Professional Documents
Culture Documents
09 GT HoaHuuco
09 GT HoaHuuco
Gio trnh
Ho hc hu c
Nm 2007
1
Gio trnh Ho hu c ..1
http://hhud.tvu.edu.vn
Li ni u
Gio trnh ho hu c ny c bin son theo cng mn hc chnh thc dng cho
khi ngnh Nng- Lm- Ng nghip do b mn ho trng i hc Nng nghip I ch tr v
c hi ng khi ngnh thng qua. Gio trnh nhm cung cp cho sinh vin nhng kin thc c
bn v Ho hu c.
Trng tm ca gio trnh l cu to v tnh cht ca cc hp cht hu c, cu to v tnh cht
ca mt s loi hp cht t nhin c lin quan nhiu n cc mn hc c s v chuyn mn ca
khi ngnh.
Tuy nhin, do thi lng mn hc rt t (2 VH), nn chng ti ci tin chng mc sao
cho gn nht. Cng chnh v vy khng trnh khi sai st khi bin son. chng ti rt mong nhn
c nhng kin ng gp ca bn c v ng nghip gio trnh c hon thin hn cho
ln ti bn sau.
H Ni, 2007
Cc tc gi
2
http://hhud.tvu.edu.vn
Chng I.
i cng
Xa kia, ngi ta khng phn bit cht v c v cht hu c, mc d t thi c i ngi ta
bit dng v sn xut mt s cht hu c nh ngi n bit ly ng t ma, bit ly
chm t cy chm; ngi Ai Cp bit ly tinh du thm, cho ln men nc ngt thnh ru. Cng
chnh v vy, khi ngi ta cha phn bit ha hc v c v ha hc hu c.
S pht trin ca ha hc hu c bt u t th k XVII, khi cc hp cht ly t cy ci v
ng vt c a vo nghin cu. n gia th k XVIII, trn c s phn ng t chy ngi ta
xc nh c cacbon, hiro, nit, oxi c trong cc hp cht tch t ng vt v thc vt, t
ha hc hu c thc s bt u pht trin. Khi nim ha hc hu c do Beczeliuyt (Bezelius)
xut nm 1807. ng cho rng c th sinh vt l xng ha hc, c b phn ring bit sn
xut cc sn phm quan trng cho s sng.
Nm 1824 Vuele (Wohler) tng hp c axit oxalic (H2C2O4) t xianogen (C2N2) v
nm 1828 ng cng tng hp c ur (H2N-CO-NH2) t amoni xianat (H4NOCN). Tip sau
hng lot cc cng trnh mi c cng b, k c cc cng trnh tng hp cc hp cht hu c
khng tch c t t nhin. n u th k XIX ngi ta khng nh rng cacbon l thnh
phn c bn khng th thiu c trong cc hp cht hu c. Ngi ta a ra nh ngha:
Ho hc hu c l hc thuyt v ho hc ca cc hp cht ca cacbon.
Trn c s nghin cu cc c im cu to chung ca cc hp cht hu c, Soolemme
(Soorlemmer) v mt s tc gi nh ngha:
Ho hc hu c l ngnh ho hc ca hirocacbon v cc dn xut ca chng.
Cho n nay c hai nh ngha trn vn c cng nhn.
S pht trin ca ho hc hu c khng nhng c tc dng trc tip n cc ngnh kinh t
quc dn c lin quan n ho hc hu c, m cn nh hng su sc n cc ngnh khoa hc
khc nh sinh hc, ho sinh, y hc, dc hc, nng nghip ...lm cho con ngi ngy cng lm
ch thin nhin v bt thin nhin, iu khin thin nhin phc v i sng con ngi.
Ho hc hu c l ho hc v nhng hp cht ca cacbon. i tng nghin cu ca mn
hc ny l cc hirocacbon v cc dn xut ca chng. i tng ny c kho st ring l do
mt s nguyn nhn sau y:
- S lng cc hp cht hu c rt ln v tng rt nhanh. Khong trn 10 triu hp cht hu
c c bit. Trong c nhng hp cht ng vai tr v cng quan trng i vi cc qu
trnh hot ng sng ca c th sinh vt nh cc hp cht gluxit, cc hp cht protein, cc axit
nucleic, cc vitamin, cc hocmon
- Vai tr to ln v ng dng phong ph ca ho hc hu c trong i sng hng ngy v
trong cc ngnh kinh t quc dn: Nhin liu v du nhn, cc loi nng dc, thuc cha bnh,
cc cht hot ng b mt, cc cht mu v phm nhum
3
http://hhud.tvu.edu.vn
1s2 2s2
2p2
Cc lp in t s v p s to nn nhng m my in t (obitan) khc nhau. Obitan s c
dng hnh cu. Cc obitan p c dng s 8 ni. Cc obitan p phn chia trong khng gian theo 3
chiu px, py v pz.
y
y
+
z
y
z
z
x
z
Trong cc hp cht hu c, nguyn t cacbon c th tham gia vo ba trng thi lai ho khc
nhau.
Lai ho sp3 hay lai ho t din : trng thi ny, mt obitan 2s trn ln vi ba obitan 2p
c bn obitan lai ho ging ht nhau hng v bn nh ca mt hnh t din u. Trc ca
cc obitan lai ho to vi nhau nhng gc bng nhau v bng 109028 (gc ho tr). y chnh l
gc ho tr bn vng nht ca nguyn t cacbon.
Trng thi lai ho sp3 l c s gii thch khi nim ca L Ben v Van Hp (1874) v thuyt
t din ca nguyn t cacbon. Trng thi lai ho sp3 gp trong cc hp cht no, trong mi lin
kt gia nguyn t cacbon vi nguyn t ca nguyn t khc hoc vi chnh nguyn t cacbon l
nhng mi lin kt n (ni n).
5
http://hhud.tvu.edu.vn
Lai ho sp2 hay lai ho tam gic: trng thi ny, obitan 2s trn ln vi hai obitan 2p to
thnh ba obitan lai ho. Ba obitan lai ho ny nm trn cng mt mt phng v trc ca chng to
vi nhau nhng gc 1200. trng thi lai ho sp2 nguyn t cacbon cn li mt in t 2p khng
tham gia vo s lai ho, trc ca n vung gc vi mt phng cha ba obitan lai ho. n t p
ny s tham gia vo s hnh thnh lin kt cng vi cc in t p ca cc nguyn t cacbon bn
cnh. Trng thi lai ho sp2 thng gp trong cc hp cht cha lin kt i (ni i).
Lai ho sp hay lai ho ng thng : trng thi ny, obitan 2s trn ln vi mt obitan 2p
c hai obitan lai ho ging ht nhau. Hai obitan ny cng nm trn mt mt phng v trc
ca chng to vi nhau gc 1800. trng thi lai ho sp, nguyn t cacbon cn hai obitan p
khng tham gia vo s lai ho. Cng ging nh in t p trng thi lai ho sp2, cc in t p ny
s tham gia vo s hnh thnh cc lin kt . Trng thi lai ho sp thng gp trong cc hp cht
cha lin kt ba (ni ba).
Di y m t hnh dng v s phn b m my in t cc trng thi lai ho khc
nhau.
+
+
+
++
+
+
Lai ho sp3
Lai ho sp2
Lai ho sp
CH2
CH2
CH2
CH2
xiclohexan
HC
HC
CH
CH
benzen
CH
CH
6
http://hhud.tvu.edu.vn
ancol etylic
CH3
CH3 -C =O
axeton
CH3 -O -CH3
imetyl ete
OH
CH3 -C =O
axit axetic
Khc vi cc nguyn t khc, ngoi kh nng c th tham gia vo c ba trng thi lai ho
sau hnh thnh nn cc lin kt khc nhau, nguyn t cacbon cn c nhng c im m cc
nguyn t khc khng c c lm tng kh nng hnh thnh cc hp cht khc nhau, lm cho
s lng cc hp cht hu c rt ln. Nhng c im l cc nguyn t cacbon c kh nng
kt hp vi nhau to thnh mch, trong lin kt cacbon- cacbon rt bn. Mch cacbon c
th l mch khng phn nhnh (mch thng), mch phn nhnh hoc mch vng. Nhng mch
c th rt ngn ch gm vi nguyn t cacbon ni vi nhau, nhng cng c th rt di, bao gm
hng trm, hng ngn nguyn t:
C
-C-C-C-C-
-C-C-C-C-
C
C
mch vng
H H
8
http://hhud.tvu.edu.vn
+ +
+
CC
CC
-
S phn b mt in t ca lin kt
Cc obitan nguyn t xen ph nhau t, do vy cc lin kt thng km bn, d b ph v
tham gia trong cc phn ng ho hc.
Lin kt khng c i xng trc, do vy cc nhm th khng c kh nng quay t do xung
quanh trc i xng. y chnh l nguyn nhn lm xut hin ng phn hnh hc cis- trans trong
cc hp cht c ni i C=C.
Trong cc hp cht hu c, lin kt c thc hin gia hai nguyn t cacbon vi nhau
nh trong cc hp cht hu c cha no cha lin kt i v lin kt ba:
C=C
C=C
C = NH
C=N
9
http://hhud.tvu.edu.vn
Th d:
+
C=O
nhng hp cht c lin kt i lin hp, chng hn nh trong phn t butaien (CH2=CHCH=CH2), cc in t linh ng, chng thng c gii to trn ton b mch lin hp lm cho
cc hp cht thuc loi ny thng c nhng tnh cht c bit so vi cc hp cht cha ni i
bnh thng.
c. Mt s c im ca lin kt cng ho tr
Lin kt cng ho tr c mt s c tnh khc vi nhng loi lin kt khc:
- di lin kt
Bng thc nghim ngi ta xc nh c rng, khong cch gia hai ht nhn nguyn t
trong lin kt cng ho tr l mt i lng khng i. Khong cch c gi l di lin
kt. di lin kt thng c k hiu l d, n v tnh bng angxtron (A0) hay nanomet (nm)
(1nm = 10A0; 1A0 = 10-8cm).
di lin kt khng phi l tng bn knh ca hai nguyn t, m l tng bn knh cng ho
tr ca hai nguyn t lin kt vi nhau.
Bit bn knh cng ho tr ca nguyn t ta c th tnh c mt cch gn ng di lin
kt. Th d, bn knh ca nguyn t hiro l 0,54A0, bn knh cng ho tr ca n l 0,37A0, th
di lin kt H-H l 0,37A0 +0,37A0 = 0,74A0, ch khng phi l 0,54A0 + 0,54A0 = 1,08A0.
Nh vy khi to thnh phn t hiro c s xen ph nhau gia hai obitan 1s ca hai
nguyn t hiro.
Cc cng trnh nghin cu chng t rng, s xen ph gia hai nguyn t cng nhiu,
di lin kt cng ngn, lin kt cng bn, cng kh b ph v. Song, di lin kt khng phi l
i lng c bn nh gi s bn vng ca mt lin kt ho hc.
- phn cc ca lin kt
Trong lin kt cng ho tr, nu obitan phn t c cu to cn i, ngha l mt in t
ca obitan phn t phn b u gia hai ht nhn, trng tm in tch dng v m trng nhau th
lin kt l khng phn cc.
Lin kt cng ho tr khng phn cc ch to thnh gia hai nguyn t ca cng mt nguyn
t. Th d, lin kt H- H trong phn t H2, lin kt Cl- Cl trong phn t Cl2, lin kt C- C trong
phn t CH3- CH3 v CCl3- CCl3...l nhng lin kt cng ho tr khng phn cc.
Trong trng hp nu obitan phn t c cu to khng cn i, ngha l mt in t ca
obitan phn t lch v pha mt trong hai nguyn t th lin kt cng ho tr l phn cc.
10
http://hhud.tvu.edu.vn
11
http://hhud.tvu.edu.vn
No
Khng no
Cc hp cht vng
Cc hp cht
ng vng
Cc hp cht
d vng
Cc hp cht Cc hp cht
vng khng thm vng thm
No
Khng no
D vng
khng thm
No
D vng
thm
Khng no
H thng phn loi trn y ly hirocacbon hoc hp cht d vng n gin nht lm hp
cht c s. Nu ta thay th nguyn t hiro ca hp cht c s bng mt nguyn t hoc nhm
12 hu c ..12
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
Hay
R:X
R. + X.
R. + X.
Hay
R X
13
http://hhud.tvu.edu.vn
CH3Cl + HCl
CH3-CH3
CH2=CH2 + H2O
14
http://hhud.tvu.edu.vn
HO- + CH3B r
Cht u
TTCT1
TTCT
TTCT2
E2
HCTG
E1
Cht u
H
Cht cui
Cht u
H
Cht cui
E l nng lng hot ha, H l hiu ng nhit ca phn ng trong iu kin ng p. Phn
ng xy ra khi H< 0.
5. Cu trc phn t hp cht hu c
Trong ho hc hu c ta thng gp nhiu hp cht khc nhau v tnh cht, song li c cng
mt cng thc phn t. Hin tng mt cng thc phn t ng vi hai hoc nhiu hp cht khc
nhau c gi l hin tng ng phn. Hin tng ng phn c gii thch trn c s
thuyt cu to ho hc ca nh bc hc Nga A. M. Butlrp. Do c hin tng ng phn m s
lng cc cc hp cht hu c c tm thy tng ln gp bi. C hin tng ng phn l do cc
cht c cu trc khc nhau.
15
http://hhud.tvu.edu.vn
Ngi ta bit rt nhiu loi ng phn khc nhau, nhng chung quy li da vo cc c
im v cu trc ta c th phn chng thnh hai loi chnh, l ng phn cu to (ng phn
mt phng) v ng phn khng gian (ng phn lp th).
5.1. ng phn cu to
Cc ng phn cu to phn bit nhau v trt t sp xp ca cc nguyn t trong phn t
hoc v loi lin kt gia cc nguyn t, tc l phn bit nhau v mt cu to. Sau y l mt s
ng phn cu to ch yu.
a. ng phn mch cacbon
Cc ng phn loi ny phn bit nhau v cch sp xp cc nguyn t cacbon trong mch.
Th d, n-pentan; isopentan v neopentan u c cng thc phn t l C5H12, nhng c cu to
mch cacbon khc nhau:
CH3-CH2-CH2-CH2-CH3
CH3
CH3-CH-CH2-CH3
n-pentan
CH3
CH3-C-CH3
CH3
neopentan
isopentan
S ng phn mch cacbon tng ln rt nhanh theo s nguyn t cacbon c trong phn t.
Th d, butan C4H10 c 2 ng phn, heptan C7H16 c 9 ng phn, ecan C10H22 c 159 ng
phn, triecan C13H28 c 803 ng phn, tricontan C30H62 c 411846763 ng phn ...
b. ng phn nhm nh chc
Cc ng phn nhm nh chc c cng thnh phn phn t, nhng khc nhau v nhm nh
chc.
Th d:
CH3-CH2-C-H v
O
anehit propionic
CH3-C-CH3
O
axeton
Hai cht ny cng c thnh phn phn t C3H6O, nhng c nhm nh chc khc nhau.
Nhm nh chc ca anehit propionic l -CH=O, cn ca axeton l >C=O. Anehit propionic c
im si 500C, tham gia c phn ng trng bc v phn ng vi thuc th Phlinh. Axeton si
400C, khng tham gia c phn ng trng bc cng nh phn ng vi thuc th Phlinh.
c. ng phn v tr nhm nh chc
Cc ng phn loi ny c cng thnh phn phn t, cng nhm nh chc, nhng phn bit
nhau v v tr ca nhm nh chc trong mch cacbon.
Th d:
CH3-CH2-CH2-OH
CH3-CH-CH3
OH
16 hu c ..16
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
propan-1-ol
propan-2-ol
Hai ng phn ny c cng thnh phn phn t C3H8O, cng nhm nh chc ru (nhm OH), nhng v tr ca nhm -OH trong mch cacbon khc nhau.
d. ng phn lin kt
Cc ng phn ny phn bit nhau v loi lin kt gia cc nguyn t cacbon. Th d, buten-2
v xiclbutan.
CH3-CH=CH-CH3
But-2-en
H2C
CH2
H2C
CH2
xiclobutan
Trong phn t hai ng phn ny cc nguyn t cacbon lin kt vi nhau theo cc cch khc
nhau.
Ngoi bn loi ng phn cu to chnh trn y, hin tng h bin hay hin tng
tautome l hin tng t chuyn ho qua li gia hai dng ng phn khng bn cng c xp
vo mt loi ca ng phn cu to.
Th d, hai dng cu to tn ti trong dung dch ca axetamit:
CH3-C-NH2
CH3-C=NH
O
OH
(dng amit)
(dng imit)
5.2. ng phn khng gian
Cc ng phn khng gian c cng thnh phn phn t, cng mt cu to, nhng khc nhau
v s phn b khng gian ca cc nguyn t hoc cc nhm nguyn t trong phn t. Hai loi
ng phn khng gian chnh l ng phn hnh hc v ng phn quang hc. hai loi ny cc
cht ng phn phn bit nhau v cu hnh, tc l s phn bit trong khng gian ca cc nguyn
t hay cc nhm nguyn t xung quanh phn cng nhc hoc phn khng trng vi nh ca
phn t. Ngoi ra, cc ng phn cu dng cng c th c coi l loi ng phn khng gian th
ba. Tt c cc loi ng phn khng gian ny nhiu khi xut hin xen k nhau.
a. ng phn hnh hc
Nu c hai nguyn t ni vi nhau bng mt lin kt cng ho tr cng nhc, ngha l
khng c s quay ca hai phn phn t quanh trc ni ca hai nguyn t ny th hai nhm th ni
vi chng c th c nhng cch phn b khng gian khc nhau: Nu chng cng pha i vi
nhau ta gi l ng phn cis, khc pha l ng phn trans.
