81

Chapter 1-1
HA HU C
Organic Chemistry
82
Chapter 1-2
MN HC: HO HC HU C

VHT: 3
TNH IM:

TIU LUN: 30%
GIA K : 20%
CUI K : 50%


83
Chapter 1-3
Ti liu hc tp
1. Trn Th Vit Hoa-Phan Thanh Sn Nam. Ho hu c. NXB i hc
QG TP HCM.2007
2. Trn Vn Thnh- Ho hu c- NXB HBK TP HCM. 2001
3. Phan Tng Sn, Trn Quc Sn, ng Nh Ti. C s ho hc
hu c. Tp 1,2, NXBGD, H ni-1980
4. L Ngc Thch Ho hc Hu c, HQG Tp HCM,2001
5. Trn Quc Sn. C s l thuyt ho hu c NXB GD Tp1(1977),
Tp 2 (1979)
6. Thi Don Tnh. C s l thuyt ho hu c, NXBKH&KT,2000
7. John.D.Robert, Matorie.C. Caser- Basic principles of organic
chemistry
8. Robert t. Morron, Robert N.Boyd- Organic chemistry


84
Chapter 1-4
cng chi tit mn hc
Phn 1 : i cng (11tit)
Chng1: Cc khi nim c bn trong ha hu c
Chng 2: Hiu ng electron
Chng 3: C ch phn ng
Phn 2: Hydrocacbon (15 tit)
Chng 1: Ankan
Chng 2: Xicloankan
Chng 3: Anken
Chng 4:Ankadien
Chng 5: Ankin
Chng 6: Aren
85
Chapter 1-5
Phn 3: Dn xut ca hidrocacbon( 19 tit)
Chng 1: Dn xut halogen- hp cht c magie
Chng 2: Ancol, phenol, ete
Chng 3: Hp cht cacbonyl (Anehit, xeton)
Chng 4: Axit cacboxylic
Chng 5: Amin
Chng 6: Amino axit
Chng 7: Hp cht Azo-iazoni

86
Chapter 1-6
HA HU C
Organic Chemistry
Phn 1
i cng ha hc hu c
87
Chapter 1-7
.
Chng 1:
CC KHI NIM C BN
TRONG HA HU C
88
Chapter 1-8
1.1 CU TO LP V ELECTRON V TRNG THI
LAI HA CA NGUYN T
1. Cu to lp v electron ca cacbon
1s
2
2s
2
2p
2
1s
2
2s
2
2p
2
Lai ho sp
3
:
Lai ho sp
2
:
Lai ho sp:
Trng thi c bn
Trng thi kch thch
2. Cc trng thi lai ho
89
Chapter 1-9
1.2.1 Lin kt ion: Khng ph bin trong ho hu c: c
hnh thnh do s ht nhau ca cc ion tri du:
CH
3
COO
-
Na
+
,
1.2.2 Lin kt cng ho tr
Bn cht: L kt qu ca s xen ph ca cc AO ca cc
nguyn t tham gia lin kt. Khi hnh thnh lin kt cng ho
tr, cu hnh e cc nguyn t ging vi nguyn t kh him
Lu : Lin kt cho nhn l 1 trng hp c bit ca LK
cng ha tr
Bn cht ca lin kt o v lin kt t
+ Lin kt sigma: do s xen ph trc ca cc AO
+ Lin kt pi: do s xen ph bn ca cc AO
1.2 LIN KT HA HC
810
Chapter 1-10
811
Chapter 1-11
c im ca lin kt cng ho tr
- S phn cc ca lin kt: tu thuc vo m in ca
cc nguyn t tham gia lin kt m ta c : LK cng ha tr
khng phn cc v lin kt cng ho tr phn cc
- di lin kt: l khong cch gia 2 ht nhn nguyn t
tham gia lin kt.
+ di lin kt ca C vi cc nguyn t khc trong phn
nhm tng t trn xung di: C-F < C- Cl < C-Br < C-I
+ di lin kt ca C vi cc nguyn t khc trong chu k
gim t tri sang phi: C-C > C-N > C-O > C-F
+ bi lin kt cng tng th di lin kt cng gim
C C < C=C < C-C
+ di lin kt ph thuc trng thi lai ho
C
sp3
-H > C
sp2
-H > C
sp
-H

