan
N-nitroso-N-methyluretan
Cng c th iu ch diazometan t aldoxim v cloramin. Mui natri ca

formaldoxim tc dng vi cloramin to thnh diazometan.
..
CH2=N-ONa + NH2Cl
+
N
CH2
N:
+ NaCl + H2O
Diazometan l tc nhn methyl ha.

O
R C OH
+ CH2N2
R C OCH3 + N2
Diazometan c dng tng mt nguyn t carbon trn mch nhnh.
.. -
..
O
.. :
+
O
+ CH2N2
+
CH2 N N :
Cyclohexanon
O
CH2 C Cl
O
.. :
+
CH2
- N2
Cycloheptanon
O
CH2 C CH2Cl
+ N2
83-85%
O
CH2 C CHN2
+ CH2N2
+ HCl
3.2. -Diazoceton (RCOCH=NN)

O
+
C CH N
N
.. :
O-
+
C CH N
N:
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:
..-
3.3.1. Danh php mui diazoni

Tn hydrocarbon (hay tn gc hydrocarbon)+ diazoni + halogenid (sulfat)
C6H5N2Cl:
Benzendiazoniclorid hay Phenyldiazoniclorid
p-CH3C6H4N2Br:
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 N2.
Phn ng ngng t khng gii phng phn t N2.
a. Phn ng gii phng phn t N2
Phn ng thy phn khi c nhit .
Dung dch mui diazoni, kh c nhit , to thnh phenol v kh N2.
NH2
+
N2
Br
Br HSO 4 +H O
2
CH3
CH3
OH
Br
+ N2
CH3
Phn ng xy ra theo c ch th i nhn SN1.

ArN2+
Ar+ + H2O
Ar+ + N2
Ar_OH2+ + 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
N2+
NH2
Cl -
NaNO 2
Cl
CuCl
+ N2
HCl
NH2
CH3
CH3
CH3
Cl
N2+
NaNO2
Cl
Br -
Br
CuBr
HBr
N2+
NH2
NaNO2
CH3
Cl -
CN
CuCN
+ N2
0-5o
HCl
5o
Cl
+ N2
CH3
CH3
p-Toluidin
p-Tolunitril
Qua cc phn ng trn chng t mui ng (I) c vai tr xc tc.

Br - , CuBr ,
- N2
NO2 , CuCl ,
+
N N:
- N2
Br
Bromobenzen
NO2
Nitrobenzen
CN
Benzonitril
CN - , CuCN ,
- N2
SCN - , Cu2(SCN)2 ,
SCN
Benzosulfocyanid
- N2
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 H3PO2 kh ha mui aryldiazoni thnh aren.
+
N N: X -
H3PO2 , H2O ( Cu+)

-N2 - HX -H3PO4
Phn ng trn c ngha trong tng hp cc cht hu c:

Khng th brom ha trc tip acid benzoic thu c acid 2,4,6tribromobenzoic. V vy phi qua chc amin nh hng brom vo v tr thch
hp sau loi chc amin qua mui diazoni.
311
COOH
Br
Br
Br
Br
NaNO2
H2SO4
- 5o c
NH2
COOH
Br
Br
H3PO2
+
o
N2 HSO4 - 5 c
COOH
Br
Br
Br
b. Phn ng ngng t khng gii phng phn t N2

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
.. +
N N
..
N N
+ ..
N N
NH2
NH2
p-Aminoazobenzen
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.
.. +
N N
..
N N
+ ..
N(CH3)2
N N
N(CH3)2+ H+
4-Dimethylaminoazobenzen
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
.. +
N N
..
N N
+ ..
OH
N N
OH
4-Hydroxyazobenzen
HO
NaO3S
N N
HO
NaO3S
+
-naphtol
N N
+ H+
Pham vang -naphtol
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
CHO
H2SO4
H2O
NO2
CHO
NaOH H2O
NaNO2 HCl
NHCOCH3
NO2
H2O
NH2
NHCOCH3
NH2
CHO
CHO
HNO3 H2SO4
CH3COOH
Fe , HCl
HNO3
NO2
CHO
CHO
CHO
NO2
CHO
H3PO2
+
N2
NO2
Chc nitro chuyn ha thnh amin. Thay th chc amin bng cc chc khc
qua giai on diazo ha. V d:
CHO
1-HNO3,H2SO4
2-Fe, HCl,H2O
3-NaNO2 ,H2SO4 , H2O
CHO
CHO
CHO
+
N2
F
CHO
CHO
CHO
CN
SH
Bi tp
1. Gi tn cc cht c CTCT sau:
; CH3
NO2
; NH2
NCO
a-
Cl
b-
NH2
NCO
c-
NH2
N N
d-
NH2
NH NH
NO2
OH
OCH3
; NH2
NO2
; C2H5_NCO
NH2
; CH3
N N
+
Cl-
NHOH
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
CH3SH
Sulfid
RSR , ArSR
Diethylsulfid
C2H5SC2H5
Sulfoxyd
R S
Dimethylsulfoxyd
CH3 S
CH3
Acid sulfenic
RSOH
Acid1-propen sulfenic
CH3_CH=CHSOH
Acid sulfinic
RSO2H
Metansulfinic
CH3SO2H
Acid sulfonic
RSO3H
Metansulfonic
CH3SO3H
Sulfohalogenid
Sulffonylhalogenid
RSO2Hal
Benzensulfoclorid
Benzensulfonylclorid
C6H5SO2Cl
Sulfinylhalogenid
RSOHal
Metansufinylclorid
CH3SOCl
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:
CH3CH2SH
Etanthiol
Ethylmercaptan .
HSCH2CH2SH
1,2-Etandithiol
1,2- Ethylendimercaptan
C6H5SH
Thiophenol
Mercaptobenzen
CH3
CH2 SH
2- Thiocresol .
SH
2-Mercaptotoluen
Phenylmetanthiol
Benzylmercaptan
di lin kt v gc lin kt trong metanthiol c trnh by di y:

H
C
S
H
Metanthiol
di lin kt (Ao)
Gc lin kt ()
C_H ................1,10.
H_S_H ...........110,2
S_H .................1,33
H_S_S ...........108
C_S .................1,82.
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.
CH3CH2_S_CH2CH3
Diethylsulfid .
C6H5CH2_S_CH2CH3
Ethylbenzylsulfid.
p-CH3C6H4_S_C6H5
Phenyl p-tolylsulfid
di lin kt v gc lin kt ca dimethylsulfid trnh by di y:

H
H
C
H
S
H
C H
H
di lin kt (Ao)
Gc lin kt ()
C_H................1,09.
H_S_H ...........109,5
C_S ..............1,80
H_S_S ........... 106.7

C_S_H ........... 98,9
Dimethylsulfid
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 -SO3H .
C cc loi acid sulfonic R_SO3H , Ar_SO3H
315
1.2.1. Danh php

c tn hydrocarbon tng ng v thm "sulfonic "
CH3CH2CH2
O
S OH
O
O
S OH
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_SO3H
+ PCl5
Ar_SO2Cl + POCl3 + HCl
Ar_SO2Cl
+ NH3
Ar_SO2_NH2 + HCl
Ar_SO2Cl
+ ROH
Ar_SO2_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
CH3-SO3H
Acid Metansulfonic
CH3CH2-SO3H
Acid Etansulfonic
tc
ts
20,0
167
- 17,0
Acid Benzensulfonic
44,0
Acid p-Toluensulfonic
106.5
Acid o-Toluensulfonic
67,5
Acid -Naphthalensulfonic
91,0
Acid -Naphthalensulfonic
102,0
SO3H
CH3
SO3H
CH3
SO3H
SO3H
SO3H
CH3SO2Cl
316
Metansulfonylclorid
160
Bng 24.2 (tip)

Cng thc
Tn gi
tc
ts
Benzensulfonylclorid
14,5
246
p-Toluensulfonylclorid
69,0
-Naphthalensulfonylclorid
68,0
-Naphthalensulfonylclorid
76,0
156,0
28
SO2Cl
CH3
SO2Cl
SO2Cl
SO2Cl
Benzensulfonamid; Benzensulfamid
SO2 NH2
-Naphthalensulfonamid ;
SO2 NH2
-Naphthalensulfamid
Ester methyl p-toluensulfonat

CH3
SO2 OCH3
SO2 OC2H5
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_SO2_Cl + H2N_R'
Ar_SO2_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, NH2 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
CH3
CH3
CH3
CH3
+ HOSO2Cl
NaOCl ( HO-)
- H2O
SO2NCl Na
+ NH3
- HCl
- HCl
SO2NH2
SO2Cl
Cloramin T
CH3
2 NaOCl
- 2NaOH
Dicloramin T
SO2NCl2
Acid o-Toluensulfonic l nguyn liu iu ch saccharin (ng ha hc) :

CH3 PCl
5
-POCl3 - HCl
SO3H
CH3
CH3
3[O],KMnO4
-H O
SO2NH2 2
+ NH3
-HCl
SO2Cl
COOH
-H2O
SO2NH2
CO
NH
SO2
Saccharin
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
PH3
Phosphoran
PH5.
Acid phosphinic
(H3PO2)
HOH2P=O
Acid phosphonic
(H3PO3)
(HO)2HP=O
Acid phosphor
(H3PO3)
(HO)3P
Acid phosphoric
(H3PO4)
(HO)3P=O
Acid pyrophosphoric (H4P2O7)
(HO)2P(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 RPH2
CH3CH2PH2
Ethylphosphin
Dialkyl R2PH
(CH3CH2CH2CH2)2PH
Di n-butylphosphin
Trialkylphosphin R3P
(C6H5)3P
Triphenylphosphin .
C th iu ch triphenylphosphin t hp cht c magnesi.