Da trn c s , ng phn hnh hc thng c cc hp cht c ni i cacbon-cacbon,
ni i gia cacbon v mt s d t no hoc gia cc d t vi nhau v cc hp cht mch
vng. l nhng phn cng nhc, lm cho cc nhm th ni vi chng khng c kh nng quay
t do. Sau y l mt s th d:
17 hu c ..17
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
h
c
cooh
hooc
cooh
hooc
h
axit fumaric (trans)
ch3
hooc
r1
h
c
ch3
hooc
r2
h
axit crotonic (trans)
C6H5
N
C 6H 5
N
C6H5
N
C 6H5
ho
oh
oxim
azobenzen
ch3
ch3
ch3
ch3
trans-1,2-imetyl xiclopropan
cis-1,2-imetylxiclopropan
Mmen lng cc: mmen lng cc ca ng phn dng cis lun lun ln hn mmen
lng cc ca dng trans.
Th d, phn t 1,2-icloeten:
H
Cl
C
C
Cl
Cl
C
C
trans-1,2-icloeten
=0
Cl
cis-1,2-icloeten
= 1,89D
18
http://hhud.tvu.edu.vn
Nhit si, nhit nng chy, t khi khc nhau. Chng hn, cis-1,2-icloeten si
60,80C, t trng l 1,283, cn trans- 1,2-icloeten si 47,90C v t trng l 1,256.
Kh nng tham gia phn ng ho hc ca ng phn dng cis thng mnh hn ng
phn dng trans.
Th d, axit maleic (dng cis) d dng tham gia phn ng loi nc to thnh anhirit
maleic.
H
O
C C OH
C C= OH
O
C C
=O
C C=
O
O
+ H 2O
trong khi dng trans (axit fumaric) khng th tham gia phn ng ny.
b. ng phn quang hc
iu kin cn v xut hin ng phn quang hc cc hp cht hu c l phn t ca
chng phi c cc trung tm bt i xng. Trung tm bt i xng ph bin nht i vi cc hp
cht hu c l nguyn t cacbon bt i, tc l nguyn t cacbon m bn ho tr ca n c lin
kt vi bn nguyn t hoc nhm nguyn t hon ton khc nhau.
Th d: Trong phn t axit lactic:
H
CH3 C COOH
OH
-COOH
19
http://hhud.tvu.edu.vn
cooh
cooh
ho
oh
h
ch3
ch3
(a)
cooh
cooh
ho
h
h
ch3
ho
oh
ch3
(b)
cooh
ho
cooh
ch3
(c)
oh
ch3
20
http://hhud.tvu.edu.vn
ch3
(ch3)2ch
(ch3)2chch2
n ch2ch3.cl
ch3
si
ch3 ; c6h5
p
n-c3h7
c6h5
COOH NO2
COOH NO
2
NO2 COOH
*
*
ch3-choh-choh-cooh
21 hu c ..21
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
oh
ho
oh
ho
ho
oh
h
ho
h
h
oh
ch3
ch3
ch3
ch3
cooh
cooh
cooh
cooh
cho
h
oh
ho
ch2-OH
D(+)glixeranehit
ch2-OH
L(-)glixeranehit
cooh
cooh
h
oh
ch3
axit d(-)lactic
ho
ch3
axit l(+)lactic
22
http://hhud.tvu.edu.vn
Th d:
cho
oh
h
ho
cho
h
ho
oh
oh
ho
oh
ho
h
ch2oh
ch2oh
D(+) glucoz
L(-) glucoz
Du (+), (-) trong cc cng thc chiu l dng ch chiu quay ca mt phng nh sng
phn cc.
Trong cc hp cht khc, nhm chun c th l SH, NH2, X, CH3.
Hin tng quang hot rt ph bin trong cc hp cht hu c, c bit trong cc hp cht t
nhin v c ngha sinh hc rt ln. Trong t nhin, c nhiu cht (gluxit, axit amin, protein,
ankaloit) l nhng cht quang hot.
c. Cu dng
Cu dng xen k:
h
h h
h
h
h
h
h
h
h
h
h
h
cu dng che khut, cc nguyn t hiro ca hai nhm metyl che khut nhau. cu dng
xen k, cc nguyn t hiro ca hai nhm metyl vo ch trng ca nhau. Cu dng xen k bn
hn cu dng che khut, hiu s nng lng gia hai dng ny l 2,8 kcal/mol.
23
http://hhud.tvu.edu.vn
ch3
h
h
ch3
ch3
h
dng i (anti)
ch3
h
h
h
ch3
ch3
cc dng lch
ch3ch3
h
h
h h
h ch3
ch3
dng khut
h ch3
h
h hh
ch3
h
cc dng na khut
Cl-CH2-C-O-H
O
axit axetic
axit cloaxetic
c hai axit trn u c nhm cacboxyl (-COOH). Trong nhm ny lin kt O-H vn l
lin kt phn cc v pha nguyn t oxi do n c m in ln hn. Mt khc, nhm cacbonyl
(>C=O) cng ht electron dng chung trong lin kt C-O v pha mnh, khin cho nguyn t oxi
24 hu c ..24
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
cng ht cp electron dng chung ca lin kt O-H v pha n mnh hn. Kt qu l lin kt O-H
cng phn cc mnh v nguyn t H trong nhm -OH tr nn linh ng. Ta c th biu din qu
trnh nh sau:
c
Qua hng s Ka ta thy tnh axit ca axit cloaxetic mnh hn rt nhiu so vi axit axetic.
Ni mt cch khc, nguyn t H trong nhm OH ca axit cloaxetic linh ng hn ca axit axetic.
Nguyn nhn ca iu c gii thch nh sau: Trong phn t axit cloaxetic, nhm cacboxyl
c lin kt trc tip vi nhm -CH2Cl, do nh hng ca nguyn t clo c m in ln m
lin kt C-Cl b phn cc v pha nguyn t clo. Nh s phn cc ny m nguyn t clo mang
phn in tch m (k hiu -), nguyn t cacbon trong nhm CH2 mang phn in tch dng (k
hiu +), nguyn t cacbon ny li ht cp electron dng chung gia n v nguyn t cacbon
trong nhm cacboxyl v pha n, t gy nh hng tip theo v cui cng dn n lin kt O-H
tr nn rt phn cc.
cl
+
ch2
+
c
Ngc li, trong phn t axit axetic, nhm cacboxyl lin kt vi nhm metyl (-CH3). Ngi
ta chng minh c rng nhm metyl c kh nng y li cp electron ra xa mnh. Trong
trng hp nhm metyl trung ho bt phn in tch dng ca nguyn t cacbon trong nhm
cacboxyl, t gy nh hng tip theo lm gim bt s phn cc ca lin kt O-H.
+
c
ch3
h
"
+
c
3
h
h
h
'
+ +
c
c
1
2
h
h
cl
+
y
+i
+
c
-i
i=0
Hiu ng +I thng thy cc nhm ankyl v cc nhm mang in tch m. Nhm ankyl
cng ln, cng phn nhnh hiu ng +I cng ln. Trong cc nhm mang in tch m, m in
cng nh hiu ng +I cng ln.
ch3
-ch3 < -ch2-ch3 < -ch
<
ch3
ch3
ch3
-c
ch3
26
http://hhud.tvu.edu.vn
ch3 - c - nh2
o
; ch2 = ch - ch = ch - ch =O
; ch2 = ch -cl
oh
;
CH
CH2
CH
CH
CH2
CH
CH2
Nu thay th mt nguyn t H nhm -CH2 bng nhm -CHO chng hn th nhm ny s tham
gia lin hp vi obitan phn t ca butaien. Nh c tnh phn cc sn c ca nhm -CHO, ton
b obitan phn t mi hnh thnh ca phn t b dch chuyn mt phn v pha nguyn t xi.
Ta ni y c hiu ng lin hp -.
27
http://hhud.tvu.edu.vn
++
CH2
CH
CH
CH
CH
CH2
CH
CH
CH
CH
cl
nh2
o
+c
-c
-c
+C
H khng phng
khng xen ph
H phng
xen ph
29
http://hhud.tvu.edu.vn
H
-C-C=C
-C-C
-C-C=O
N ;
H
c
c ;
N ;
Hiu ng siu lin hp c k hiu bng ch H (hyperconjugate effect). Hiu ng siu lin
hp tng theo s lng lin kt C-H v tr ca nhm ankyl.
- CH3 > - CH2- CH3 > -CH(CH3)2 > - C(CH3)3
Trn y chng ta cp n ba loi hiu ng chnh thng c biu hin trong cc hp
cht hu c. Vic xem xt cc hiu ng ny cho php ta tin on c kh nng phn ng v
nhng chiu hng chnh s xy ra ca cc phn ng hu c, ng thi cn cho php gii thch
cnhiu tnh cht ca cc hp cht hu c. V vy hiu c chng l rt cn thit nghin
cu v cc hp cht hu c v cc phn ng hu c.
30
http://hhud.tvu.edu.vn
Cu hi v bi tp
1. Cc loi ng phn? Biu din cc ng phn bng cng thc cu to hoc cu hnh
khng gian thch hp.
2. Cc loi hiu ng in t trong phn t hp cht hu c. ng dng ca vic xt cc hiu
ng in t trong ho hc hu c.
3. Vit cng thc cu to cc ng phn c th c ca cc hp cht c cng thc phn t
C6H12; C4H8; C2H4O2; C3H6O.
4. Cu hnh khng gian v gi tn cc ng phn hnh hc ca cc hp cht sau:
But-2-en
2-metylbut-2-enoic
1,2- iclo xiclopropan
But-2-enioic
5. Cng thc chiu Fis v gi tn cc ng phn quang hc ca cc hp cht sau:
Axit lactic
Alanin
Anehit glixeric
Serin
Glucoz
Fructoz
6. So snh tnh linh ng ca nguyn t H trong nhm -OH ca cc hp cht sau v gii
thch bng cc hiu ng in t:
HOH; C2H5OH; HCOOH
7. So snh tnh axit ca cc axit sau v gii thch:
HCOOH; CH3- CH2- COOH; CH3- CH2-CH2- COOH v CH3- CH- COOH
CH3
CH3- CH2- CH2- COOH; CH2= CH- CH2- COOH v CH3- CH= CH- COOH
CH3- CH2- COOH; CH3- CH- COOH v CH2- CH2 - COOH
Cl
Cl
8. So snh s phn cc ca lin kt C- Cl gia cc hp cht sau v gii thch.
CH3
CH3- CH2- CH2- Cl; CH3- CH- Cl v CH3- C- Cl
CH3
CH3
CH3- CH2- Cl v C6H5- Cl
9. Xt chiu phn cc ca cc lin kt trong cc hp cht sau y v gii thch.
Pent- 2-en
2- metylbut-2-en
Vinyl clorua
Allyl clorua
31
http://hhud.tvu.edu.vn
Chng II
Hirocacbon
C2H6
etan
C3H8
propan
C6H14
hexan
C9H20
nonan
C7H16
heptan
C10H22
ecan
32
http://hhud.tvu.edu.vn
C4H8
butan
ch hircacbon khng phn nhnh thng thm tip u ng n (normal) hoc khng
c. Tip u ng iso gi nhng hp cht c hai nhm metyl u mch khng phn nhnh,
cn tip u ng neo ch hp cht c 3 nhm metyl u mch khng phn nhnh.
Th d:
CH3- CH2 -CH2- CH2- CH3
n-pentan
CH3
CH3- C- CH3
CH3
neopentan
b. Tn gc v bc ca gc
C2H5etyl
C3H7propyl
Th d:
CH3 - CH - CH - CH2 - CH2 - CH3
CH3 CH3
CH3
CH3 -C - CH - CH2 - CH2 - CH3
CH3 CH2-CH3
2,2-imetyl-3-etyl-hexan
Cc xicloankan c gi tn theo cch gi IUPAC. Mch chnh lun phi l mch vng.
Vic nh s ch c tin hnh i vi cc xicloankan c hai nhnh tr ln. Bt u nh s t
nguyn t cacbon lin kt vi nhnh n gin nht v theo chiu sao cho tng s s ch v tr
mch nhnh l nh nht, sau gi tn theo th t:
V tr nhnh + tn nhnh + xiclo + tn ankan tng ng
Th d:
CH3
CH3
CH2 -CH3
1-mtyl-2-tylxiclpentan
mtylxiclhexan
d. ng phn
CH3
CH3
* -CH -CH
CH3 -CH -CH
2
3
CH3
Th d 3: ng phn cu dng ca n-butan
CH3
CH3CH3
H
H
H
CH3
H
H
dng i ca butan
dng khut ca butan
Xicloankan c s ng phn nhiu hn s ng phn ca ankan. Xicloankan c cc loi
ng phn sau:
34 hu c ..34
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
isopropylxiclopentan
CH3
metylxiclopentan
- ng phn v v tr nhnh
Th d:
CH3
CH2 -CH3
xiclohexan
CH3
CH2 -CH3
1-metyl-2-etyl xiclohexan
- ng phn hnh hc
Th d:
CH3
1-metyl-4-etyl xiclohexan
CH3
CH3
CH3
cis -1,2-imetyl
xiclopropan
trans -1,2-imetyl
xiclopropan
Nguyn tc ca phng php ny l cho dn xut halgen tc dng vi kim loi Na.
0
CH3 - CH -Cl + 2 Na + Cl - CH -CH3 t CH3 - CH2 - CH -CH3 + 2NaCl
2
CH3
t0
CH3
+ 2NaBr
b. Phn ng cacboxyl ho
iu kin nhit cao v c xc tc, axit cacboxylic b loi CO2 to thnh ankan.
35
http://hhud.tvu.edu.vn
Th d:
t0
xt
CH3 - CH2-COOH
CH2 - CH2-C
CH2 - CH2-C
O
O
OH MnO , t0 CH2 - CH2
2
C =O
OH - H2O, -CO2 CH2 - CH
2
CH2 - CH2
[H]
CH2
Zn + HCl CH2 - CH2
- H 2O
O
O
CH2 - CH2-C
O
O
Ca
CaO CH + Na CO
4
2
3
t0
CH2 - CH2
t0
C =O
-CaCO3 CH2 - CH
2
CH2 - CH2
[H]
CH2
Zn + HCl CH2 - CH2
- H2O
p R -R + 2 NaOH + 2 CO + H
2
2
1.4. Cu to
Trong phn t ankan v xiclankan cc nguyn t cacbon u trng thi lai ho sp3. Bn
obitan lai ho sp3 ca nguyn t cacbon c hnh dng, mc nng lng nh nhau hng v bn
nh ca mt t din u. Gc ho tr l 109028. Bn obitan lai ho sp3ca nguyn t cacbon ny
to vi obitan sp3 ca nguyn t cacbon khc hoc vi obitan s ca nguyn t hir bn lin kt
36 hu c ..36
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
109028' -
2
3
+24044
4
+9044
5
+0044
6
-5016
7
-9033
8
-12051
37
http://hhud.tvu.edu.vn
1600 600
Lin kt ny km hiu qu, l trung gian gia lin kt v lin kt . iu cho php gii
thch xiclopropan c khuynh hng tham gia phn ng cng hp m vng.
Khi tng kch thc ca vng chnh lch ca gc ho tr so vi gc l tng gim. Nhng
xiclohexan c gc ca vng l 1200, vy n phi c sc cng ln hn xiclopentan. Kt lun ny
mu thun vi tnh cht. S d nh vy l v thuyt sc cng Bayer da vo gi thuyt cu to
phng ca mi h thng xicloankan. Thc t chng c s sp xp khng gian khng phng ca
cc nguyn t cacbon trong vng, do sc cng gim.
h
(t0)
RX
+ HX
h
(t0)
C -X + HX
X X
2X
C + HX
CX + X
+ X2
C C
C -X
X2
Cc vng 3, 4 cnh km bn, c tnh cht ging anken, chng d dng tham gia cc phn
ng cng hp m vng.
Th d:
CH2
H2C
CH2
+ Br2
c. Phn ng oxi ho
iu kin bnh thng cc ankan khng b oxi ho bi oxi khng kh, cc cht oxi ho
mnh nh H2SO4 c, KMnO4Nhng nhit cao, cc ankan b oxi ho to thnh sn
phm cha oxi. Khi un nng t 100 - 1600C vi s c mt ca cc cht xc tc (KMnO4,
Na2CO3) cc ankan b oxi ho bi oxi khng kh to thnh cc axit.
39
http://hhud.tvu.edu.vn
Th d:
100 -1600C
CH3 -(CH2)16 -CH3 + 3 O2
2CH3 -(CH2)16 -COOH + 2 H2O
O2,xt
Khi c mt oxi d, cc ankan b chy to thnh kh CO2 v H2O, ng thi gii phng mt
lng nhit ln.
Th d:
CH4 + 2 O2
nhit cao, khng c oxi khng kh, cc ankan b phn hu gy mch to thnh cc ankan
v cc hirocacbon khng no (anken) c mch ngn hn. Qu trnh ny c gi l qu trnh
crckinh.
crckinh
CnH 2n+2
CxH 2x+2 + CyH 2y
ankan
anken
2 CH3-CH2-CH2-CH3
CH2=C = CH2
CH3- CH = C = CH2
prop-1,2-ien
but-1,2-ien
CH2=CH - CH = CH2
but-1,3 -ien
CH2=C - CH = CH2
CH3
2-metylbut-1,3-ien
(iso pren)
- Ankin l hirocacbon cha no, mch h c mt lin kt ba trong phn t. Cng thc
chung l CnH2n -2 (n2). Chng lp thnh mt dy ng ng, ng u dy ng
ng l axetylen (C2H2).