- Nng lng lin kt
812
Chapter 1-12
1.2.3 Lin kt hydro
813
Chapter 1-13
Bn cht
Bn cht l lin kt c to thnh gia nguyn
t H tham gia lin kt cng ho tr, mang mt
phn in tch dng X
o-
H
o+
v nguyn t Y:
o-

mang cp electron t do nh tng tc tnh in
yu.
Lin kt cng ho tr phn cc
X
o -
H
o+
. . . :Y
o-
Lin kt Hydr
iu kin:
+ X c m in ln: (O,N, halogen)
+ Y c cp electron cha s dng, bn knh nh
(F,O,N)
814
Chapter 1-14
Cc loi lin kt H
+ Lin phn t
+ Ni phn t: k: to vng 5-6 cnh
nh hng ca lin kt hydro
+ Nhit si, nhit nng chy
+ Tnh tan
+ Ph
+ Cu dng


815
Chapter 1-15
1.3. NG NG- NG PHN
1.3.1 Khi nim ng ng:
Hp cht c tnh cht vt l, ha gn ging
nhau,nhng trong thnh phn khc nhau mt
hoc mt s nhm nht nh
Theo ngha hp (thng gp) l ng ng
metylen (-CH
2
-)
V d: CH
3
CH
2
CH
2
CH
3
v CH
3
CH
2
CH
2
CH
2
CH
3

Nm trong 1 dy ng ng, nhng cht nm
trong dy gi l cht ng ng
816
Chapter 1-16
1.3.2 Khi nim ng phn
1. Phn bit cc khi nim: Cu to, cu hnh, cu
dng, cu trc
Cu to : ni ln trt t kt hp cc nguyn t trong
phn t, c im ca lin kt
Cu hnh: Ni ln s b tr trong khng gian ca
cc nguyn t trong phn t xung quanh mt b
phn cng nhc (hoc trung tm bt i) no
trong phn t
Cu dng: ni ln s b tr trong khng gian ca
cc nguyn t trong phn t khi c tnh n s quay
t do ca lin kt n
Cu trc: bao trm cc khi nim trn
817
Chapter 1-17
2. NG PHN
A Khi nim v ng phn:
ng phn l hin tng cc cht c cng cng thc phn t,
cng khi lng phn t nhng khc nhau v cu to hoc
cu hnh nn c nhng tnh cht (vt l, ha hc) khc nhau.
CH
3
CH
2
OH v CH
3
-O-CH
3

c cng cng thc phn t l C
2
H
6
O

B Phn loi ng phn :
+ ng phn cu tao
+ ng phn khng gian (lp th):ng phn cu hnh
( hnh hc , quang hc) v ng phn cu dng
818
Chapter 1-18
ong phn
Cu hnh
khng gian
Cu dang
Cu tao
hnh hoc quang hoc
819
Chapter 1-19
C. ng phn cu to
C
1
) Khi nim: l cc cht c cng cng thc phn t nhng
khc nhau v cu to ha hc
C
2
Phn loi
ng phn mch cacbon: l ng phn v cch sp xp
mch cacbon theo cch khc nhau: v d C
5
H
12
:




ng phn nhm chc: c cng cng thc phn t
nhng c nhm chc khc nhau . V d C
2
H
6
O

C
CH
3
H
3
C CH
3
CH
3
H
3
C
CH
2
CH
2
CH
2
CH
3
CH
3
CH CH
2
CH
3
CH
3
2,2-Dimethyl-propan
Pentan 2-Methyl-butan
CH
3
CH
2
OH CH
3
OCH
3
Ethanol Dimethyl ether
820
Chapter 1-20
ng phn v tr nhm chc

CH
3
CH
2
CH
2
OH CH
3
CH(OH)CH
3
1- propanol 2-propanol

ng phn v cch chia mch cacbon khc nhau
ca nhm chc
H-COO-C
2
H
5
CH
3
-COO-CH
3
etyl Focmiat metyl axetat
821
Chapter 1-21
H
3
C
C CH
2
COOEt
O
H
3
C
C CH COOEt
OH
Xeto Enol
ng phn h bin (tautomer)
S bin i gia hai ng phn h bin thng xy
ra rt nhanh trong dung dch khi c mt vt axit yu,
baz hoc nc.
822
Chapter 1-22
D. ng phn khng gian
D
1
.Cch biu din cu trc khng gian ca phn t
a. Cng thc phi cnh:
Qui c biu din:
Lin kt nm trong mt phng c biu din bng
ng lin tc
Lin kt hng ra pha trc biu din bng ng m
Lin kt pha sau biu din bng ng t on
a
C
b
c
d
H
C
H
H
H
Metan
823
Chapter 1-23
Theo mt cch khc: biu din phn t c 2 nguyn t
C th lin kt gia 2 C c biu din bng ng thng
t tri sang phi v xa dn ngi quan st, cc nguyn t
v nhm nguyn t lin kt vi c cng c biu din
trong khng gian bng on thng xut pht t C1 v C2
V d Cabc-Cabc

a
b
c
a'
c'
b'
a
a'
c
c'
b'
b
xen ke che khuat
824
Chapter 1-24
b. Cng thc chiu Niumen (Newman)