6C6H5MgBr + 2PCl3
318
2(C6H5)3P + 3MgCl2 + 3MgBr2

2.2. Cc alkyl ca acid cha phosphor

2.2.1. Acid dialkylphosphinic
H
OH
2[ O]
CH3CH2 P
R P O
OH
CH3CH2 P O
CH2CH3
R'
CH2CH3
Acid Diethylphosphinic
Diethylphosphin
Acid Dialkylphosphinic
2.2.2. Acid Alkylphosphonic

H
OH
CH3CH2 P
R P O
OH
3[ O]
Acid Ethylphosphonic
Ethylphosphin
Acid Alkylphosphonic
OH
CH3CH2 P O
OH
2.3. Cc ester ca acid cha phosphor

2.3.1. Ester ca acid phosphonic
OCH2CH3
OR'
CH3CH2 P O
R P O
OR''
OCH2CH3
Ester dialkyl cua acid alkylphosphonic

Ester dialkyl alkylphosphonat
Ester diethyl cua acid ethylphosphonic

Ester diethyl ethylphosphonat
2.3.2. Ester ca acid phosphor

OR'
P OR
OH
OH
Ester diethylphosphit
P OCH2CH3
P OR
OR''
P OCH2CH3
Ester Dialkylphosphit
OCH2CH3
OR'
OCH2CH3
OCH2CH3
Ester trialkylphosphit
Ester Triethylphosphit
2.3.3. Ester ca acid phosphoric

OCH2CH3
OR'
RO P O
OR''
CH3CH2O P O
OCH2CH3
Ester Triethylphosphat
Ester Trialkylphosphat
2.3.4. Ester ca acid pyrophosphoric

OR'
OR'''
RO P O P OR''
O
O
Ester Tetraalkylpyrophosphat
C2H5O
OC2H5
C2H5O P O P OC2H5
O
O
Ester Tetraethylpyrophosphat
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

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Hp cht hu c n chc v a chc

TS. Nguyn Mnh Pha

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

Chng1: Cu trc in t ca nguyn t carbon v s to thnh

ThS. Nguyn Anh Tun

2. Hiu ng lin hp (cng hng)

Chng 3: Cu trc phn t hp cht hu c. ng phn v cu dng

2. ng phn lp th - ng phn khng gian

Chng 4: Khi nim acid -base trong ha hu c

ThS. Nguyn Anh Tun

3. Hng s cn bng acid base

Chng 5: Cc loi phn ng trong ha hu c v khi nim v c ch phn ng

ThS. Nguyn Anh Tun

ThS. Nguyn Anh Tun

Chng 7: Alkan - Hydrocarbon no

Chng 9: Alken - Hydrocarbon etylenic

Chng 10: Alkyn - Hydrocarbon acetylenic

Chng13: H thng lin hp v alkadien

PGS. TS. ng Vn Tnh

4. Phn ng Diels Alder

Chng 14: Dn xut halogen

ThS. Trng Ngc Tuyn

Chng 15: Hp cht c kim

ThS. Trng Ngc Tuyn

4. Phng php iu ch cc hp cht c kim

Chng 16: Alcol

Chng 17: Phenol

Chng 18: Ether

Chng 19: Aldehyd , Ceton v Quinon

3. Aldehyd - ceton a chc

Chng 20: Acid carboxylic

ThS. Nguyn Anh Tun

7. Acid a chc polyacid

Chng 21: Cc dn xut ca acid carboxylic

ThS. Nguyn Anh Tun

Chng 22: Amin

7. Amin cha no c mt lin kt i Enamin

Chng 23: Cc hp cht khc cha nit

TS. Phm Khnh Phong Lan

Ti liu tham kho

CU TRC in t CA NGUYN T CARBON

Cc gc ha tr tm u bng nhau v bng 10928'. Khi nguyn t carbon

Carbon hp thu nng lng 60-70 kcal/mol, mt in t 2s2 chuyn ln trng

2px 2py 2pz

Carbon c cu hnh in t 1s22s12p3 l carbon kch thch (1s22s12px2py2pz).

Cc kt qu tnh ton cho thy rng nu xem kh nng xen ph ca orbital

Nh vy trn carbon lai ha sp2 cn c mt in t trn orbital 2pz khng lai

2 Orbital 2py v 2pz

S lai ha gia orbital s v p cng xy ra trong cc nguyn t oxy, nit ...

Ty theo c im i xng ca cc orbital nguyn t, s xen ph ca chng

2.2. Lin kt v lin kt trong cc hp cht hu c

Orbital Py hoc Pz ca cc nguyn t carbon xen ph vi nhau tng i mt

S to thnh lin kt trong phn t ethylen, acetylen c th minh ha nh sau:

Hai lin kt trong acetylen c to thnh do s xen ph cc i v 2 pha

S to thnh lin kt trong h thng alen C=C=C .

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

H thng lin hp thng thng v n gin l nhng h m hai lin kt

S to thnh cc lin kt v trong h thng lin hp lm cho di

Khi hai nguyn t lin kt vi nhau khng ng nht (phn t c dng

Trong cc phn t H2C =O v CH3 _CN, v.v .. c s phn cc ca lin kt .

V d: CH3 Cl ; CH3 Cl ; H2C=O ; H2C=O hoc: H2C==O

Cc hp cht hu c c lin kt cng ha tr (l nhng lin kt c phn