CH3-CH=CH2
propylen
CH3-C=CH2
CH3
isobutylen
CH2=CH-CH=CH2
CH2=CH-CH2-CH2-CH=CH2
CH2=C-CH=CH2
CH3
allen
ivinyl
iallyl
isopren
i vi cc ankin, ngi ta ly axetilen lm cht gc, cn cc ng ng ca axetilen c
coi l dn xut th ca axetilen khi th nguyn t hir trong axetilen bng gc ankyl v gi tn nh
sau:
Tn gc ankyl + axetilen
Th d:
CH3-C CH
CH3-C C-CH3
metyl axetilen
imetyl axetilen
41
http://hhud.tvu.edu.vn
b. Tn gi IUPAC
CH2=C-CH=CH2
CH3
2-metylbut-1,3-ien
but-2-en
CH3 C C-CH-CH3
CH3
4-metyl pent-2-in
CH3-CH2-CH2-CH=CH2
pent-1-en
(pentylen)
- ng phn v v tr lin kt kp
CH3 -CH2 -C=CH
but-1-in
but-2-in
42
http://hhud.tvu.edu.vn
- ng phn hnh hc
CH3
H
C =C
CH2 -CH3
H
trans-pent-2-en
CH3
CH2 -CH3
C =C
H
H
cis-pent-2-en
KOH CH - C =C + 2 HCl
3
ru
b. i t ancol
H2SO4
CH2 = CH2 + H2O
>1700C
H SO
CH3 -CH -CH2 -OH 2 04 CH3 - C = CH + 2H2O
>170 C
OH
H SO
CH2 -CH2 -CH2 -CH2 2 04 CH2 = CH - CH =CH2 + 2H2O
>170 C
OH
OH
Al2O3
CH2 = CH - CH =CH2 + 2H2O + H2
t0
CaC2 + 2 H2O
Ca(OH)2 + C2H2
43 hu c ..43
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
2 CH4
15000C
CH =CH + 3 H2
2.4. Cu to
a. Cu to ca cc anken
Hai nguyn t cacbon lin kt i trng thi lai ho sp2. Ba obitan lai ho sp2 ca nguyn
t cacbon ni i hnh thnh ba lin kt , trong c mt lin kt (C-C) hnh thnh do s
xen ph ca obitan sp2- sp2 v hai lin kt khc c th l lin kt (C-H) do s xen ph ca
obitan sp2- s hoc lin kt (C-C) do s xen ph ca obitan sp2 ca cabon ni i v sp3 ca
cacbon. Mi nguyn t cacbon lin kt i cn li mt obitan 2pz cha tham gia lai ho, chng
c trc vung gc vi mt phng cha lin kt , song song vi nhau, c spin ngc chiu nhau,
chng xen ph vi nhau hnh thnh lin kt . Do lin kt i gm mt lin kt v mt lin
kt . V trong phn t c cha lin kt km bn, d dng b ph v tham gia cc phn ng
cng hp, oxi ho v trng hp.
H
H
C C
H
H
H
H
H
H
c. Cu to ca ankin
Hai nguyn t cacbon lin kt ba trng thi lai ho sp. Hai obitan lai ho sp to thnh
hai lin kt , trong c mt lin kt (C-C) hnh thnh do s xen ph ca hai obitan lai ho
sp, v mt lin kt , do s xen ph ca obitan lai ho sp ca cacbon ni ba vi obitan s ca
nguyn t hir hoc hnh thnh do s xen ph ca hai obitan lai ho sp vi sp3.
Mi nguyn t cacbon ni ba cn li hai obitan p cha tham gia lai ho, chng c trc
vung gc vi mt phng cha lin kt , song song vi nhau v c spin ngc chiu nhau. Cc
obitan p ny xen ph vi nhau tng i mt hnh thnh nn hai lin kt . Cc lin kt km bn
nn cc ankin l hp cht hot ng ho hc mnh, d dng tham gia cc phn ng cng hp, xi
ho, phn ng trng hp.
H
+
C
C
+ A+B-
A
C
B
y AB c th l X2, HOH, HX, HOX, H2SO4
Phn ng xy ra theo c ch cng hp i in t qua hai gia on:
- giai on u, tc nhn i in t (cation A+) cng hp vo nguyn t cacbon mang
phn in tch m ni i to thnh cacbocation trung gian. y l giai on chm,
thun nghch, quyt nh tc phn ng.
AB
A+ + B-
45
http://hhud.tvu.edu.vn
+
C
chm
+ A+
+
C
- giai on sau, cacbocation trung gian tc dng vi anion B- cho sn phm. Giai on
ny phn ng xy ra nhanh, mt chiu.
A
A
+
nhanh
C
C
+ BC
C
B
+ X2
Br
CH3 -C =CH
Br2
CH3 -C =CH
Br2
Br Br
Br
Br Br
CH -C -CH
Br
Br
Br Br
+
C
C
+ HX
C C
Th d:
+
CH3 -C = CH -CH3
CH3
Br
+ HBr
46 hu c ..46
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
C ch cng hp i in t:
HBr
H+ + Br+
CH3 -C = CH -CH3 + H
CH3
Th d:
Br
CH3 -C -CH =CH2 + CH3 -C =CH -CH2
2 CH2 =C - CH =CH2 +2 HBr
Br
CH3
CH3
CH3
C ch phn ng:
HBr
H+ + Br+
CH2 C - CH
CH2 + H+
CH3 - C CH CH2
CH3
CH3
Trong cacbocation lin hp in tch dng gii to trn c ba nguyn t cacbon, nhng tp
trung hn l C2, C4.
Br
+
+
CH3 - C CH CH2
CH3 - C CH CH2
CH2 + 2Br
2 CH3 C CH
CH3
Br
CH3
CH3
Hirohalogenua cng hp vo ankin s cho sn phm l gem ihalogen ankan.
Th d:
Cl
+ HCl
+ HCl
CH3 -C=C -CH3
CH3 -C =CH -CH3
CH3 -C -CH2 -CH3
Cl
Cl
- Cng hp nc
Trong mi trng axit cc anken v ankaien cng hp nc to ra cc ancol.
C
+ HOH
OH
Th d:
CH3 -CH =CH2 + H2O
CH2 =CH -CH =CH2 + H2O
H
H
47 hu c ..47
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
Hg2+
chuyn v
CH3-C= CH2
CH3 -C -CH3
H2SO4
O
OH
=
CH3 -C = CH + H2O
b. Phn ng oxi ho
Th d:
CH3 - Ch = CH2 +KMnO4 +H2O
K2Cr2O7 +H2SO4
Ch3 - C = CH2
CH3
K2Cr2O7 +H2SO4
O O
48
http://hhud.tvu.edu.vn
O
CH2
O
CH - CH
O O
H2O
O O
O
CH3 - C
CH -CH3
CH3 O O
H2 O
Ch3 - C = CH -CH3 + O3
CH3
CH2
Khi c mt cht xc tc Ag kim loi 150 -3500C hirocacbon cha no b oxi ho bi oxi
khng kh to thnh ete oxit.
Th d:
O
Ag
CH2 =CH2 + O2
CH
2 CH2
1500-3500C
O
O
Ag
CH2 =C - CH =CH2 +O2
C - CH CH2
0
0 CH2
150 -350 C
CH3
CH3
Phn ng oxi ho ng vai tr quan trng trong vic xc nh cu to ca nhng hp cht t
nhin phc tp v xc dnh cu to ca nhng hp cht cha lin kt i.
c. Phn ng trng hp
Phn ng trng hp l phn ng to thnh hp cht cao phn t t nhng phn t n gin.
Th d:
1900-2100C n ( - CH - CH -)
n CH2 =CH2
(-CH2 -CH2 -)n
2
2
1500-2000at
pli tylen
tylen
n ( -CH2 -CH =CH -CH2 -)
(-CH2 -CH =CH -CH2 -)n
n CH2 =Ch - CH = CH2
cao su buna
d. Phn ng th
Nhng ankin c cha nguyn t hiro lin kt vi cacbon trng thi lai ho sp c th tham
gia phn ng th. Nguyn t hiro c thay th bi nguyn t kim loi to thnh mui. Trong
phn ng ny ankin th hin tnh axit. iu ny c gii thch do nguyn t cacbon trng thi
lai ho sp c m in ln, lin kt Csp-H b phn cc mnh.
Kali hiroxit khan c th chuyn ankin-1 thnh kali axetilua, tuy nhin phn ng ny xy ra
thun li hn nu ta dng kali amiua trong amniac lng.
R -C =CH + KNH2
NH3 lng
R -C =C -K + NH3
R -C =CH + 2[Ag(NH3)2]OH
HC =CH +2[Ag(NH3)2]OH
R -C =C Ag + 2NH3 + H2O
3. hirocacbon thm
metylbenzen
(toluen)
CH3
CH -CH3
CH3
isopropylbenzen
(cumen)
CH3
CH3
CH3
CH3
o-xilen
CH3
p-xilen
50
http://hhud.tvu.edu.vn
m-xilen
Nhn thm c hai nhm th ankyl tr ln th hnh thnh ng phn v v tr nhm th.
gi tn cc ng phn ngi ta tin hnh nh s cc nguyn t cacbon ca vng benzen. Bt u
nh s t nguyn t cacbon trong vng benzen lin kt vi nhm th n gin nht. nh s
theo chiu sao cho tng cc con s ch v tr nhm th l nh nht. Gi tn theo nguyn tc:
V tr nhm th + tn nhm th + benzen
Th d:
CH3
CH3
CH3
CH2 -CH3
CH2 -CH3
1-metyl-2-etylbenzen
CH2 -CH3
1-metyl-4-etylbenzen
1-metyl-3-etylbenzen
NO2
nitrobenzen
Br
Br
clobenzen
NO2
Cl
Br
1,2-ibrom benzen
3-clo-5-brom nitrobenzen
anilin
OH
phenol
OCH3
anisol
51
http://hhud.tvu.edu.vn
CHO
benzanehit
COOH
axit benzoic
n- propylbenzen
- ng phn v v tr nhm th
CH3
CH3
CH3
CH3
CH3
1,2-imetylbenzen
1,3-imetylbenzen
CH3
1,4-imetylbenzen
b. Phng php iu ch
Ar -X + 2Na + X -R
Th d:
Cl
Ar -R + 2NaX
CH3
+ 2Na + Cl -CH3
+ 2NaCl
- Phn ng Frien-Crap
R
+ RX
AlCl3
HX
Th d:
CH2 -CH3
+CH3 -CH2 -Cl
AlCl3
HCl
c. Tnh cht vt l
52
http://hhud.tvu.edu.vn
d. Cu to ca benzen
h
C
C
C
C
h
biu din cng thc cu to ca benzen ta c th dng mt trong ba cng thc sau:
53
http://hhud.tvu.edu.vn
c. Tnh cht ho hc
- Phn ng th
Benzen v ng ng ca benzen d dng tham gia phn ng th nguyn t hiro trong nhn
thm bng nguyn t hoc nhm nguyn t khc.
Phng trnh phn ng tng qut:
Ar -H + AB
xt
Ar -A + HB
Ar -H + A
H
Ar - A
Ar
H
A
Ar
A + H
L phn ng thay th nguyn t hiro trong nhn benzen bng nguyn t halogen. Tc nhn
ca phn ng l halogen v xc tc thng dng l cc axit liuyt nh AlCl3, FeX3.
Trong thc t phn ng ny thng dng xc tc l bt st. Bt st tc dng vi cc halogen
to thnh cc axit liuyt l FeX3.
S phn ng tng qut nh sau:
X
+ X2
Fe bt
+ HX
Cl2 v Br2 halogen ho benzen mt cch bnh thng, I2 phn ng thun nghch, F2 khng
phn ng trc tip vi benzen.
54
http://hhud.tvu.edu.vn
Th d:
Br
+ Br2
Fe bt
CH3
+ 2Br2 Fe bt
+ HBr
CH3
Br
CH3
+
+ 2HBr
Br
FeX3 + X2
X. ..... X. ....FeX3
Sau phn ng xy ra.
H
+
+ X
+X
FeX4 + X
+
+ H
iu kin nhit cao hoc chiu nh sng t ngoi, cc ng ng ca benzen thc hin
phn ng halogen ho phn nhnh theo c ch th gc tng t cc ankan.
Th d:
CH -CH3
+ Cl2
CH3
Cl
C -CH3
+ HCl
CH3
h
t0
- Phn ng nitro ho
+HNO3
NO2
+
H2SO4
H2O
55
http://hhud.tvu.edu.vn
H
NO2
NO2
+ H
H + 2HSO4 + H3O
H2SO4 + H2O
- Phn ng ankyl ho
AlCl3
+R -X
+
AlCl3 ....X....R
AlCl3 + RX
+
AlCl3X + R
H
R
+
R+
+ R+
H+ + AlCl3X - Phn ng axyl ho
+
+ H
HX + AlCl3
C -R
O + HX
+ R -C -X
O
C -R
+
O +H
H
C -R
O
+
+
+ R -C
O
+
H + AlCl4
HCl + AlCl3
+
R -C + AlCl4
O
=
+ AlCl3
R -C -Cl
O
+C NH2
-I
+C OH
-I
- Nhng nhm th nh hng meta: Gm c -CN, -NO2, -CH=O, -COR, -COOH, -COOR
Nhng nhm ny c ng thi hai hiu ng ht in t (-I, -C) lm mt in t trong
nhn gim i, phn hot ho nhn thm v gim ch yu cc v tr octo v para. Phn ng th
xy ra kh khn hn so vi benzen v cho sn phm th v tr meta.
Th d:
-C
-I
-C
O
H
-I
-C
O
OH
-I
O
O
- Phn ng cng hp
+ 3 H2
benzen
CH3
xiclohexan
CH3
+3H2
toluen
metyl xiclohexan
- Cng hp halogen: Quan trng hn c l phn ng cng hp clo. Khi cho clo i qua
benzen c chiu nh sng khuch tn, phn ng xy ra ta thu c hexaclo xiclohexan.
Cl
Cl
0
Cl
50 C
+ 3 Cl2
h
Cl
Cl
Cl
Hexaclo xiclohexan c nhiu ng phn lp th, trong ng phn gamma () c hot tnh
c i vi cn trng, v vy ng phn ny c dng lm thuc tr su (c tn gi l thuc tr
su 6.6.6). Hin nay thuc tr su ny c cm s dng do s tn lu lu di v gy c hi
i vi mi trng.
Phn ng oxi ho
Benzen ch b oxi ho khi cho oxi khng kh tc dng nhit cao, c V2O5 xc tc to
thnh anhirit maleic.
+ O2
O
C=
O + CO2
C=
O
4000C-4500C
V2O5
anhirit maleic
Benzen cng tham gia phn ng ozon ho to thnh glioxal.
+ O3
H 2O
CHO
CHO
58
http://hhud.tvu.edu.vn
+ H2 O 2
n- propyl clorua
axit benzoic
CH3
t0
+ KMnO4 + H2SO4
CH3
o-xilen
COOH
+ CH3COOH + K2SO4 + MnSO4 + H2O
COOH
axit o- phtalic
iphenyl
iphenylmetan
naphtalen
anthraxen
- i phenyl
i phenyl c th c iu ch t dn xut monohalogen thm bng phn ng Fittic.
59 hu c ..59
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
Th d:
Br +2Na +
Br
+ 2NaBr
iphenyl l nhng tinh th rn, khng mu, nng chy 710C, tan tt trong etanol v ete.
iphenyl cng tham gia cc phn ng th i in t nh nitro ho, halogen ho
u tin phn ng v tr 4, sau l v tr 4.
Th d:
HNO3
H2SO4
O 2N
NO2
NO2
9
10
1
2
3
4
Naphtalen nguyn cht l cht kt tinh thnh nhng l mng ng nh, nng chy 80,30C
v si 2180C, c mi thm c trng, d bay hi v d thng hoa.
Naphtalen ging benzen nhiu phn ng, nhng kh nng phn ng ca naphtalen mnh
hn benzen.
Nhng phn ng th c th xy ra v tr (v tr 1, 4, 5 hoc 8)
Th d:
NO2
+ H2O
+ HNO3
=O
O +2 H2O
C
O
60
http://hhud.tvu.edu.vn
- Phenanthren
Phenanthren l cht rn kt tinh di dng tinh th khng mu, nng chy 1010C v si
3400C. Phenanthren c tnh cht ho hc tng t nh naphtalen. Phenanthren rt gn vi nhiu
hp cht t nhin c hot tnh sinh l quan trng nh vitamin D, cc kch thch t sinh dc.
61
http://hhud.tvu.edu.vn
Cu hi v bi tp
1. C ch th gc t do v hng ca phn ng halogen ho ankan? Gii thch bn ca
cc xicloankan.
2. Cu to v tnh cht ca cc hirocacbon khng no. C ch cng hp i in t v hng
ca phn ng cng hp vo lin kt i C=C; lin kt ba CC.
3. Cu to ca benzen. Tnh thm v tnh cht ho hc ca cac hirocacbon thm. C ch
th i in t v quy lut th trong nhn thm.
4. Gi tn cc hp cht sau y theo tn gi thng thng v tn gi IUPAC.
4.1. CH3- CH2- CH2- CH2- CH3
4.2. CH3- CH- CH2- CH2- CH3
CH3
CH3
4.3. CH3- C- CH2- CH2- CH3
CH3
4.4. CH3- C=CH2
CH3
CH3- CH2- CCH
5. Vit cng thc cu to ca cc hp cht sau:
5.1. 2,5-imetyl octan
5.2. neoheptan
5.3. 2,5,5-trimetyl hept-3-en
5.4. isopropylbenzen
6. Vit cng thc cu to cc ng phn ca cc hirocacbon c cng thc phn t C6H14;
C5H10 v gi tn chng theo tn gi IUPAC.
7. Vit phng trnh v c ch cc phn ng sau:
7.1. 2-metyl propan + Cl2 askt
7.3.
7.4.
7.5.
7.6.
7.7.
7.8.
t
isopropyl benzen + Cl2
Bezen + HNO3
Fe
Toluen + Br2
9.2. C4H8; khi cho tc dng vi dung dch KMnO4 thu c ru hai chc, trong c
mt nhm chc ru bc mt v mt nhm chc ru bc 3.
9.3. C9H12; khi halogen ho nhit cao thu c dn xut halogen bc 3.
9.4. C5H10; oxi ho bng ozon, sau thu phn thu c anehit axetic v axeton.
10. T benzen v cc hp cht khc, hy vit phng trnh phn ng ho hc dng iu ch:
10.1. Axit o v m nitro benzoic.
10.2. Metyl phenyl xeton.
10.3. 2-clo- 2- phenylpropan.
10.4. p v m clo nitrobenzen.