Qui c: Nhn phn t dc theo 1 lin kt no , thng
l lin kt C-C
Nguyn t C u lin kt xa mt (b che khut C2)
c th hin bng hnh trn v nguyn t gn mt
quan st (C1) c biu din bng tm ca hnh trn.
Cc lin kt t C1 c nhn thy ton b v xut
pht t tm hnh trn (C1).
Cc lin kt t C2 ch nhn thy c phn l ra t
chu vi ca hnh trn C2.
H
H
H
H
H
H
H H
H
H H
H
Newman
825
Chapter 1-25
c. Cng thc Fischer

Qui c:
Cu trc KG ca phn t c biu din trn mt phng
bng cch chiu ln mt phng giy
t cng thc phi cnh ca phn t sao cho nguyn t
C c chn nm trong mt phng trang giy, hai nhm
th gn mt ngi quan st khi chiu ln mt phng th
nm bn phi v bn tri nguyn t C, 2 nhm nguyn
t cn li xa mt ngi quan st khi chiu ln nm trn
trc dc ca cng thc Fis (Fischer)
Nhm nguyn t c s oxi ha cao hn th c vit
pha trn.
CHO
C
H OH
CH
2
OH
CHO
C H OH
CH
2
OH
CHO
C H HO
CH
2
OH
Cng thc phi cnh
Cng thc Fis
826
Chapter 1-26
Nu phn t c nhiu nguyn t
C th trc dc l trc ca nguyn
t C
Nu hai nguyn t C u mch
c s oxi ho nh nhau th pha
trn l nhm th c s th t nh
hn trong tn gi
Lu
Thng thng ngi ta biu din
cng thc Fischer ch cc
nguyn t C bt i, cn khi
khng c C bt i th ngi ta
thng biu din dng cng thc
rt gn cng thc t phc tp
CH
3
-CHCl-CH
2
-CH
3
CH
3
C
2
H
5
H
Cl
Cl
H
CH
3
C
2
H
5
827
Chapter 1-27
i ch bt k 2 nhm th no nguyn t carbon bt
i cng lm quay cu hnh v s sinh ra dng ng
phn khc.




Nu dch chuyn ng thi c 3 nhm th theo chiu
kim ng h hay theo chiu ngc li th cng thc
Fisher vn gi nguyn ngha.
Khng c quay cng thc Fisher trn mt phng mt
gc 90
0
hay 270
0
v s lm quay cu hnh nhng c th
quay mt gc 180
0
.



C O H
OH
H C
2
OH
H
O H
H C
2
OH
H
C O H
S
(1)
(2)
(3)
R
R
H
H
H C
2
OH
C O
OH
828
Chapter 1-28
D
2
ng phn hnh hc
1.Khi nim:
l mt loi ng phn cu hnh, trong c s phn b khc
nhau trong khng gian ca cc nhm th i vi 1 mt
phng (mt phng t hay vng no)
ng phn hnh hc cn gi l ng phn cis-trans hay Z- E
2. iu kin:
-Cn: c b phn cng nhc trong phn t ( ni i: C=C,
C=N, N=N..hoc vng no) lm cn tr s quay t do ca
cc nhm th
-: Hai nguyn t hoc nhm nguyn t lin kt vi b
phn cng nhc phi c bn cht khc nhau
Xt phn t abC=Cde trong a = b ; d =e , nhng a hay
b c th ging d hay e.




829
Chapter 1-29
3. Danh php
a. Danh php cis- trans
a1. Da vo bn cht nhm th Nu hai phi t
( nhm th) ging nhau nm cng mt bn mt
phng tham chiu th ng phn gi l : cis ,
ngc li l ng phn trans;





C C
Me
H
H
Me
C C
H
Me
H
Me
cis-2-Buten trans-2-Buten
830
Chapter 1-30
a2 Da vo mch chnh: nu cc nhm th
nm trn mch chnh cng pha l cis, khc
pha l trans

CH
3
C
2
H
5
H H
C = C
CH
3
H
H C
2
H
5
C = C
cis
trans
831
Chapter 1-31
i vi loi c nhiu ni i
C C
H
H
C C
H
C
3
H
C C
H
H
C C
H
3 2
H H C C
4-metylhept-3,5-dien 4-metylhept-3,5-dien
trans
-
trans
-
3 2
H H C C
3
CH
3
CH
C
3
H
cis
-
trans
-
i vi hp cht vng no
CH
3
CH
3
H
3
C
CH
3
cis
trans
832
Chapter 1-32
b. Cch gi tn theo danh php Z-E :
- p dng qui tc Cahn-Ingold-Prelog: Da vo s u tin
trn s th t trong HTTH.cc nhm th c s th t
cao hn th c u tin ( hn cp ) ln hn
- ng phn no c hai nhm u tin ln nm v mt bn
ca mt phng qui chiu l : Z, ngc li l E.