63
http://hhud.tvu.edu.vn
Chng III
Dn xut ca hirocacbon
Dn xut ca hirocacbon l nhng hp cht m trong phn t ca chng cha mt hay mt
s nhm chc lin kt vi gc hirocacbon.
Da vo bn cht ca nhm chc m dn xut ca hirocacbon c chia thnh nhng loi
khc nhau. Th d dn xut halogen, ancol, ete, axit cacboxylic vv
Trong ni dung chng ny chng ta ch xt mt s dn xut quan trng, l dn xut
halogen, ancol- phenol, anehit-xeton, axit cacboxylic v amin.
1. Dn xut halogen
CH2=CH-Br, CH2=CH-CH2-Cl
Cl
Cl
dn xut halogen vng no
CCl4
64 hu c ..64
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
dn xut monohalogen
dn xut polihalogen
CH3- CH2-Cl
dn xut bc 1
CH3
CH3-C-CH3
Cl
dn xut bc 3
dn xut bc 2
vinyl clorua
allyl clorua
Br
phenylbrmua
CH2 -Cl
benzylclorua
b. Tn gi IUPAC
CH2 -Cl
Cl
CH C -Cl
clo etin
clo phenylmetan
clo benzen
c. ng phn
Dn xut halogen khng vng no c ng phn mch cacbon v ng phn v tr nhm chc. Dn
xut halogen khng vng cha no c thm ng phn v tr ca lin kt i v ng phn hnh hc.
Th d 1: C4H9Cl c cc ng phn mch cacbon:
CH3-CH2-CH2-CH2-Cl
CH3-CH-CH2-Cl
CH3
1- clo butan
1- clo- 2- metylpropan
ng vi mi ng phn mch cacbon trn li c mt ng phn v tr nhm chc:
Cl
CH3
CH3-CH-CH2CH3
CH3-C-Cl
CH3-CH2-CH2-CH2-Cl
CH3
2- clobutan
2- clo-2- metylpropan
1-clobutan
th d 2: C3H5Cl c cc ng phn v tr ca lin kt i v ng phn v tr nhm chc:
CH2=CH-CH2-Cl
CH3-CH=CH-Cl
CH2=C-CH3
Cl
1-cloprop-2-en
1-cloprop-1-en
2-cloprop-1-en
Th d 3: C2H2Cl2 c cc ng phn hnh hc:
h
c= C
Cl
cl
cl
c= C
Cl
Ty thuc vo iu kin phn ng (chiu sng hoc nhit thch hp), ngi ta c th
iu ch dn xut halogen bng phn ng thay th nguyn t hiro trong hirocacbon bng
nguyn t halogen.
Th d:
askt
CH3 - CH3 + Cl2
CH3 - CH2 - Cl + HCl
CH2 = CH2 + Cl2
5000C
CH2 = CH - Cl + HCl
vinyl clorua
66
http://hhud.tvu.edu.vn
450 -5000C
CH2 = CH - CH3 + Cl2
CH2 = CH -CH2 -Cl + HCl
allyl clorua
+Br2
Br
Fe
+ HBr
Th d:
CH2 = CH - CH3 + HBr
CH3 - CH - CH3
Br
2-brom propan
67
http://hhud.tvu.edu.vn
R
R
CH2
CH
R
R
R
Gc vinyl v gc phenyl gy hiu ng lin hp C lm gim s phn cc ca lin kt C-X.
Th d:
+C
X
-C
+C
CH2
CH
X
-C
Do kh nng phn ng ca nguyn t halogen trong dn xut thm ( kiu clo benzen) v
trong dn xut cha no (kiu vinyl clorua) kh khn hn so vi dn xut khng vng no.
Lin kt C-H cng l mt trung tm phn ng ca dn xut halogen. Do nh hng ca
hiu ng cm ng m -I ca nguyn t halogen m lin kt C-H phn cc mnh, nguyn t H
hot ng.
S phn cc c m t nh sau:
+
C
+
C
X +Y
+X
+
C
C +
Chm
C +
nhanh
+
C
C +X
ROH
HX
R : gc hirocacbon.
cho phn ng ch xy ra theo chiu thun, ngi ta tin hnh trong mi trng kim:
RX + H2O
OH-
ROH
HX
Phn ng thu phn ankyl halogenua d dng xy ra khi un nng vi kim trong dung dch
nc hay etanol-nc.
Th d:
to
CH3Cl +KOH
CH3OH + KCl
Cc dn xut kiu vinyl v phenyl halogenua ch b thu phn trong nhng iu kin rt khc
nghit.
69 hu c ..69
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
Th d:
OH
Cl
400 C
+NaOH
(rn)200at
clo benzen
+ NaCl
phenol
OH -3 HCl
- H2O
OH
gem triol (khng bn)
Cl
clorofoc
H -C -OH
O
=
Cl
C Cl + 3 HOH
axit fomic
+ Phn ng vi amoniac
Phn ng ny c dng iu ch cc amin
R -X + NH3
to
R -NH2 + HX
Th d:
NH2
Cl
0
+ 2 NH3
clo benzen
200 C
60-100 at
xt
+ NH4Cl
anilin
R -CN + KX
70
http://hhud.tvu.edu.vn
kim-ancol
+ HX
Hoc:
H
kim-ancol
OH- + HX
+ HX
HOH + X-
Th d:
CH3 -CH2 -Cl
KOH
CH2 =CH2 + HCl
C2H5OH
chm
H
cacbocation
nhanh
C =C
H
- C ch tch loi i nhn lng phn t (E2)
C ch E2 xy ra mt giai on qua phc trung gian hot ng hay trng thi chuyn tip.
C ch E2 tng t c ch SN2.
+ HY + X
Th d:
KOH
CH3 - CH =CH2 + HBr
C2H5OH
71
http://hhud.tvu.edu.vn
Th d:
2 CH3 -CH -CH2 -CH3 KOH CH3 - CH =CH -CH3 + CH2 =CH -CH2 -CH3 + 2 HBr
C2H5OH
(chnh)
(ph)
Br
Trong mi trng ete khan, dn xut halogen tc dng vi magi to hp cht c magi, cn
gi l hp cht Grinha.
0
t
R -X + Mg
R -Mg -X
ete khan
Th d:
t0
CH3 -CH2 -Br + Mg
CH -CH2 -Mg -Br
ete khan 3
etylmagi bromua
d. Phn ng ca gc hirocacbon
Nhng gc cha no v gc thm ca ankenyl v aryl halogenua c nhng tnh cht tng t
anken v tng t hirocacbon thm.
Cc dn xut cha no d dng tham gia cc phn ng cng hp theo c ch i in t.
Th d:
CH2
CH
Cl
+ HBr
CH3 - CH - Cl
Br
CH2
CH
CH2
Cl + HBr
CH3
CH
CH2Cl
Br
CH2 -CH
Cl
P.V.C
72
http://hhud.tvu.edu.vn
Nhng dn xut halogen thm tham gia cc phn ng th nguyn t H nhn thm theo c
ch th i in t.
Th d:
Fe
CH2Br
CH2Br
CH2Br
+ 2 HBr
+2 Br2
Br
Br
2. Ancol v phenol
Khi thay th nguyn t hiro trong phn t hirocacbon bng nhm OH (nhm hiroxyl) ta
c cc dn xut hyroxyl. Tu theo bn cht ca gc hirocacbon lin kt vi nhm hyroxyl
m ta phn bit ancol (ru) v phenol.
Phenol khc ancol l nhm hyroxyl lin kt trc tip vi nhn thm, cn ancol nhm
hyroxyl lin kt vi gc hirocacbon mch h hay mch nhnh ca nhn thm.
Th d:
OH
phenol
CH2OH
CH3 -CH2 -OH
ancol no
ancol cha no
ancol thm
Tu theo s lng nhm hyroxyl c trong phn t, ta phn bit thnh dn xut mono,
polihyroxyl.
Th d:
OH
OH
OH
OH
mono phenol
CH3 -CH2 -OH
mono ancol
i phenol
HO -CH2 -CH2 -OH
i ancol
HO
OH
tri phenol
i vi cc ancol, ngi ta cn phn bit ancol bc mt, ancol bc hai v ancol bc ba tng
ng vi nhm hyroxyl lin kt vi cacbon bc mt, cacbon bc hai, cacbon bc ba.
73 hu c ..73
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
R
R -CH2 -OH
R -CH -OH
R
ancol bc 1
R -CH -OH
R
ancol bc 2
ancol bc 3
CH2 =CH - OH
Nhng ancol cha no khc c nhm hyroxyl lin kt khng trc tip vi nguyn t cacbon
sp2, i din tiu biu l ancol allylic CH2=CH-CH2-OH.
2.2. Cch gi tn v ng phn
a. Tn gi thng thng
CH3CH2CH2-OH
CH3 -CH-OH
CH3
CH3-CH-CH2-OH
CH3
ancol etylic
ancol n propylic
ancol isopropylic
ancol isobutylic
CH2 -OH
ancol benzylic
b. Tn gi IUPAC
Th d:
CH3CH2CH2-OH
propan-1-ol
CH3-CH-CH3
OH
propan-2-ol
CH3-CH-CH2-OH
CH3
CH2=CH-CH2-OH
2-metyl propan-1-ol
CH2-OH
CH2-OH
etan -1,2-iol (etylen glicol)
prop-2-en-1-ol
CH2OH-CHOH-CH2OH
propan-1,2,3-triol (glixrin)
c. ng phn
Tng t dn xut halogen, ancol c ng phn mch cacbon, ng phn v tr nhm chc
v ng phn lin kt.
Th d 1:
C4H9OH c cc ng phn:
CH3
CH3-CH2-CH2-CH2-OH CH3-CH -CH2-OH CH3-CH-CH2-CH3
CH3
OH
butan-1-ol
2-metylpropan-1-ol
butan-2-ol
CH3
CH3-C-CH3
OH
2-metylpropan-2-ol
Cc anehit khc hoc dn xut ankyl th ca etylen oxit tc dng vi hp cht c magi
cho ancol bc hai:
R'
R -CH=O
R MgX
HOH
R -CH -O -MgX
R'
R -CH-OH
X
Mg OH
Xeton, este hoc clorua axit tc dng vi hp cht c magi cho ancol bc ba:
R -C -R
R MgX
O
=
R
R -C -O -MgX
HOH
R
R -C-OH
X
Mg OH
H+
CH2 + H2O
R -CH
CH3
OH
Th d:
CH3 - CH
CH2 + H2O
H+
Th d:
CH2 -Cl
+ HOH
benzyl clorua
Cl
+NaOH rn
clo benzen
OH-
CH2 -OH
+ HCl
ancol benzylic
OH
4000C
+ NaCl
200at
phenol
R
H
R
R
nhit thng, phenol l cht rn kt tinh khng mu. Phenol t tan vo nc, tan nhiu
trong nhng dung mi hu c.
2.5. Cu to ca ancol v phenol
xt cu to ca ancol v phenol ta xt bn cht ca lin kt oxi-hiro, nhng yu t nh
hng n s phn cc ca lin kt ny v nh hng ca nhm hiroxyl n gc hirocacbon.
Lin kt oxi-hiro l lin kt phn cc v pha nguyn t oxi, do oxi c m in ln hn
m in ca hiro.
Gc hirocacbon gy nhng hiu ng quyt nh s phn cc mnh hay yu ca lin kt
ny:
- Cc gc ankyl gy hiu ng cm ng dng +I lm gim s phn cc ca lin kt oxihiro. Khi s lng ca gc R tng, hiu ng +I tng, do vy s phn cc ca lin kt O-H gim
dn t ancol bc mt, ancol bc hai, ancol bc ba.
R"
R
CH2
CH
R'
R'
H
- Gc phenyl c hiu ng lin hp -C vi cp in t p ca oxi trong nhm OH, ng thi
cn c hiu ng -I. Nhng hiu ng ny u lm tng s phn cc ca lin kt O-H, quyt nh
tnh axit ca phenol.
77
http://hhud.tvu.edu.vn
-C
O
-I
CH2
CH2 -I
CH2
O
-I
CH OH
CH -I OH
-I
CH2 OH
CH
OH
CH2-I OH
tylenglicol
glixrin
CH2
OH
CH
OH
OH
Ngc li, trong phn t phenol th s phn cc ca lin kt C-O b gim i do hiu ng +C
ca nhm OH.
+C
OH
Bn cnh nhng trung tm phn ng c xt trn, chng ta thy nhm hyroxyl cng
gy nh hng ng k n hot ng ca gc hirocacbon.
i vi cc gc no, nhm OH gy hiu ng -I lm tng kh nng hot ng ca nhng nguyn t
H.
78
http://hhud.tvu.edu.vn
OH
CH2
OH
OH
Ancol no tc dng vi kim loi kim v mt vi kim loi khc to thnh ancolat.
Th d:
2C2H5-OH +2 Na
2 C2H5-ONa + H2
C2H5-OH + NaOH
Poliancol v phenol c tnh axit yu nn chng khng ch phn ng vi kim loi kim m
cn phn ng vi hiroxit kim loi.
Th d: Glixerin tc dng vi Cu(OH)2 to ra phc mu xanh.
79
http://hhud.tvu.edu.vn
CH2 - O
CH2 - OH
2 CH -OH
Cu(OH)2
O -CH2
Cu
CH -O
H
CH2 - OH
CH2 - OH
O -CH
H
2 H2 O
HO -CH2
O Na
+ NaOH
+ H2O
phenol
O Na
natri phenolat
OH
+ NaHCO3
+ CO2 + H2O
- Phn ng este ho
Ancol phn ng vi axit cacboxylic, anhirit axit, axyl halogenua v axit v c khc to
ra cc este. Phn ng ny c gi l phn ng este ho.
H+
O C R
t0
OH
+ (R -C -O)2
H+
t0
+RCOOH
Th d:
H2SO4
t0
ancol isoamylic
Nhm hiroxyl trong ancol d dng c thay th bng nhm NH2 hoc bng nguyn t
halogen khi ancol phn ng vi amoniac, HX, PCl3, PCl5 hay SOCl2.
80
http://hhud.tvu.edu.vn
R -OH + NH3
Al2O3
R -NH2 + H2O
R -OH + HX
R -X + H2O
R -OH + PCl5
Khi c mt cht ht nc (H2SO4 c) nhit cao (1700C), cc ancol tham gia phn ng
hirat ho to thnh cc hirocabon khng no.
R- CH
H
CH2
OH
H+
t0
R- CH
CH2 + H2O
C ch:
R - CH2 - CH2 -OH + HOSO3H
-H2O
R - CH2 - CH2 -OSO3H
t0
H2SO4
R -CH =CH2
ietyl ete
81 hu c ..81
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
d. Phn ng oxi ho
Ancol d dng b oxi ho bi cc tc nhn khc nhau, trong nhng iu kin khc nhau
to thnh hp cht cacbonyl, hoc axit cacboxylic.
Trong phng th nghim ngi ta oxi ho ancol bng CuO v nhit , KMnO4 trong mi
trng kim hay mi trng trung tnh, trong c th sng c s tham gia ca men hirogenaza.
Trong nhng iu kin nh trn, oxi ho ancol bc mt cho anehit, ancol bc hai cho
xeton.
R- CH2- OH
R-CHO + H2O
anehit
R- C R + H2O
R-CH- OH
R
O
axeton
Phn ng oxi ho ancol bc mt v ancol bc hai xy ra qua giai on to thnh gem iol.
H
H
[O]
R C OH
R C OH
R -CH =O + H2O
H
OH
gem iol
R3
R3
H2SO4 c, t0
[O]
R1 -CH2 -C -OH
R1 -CH =C -CH2 -R2
-H2O
-R
1COOH
CH2 R2
R2 -COOH + R3 -COOH
R2 -CH =C -R3
R2 -CH2 -C -R3
OH
O
82
http://hhud.tvu.edu.vn
OH
[O]
+H2O
=
O
quinon
phenol
c. Phn ng ca gc hirocacbon
Th d:
CH2 = CH - CH2 - OH + HBr
CH3 - CH - CH2OH
Br
Ancol thm v phenol d dng tham gia phn ng th i in t trong nhn thm:
Th d:
CH2OH
+ 2Br2
CH2OH
CH2OH
Br
+2HBr
+
Br
op- brom
p o- brom
ancol benzylic
ancol benzylic
ancol benzylic
OH
Br
OH
Br
+ 3Br2
phenol
+ 3HBr
Br
2, 4,6- tribrom phenol
83
http://hhud.tvu.edu.vn
R-C-R
O
anehit
xeton
CH3-C-CH3
O
axeton
axetanehit
CH=O
C
O
xiclhexyl cacbxanhit
C CH3
O
axeto phenon
benzanehit
- Hp cht cacbonyl cha no: Tiu biu l hp cht cacbonyl cha no c hai lin kt i lin
hp.
Th d:
CH2=CH-CH=O
Th d:
O=CH-CH=O
glioxan
O=CH-C6H4-CH2-CH=O
anehit phtalic
=
anehit benzoic
(benzanehit)
Tn ca xeton c gi theo quy tc:
Tn gc hirocacbon + xeton
Th d:
CH3-CO-CH3
imetyl xeton (axeton)
CH3-CO-CH2-CH3
metyl etyl xeton
CH2=CH-CO-CH3
metyl vinyl xeton
b. Tn gi IUPAC
CH2=CH-CH=O
prop-2-enal
CH3-CH=CH-CH=O
but-2-enal
c. ng phn
(CH3)2CH-CH=O
2-metylpropanal
CH2=C-CH=O
CH3
2-metylprop-2-enal
- ng phn v tr lin kt :
CH2=CH-CH2-CH=O
But-3-enal
CH3-CH=CH-CH=O
but-2-enal
CH=O
fomyl xiclprpan
86
http://hhud.tvu.edu.vn
cHO
c
h
c
CH3
CH3
cHO
cis buten-2-al
trans buten-2-al
Mono xeton c y cc loi ng phn nh mono anehit v cn thm ng phn v tr nhm
chc.
Th d 1: C4H10C=O c cc ng phn mch cacbon v ng phn v tr nhm chc.
=
pentanon-2
pentanon-3
CH2 = CH -C -CH3
CH2
H2C C=O
xicl butanon
O
mtyl vinyl xtn
Th d 3:
C4H8C=O c cc ng phn v tr ca lin kt , ng phn hnh hc v cc ng phn khc:
CH3
CH3
cis penten-3-on-2
h
c
C -CH3
O
C -CH3
C
O
h
=
c
h
trans penten-3-on-2
Ngi ta c th oxi ho nhng hirocacbon khc nhau. Th d khi t chy chm n-ankan
tng kh sinh ra mt lng nh anehit, hoc xeton.
87 hu c ..87
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
Th d:
600-7000C
H -CH=O + H2O
xt
metanal
CH4 + O2
CH2 -CH3
O2
0
xt, t
C - CH3+ H2O
O
axeto phenon
xt
1
CH2 = CH2 + O2 0
2 50 C
CH3 -CH=O
axetanehit
b. oxi ho ancol
Th d:
AlCl3
AlCl3
AlCl3
C6H6 + (CH3CO)2O
+ H2O
OH
- HX
OH - H2O
OH
Th d:
C6H5 -CHCl2
+ 2 H2O
OH
benzylien clorua
88
http://hhud.tvu.edu.vn
C6H5 - CH=O +
benzanehit
R -C -R
O
=
HCl
1200
Lin kt trong nhm C=O lun phn cc v pha oxi, v oxi c m in ln hn m
in ca cacbon. Ta c th m t:
C
O
R
R
C
R
CH
O
> '
O
'
CH
+C
- Trong phn t anehit v xeton cha no lin hp, gc vinyl gy hiu ng lin hp dng
+C. Hiu ng ny lm gim gi tr in tch dng ca cacbon chc.
Th d:
+C
CH2
CH
CH
O
Vi cc policacbonyl, c bit 1,2-icacbonyl, cc nhm C=O gy hiu ng I v nh
hng tng h ln nhau. nh hng lm tng gi tr in tch dng ca cacbon chc.
Th d:
89 hu c ..89
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
-I
CH
CH
Th d:
H
H
-I
CH=O
H
- Vi cc gc thm, nhm C=O gy cc hiu ng ht in t I v -C. Nhng hiu ng ny
lm gim mt in t trong nhn thm, v ch yu gim v tr octo v para. Do vy to ra
trung tm phn ng th i in t v tr meta.
Th d:
-C
CH O
-I
Nhng hp cht cacbonyl cha no lin hp, nhm C=O gy hiu ng lin hp m (-C). Hiu
ng ny lm phn cc ho h lin hp.
Th d:
CH2
-C
CH
CH
Cc lin kt trong nhm C=O lun phn cc v pha oxi, lm cho mt in t cacbon
gim i, cacbon mang mt phn in tch dng, dn n lm tng s phn cc ca lin kt CchcH trong anehit v to ra trung tm ca phn ng oxi ho lin kt ny.
O
H
+
O +H Y
hoc X Y
OH
Y
chm
O +Y
O nhanh
Y H
OH
Y
- Cc phn ng c th
+ Cng ancol: Phn ng ca anehit, xeton vi ancol to thnh sn phm gi l hp cht bn
axetal.
R - CH - OH
OR
Khi un nng bn axetal vi lng d ancol s thu c axetal.
R - CH - OH
OH2
R - CH - OR'
R OH
OR
OR
axetal
bn axetal
+ Cng hiro xianua (HCN)
OH
+
C
C
O + HCN
CN
Phn ng xy ra khi c baz lm cht xc tc v to ra sn phm xianhirin.
Th d:
CH3
CH3
CH3 C OH
CH3 C = O + HCN
CN
Khi thu phn hp cht xianhirin s to thnh - hiroxi axit.
CH3
CH3
CH3 C OH
2 H 2O
CH3 C COOH
NH3
CN
OH
+ Cng natribisunfit (NaHSO3)
OH
+
C
C
O + NaHSO3
SO3Na
R
CH = O + R OH
http://hhud.tvu.edu.vn
C OMgX
R
HOH
-MgXOH
C OH
R
N -B
NH2 -B
NH -B
H2 O
C = N -B
OH
http://hhud.tvu.edu.vn
C O
Th d:
CH =O H2N -NH -C6H5 CH =N -NH -C6H5 H2N -NH -C6H5 CH =N -NH -C6H5
CH =N -NH -C6H5
CH =O
CH =O
- H2O
- H2O
bis phenylhirazon
b. Phn ng oxi ho
R -C =O
OH
anehit
axit cacboxylic
Phn ng vi thuc th Tlens v Phlinh c dng pht hin nhm chc anehit.
Anehit phn ng vi thuc th Tlens to thnh bc kt ta.
R-CH=O + 2[Ag(NH3)2]OH
thuc th Tlens
Thuc th Tlens c iu ch bng cch cho AgNO3 phn ng vi NH4OH d.
AgNO3 + NH4OH
AgOH + NH4NO3
AgOH + 2 NH4OH
[Ag(NH3)2]OH + H2O
acrlin
Anehit khi phn ng vi thuc th Phlinh, ta thy xut hin kt ta mu gch ca Cu2O.
http://hhud.tvu.edu.vn
R CH =O
COOK
CH O
2
Cu + 2H2O
CH O
COONa
t0
R -COOH
COOK
CH OH
2 CH
OH
COONa
Cu2O
Cu(OH)2 + Na2SO4
COOK
CH O H
Cu(OH)2
CH OH
COONa
kali natri tactrat
COOK
CH O
Cu
CH O
COONa
2 H2O
2C6H5COOH
anehit benzoic
axit benzoic
Trc khi b oxi ho, dng xeton ng phn ho thnh dng enol.
R -CH2 -C -R'
O
dng xeton
R -CH =C -R'
OH
dng enol
[O]
[O]
2CH3 -COOH
c. Phn ng ca gc hirocacbon
- Th H bng halogen
Do nh hng ca nhm cacbonyl m nguyn t H linh ng v d dng c th bi clo,
brom, thm ch c iot.
Th d:
CH3 -CH =O + Cl2
hv
xt
clo axetanehit
Nhng hp cht kiu R-CO-CH3 khi halogen ho trong mi trng kim cho dn xut
trihalogen.
R - C -CH3 + 3X2 + 3 NaOH
R -C -CX3 + 3NaX + 3 H2O
O
O
Dn xut trihalogen b phn ct to halofoc.
R -C -CX3 + NaOH
CHX3 + R -COONa
O
- Phn ng th nhn thm
Th d:
CHO
Fe
CH = O+ Br2
+ HBr
=
Br
m- brombenzanehit
- Phn ng cng hp
Hp cht cacbonyl cha no d dng tham gia phn ng cng hp theo c ch i in t vo
lin kt ca gc hirocacbon cha no.
Nhng hp cht cacbonyl cha no lin hp tham gia phn ng cho sn phm cng hp 3,4 l ch
yu.
Th d:
CH2 =CH -CH=O + HBr
C ch:
http://hhud.tvu.edu.vn
CH2
CH -CH
CH2 CH
CH2 CH
+H
Br
CH - OH
CH - OH
CH2 -CH2 CH=O
Br
4. Axit cacboxylic
axit benzoic
- Axit cacboxylic cha no, th d:
CH2=CH-COOH
axit acrylic
CHC-COOH
axit propinoic
COOH
axit xiclpentan cacbxylic
http://hhud.tvu.edu.vn
CH3-CH=CH-COOH
axit fomic
axit crotonic
CH3- COOH
HOOC-CH2-CH2-COOH
axit axetic
axit sucxinic
HOOC-CH2-CH2-CH2-COOH
axit butyric
axit glutaric
CH2COOH
axit phenyl axetic
b. Tn gi IUPAC
http://hhud.tvu.edu.vn
CH2 = C-COOH
CH3
axit 2-mtyl prpenic
CH3 - C H-COOH
CH3
axit 2-mtyl prpanic
c. ng phn
Axit cacboxylic khng vng no c cc loi ng phn tng t mono anehit khng vng
no, cc axit mono cacboxylic cha no (c mt lin kt i) c thm ng phn hnh hc.
Th d 1:
C3H7-COOH c hai ng phn mch cacbon.
CH3- CH2- CH2- COOH
axit butanoic
axit 2-metyl propanoic
CH3 - C H-COOH
CH3
Th d 2: C3H5-COOH c cc ng phn mch cacbon, ng phn loi lin kt v ng phn
hnh hc.
CH2=CH-CH2-COOH
axit but-3-enoic
CH3-CH=CH-COOH
axit but-2-enoic
CH2 = C-COOH
CH3
COOH
h
c
COOH
cOOH
C
h
H
R -C -Y + HOH
R -C -OH + HY
O
O
Y c th l halogen (halogenua axit), -OCOR (anhirit axit), -NH2 (amit), -OR ( este), v.v
Th d:
http://hhud.tvu.edu.vn
H
CH3 -C -OH + CH3 -CH2 -OH
CH3 -C -O -CH2 -CH3 + HOH
O
O
+ Cc hp cht nitrin khi b thu phn trong mi trng axit hay baz cng sinh ra axit
cacboxylic.
R -C N + 2 HOH
R -COOH + NH3
Th d:
H2SO4
CH2=CH -CN + 2H2O
CH2=CH -COOH + NH3
+ Thu phn dn xut poli halogen
Cl
OH
+3H2O
-HOH
R -C -Cl
R - C - OH
R -C -OH
-3HCl
Cl
O
OH
Th d:
CH3 -CH2 MgBr + CO2
CH2 =CH2 +CO
H2O/H+
CH3CH2COOH + Mg(OH)Br
xt
CH3 -CH2 -COOH
+ H2O
-C
-I
O
Nhng gc hirocacbon khc nhau c nh hng rt khc nhau n s phn cc ca lin kt
O-H.
Th d:
C
O
-I
axit benzoic
V vy nguyn t hiro trong nhm OH ca axit thm hot ng nmnh hn so vi nhng
axit khng vng no. Nhng gc cha no, tng t cc gc thm, gy hiu ng -I lm tng s phn
cc ca lin kt O-H, do vy cc axit cha no u c tnh axit mnh hn axit no tng ng. Khi
lin kt i C=C cng xa lin kt O-H, th nh hng -I ca gc cha no yu dn. Khi lin kt
i C=C v tr , th ngoi hiu ng -I, n cn tham gia lin hp vi nhm C=O ca chc axit,
hiu ng lin hp +C ny lm gim s phn cc ca lin kt O-H. Do vy trong dy ng ng
ca cc axit cacboxylic cha no, axit cha no , c lin kt O-H phn cc yu nht v axit cha
no , c lin kt O-H phn cc mnh nht.
Th d:
+C
H
CH2 =CH
CH2 =CH -I CH2 - C O
H
C O
-I
-C O
O
Trong phn t axit poli cacboxylic, nhm cacboxyl gy hiu ng -I v chng c nh hng
tng h ln nhau lm tng s phn cc ca lin kt O-H.
Th d:
H
HOOC -I CH - C O
O
100 hu c ..100
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
Khi hai nhm cacboxyl nhng v tr cng xa nhau th nh hng tng h yu dn, s
phn cc ca lin kt O-H gim dn.
- Lin kt cacbon-oxi: Nhng lin kt C-O u l nhng lin kt phn cc v pha oxi, v
nguyn t oxi c m in cao hn m in ca nguyn t cacbon.
OH
C
O
Mi hiu ng cng phng, cng chiu vi chiu phn cc ca lin kt C-O u lm tng s
phn cc ca lin kt ny.
Gc ankyl gy hiu ng y in t +I cng phng, cng chiu lm tng s phn cc ca lin kt
C-O.
OH
O
Nhng hiu ng cng phng nhng ngc chiu vi chiu phn cc ca lin kt C-O u
lm gim s phn cc ca lin kt ny.
Th d:
C
O
-I
OH
O
OH
101 hu c ..101
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
RCOOH + H2O
RCOO + H3O
ion cacboxylat
Tt c mi yu t (hiu ng) lm tng s phn cc ca lin kt O-H v lm tng bn ca
anion cacboxylat u lm tng s phn li axit.
- Do c tnh axit nn axit cacboxylic phn ng c vi mt s kim loi, oxit kim loi v
kim to mui.
2R-COOH + 2 Na
2R-COOH + MgO
R-COOH + NaOH
2R-COONa + H2
(R-COO)2Mg + H2O
R-COONa + H2O
V axit cacboxylic l axit yu nn mui ca n b thu phn trong dung dch nc.
R-COONa + H2O
R-COOH + NaOH
b. Phn ng ca nhm OH
R -COOR' + H2O
- H 2O
OH t0
R C OH
OH
R C O R
OH
+
R
OH
OH H
R C O R
OH
O
R +H
Th d:
102 hu c ..102
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
H
CH3COOH + CH3CHCH2CH2 -OH 0 CH3C -O -CH2CH2CHCH3 H2O
t
CH3
CH3
O
axit axetic
ancol isoamylic
iso amylaxetat (du chui)
- Phn ng vi amoniac to amit
Khi phn ng xy ra ta thu c mui amoni, khi un nng mui amoni tch nc to thnh amit.
t0
R -C -NH2 + H2O
R -COOH + NH3
R-COONH4
R -C -Cl
O
+ HCl + SO2
R -C -OH + COCl2
O
- Phn ng to thnh anhirit axit
R -C -Cl
O
+ HCl + CO2
+ SOCl2
R -C -OH
O
R -C
O + H2 O
R -C
2 R -C -OH
O
Nhng axit i cacboxylic c 4, 5 nguyn t cacbon khi loi nc cho anhirit ni phn.
Th d:
O
CH2 -COOH
CH2 -COOH
3000C
CH2 -C
CH2 -C
O + H2O
O
C th thc hin phn ng cacboxyl ho bng cch nhit phn axit cacboxylic hoc nhit
phn mt s mui ca axit.
Th d:
103 hu c ..103
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
xt
CO2 + H2
tia t ngoi
H2SO4
CO2 + H2
H -COOH
Nhng axit i cacboxylic v tr 1,2 hoc 1,3 khi nhit phn to axit mono cacboxylic.
Th d:
HOOC -COOH
H -COOH + CO2
axit oxalic
axit fomic
H -COOH
Nhng axit i cacboxylic 1,6; 1,7 hoc xa hn na khi b nhit phn to xeton vng.
Th d:
CH2 -CH2 -COOH 3000C CH2 -CH2
C =O + CO2 + H2O
CH2 -CH2
CH2 -CH2 -COOH
axit aipic
xiclo pentanon
Axit axetic kh b cacboxyl ho hn axit fomic. Do vy cn phi nhit phn mui natri
axetat vi vi ti xt.
t0
CH3 -COONa + NaOH
CH4 + Na2CO3
CaO
d. Phn ng ca gc hirocacbon
- oxi ho: Nhm cacboxyl ca axit cacboxylic rt tr vi tc dng ca cc cht oxi ho, v
nguyn t cacbon-cacboxyl c s oxi ho cao nht. Ring axit fomic H-COOH, do cu to
trong phn t cn nhm chc anehit, nn axit fomic d b oxi ho ngay bi cc tc nhn oxi ho
yu nh thuc th Tlens v thuc th Phlinh.
Th d:
t0
H -C -OH + [Ag(NH3)]OH
H2O + CO2 + Ag
- NH3
O
Trong cc qu trnh sinh hc s oxi ho xy ra nh cht xc tc enzim hirogenaza v xy
ra v tr .
R -C -CH2 -COOH
O
=
R -C -CH 2 -COOH
O
enzim
CH3 -COOH+ R -COOH
H 2O
104 hu c ..104
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
Axit cacboxylic mi to thnh li tip tc b oxi ho. Sn phm cui cng ca qu trnh oxi
ho trong c th sng l axit axetic tn ti di dng axetyl coenzim-A (CH3-CCoA).
O
- Halogen ho gc ankyl
Tu iu kin ca phn ng m qu trnh halogen ho gc ankyl ca axit cacboxylic c th
xy ra theo nhng c ch khc nhau (c ch gc hay c ch ion). Nu dng clo, hoc brom v c
mt P hoc FeCl3...th phn ng xy ra ch yu v tr .
P, Br2
P, Br2
R -CH2 -COOH
R-CHBr -COOH
R -CBr2 -COOH
-HBr
-HBr
Nu dng clo c nh sng khuch tn th phn ng ch yu cc v tr v ch mt lng
rt nh v tr .
- Phn ng th gc thm
Nhm -COOH phn hot ho nhn thm, nn cc phn ng th i in t trong nhn thm
ca axit cacboxylic thm thng xy ra kh khn hn so vi benzen, ng thi phn ng u tin
th v tr meta.
Th d:
H2SO4
COOH + HNO3
COOH + H2O
t0
NO2
axit benzoic
axit m- nitro benzoic
Do s phn hot ho nhn thm ca nhm cacboxyl m axit benzoic khng tham gia phn
ng Frien-Crap.
- Phn ng cng hp
Axit cha no tham gia phn ng cng hp i in t tng t cc anken.
Th d:
CH2 -CH2 COOH
Br
C ch cng hp vo axit cha no lin hp tng t nh phn ng ca but-1,3-ien v
acrolein.
C ch nh sau:
105 hu c ..105
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
COOH
(COOH)n
v
R
OH
(OH)m
Cc hiroxi axit thng c gi theo tn ring, tn thng thng hay tn IUPAC nh l
axit th. V tr nhm hiroxyl c k hiu bng ch s Hilp hoc bng ch s.
CH3
CH3 -CH -COOH
CH3 -C -COOH
OH
OH
axit lactic
axit - hiroxi isobutyric
axit 2-hiroxi-2-metyl propanoic
axit - hiroxi propionic
axit 2-hiroxi propionic
Hiroxi axit c cc ng phn v mch cacbon, ng phn v tr tng i gia cc nhm
chc v ng phn quang hc.