833
Chapter 1-33
Cch tnh u tin ( hn cp)
Qui tc: Cc nguyn t nh vi C
sp2
ca nguyn t c th t
ln hn trong bng HTTH th c hn cp ln hn.
Xt nguyn t lin kt trc tip vi trung tm cn xc nh cu
hnh (gi l nguyn t th nht ca nhm)
Br> Cl> S> P> O.>N >C>H
Nu lp th nht nh nhau th xt lp tip n cc nguyn t
lp th 2 (lin kt trc tip vi nguyn t th nht)
- CH(CH
3
)
2
> -CH
2
CH
3
> -CH
3

1H + 2C=13 2H+ 1C=2 3H =3
Tng t nh vy i vi lp th 3 nu lp th 2 nh nhau
Cc nguyn t cha lin kt bi th tnh bi ln
-CH=O > -CH
2
OH; -CN > CH
2
-NH
2

17 8 21 9
-
834
Chapter 1-34






F
Cl
H
3
C
H
Cl
F
H
3
C
H
(E)-1-Clo-1-flopro-1-en
(Z)-1-Clo-1-flopro-1-en
- Trong s ng v , nguyn t c s khi ln hn th c
hn cp ln hn

18
O >
16
O ,
15
N >
14
N , D > H
835
Chapter 1-35
4. nh hng ca ng phn hnh hc n tnh cht
bn tng i
Khong cch ca cc nhm th
Tnh cht vt l (nhit si, nhit nng chy,
momen lng cc)
836
Chapter 1-36
D3. ng phn quang hc

Tnh hot ng quang hc
l kh nng ca cht lm quay mt phng dao ng ca
nh sng phn cc.




1 2 3 4 5
1-Ngun nh sng, 2-Lng knh Nicol, 3-nh sng phn cc,
4-Cht quang hot, 5-Anh sng sau khi i qua cht quang hot
837
Chapter 1-37
1.Khi nim ng phn quang hc
Nhng hp cht c cng cu to ha hc, c tnh cht
vt l v ha hc ging nhau, nhng khc nhau v b tr
trong khng gian xung quanh mt trung tm bt i no
trong phn t v vy kh nng lm quay mt phng
nh sng phn cc v tnh cht sinh ha gi l ng
phn quang hc.
2. iu kin c ng phn quang hc
C yu t khng trng vt nh: s cho vt v nh i
xng nhau nhng khng chng kht c vi nhau
C 2 loi : bt i nguyn t v bt i phn t
+ Nguyn t bt i l nguyn t lin kt vi 4 nhm th c
bn cht khc nhau
+ Bt i phn t: trong phn t c nhng b phn hoc
nhm th m lm cho 4 nhm th c bn cht khc nhau
b tr trn 2 mt phng vung gc hoc gn vung gc
vi nhau
838
Chapter 1-38
3. Mt s ng phn quang hc thng gp
Phn t c 1 C bt i xng: Nhng nguyn t
cacbon nh vi 4 nguyn t hoc nhm nguyn t
khc nhau gi l cacon bt i k hiu: C*.
Cc phn t ny c 2 ng phn quang hc to
thnh 1 cp i quang
Phn t c nhiu C bt i : S lng ng phn
quang hc = 2
n
(n = s lng cacbon bt i).
Nhng nu trong phn t c yu t i xng th s
ng phn quang hc nh hn 2
n
v c xut hin
loi ng phn quang hc khng c tnh quang hot
l ng phn mezo


839
Chapter 1-39
Axit lactic c 2 i quang l ng phn quay phi v ng phn quay
tri, 2 i quang ny chng rt ging nhau nhng khng th chng
kht ln nhau c
Hn hp 50% ng phn quay phi v 50% ng phn quay tri gi l
hn hp raxemic
COOH
C
H
HO
H
3
C
COOH
C
H
OH
CH
3
Axit L (-)-lactic Axit D (+)-lactic
t
o
nc
t
o
s
26 26
122/14 mmHg
122/14 mmHg
|o|
25
D
+3.8
o
-3.8
o
V d
840
Chapter 1-40
Hp cht c nhiu trung tm bt i
Xt phn t: aldotetroz, nu ta gi gc quay ca cacbon
bt i th nht l (a), gc quay cacbon th hai l (b) th
gc quay ca phn t s bng tng i s ca cc gc
quay cc ca tng nguyn t cacbon bt i.