CH3 -CH2 -CH -COOH
OH
COOH
C OH
HO
C OH
HO
COOH
axit D-tactric
COOH
COOH
C H
C H
HO
H
C H
C OH
COOH
H
HO
C OH
C H
COOH
COOH
axit meso tatric
COOH
axit L-tatric
HO C=O
HO -CH -CH3
t0
+ H2 O
O=C - O - CH -CH3
- - hiroxi axit tch nc ni phn t cho axit cha no.
106 hu c ..106
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
t0
CH3 -CH -CH2 -COOH
OH
- v - hiroxi axit to thnh lacton.
CH2 -CH2
t0
C=O
CH2
OH
OH
CH2
CH2 -CH2
C=O + H2O
O
-butyro lacton
Axit - hiroxi butyric
Cc hiroxi axit tiu biu nht l axit lactic v axit xitric.
Axit lactic to thnh trong sa, rau, hoa qu khi c tc dng ca enzim. Axit lactic c trong
c bp, u khp xng, l sn phm phn tch ca glicogen. Khi lm vic c bp hm lng axit
lactic tng mnh lm ngi mt mi. Khi c ngh ngi, mt phn chuyn li glicogen, mt
phn b oxi ho thnh CO2 v nc.
Axit xitric (cn gi l axit limonic) c cng thc:
OH
HOOC -CH2 -C -CH2 -COOH
COOH
Axit xitric c trong thc vt, c bit l trong qu chanh (7-10%). Axit xitric ng vai tr
quan trng trong qu trnh trao i cht ca c th sng, trong chu trnh xitric.
4.8. amit
amit bc 1
R - C NH - C - R
O
O
R C=O
R - C N - C - R'
O
O
amit bc 2
amit bc 3
Th d:
H-CO-NH2
fomamit
CH3-CO-NH2
axetamit
C6H5-CO-NH2
benzamit
CH2-CO NH
CH2-CO
sucxinimit
R - C - NH2
R - C = NH
OH
O
Ging nh amin, amoniac, amit c tnh baz, nhng do cp in t t do ca nit lin hp
vi nhm >C=O, nn tnh baz rt yu. Dung dch nc ca cc amit khng to ra mi trng
kim.
R - C NH2
O
dng cu to th hai, cp in t t do ca oxi trong nhm -OH lin hp vi nhm >C=N
lm cho lin kt O-H phn cc mnh, nguyn t hiro linh ng quyt nh tnh axit ca amit.
R-C
OH
NH
CH3 - C - NH3 Cl
O
CH3 - C = NH + H2O
ONa
5. Amin
amin bc 2
R -N -R1
amin bc 3
R3
Bc ca amin c xc nh bi s gc hirocacbon lin kt trc tip vi nguyn t nit.
a. Tn gi thng thng
Tn gi thng thng ca cc amin tun theo theo quy tc:
108 hu c ..108
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
Tn gc hirocacbon + amin
Cc amin thm c nguyn t nit lin kt trc tip vi vng thm cn c gi nh dn xut
ca anilin.
Th d:
CH3 -NH -CH2 -CH3
CH3 -CH -NH2
CH3
isopropy lamin
NH2
b. Tn gi IUPAC
Th d:
3
4
2 1
CH3 -CH - CH -CH3
CH3 NH2
2- amin 3-mtyl butan
3
4
5
CH3 -CH2 -CH -CH2 -CH3
2 CH -NH -CH3
1 CH3
2- mtylamin 3-tyl pentan
5
7
6
4
CH3 -CH2 -CH -CH2 -CH2 -CH3
3 CH - N -CH2 -CH3
2 CH2 CH3
1 CH3
3- mtyl tyl amin 4-tyl heptan
Ankyl ho amoniac bng akyl halogenua ta c amin c cc bc khc nhau v mui amoni
bc bn.
109 hu c ..109
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
R - X + NH3
RNH3X
R - X + R -NH2
R2NH2X
R - X + R2NH
R3NHX
NH3
NH3
NH3
R -NH2 + NH4X
R2NH + NH4X
R3N + NH4X
R - X + R3 N
R4NX
Tu theo t l s mol ca cc cht tham gia phn ng, ta c th nhn c cc amin c bc
khc nhau.
Nu i t dn xut halogen thm ankyl ho amoniac, thng phi thc hin phn ng
nhit cao v p sut cao.
Th d:
X
+ 2 NH3
3400C
340at
NH2
+ NH4Cl
b. Kh hp cht nitro
Phng php kh hp cht nitro cho php iu ch amin bc mt, c bit l amin thm.
Ar-NO2 + 6 H
Ar-NH2 + 2 H2O
Th d:
NO2
NH2
+ 3Fe + 6HCl
+ 3 FeCl2 + H2O
Khi cho amit tc dng vi brom trong kim hay natri hipoclorit hoc natri hipobromit, ta thu
c amin bc mt c s nguyn t cacbon t hn amit ban u mt nguyn t.
=
R -C -NH2
O
+ Br2
+ NaOH
R -NH2
CO2
+ NaBr
Th d:
=
CH3(CH2)4 -C -NH2
O
+ NaOBrH
CH3(CH2)4 -NH2 + CO2 + NaBr
Cc amin thp l nhng cht kh, c mi gn ging mi amoniac, cc amin cao l nhng
cht lng, mt s l cht rn.
5.4. Cu to ca amin
N
R
R
Cp in t t do ca nit hot ng cng mnh, hay ni cch khc, mt in t
nguyn t nit cng ln th tnh baz ca amin cng mnh.
Mt in t nguyn t nit li ph thuc ch yu vo gc hirocacbon lin kt vi n.
Gc ankyl gy hiu ng cm ng dng +I lm tng mt in t nit. S gc ankyl lin
kt vi nguyn t nit tng ln th hiu ng +I tng ln v mt in t nit tng ln. iu
c m t nh sau:
R1
R1
R2 NH
R NH2
R2 N
R3
Tuy nhin, do nh hng hiu ng khng gian ba gc ankyl, amin bc ba c tnh baz yu nht.
Trong cc amin thm, gc phnyl gy hiu ng -C v -I nhng hiu ng ny lm mt
in t nit gim i. Tnh baz ca anilin yu hn tnh baz ca cc amin khng vng no.
+C
-C
NH2
-I
R -NH2 + HOH
R -NH3OH
R -NH3 + OH
R -NH3Cl
Tuy nhin cc amin u c tnh baz yu hn kim, cc mui amoni b kim phn tch:
R -NH3Cl + NaOH
Cc amin c bc khc nhau, khi phn ng vi axit nitr s to ra nhng sn phm khc
nhau.
Cc amin bc mt tc dng vi axit nitr to thnh ancol hoc phenol v gii phng nit.
Th d:
C2H5OH + N2 + H2O
C2H5NH2 + HONO
NH2
+HONO
N N Cl
HCl
OH2
OH
t0
OH2
+ HCl + N2
phenyl iazoniclorua
Cc amin bc hai u d dng tc dng vi axit nitr to nitrozamin.
Th d:
(CH3 -CH2)2 N-N=O + H2O
(CH3-CH2)2 NH + HONO
ietylnitrozamin
Khi un nng, nitrozamin thm d dng chuyn v thnh p- nitrozo amin.
Th d:
H
H
N CH3
CH3 N N=O
N CH3
t0
HONO
N =O
N -nitrozo
N -meylanilin
N -metylanilin
p. nitrozo metylanilin
Cc amin bc ba ni chung khng phn ng vi axit nitr, tr amin bc ba kiu Ar-NR2
tham gia phn ng nitrozo ho nhn thm.
CH3
CH3
CH3
N
CH3
N
HONO
-H2O
N, N -imetylanilin
N =O
P- nitrozo imetylanilin
112 hu c ..112
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
Cc amin thm tham gia nhng phn ng th i in t tng t hirocacbon thm. Nhm
amino trong amin thm gy hiu ng +C hot ho nhn thm v inh hng nhm th mi vo v
tr octo v para.
- Phn ng halogen ho
Khi brom ho hoc clo ho anilin ta thu c sn phm th ba ln, cn it ho ch cho sn
phm th mt ln v tr para.
Th d:
NH2
NH2
Br
Br
3 Br2
3 HBr
Br
trng
- Phn ng nitro ho
Nhm amino d b oxi ho bi axit nitric, nn trc khi thc hin phn ng nitro ho cn
phi kho nhm amino bng phn ng axyl ho.
Th d iu ch p- nitro anilin:
NH2
NH -COCH3
NH2
NH -COCH3
(CH3CO)2O
- CH3COOH
HNO3
-H2O
-H2O
- CH3COOH
NO2
NO2
Cu hi v bi tp
1. Tnh cht ho hc ca dn xut halogen. C ch th i nhn SN1, SN2.
2. nh hng ca cc gc hirocacbon khc nhau v nh hng tng h ca cc nhm
OH n s phn cc ca lin kt O- H trong ancol v phenol. Tnh cht ho hc ca
ancol v phenol.
3. Tnh cht ho hc ca anehit v xeton. C ch cng hp i nhn (AN) vo nhm
cabonyl.
4. Cu to ca nhm cacboxyl v tnh axit ca cc axit cacboxylic. Tnh cht ho hc ca
axit cacboxylic.
5. Gii thch tnh baz ca cc amin. nh hng ca cc gc hirocacbon n tnh baz
ca cc amin.
6. Gi tn cc hp cht sau y theo tn gi IUPAC.
CH3- CH2- CH- Cl
CH3
CH3
CH3- C- CH3
Br
CH3
CH3- C- CH2- CHO
113 hu c ..113
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
CH3
CH2= C- CHO
CH3
CH3- CH- CH- C- CH3
CH3 CH3 O
CH3- CH- COOH
CH3
HOOC- CH2- CH2- CH3
7. Vit cng thc cu to cc ng phn ca cc cht c cng thc phn t sau y v gi
tn chng: C4H10O; C2H4O2 v C3H9N.
8. Cho bit cng thc cu to v gi tn cc cht:
8.1. Dn xut halogen bc 3 thu c khi halogen ho hirocacbon C4H10.
8.2. Dn xut halogen bc 1 c cng thc phn t C3H5Cl.
8.3. Thu c khi cho ankin- 1 c 4 nguyn t cacbon tc dng vi nc trong iu kin
thch hp.
8.4. Axit thm thu c khi oxi ho ankyl benzen.
8.5. C cng thc phn t C7H8O, khi tc dng vi FeCl3 cho mu xanh tm.
9. Gii thch bng cu to v chng minh bng cc phn ng ho hc:
9.1. Hot tnh ca nguyn t H trong nhm OH ca glixerin v phenol.
9.2. Tnh axit ca nguyn t H trong nhm cacboxyl.
9.3. Tnh baz ca cc amin.
10. Vit phng trnh v c ch cc phn ng sau:
10.1. 2- brombutan + KOH
10.2. 2- clo-2- metylpentan + NaOH
10.3. Axeto + C6H5- NH- NH2
10.4. Ancol allylic + HBr
10.5. Anehit acrylic + NaHSO3
Fe
10.6. Axit benzoic + Br2
11. Hon thnh cc s phn ng sau:
OH-/ru
11.1. 2-clo-2-metylpentan
HBr
B
H2SO4/1800C
KOH/H2O
11.2. 2-brom-2-metylbutan
CH3CHO
H2O
E
H2SO4/1800C
H2O
11.3. Ancol bc 3
2-metylbut-2-en
11.4. CH3- CHO + B C
H2O
butan-2-ol
H2O
114 hu c ..114
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
11.5. HCHO + A B
butan-1-ol
H2O
C
H2O
pentan-3-ol
H2O
2-metyl propan-2-ol
chng IV
Cc hp cht thin nhin
Trong cc b phn ca thc vt, ng vt, trong c th ca vi sinh vt, thm ch trong thnh
phn cc cht hu c ca t c cha mt lng ln cc hp cht gluxit. Trong c th sinh vt cc
hp cht ny tham gia vo cc qu trnh trao i cht, cung cp cc cht dinh dng v nng
lng cho s pht trin ca c th. Trong t, khi phn hu cc di tch thc vt v phn hu c,
cc cht ny chu nhng tc ng ca cc qu trnh sinh ho khc nhau v ng vai tr quan trng
trong vic hnh thnh nhng tnh cht, xc nh ph ca t, chng tham gia vo qu trnh hnh
thnh mn t v cc cht hot ng sinh hc khc ca t.
Thc vt c kh nng quang hp tng hp nn phn t glucoz l mt gluxit n gin t
kh cacbonic v nc. Qu trnh ny xy ra rt phc tp, nhng c th tm tt nh sau:
6 co2 + 6 h2o
nh sng
dip lc t
c6h12o6 + 6 o2
T phn t glucoz bng nhng cch kt hp khc nhau s to nn nhng hp cht gluxit
phc tp nh tinh bt, xenluloz, vv
Cc hp cht gluxit n gin, trong phn t ca chng lun lun bao gm nhm cacbonyl (
ca anehit hoc xeton) v nhiu nhm hiroxyl. Cc hp cht gluxit phc tp khi thu phn n
cng lun to thnh cc phn t gluxit n gin.
Do vy, gluxit l nhng poli hiroxicacbonyl (poli hiroxi anehit hoc poli hiroxi xeton)
cng cc sn phm ngng t ca chng.
C nhiu cch phn loi cc hp cht gluxit. Cch ph bin nht l da vo mc phc
tp ca phn t. Theo cch ny cc hp cht gluxit c chia thnh ba loi chnh:
- Mono saccarit (monoz)
- Oligo saccarit
- Polisaccarit (polioz)
Cc hp cht gluxit cn c phn chia thnh cc gluxit kh v gluxit khng kh tu thuc
vo quan h tnh cht ca chng vi cc tc nhn oxi ho l thuc th Tlens v thuc th
Phlinh.
CH2OH
C=O
(CHOH)n
CH2OH
xetoz
CHO
CH2
(CHOH)n
CH2OH
ng oxi
CHO
CHO
CHNH2
(CHOH)n
(CHOH)n
COOH
CH2OH
ng amin axit uronic
a. Cu to ca cc monosaccarit
dng vng
Dng cu to khng vng ca cc anoz c th biu din bng cng thc tng qut:
(CHOH)n C -H
=
CH2OH
CH2OH
*
(CHOH)4
CHO
117 hu c ..117
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
CHO
CHO
H C OH
HO C H
HO C H
H C OH
HO C H
H C OH
H C OH
HO C H
H C OH
H C OH
HO C H
H C OH
CHO
CH2OH
CH2OH
D (+) aloz
L (-) aloz
H C OH
HO C H
HO C H
HO C H
CH2OH
CH2OH
D (+) altroz
CHO
CHO
CHO
L (-) altroz
CHO
CHO
HO C H
H C OH
HO C H
H C OH
HO C H
H C OH
HO C H
H C OH
H C OH
H C OH
HO C H
H C OH
HO C H
D (+) manoz
HO C H
H C OH
H C OH
HO C H
H C OH
HO C H
HO C H
HO C H
H C OH
CH2OH
D (+) galactza
CHO
CHO
C OH
HO C H
C OH
HO C H
H
C OH
HO C H
H C OH
HO C H
CH2OH
CH2OH
L (-) glucoz
D (+) huloz
L (-) huloz
CHO
CHO
HO C H
HO C H
CHO
H C OH
L (-) taloz
CH2OH
CH2OH
D (+) glucoz
CH2OH
D (+) taloz
CHO
HO C H
HO C H
CH2OH
L (-) manoz
CHO
C OH
H C OH
CH2OH
CH2OH
HO C H
H C OH
C OH
HO C H
CH2OH
L (-) galactza
Th d 2.
C OH
HO C H
H C OH
CH2OH
D (+) Iza
H C OH
HO C H
H
C OH
HO C H
CH2OH
L (-) Iza
*
(CHOH)3 C -CH2OH
O
=
Xthexza : CH2OH
CHO
CH2OH
C O
H C OH
H C OH
H C OH
CH2OH
D (-) aluloz
CH2OH
C O
CH2OH
C O
HO C H
HO C H
HO C H
CH2OH
L (+) aluloz
CH2OH
C O
H C OH
HO C H
H C OH
HO C H
CH2OH
CH2OH
H C OH
HO C H
D (-) socboz
L (+) socboz
CH2OH
CH2OH
C O
C O
HO C H
H C OH
H C OH
CH2OH
H C OH
HO C H
HO C H
CH2OH
D (-) fructoz
L (+) fructoz
CH2OH
CH2OH
C O
C O
HO C H
H C OH
HO C H
H C OH
H C OH
HO C H
CH2OH
CH2OH
D (-)tagaloz
L (+) tagaloz
119 hu c ..119
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
Nhng tnh cht khng bnh thng trn y gii thch c khi cc nh khoa hc cho
rng, trong dung dch cc monosaccarit ngoi dng cu to khng vng cn tn ti dng cu to
vng. Dng cu to vng c hnh thnh do kt qu ca phn ng cng hp i nhn gia nhm
-OH vi nhm >C=O. Th d, qu trnh to thnh vng 6 cnh ca phn t D (+) glucoz v 5
cnh ca phn t D (-) fructoz c biu din nh sau:
H
OH
H
H
HO
H
H
C
C OH
C H O
C OH
C
CH2OH
-D (+) glucopyranoz
CH2OH
OH
C
HO C H
CHO
H C OH
HO C H
H C OH
H C OH
CH2OH
D (+) glucoz
CH2OH
C O
HO C H
H C OH O
H C OH
H C
H C OH
CH2OH
D (-) fructofuranoz
CH2OH
D (-) fructoz
HO
H
HO
H
H
C
C OH
C H O
C OH
C
CH2OH
-D (+) glucopyranoz
CH2OH
HO C
HO C H
H C OH O
H C
CH2OH
D (-) fructofuranoz
HO C H
CH2OH
O
H
H
OH
OH
OH
C OH
HO C H
H
OH
C OH
H C OH
H C OH
H C
H C OH
H C
CH2OH
HO
OH
H
OH
HO C
OH
CH2OH
-D (-) fructofuranoz
OHO
C
CH2OH
HO
CH2OH
C O
C OH
HO
H
OH
OH
H
CH2OH
H
OHO H
OH
OH
CH2OH
D (-) fructoz
CH2OH
O
H
OH H
OH
CH2OH
CH2OH
-D (+) glucopyranoz
CH2OH
D (+) glucoz
CH2OH
C OH
HO C H
HO C H
H C OH
-D (+) glucopyranoz
CH2OH
H C OH
CHO
CH2OH
OH
OH
OH
CH2OH
-D (-) fructofuranoz
COOH
HO C OH
HO C H
+ Ag + NH3 + H2O
H C OH
[Ag(NH3)2]OH
CHO
HO C OH
H C OH
HO C H
H C OH
CH2OH
COOH
H C OH
KMnO4 + H2SO4 HO C OH
HO C H + MnSO4 + K2SO4 + H2O
CH2OH
H C OH
H C OH
COOH
CH2OH (CHOH)4
glucoz
CHO
[O]
glucoz
COOH
[O]
(CHOH)2
COOH
H2O
COOH
COOH
Cc phn ng oxi ho ca cc monosaccarit rt c ngha trong thc tin. Chng hn, phn
ng oxi ho bng tc nhn oxi ho Tlens c s dng trong cng ngh trng gng, trng rut
phch, vvphn ng oxi ho bi thuc th Phlinh c dng nh lng ng trong c th sinh
vt.