C 4 cu hnh, 4 ng phn quang hc

Hai oi quang erytro
ong phan quang hoc aldotetrazo
Hai oi quang treo
H C
2
OH
C O H
OH H
OH H
C O H
H C
2
H
H
OH
O
H
O H
C O H
H C
2
H
OH H
OH
O H
H C
2
OH
C O H
H
OH H
O H
841
Chapter 1-41
Xt Acid tartric (HOOC CHOHCHOH_ COOH), c hai C* nhng
ch c 3 ng phn quang hc. Trong c mt ng phn meso to
thnh do mt phng i xng trong phn t,
COOH
H OH
H OH
COOH
Enantiomer
C 3 ng phn quang hc: 2 hot ng quang hc gi enantiomer
v 1 khng hot ng quang hc gi meso
meso
842
Chapter 1-42
4. Danh php ng phn quang hc
a. Danh php D,L:
gi theo tn ca cht chun l D v L glyxerandehit




H
CHO
OH
CH
2
OH
CHO
H
CH
2
OH
HO
D- glyxerandehit L- glyxerandehit
Lu : khi gi tn theo D,L th cng thc dng Fischer
ca cht nghin cu phi dng chun
843
Chapter 1-43
b. Danh php R,S
Quy tc ny da trn c s tng s u tin ca nhm th
nh vi trung tm bt i xng theo th t u tin t ln
nht (1) cho n nhm nh nht (4) vi iu kin nhm
nh nht phi xa vj tr ngi quan st v sau mt phng
Nu nhn t C bt i n nhm c hn cp (u tin)
nh nht m t 123 theo chiu kim ng h l R ,
ngc chiu l S
844
Chapter 1-44
c tn cu hnh R, S
Kinh nghim: Nu c theo R,S t cng thc Fischer c
nhm th c hn cp nh nht nm trc ngang, t
123 theo kim ng h l S , ngc kim ng h l R
845
Chapter 1-45
D
4
. ng phn cu dng
1. Khi nim v cu dng v ng phn cu dng
Cu dng l cc dng cu trc khng gian sinh ra khi c tnh
n s quay t do ca cc lin kt n, cc ng phn sinh
ra do s quay t do gi l ng phn cu dng
2. Cu dng ca hp cht hidocacbon no mch h
+ Ca etan : xen k bn
hn che khut
+ Ca n- butan:
bn ca cc dng xen k anti > xen k syn > che khut tng
phn> che khut ton phn
xen ke che khuat
?
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
H
3
C
xen ke anti
che khuat tung phn xen ke syn
che khuat ton phn
?
?
?
846
Chapter 1-46
3 Cu dng ca xiclohexan v dn xut
i vi xiclohexan: gim sc cng Baye: vng khng
phng, gc ha tr t 109
0
28
+Cu dng gh bn hn cu dng thuyn v thuyn vn (xon)




i vi xiclohexan c nhm th: cc nhm th v tr bin
bn hn khi v tr trc

gh
thuyn van
thuyn
CH
3
CH
3
847
Chapter 1-47
1.4. Phn loi hp cht hu c

HP CHAT HU C
HP CHAT VONG
HP CHAT KHONG VONG
NO
KHONG NO
THM
KHONG THM
HP CHAT DVONG
HP CHAT DONG VONG
THM
KHONG THM
S
O
N
H
848
Chapter 1-48
1.2 Cc loi hiu ng
1. 2.1 Hiu ng cm ng
1.2.1 Bn cht : S dch chuyn mt electron dc theo
mch C trong phn t gy ra bi s chnh lch v m
in gi l hiu ng cm ng (I),
.
H - C - C - C - C Cl
H H H H
H H H H
o
o
Hiu ng cm ng c vit tt bng ch I (inductive effect)
v c biu din bng mi tn thng () t nguyn t c
m in nh n nguyn t c m in ln
849
Chapter 1-49
1.2.2 Phn loi
Hiu ng cm ng dng v hiu ng cm ng m:
nhng nguyn t gy ra hiu ng cm ng bng cch y
electron, ngi ta gi l hiu ng cm ng dng k hiu
(+I), ngc li ht electron v phi mnh l hiu ng cm ng
m (-I)
Hiu ng cm ng tnh (I
S
) v hiu ng cm ng ng (I

)
Hiu ng cm ng tnh l c sn trong phn t, cn ng l
hiu ng xut hin do tc ng ca cc yu t ngoi
V lin kt sigma bn , khng linh ng nn hiu ng cm ng
ng rt nh ngi ta thng b qua

850
Chapter 1-50
1.2.3 c im ca hiu ng cm ng
H
3
C CH
2
CH
2
COOH
H
3
C CH
2
CH COOH
Cl
K
a
= 1,54.10
-5
K
a
= 1,39.10
-3
H
3
C CH CH
2
COOH
H
2
C CH
2
CH
2
COOH
Cl
Cl
K
a
= 8,9.10
-5
K
a
= 3,0.10
-5
Gim rt nhanh khi tng chiu di ca mch cacbon
851
Chapter 1-51
1.2.4 Quy lut
a) Cc nhm mang in tch dng c hiu ng I , in
tch m c hiu ng +I,



b) i vi cc nhm I:
m in cng ln th hiu ng I cng ln
+ Theo phn nhm: gim t trn xung:
-I < -Br < -C l < -F
+ Theo chu k tng t tri sang phi:
-CH3 < -CNH
2
< -OH < -F
+ Ph thuc trng thi lai ho
-CH
2
=CH
2
< -C
6
H
5
<



OH
+I:
N(CH
3
)
3
S
-I:
C CH
852
Chapter 1-52
c) i vi cc nhm c hiu ng cm ng dng +I
Cc nhm c hiu ng + I l nhng nhm c m in
thp hn nguyn t bn cnh
-CH
3
< - CH
3
CH
2
<- CH(CH
3
)
2
< -C(CH
3
)
3

Cc nhm ankyl c hiu ng +I v tng theo mc phn
nhnh ca nhm ankyl
H-COOH CH
3
-COOH CH
3
-CH
2
-COOH
K
a
= 1,72.10
-4
K
a
= 1,76.10
-5
K
a
= 1,34.10
-5
K
a
= 9,4.10
-6
(CH
3
)
3
C-COOH
853
Chapter 1-53
2.2. Hiu ng lin hp
2.2.1 Cc loi h lin hp thng gp
H lin hp t-t, Khi cc lin kt bi cch nhau ng 1
lin kt n th to thnh 1 h lin hp gi l h lin
hp t-t,
V d:CH
2
=CH- CH=CH
2
; CH
2
=CH-CH=O

H lin hp t-p, Khi 1 lin kt bi cch 1 obitan p c
cp electron mt lin kt n th to thnh 1 h lin hp
gi l h lin hp t-p,
V d

Ngoi ra cn c h lin hp ng: xut hin trong cc tiu
phn trung gian ca phn ng:
CH
2
CH Cl
854
Chapter 1-54
2.2.2 Bn cht ca hiu ng lin hp
Bn cht:Cc electron t hoc p khi tham gia trong h lin
hp th khng cn c tr ring 1 v tr no m chuyn
dch trong ton h lin hp. Khi cc nhm nguyn t lin
hp vi nhau th mt electron t v p b thay i ngi
ta gi l hiu ng lin hp (C).
Nh vy bn cht ca hiu ng lin hp l hin tng dch
chuyn electron trong h lin hp, gy nn s phn cc
ca cc lin kt t trong h

.
CH
2
= CH-CH = O
CH
2
= CH- Cl
N = O
O
855
Chapter 1-55
2.2.3 Phn loi hiu ng lin hp
Hiu ng lin hp m (-C):l cc nhm khng no ht
electron: -NO
2
, -C=O , -C N,
Hiu ng lin hp dng (+C): Hu ht c nguyn t c
cp electron p t do, hoc ni i lin kt vi h ni i khc
m in hn
CH
2
CH Cl
o
H
2
C CH C
H
CH
2
o o
H
2
C CH C
H
CH
2
o
o
H
2
C CH C
H
O
o
o
+ C - C - C + C
+ C - C + C + C
+ C
- C
NH
2 N
O
O
+C
-C
856
Chapter 1-56
Hiu ng lin hp tnh v hiu ng lin hp
ng
+ Hiu ng lin hp tnh: c sn trong phn t
+ Hiu ng lin hp ng: do tc ng bn ngoi
hoc sinh ra trong cc tiu phn trung gian ca
phn ng


CH
2
= CH-CH
3
+ Cl
2
500
o
C
-HCl ;- Cl
.
CH
2
=CH-CH
2
CH
2
= CH-CH
2
Cl + NaOH
S
N
1
CH
2
=CH-CH
2
857
Chapter 1-57
2.2.4 c im ca hiu ng lin hp
t b thay i khi tng chiu di ca h lin hp
V d nguyn t H u mch (CH
3
) ca cc hp cht
andehyt cha no lin hp H-CH
2
-(CH=CH)
n
-CH=O khi tham
gia phn ng andol ho vi tc nh nhau