Cc monosaccarit tham gia phn ng cng hp i nhn tng t nh cc anehit v xeton.
Ring phn ng cng hp natribisunfit (NaHSO3) khng xy ra bi v trong mi trng ca phn
ng ny cc monosaccarit ch tn ti di dng cu to vng.
122 hu c ..122
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
CH2OH
C=N -NH -C6H5
(CHOH)n
CH2OH
phenylhirazon
Th d.
Phn ng ca D (+) glucoz vi phenylhirazin to thnh phenylhirazon v ozazon xy
ra nh sau:
H
HO
H
H
CHO
C OH
+C6H5NHNH2
C H
C OH
-H2O
C OH
CH2OH
H
HO
H
H
C =N -NH -C6H5
C OH
C H
+ C6H5NHNH2
C OH
(C6H5 -NH2 + NH3)
C OH
CH2OH
phenyl hirazon
C =N -NH -C6H5
C= O
HO C H +C6H5NHNH2
H C OH
-H2O
H C OH
CH2OH
CH =N -NH -C6H5
C = N -NH -C6H5
HO C H
H C OH
H C OH
CH2OH
ozazon
123 hu c ..123
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
C= N N
Ch
H
O
(CHOH)2
H
CH2OH
H
+CH3OH
OH
OH
H
OH
-D (+) glucopyranoz
HCl
t
OH
CH2OH
O
H
H
OH
H
+ H2O
OCH3
H
OH
-D (+) metylglucopyranozit
H
OH
CH2OH
O
H
OH H
H
+5CH3I
OH
H
OH
-D (+) glucopyranoz
CH2OCH3
O H
H
Ag2O
H
+ 5hi
0
OCH3 H
t
OCH3
CH3O
OCH3
H
-D (+) pentametylglucopyranozit
H
OH
CH2OH
O
H
OH H
H
OPO3H2
H
OH
-D (+) glucozo-1photphat
CH2OPO3H2
OH
O
H
OH
H
CH2OPO3H2
H
OH
-D (-) fructozo-1,6-iphotphat
Nhm hiroxyl glucozit cn c th tham gia phn ng ngng t vi nhm hiroxyl ancol
hoc nhm hiroxyl glucozit ca phn t monosaccarit khc to thnh cc hp cht glucozit
khc nhau.
CH2OH
O H
H
H
OH H
OH
OH
H
OH
CH2OH
CH2OH
O H
O H
H
H
H
H
+H2O
OH H
OH H
O
OH
OH
H
H
OH
OH
125 hu c ..125
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
CHO
CHO
HO C
H C OH
HO C H
pime ho
HO C H
H C OH
H C OH
H C OH
H C OH
CH2OH
CH2OH
D(+)manoz
D(+)glucoz
ph
ng
o
nh
CH -OH
CH2 -OH
C OH
C O
HO C H
HO C H
H C OH
H C OH
H C OH
H C OH
CH2OH
CH2OH
D(-)fructoz
2 C2H5OH + 2 CO2
S ln men lactic:
C6H12O6
S ln men xitric:
C6H12O6
CH2-COOH
HO C COOH
CH2 -COOH
2 H2O
Phn ng ny c ng dng vi nhiu mc ch khc nhau trong sinh hot cng nh trong
cng nghip.
126 hu c ..126
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
1.2. oligosaccarit
Oligosaccarit cn c gi l cc polisaccarit c tnh cht ng. Nhm ny c v ngt, tan
trong nc. Oligosaccarit quan trng v ph bin nht trong t nhin l cc isaccarit. isaccarit
l nhng gluxit phc tp khi thu phn to thnh hai phn t monosaccarit tng ng. Chng c
cng thc chung l C12H22O11.
Cn c vo cu to v tnh cht ngi ta chia cc isaccarit thnh hai loi: isaccarit khng
c tnh kh v isaccarit c tnh kh.
a. Cu to ca cc isaccarit.
CH2OH
5
O H
H
H
1
4
OH H
OH 3
2
H
OH
O
1
HOCH2
O
OH H
CH2OH
OH
Dung dch saccaroz c gc quay cc ring []D=+6605. Khi thu phn gc quay cc thay
i t []D=- 4005 th n nh. Hin tng ny c gi l s nghch o ng.
- isaccarit c tnh kh
127 hu c ..127
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
CH2OH
CH2OH
H
O
O H
H
H
H
H
OH H
OH H
O
OH
OH
H
H
OH
OH
Xenlobioz: C12H22O11
Xenlobioz ch khc mantoz ch l khi n thu phn di tc dng ca enzim emunxina
ch khng phi l enzimmantaza. Enzim emunxina ch thu phn lin kt - glucozit, v vy, cu
to ca xenlobioz khc cu to mantoz ch, cc gc -D (+) glucopyranoz lin kt vi nhau
bng lin kt -1,4- glucozit.
CH2OH
CH2OH
H
O
O OH
H
H
H
O
OH H
OH H
H
H
OH
H
H
OH
OH
Cc isaccarit c tnh cht tng t nh cc monosaccarit: C tnh cht hot quang, lm tan
kt ta ca Cu(OH)2, khi cng hp vi phenylhirazin to thnh ozazon. Ngoi ra, cc isaccarit
l do cc monosaccarit lin kt vi nhau bng lin kt glucozit, bn cht ca cc lin kt ny l
lin kt cu ete, do vy isaccarit cn c phn ng thu phn. Khi b thu phn cc isaccarit to
thnh cc monosaccarit tng ng.
Th d, khi thu phn mantoz bng xc tc axit thu c hai phn t monosaccarit l -D
(+) glucopyranoz.
128 hu c ..128
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
CH2OH
CH2OH
O H
O H
H
H
H
H
+H2O
OH H
OH H
O
OH
OH
H
H
OH
OH
H+
CH2OH
O H
H
H
2
OH H
OH
OH
H
OH
t0
CH2OH
OH
+ Ag + NH3 + H2O
H
COOH
H
OH
H
OH
CH2OH
O
H
H
OH H
H
OH
H
O
CH2OH
O
H
H
OH H
H
OH
H
O
CH2OH
O
H
H
OH H
H
H
O
OH
129 hu c ..129
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
Mt khc, bng tia Rnghen ngi ta chng minh c rng amyloz c cu trc xon c
to ra cc ng t do, mi vng xon gm khong 6 gc -D(+) glucopyranoz.
Amylopectin c cu to t 600 - 6000 gc -D(+) glucopyranoz, vi phn t lng
khong 100.000 - 1000.000 vC. Cc gc -D(+) glucopyranoz lin kt vi nhau ch yu bng
lin kt -1,4-glucozit, ti cc im phn nhnh l lin kt -1,6-glucozit. Do vy amylopectin c
cu to phn nhnh, cc nhnh cch nhau chng 18 -26 gc.
CH2OH
CH2OH
H
O
H
OH
O
H
OH
H
O
H
OH
H
OH
O
H
OH
OH O
CH2
H
CH2OH
O
H
H
O
CH2OH
O
H
OH H
H
OH
O
H
OH H
O
H
H
O
OH
Tinh bt khng tan trong nc lnh, trong nc nng to thnh dung dch keo gi l h tinh
bt. Dung dch h tinh bt c gc quay cc ring []D=+1500 -2200. H tinh bt phn ng vi it
to thnh dung dch mu xanh. Phn ng ny do mch polime ca amyloz cun theo ng xon
c to thnh ng, phn t it chui va lt vo ng to thnh phn t mu xanh c thnh phn
(C6H10O5)n.I2, mu xanh ny mt i khi un nng v li xut hin tr li khi ngui.
Tinh bt khng c tnh kh, khng tham gia phn ng oxi ho. Cc nhm hiroxyl C2, C3
v C6 trong mi mt xch ca phn t tinh bt c th tham gia cc phn ng ete ho v este ho.
Khi tham gia phn ng thu phn cc lin kt glucozit b ph v dn dn to thnh cc
phn t extrin (tinh bt tan), sau l mantoz v nu thu phn hon ton tinh bt s to thnh
-D(+) glucopyranoz.
H2O (H+)
H2O (H+)
H2O (H+)
(c6h10o5)x
C12H22O11
C6H12O6
(c6h10o5)n
x <n
-D(+)glucopyranoz
tinh bt
mantoz
cc extrin
Trong c th sinh vt tinh bt b thu phn bi hai h thng enzim l -amylaza v enzim
mantaza, enzim -amylaza xc tc cho qu trnh thu phn tinh bt n to thnh mantoz, sau
enzim mantaza xc tc cho qu trnh thu phn tip theo t mantoz thnh glucoz.
b. Glicozen : (C6H10O5)n
H
OH
H
O
H
H
O
H
OH
CH2OH
CH2OH
O
H
OH H
O
H
OH
H
OH
O
H
O
H
OH
Xenluloz l cht rn, c dng si, c tnh thm nc, khng tan trong nc, ete v ru, ch
tan c trong mt s dung mi c bit nh dung dch Svyze ( hn hp Cu(OH)2 v NH3 m
c), dung dch H2SO4 c (trn 72%), dung dch HCl c c ho tan ZnCl2.
Xenluloz kh b thu phn hn tinh bt, phi un nng lu vi axit v c long, i khi
phi dng p sut cao. Xenluloz b thu phn dn dn thnh amyloit, xenlobioz v cui cng l
-D(+) glucopyranoz.
H2O (H+)
H2O (H+)
H2O (H+)
(c6h10o5)x
C12H22O11
C6H12O6
x <n
xenlobioz
D(+)glucopyranoz
xenluloz
amyloit
(c6h10o5)n
Cng vi cc cht gluxit, protit, lipit l nhng cht rt quan trng trong i sng ca con
ngi. Lipit l ngun nguyn liu cung cp nng lng cho cc qu trnh bin i sinh ho
trong c th sinh vt.
Lipit ca ng vt thng c gi l m (m ln, m b, m cu, vv), cn lipit thc vt
c gi l du ( du lc, du da, du liu, vv). M v du c tnh cht ging nhau nhng li
c vai tr khc nhau trong c th.
Trong c th sinh vt c th bt gp nhiu loi lipit khc nhau, nhng ph bin nht l lipit
n gin v phtpholipit. Do vy chng ta ch i su nghin cu v cu to v tnh cht ca hai
loi lipit ny.
Lipit n gin hay cn gi l glixerit c th c cc loi sau y:
CH2 - O - R
R'
CH - O - C
CH2 - O - Gl
R'
O
triglixerit
R'
O
CH2 - O - C R"
O
glicozyliglixerit
=
O
CH2 - O - C R"
O
ankyliglixerit
=
R"
CH - O - C
=
CH2 - O - C
O
CH - O - C
O
CH2 - O - C
CH2 - O - C C15H31
O
CH - O - C C17H33
O
CH2 - O - C C17H35
O
panmito - oleo -stearin
=
Cc axit tham gia vo thnh phn cu to ca triglixerit c th l axit bo no hoc khng no,
nhng u c cu to mch khng phn nhnh, s nguyn t cacbon trong phn t thng chn v
trongkhong t 4- 26, ch yu l 16 v 18. Cc axit thng gp l axit panmitic C15H31COOH,
axit stearic C17H35COOH, axit lic C17H33COOH, axit linoleic C17H31COOH, axit linolenoic
C17H29COOH, vv
Trong lipit thc vt th axit cha no chim thnh phn ch yu, cn trong lipit ng vt th
phn ln li l cc axit bo no.
Photpholipit hay photphatit t nhin ch yu c cu to dng tng qut:
=
CH2 - O - C R
O
CH - O - C R'
OH
O
CH2 - O - P
X
O
(X l gc ancolat cha nit)
=
Th d.
Cholinphotphatit
=
CH2 - O - C R
O
R'
CH - O - C
O OH
CH2 - O - P O - CH2 - CH2 - CH2 -N (CH3)3
O
=
Serinphotphatit
=
CH2 - O - C R
O
R'
CH - O - C
O OH
CH2 - O - P O - CH2 - CH - COOH
O
NH2
=
Cc lipit ni chung c tnh k nc, khng tan trong nc nhng tan nhiu trong ru, ete v
cc dung mi hu c khc.
133 hu c ..133
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
Tnh cht ho hc c bn ca lipit l tham gia phn ng thu phn. Phn ng thu phn xy
ra di tc dng ca axit, kim hoc men, i khi c th un si n vi nc p sut cao, nhit
cao ( 25 atm, 2200C). Sn phm thu phn rt khc nhau tu thuc vo chng loi v cu to
ca lipit. Chng hn, khi thu phn cc triglixerit xy ra nh sau:
=
CH2 - O - C
O
CH - O - C
O
CH2 - O - C
O
R
R'
3 HOH
R"
xt
CH2 - O H
RCOOH
CH - OH
R'COOH
CH2 - OH
R"COOH
Trong cc axit amin t nhin hay gp ch yu l cc - amino axit, ngha l trong phn t
ca chng lun lun c mt nhm amino v tr C so vi nhm cacboxyl.
3.1. Gi tn v phn loi
a s axit amin c gi theo tn ring hoc gi theo tn cc axit tng ng vi tip u
ng amino v v tr ca nhm ny bng cc ch s , , , vv
Th d:
CH2-COOH
NH2
glixin, glicocol
( axit amino axetic)
CH3 - CH-COOH
NH2
alanin
( axit amino propionic)
134 hu c ..134
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
HO -CH2 - CH-COOH
NH2
serin
(axit -amino - hiroxipropionic)
HS -CH2 - CH-COOH
NH2
xistein
(axit -amino - thiopropionic)
CH2 - CH-COOH
NH2
phenylalanin
(axit -amino - phenylpropionic)
CH2 - CH-COOH
NH2
tyrozin
(axit -amino - (p-hiroxiphenyl) propionic)
N
N
CH2 - CH-COOH
NH2
histiin
NH
CH2 - CH-COOH
NH2
triptophan
(axit - amino - -inolylpropionic)
135 hu c ..135
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
Th d:
CH3 - CH-COOH
Cl
NH3
CH3 - CH-COOH
NH2
HCl
O
C
N -K
Cl -CH2 -COOC2H5
N - CH2 -COOC2H5
C
O
C
O
KCl
H2O
COOH
C2H5OH
Trong dung dch nc, axit amin in li theo hai kiu: kiu axit v kiu baz.
(COOH)m
R
(COO)m
+ mHOH
(NH2)n
(NH2)n
(COOH)m
R
+m H3O
+ nHOH
(NH2)n
(COOH)m
+ n OH
R
(NH3)n
136 hu c ..136
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
(COO)m
R
(COOH)m
+ mH
(NH3)n
(NH3)n
(COO)m
+ nOH-
R
(NH3)n
+ nH2O
R
(NH2)n
Nh vy, bng cch iu chnh pH ca mi trng ta c th lm cho dung dch axit amin
trung ho in.
Gi tr pH ti phn t axit amin trung ho in tch gi l im ng in ca axit amin.
im ng in c k hiu l pI. Cc axit amin khc nhau c im ng in khc nhau. Ti
im ng in axit amin khng bn, d b kt ta. Bit im ng in ta c th tch c cc
axit amin trong hn hp ra khi nhau bng phng php kt ta hay phng php in di.
b. Tnh cht quang hot
Tt c cc axit amin t nhin (tr glixin), trong phn t ca chng u c nguyn t cacbon
bt i, do chng u c tnh hot quang. Tuy nhin, trong c th ng vt v thc vt cc axit
amin u tn ti dng ng phn c cu hnh L.
COOH
H2N -C -H
R
L -axit amin
c. Tnh cht ho hc
Trong phn t axit amin c nhm cacboxyl mang tnh axit v nhm amin mang tnh baz,
do vy axit amin l hp cht c tnh lng tnh, khi phn ng vi axit hoc baz u to mui.
Th d:
CH3 - CH-COOH
NH2
CH3 - CH-COOH
NH2
HCl
CH3 - CH-COOH
NaOH
NH3Cl
CH3 - CH-COONa
NH2
H 2O
Phn ng ngng t
Cc axit amin ngng t vi nhau to thnh cc hp cht peptit. Trong phn ng ngng t,
phn t nc c tch ra t nhm -OH trong nhm -COOH ca phn t axit amin ny vi
nguyn t H trong nhm -NH2 ca phn t axit amin kia.
- H2O
.... H - NH - CH-CO OH H - NH - CH-CO OH
....
r
r
.... - NH - CH-CO - NH - CH-CO - ....
r
r
Lin kt -CO -NH- c gi l lin kt peptit.
Khi hai phn t axit amin ngng t vi nhau s to thnh hp cht ipeptit, ba phn t axit
amin ngng t to thnh hp cht tripeptit, v nu nhiu phn t axit amin ngng t vi nhau s
c hp cht polipeptit.