Ch pht huy tc dng trong h phng (chu nh hng ca
yu t khng gian)

H-CH
2
-(CH=CH)
n
-CH=O + CH
3
CH=O
OH
CH
3
CH(OH)-CH
2
-(CH=CH)
n
CH=O
N
O
O
N
O
O
CH
3
CH
3
858
Chapter 1-58
2.2.5 Quy lut
a) i vi cc nhm c hiu ng +C
Cc nguyn t hoc nhm nguyn t mang in tch m c
hiu ng + C ln hn nhm tng t khng mang in tch
- O
-
> -OH; -OR; -S
-
> -SH, -SR
Trong mt chu k hiu ng +C gim dn t u n cui
-NR
2
> -OR > -F
Trong mt phn nhm chnh: gim t trn xung di
-F > -Cl > -Br > -I
859
Chapter 1-59
b) i vi cc nhm c hiu ng C:
Chng thng c cu to dng C=Z
Nu Z c m in cng cao th C cng ln


i vi cc nhm tng t, nhm no mang in tch
dng th c hiu ng C cng ln


* Lu : c mt s nhm nh vinyl v phenyl du ca hiu
ng lin hp khng c nh, tu thuc vo bn cht
nhm th m chng lin kt
C = O > C = NR > C = CR
2
C = NR
2
> C = NR
860
Chapter 1-60
2.3 Hiu ng siu lin hp
2.3.1 Bn cht: l hiu ng lin hp ca cc lin kt o
C-H
hoc
vng no nh vi cc lin kt bi C=C, CC cch cc lin kt
C-H hoc vng no nh 1 lin kt n



2.3.2. Phn loi : h. ng siu lin hp dng(+H) v m (-H)





H
H
H
C
CH = CH
2
CH = CH
2
H C CH = CH
2
H
H
H C
H
H
F
F
F
C
CH = CH
2
-H
+H
861
Chapter 1-61
2.3.3 Qui lut

Cng nhiu lin kt C-H th hiu ng +H cng mnh
-CH
3
> -CH
2
-CH
3
> -CH(CH
3
)
2

Hiu ng siu lin hp pht huy tc dng mnh trng
thi ng


862
Chapter 1-62
2.4 Hiu ng khng gian
2.4.1 Hiu ng khng gian loi 1 (S
I
)
L loi hiu ng ca cc nhm c th tch ln lm cn
tr mt v tr hoc mt nhm chc no


O
O
CH
3
CH
3
1 2
NH
2
OH
2.4.2 Hiu ng khng gian loi 2 (S
II
)
L loi hiu ng ca cc nhm th c V ln lm nh hng
n s ng phng ca h lin hp, nn lm gim hiu ng
lin hp, nn thay i tnh cht v kh nng phn ng
2.4.3 Hiu ng ortho:
L hiu ng ca nhm th v tr ortho i vi trung tm phn
ng, n l hiu ng tng hp ca cc loi hiu ng: electron,
khng gian, trng, lin kt H
863
Chapter 1-63
2.5 Cc phng php bn nh lng v nh hng
ca nhm th trong phn t
2.5.1 Phng trnh Hammet
L pt ni ln nh hng ca nhm th
trong nhn thm khi v tr meta v para
K v K
0
:

l hng s phn ng khi c nhm th ( v tr meta
hoc para) v khng c nhm th.
: l thng s c trng cho tng loi phn ng
o: l hng s cho mi nhm th v tr nht nh, nu c
gi tr dng th nhm ht e, m l y e, tr s cng
ln th kh nng ht (hoc y) cng ln. V d
o
p-OCH3
=-0,268; o
p- NH2
= -0,66 OH para y mnh
hn OCH
3

o
p-NO2
= + 0,78; o
p-Cl
= 0,23 NO
2
ht mnh hn Cl
lg
K
K
o
=
o
Lu : nh hng y l nh hng tng cng ca cc loi
hiu ng
864
Chapter 1-64
2.5.2 Phng trnh Tap
Phng trnh c dng
lg
K
K
o
=
-
o
-
Phng trnh ny p dng cho loi hp cht dy bo,
nhng khc vi phng trnh Hammet, trong Hammet th H
c ly lm chun cn trong phng trnh Tap th nhm
ly lm chun l CH
3