Theo nguyn tc ca phn ng ngng t, khi cc axit amin ging nhau ngng t ch thu
c mt hp cht peptit duy nht, nhng khi ngng t cc axit amin khc nhau ta c th thu
c nhiu hp cht peptit khc nhau.
Trong c th sinh vt phn ng ngng t xy ra di tc dng ca men. Phn ng ny l c
s ca cc qu trnh hnh thnh cc hp cht peptit v protein t cc axit amin.
To mui phc ni
Cc axit amin c th to mui phc ni vi kim loi nng. Cc mui ny thng rt bn,
kh tan v c mu c trng. Th d, mui phc ca glixin vi ng v coban:
138 hu c ..138
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
CH2 -NH2
CO-O
O-CO
Cu
O - CO
Co
NH2 -CH2
nh2 CH2
Phn ng cacboxyl ho
CH3 - CH-COOH
NH2
CO2
HNO2
CH3 - CH-COOH
OH
N2 + H 2 O
Di tc dng ca men s xy ra phn ng loi b nhm amino, gii phng NH3 to thnh
xeto axit.
CH3 - C-COOH
O
axit piruvic
NH3
[O]
men
CH3 - CH-COOH
NH2
0
C =O t
RCHO +CO2
C =N -C
C
O
C
O
R -CH -COOH
NH2
O
C
O
C
O
C
C
OH
4. Protit
139 hu c ..139
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
1200
R
0
C
1,3
1140
C
R
N
H
2A
C
1,28A0
O
125
110
H
N
121 0
H
N 1,4
7A 0
C
H
7,2A0
141 hu c ..141
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
I leu
Val Glu
Xis
Xis
11
Leu
Tir
28 Xis
Ala
Gli
Xis Val
Val
Leu His Glu Asp
Phe
Gli
Ser
Ser
Ser
Glu
Leu
Gli
His Leu
Val
Glu
Ala
Leu
Asp
Tir
20
40
Xis
Xis
Asp
Gli
Val Leu
Glu
Arg Gli
Tir
Phe
Ala 51
Met
Pro
Lin kt hiro c hnh thnh gia nhm imino (>NH) ca lin kt peptit ny vi nhm
cacbonyl ( >C=O) ca lin kt peptit khc. Lin kt ny c th c thc hin gia hai mch
polipeptit hoc trn cng mt mch polipeptit. Nh lin kt ny m phn t protein thng c
nhng hnh dng khng gian khc nhau: dui thng, un cong, cun trn, xon, vvCu trc
khng gian ny c gi l cu trc bc hai ca phn t protein. Cu trc bc hai l cu dng
ca phn t protein, trong mi axit amin chim mt v tr khng gian xc nh ca mch
polipeptit. C hai cu dng: cu dng xon v cu dng gp .
142 hu c ..142
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
H
N
C
C
H O H
N
C
N C C
O
C HO
N
C C
C
O
H
O
H N C
N C
H C O
NC
H
C O
N
C
C H
H
O
N
N
C
C
O
=
H H
C
H R N
N
R
C C
H
O
H
H
O
C
N C
C
O
C
H
=
O
C N
C
H
R
R O
HC
H
C
N
N
C
H
C
H O
R
C C
O
H O
H C C
R
H
N R
C C
O
R
H H
C
C
NC
N
H
H
O
=
H
N
Cu dng xon v gp
Trong cu dng xon lin kt hiro hnh thnh gia hai mt xch ca cng mt chui
polipeptit, cn trong dng gp , lin kt hiro xut hin gia hai hoc nhiu chui polipeptit trn
tng mt phng khc nhau.
Lin kt i sunfua ( -S-S-)
Lin kt i sunfua c hnh thnh do s oxi ho nhm -SH ca nhng gc axit amin xistein
c trong mch polipeptit. Cng nh lin kt hiro, lin kt i sunfua c th c thc hin trn
hai mch polipeptit khc nhau hoc trn cng mt mch polipeptit.
CH2 - S
CH2 - S
O
O
- NH - CH -C - NH -CH -C =
O
- NH - CH -C -NH -
CH2 -S - S - CH2
- NH - CH -C -NH O
Lin kt i sunfua l mt trong nhng nhn t quyt nh cu trc bc ba v cu trc bc
bn ca phn t protein.
H2O polipeptit
H2O ipeptit
H2 O
axit amin
144 hu c ..144
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
N=
O2N
OH
O2N
N=
OH NH OH
4
HNO3c
ONH4
CH2 -CH -C
CH2 -CH -C
NH O
Ch2 -CH -C
NH O
NH O
baz
O
O
P
OH
gluxit
O
O
OH
C hai loi axit nucleic tu thuc vo bn cht ca cu t gluxit trong phn t. Thnh phn
gluxit l D-riboz gi l axit ribonucleic (ARN), l D-2-eoxiriboz th gi l axit
eoxiribonucleic (ADN).
C hai loi gluxit ny u tn ti dng cu to furanoz lin kt vi gc photphat qua cc
nhm hiroxyl C3 v C5.
5
CH2OH
OH
O
4 H
H 1
2 H
H 3
OH
OH
D- riboz
5
CH2OH
OH
O
4 H
H 1
2 H
H 3
OH
H
D- 2- eoxirib
145 hu c ..145
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
O
CH2
H
O
OH
HO P=O
OCH2
R
O
H
H
H
H
O
OH
HO P=O
O CH2
R
O
H
H
H
H
O
OH
HO P=O
ARN
CH2
H
ADN
NH2
N
NH
N
H
N
N
H
aenin
NH2
NH2
guanin
O
H3C
N
O
N
H
xitozin
NH
N
H
timin
NH
N
O
H
uraxin
NH2
N
O
CH2
aenozin
axit aenilic
H
H
aenin
O
HO P= O
O
H
H
OH
(ADP) v axit aenozintriphotphat (ATP). Nhng hp cht ny c lin kt cao nng, khi phn gii
chng s gii phng nng lng. Nhng hp cht ny c gi l cc hp cht cho nng lng.
Thnh phn ca cc nucleotit trong cc axit nucleic lun lun tun theo mt quy lut cht
ch. Da trn nhiu cng trnh nghin cu Chahaff a ra quy tc sau:
-
Nhng nghin cu bng phng php Rnghen chng minh rng, phn t ADN c to
thnh bi hai mch polinucleotit kt hp vi nhau theo kiu xon c sao cho mch cacbon, photphat
v gluxit ezoxiriboza pha ngoi, cn cc baz nit pha trong. Hai mch ny lin kt vi nhau
bng lin kt hiro sinh ra gia cc baz pirimiin v purin ca cc nucleotit ring bit.
S phn b ca cc nucleotit ring bit trong mch rt nghim ngt, ng thi cu trc ca
mt mch s phn nh cu trc ca mch kia theo quy lut: timin tng ng vi aenin, xitozin
tng ng vi guanin v ngc li. Lin kt hiro ni hai mch nucleotit phtphat to thnh mt
h thng nht lm cho phn t ADN tr nn bn vng.
Khc vi ADN, s xon c ca mch polinucleotit ca ARN c thc hin trong gii hn ca
mt phn t.
Axit nucleic l nhng cht mu trng, c cu to dng si. trng thi t do kh ho tan trong
nc, nhng dng mui ca cc kim loi kim li rt d ho tan. D ho tan trong cc dung dch
mui.
Axit nucleic c tnh quang hot, dung dch ca chng c nht cao. Khi un nng n
nhit 80-900C axit nucleic nng chy, ng thi km theo s thay i nht. Trong qu trnh
nng chy cc lin kt hiro vn c gia cc baz pirimiin v purin b t, khi lm lnh cu trc
ban u li c ti to.
V mt ho hc, ni chung cc axit nucleic rt tr. Chng lin kt mt cch bn cht vi cc
ion kim loi, c bit l ion Cu2+, Mg2+ to thnh nhng phc hp khng tan.
Nhng phn ng quan trng nht ca axit nucleic l s ankyl ho nhm amin ca aenin,
guanin v qu trnh kh amin ho cc baz .
6. tecpenoit
Tecpen l tn gi chung ca nhng hirocacbon t nhin c thnh phn c biu din bng
cng thc chung (C5H8)n (n2).
Cn c theo thnh phn v cu to, cc tecpen c chia thnh 3 loi:
147 hu c ..147
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
Tecpen chnh thc c cng thc C10H16. Nhm ny bao gm cc tecpen khng vng vi
ba lin kt i, tecpen mt vng vi hai lin kt i v tecpen hai vng vi mt lin kt
i.
Sesquitecpen c cng thc chung (C5H8)3 . Nu n= 4 ta c tecpen C20H32 gi l itecpen,
n=6 ta c (C30H48 l cc tritecpen
CH2
CH2OH
CH2OH
CHO
CHO
geranddiol
linalool
xitrtonelol
roinol
xitral
xitronelal
Geraniol c trong tinh du hoa hng, linalool c trong tinh du hoa linh lan, cn xitral v
xitronelal c trong v chanh, v cam, l bi
148 hu c ..148
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
mentan
caran
piran
camphan
Ancaloit l nhng hp cht c ngun gc thc vt, c tnh kim v phn ln c tc dng
sinh l mnh.
Theo A.P.Orkhp, cc ancaloit ch gm cc hp cht hu c t nhin hay tng hp c cc
nhn d vng, c tnh kim.
Vic phn loi cc ancaloit c da trn c s cu to ho hc. Chng bao gm:
-
Cc dn xut ca:
N
H
piroliin
piriin
Cc ancaloit steroit
quinolin
N
N
N
H
inol
quinoxalin
isoquinolin
N
N
H
imiazol
NH
N
purin
Vai tr ca cc ancaloit cho n nay cha c gii thch r rng. Theo A.P.Orkhp v mt
s tc gi th ancaloit l nhng cht xc tc hot tnh c tc dng gii c v cc sn phn c ca
s chuyn ho. Mt s ancaloit (nicotin, covolamin...) c kh nng chuyn ho cacs nhm metyl
ca mnh cho cc cht khc. Mt s ancaloit khc di dng N-oxit (platifilin, senesefilin) c kh
nng cho oxi v chng tham gia vo cc phn ng oxi ho kh ca t bo. Ngi ta cng cn
149 hu c ..149
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
nicotin
N
CH3
N
H
anabaxin
Nicotin thuc loi hp cht c, tc dng n h thn kinh trung ng v ngoi bin. N
c dng lm cht phng tr su bnh cho cy trng, thuc cha bnh ngoi da cho gia sc.
Anabaxin cu to t d vng piriin v piperiin. Ch yu n c dng lm cht st trng,
c tc dng c i vi cn trng.
7.2. cc ancaloit nhm quinin
CH2
6 CH
2
8
N1
5
HO-CH
5'
CH3O
4'
6'
3
2
3'
7'
N 1'
8'
2'
N-CH3
HO
151 hu c ..151
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
Dung dch mocphin trong nc khng mu, trung tnh. Vi FeCl3 hoc axit fomalin sunfuric
cho mu xanh nc bin. Vi hn hp HNO3 + H2SO4 cho mu mu, khi mocphin chuyn
thnh apomocphin.
-H2O
C17H19O3N
C17H19O2N
C17H18O3N
C17H18O3N
+ 3 K3[Fe(CN)6] + H4[Fe(CN)6]
Mocphin b kt ta bi amoniac to thnh mocphin baz, cht ny ho tan trong cc kim mnh.
Ngoi khng kh khi c kim, mocphin b oxi ho thnh pseumcphin hay oximocphin:
Mocphin c tc dng gim au, gy ng, nhng c nhc im quen thuc v gy nghin.
b. Coein : C18H21O3N
CH3O
O
N-CH3
HO
Coein l nhng tinh th khng mu hoc bt kt tinh trng, v ng, tan t t trong nc,
d tan trong ancol, ete, clorofocm, benzen v cacbon isunfua. Gn nh khng tan trong kim.
Khng b kt ta bi amoniac, b kt ta bi kim mnh, []15D =-138,50. Vi FeCl3 khi c mt
H2SO4 m c cho mu xanh, cho thm HNO3 chuyn thnh mu mu.
Coein c tc dng tng t nh mocphin. Ch yu c dng cha ho v gim au khi
vim phi.
c. Papaverin : C20H20O3N
CH2
CH3O
CH3O
N
OCH3
OCH3
152 hu c ..152
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
Cc ancaloit nhm ny c nhiu trong t nhin nh trong cc loi ch (Thea chinensis. L),
qu ca cao ( Thea brome cacao L),...Trong l ch v ht c ph c t 1-3% cafein, trong qu ca
cao c 3% theobromin.
CH3
N
H2O
N CH N
3
Cafein l nhng si hnh kim di, v ng, khng mi, nng chy 234-2370C. Tan nhiu
trong CHCl3, CCl4, t tan trong ete, benzen, CS2...Kt tinh vi mt phn t nc, nc bay hi mt
phn trong khng kh v hon ton mt nc 1000C, qu 1000C bt u thng hoa.
Cafein l mt kim yu. T phn li trong dung dch nc. Cafein b kt ta bi cc thuc th
ca ancaloit v c vi tanin (kt ta b tan trong thuc th d).
N
CH3
Theobromin l cht bt kt tinh mu trng, nng chy 342-3430C, thng hoa 3900C, rt
t tan trong nc, ancol, khng tan trong ete v clorofoc. Tan trong cc dung dch kim mnh to
thnh cc dn xut kim loi. Vi axit to mui d phn li. Khi oxi ho phn hu thnh 3-metyl
alloxan v metyl ure.
O
CH3
HN
O
CH3
+ CH3-NH-C-NH2
O
=
[O]
N-CH3
HN
153 hu c ..153
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
O
N-CH3
AgN
=
N
CH3
Nhm ny gm cc ancaloit c nguyn t nit ngoi nhn. Cht tiu biu ca nhm ny l
colchamin v colchixin.
Colchamin (C21H25O5N):
CH3O
NH-CH3
CH3O
CH3O
=O
OCH3
NH-C-CH3
O
CH3O
CH3O
=O
OCH3
Colchixin t tan trong nc, tan nhiu trong ru, benzen, clorofocm.
Colchixin c tc dng kch thch gy t bin ging cy trng.
8. STEROIT
V vic cu to, steroit chnh l dn xut ca hirocacbon nhiu vng ngng t xyclo pentan
pehirophenantren:
C
A
Sterol l nhng cht c ngun gc thc vt. Este ca n vi axit l cc sterit. Sterol v sterit
u l cu t ca cht bo thc vt. Cht quan trng nht trong nhm ny l colesterol c cng
thc cu to nh sau:
CH3
CH3
A
CH3
C D
CH3
CH3
HO
Colesterol l ancol bc 2, l cht rn kt tinh, nng chy 1480C, c tnh cht hot quang
[] = -360 ( trong clorofocm ).
Khi oxi ho colesterol thu c colesteron c cng thc nh sau:
OH
Sapogenin c bn cht steroit rt ph bin trong thc vt thng ng. Trong thc vt,
sapogenin tn ti dng glucozit-saponin.
Saponin l nhng cht c, ng thi l nhng cht to bt rt tt nn c dng trong
nhng dng c dp tt la.
Th d, igosgenin l sapogenin ca glucozit saponin , c cng thc nh sau:
O
O
OH
OH
156 hu c ..156
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
CH3
O
OH
solasoin
solaniiza
Ni chung, cac ancaloit u lm cho cy c v ng, nn ngi ta cho rng, chc nng ch
yu ca chng l bo v cy khi b cn trng ph hi.
8.4. Cc steroit glucozit tim
Steroit -glucozit tim thng gp trong 11 h thc vt, ngoi ra khng thy trong cc sn
phm thin nhin khc.
Steroit -glucozit tim c hai dng l cacenolit v bufaienolit. Hai loi ny khng bao gi
tn ti trong cng mt h thc vt.
Cc cht tiu biu ca steroit loi ny l egoxigenin v benebrigenin. Chng c cu to
nh sau:
O
O
=O
=O
HO
CHO
OH
HO
OH
HO
egoxigenin
benebrigenin
157 hu c ..157
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
HO
OH
HO
HO
estraiol
HO
estron
estriol
Estraiol c to thnh trong bung trng, estron v estriol l sn phm oxi ho estraiol
trong c th v c thi ra ngoi theo nc tiu.
Hocmon sinh dc nam (anragen ) gm c testosteron v anrosteron.
Testosteron c to thnh trong tinh hon. Cn anrosteron l dn xut ca testosteron, n
c thi ra ngoi theo nc tiu. Cng thc ca chng nh sau:
HO
O
HO
testosteron
anrosteron
Hocmon v tuyn thng thn costicosteroit: T v tuyn thng thn ngi ta tch ra c
gn 40 hocmon khc nhau. Cc hocmon ny iu khin s trao i cht khong, nc v gluxit
trong c th. Tt c cc costicosteroit u l dn xut ca pregnan.
Cc cht tiu biu ca nhm ny l: hirocortizon v cortizon. Cng thc ca hirocortizon
v cortizon nh sau:
CH2OH
CH2OH
C=O
C=O
OH
OH
HO
O
O
hirocortizon
cortizon
158 hu c ..158
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
Cu hi v bi tp
+ NaOH
+ HCl
H+
+ H2O
+ glixin
Tolens
Phlinh
159 hu c ..159
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
1.
2.
3.
4.
160 hu c ..160
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
Mc lc
Chng 1. i cng..
1. Cu to v c im ca Cacbon
12
4. C ch phn ng
15
15
24
Cu hi v bi tp
31
32
32
40
3. Hirocacbon thm
50
Cu hi v bi tp
62
64
1. Dn xut halogen
64
2. Ancol v phenol
73
83
4. Axit cacboxylic
95
5. Amin
108
Cu hi v bi tp
113
161 hu c ..161
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn
115
115
131
133
4. Protit
139
5. Axit nucleic
144
6. Tecpenoit
146
7. Ancaloit
148
8. Steroit
153
Cu hi v bi tp
158
162 hu c ..162
Trng i hc Nng nghip H Ni - - Gio trnh Ho
http://hhud.tvu.edu.vn