ngha ca cc i lng K, K
0,
cng tng t nh
phng trnh Hammet
865
Chapter 1-65
2.6 nh hng ca hiu ng n tnh axit baz
2.6.1 Khi nim v axit baz
2.6.2 Tnh axit ca cc hp cht hu c :
a s hp cht hu c c tnh axit khi c lin kt Z-H phn
cc, m ph bin nht l cha nhm - O-H
Nu lin kt O-H cng phn cc v nu tch H
+
m anion to
ra cng bn th tnh axit cng ln. V vy:
+ Trong hp cht nu O-H lin kt vi nhm ht electron th
tng tnh axit, ngc li vi nhm y th tnh axit gim
+ ancol < nc < phenol < axit cacboxylic
i vi ancol : bc 1 > bc 2 > bc 3
i vi phenol : tnh axit ph thuc vo bn cht v v tr ca
cc nhm th: tr v tr ortho c nhiu ngoi l, cn cc nhm
th c hiu ng +C v tr para th c tnh axit yu hn meta,
nhng c nhm ht e ( hiu ng C) th v tr para s mnh
hn v tr meta v khi hiu ng lin hp pht huy tc dng
866
Chapter 1-66
Tnh cht axit
i vi axit cacboxylic
Axit no: mch cacbon cng di th tnh axit cng gim, thay
H bng cc nhm ht electron th tnh axit cng tng
Axit khng no:
+Ni chung c tnh axit mnh hn axit no tng ng,
+ Nhm khng no cng gn nhm COOH th tnh axit cng
tng , tr trng hn lin kt i C=C v tr o,;
+ Lin kt ba CC lm tng tnh axit k c khi v tr o,
Axit icacboxylic:
+ nc 1 c tnh axit tng, nhng nc th 2 c nhm COO
-
y electron nn c tnh axit gim r rt
+ ng phn cis c tnh axit cao hn trans
Axit thm c quy lut tng t nh phenol ( lu hiu ng
ortho; bt k nhm th y hay ht e u tng tnh axit so
vi axit benzoic)
867
Chapter 1-67
2.6.3 Tnh baz ca hp cht hu c
a s cc baz do c cp electron cha s dng nn kt
hp c vi proton. Nu mt eletron cng cao v cng
linh ng th tnh baz cng ln.
V vy
Tnh baz ca amin > ancol > nc
Baz cng mnh th tnh axit cng yu v ngc li axit
cng yu th baz lin hp ca n cng mnh
- Tnh axit: C
6
H
5
OH > H
2
O > C
2
H
5
OH
- Tnh baz :C
6
H
5
O
-

< HO
-
< C
2
H
5
O
-


868
Chapter 1-68
Tnh bazo ca cc hp cht cha nit
i vi cc hp cht cha nit, ni chung c tnh baz, nu
mt electron cng ln th tnh baz cng mnh
i vi amin: amin bo > amoniac > amin thm
Tnh bazo cn ph thuc vo dung mi
+ Trong dung mi khng c kh nng solvat ha (clobenzen)
Amin bo bc 3 > bo bc 2>bo bc 1> NH
3
> amin thm bc
1> thm bc 2 > thm bc 3
+ Trong dung mi c kh nng solvat ha (nh nc)
Amin bo bc 2 > bo bc 3 v bc 1> NH
3
> amin thm bc
1> thm bc 2 > thm bc 3
Cc amin thm c nhm th: tnh bazo ph thuc vo bn
cht v v tr ca nhm th nhn
Cc d vng thm c tnh bazo thp, cn d vng no c tnh
bazo tng t hp cht no

869
Chapter 1-69
Chng 3: C ch phn ng
Phn loi phn ng
+Phn ng th : S
+ Phn ng cng : A
+ Phn ng tch: E
Phn loi theo tc nhn phn ng
Phn ng i nhn (nucleophin)
Phn ng i in t ( electrophin)
Phn ng gc t do
Phn loi c ch phn ng: kt hp c hai cch phn loi
ny v s tiu phn tham gia giai on quyt nh tc
phn ng
S
N
1, S
N
2, S
E
, S
R

A
N
, A
E
, A
R
E
1
, E
2


870
Chapter 1-70
Nh vy
ch mt c ch phn ng, ngi ta thng dng mt
s k hiu sau:
S: Phn ng th;
A: Phn ng cng;
E: Phn ng tch;
Tc nhn nucleophin c k hiu bng ch N v ghi
chn k hiu phn ng;
Tc nhn electrophin k hiu bng ch E v c ghi
chn k hiu phn ng;
Tc nhn gc t do k hiu bng ch R v c ghi
chn k hiu phn ng;
Cc phn ng n phn t, lng phn t c k hiu
bng cc ch s 1, 2 v ghi di dng s m i vi tc
nhn
871
Chapter 1-71
872
Chapter 1-72
Phn ng th Nucleophil
A nucleophile l mt nhm c cha i in t t
do m c th phn ng c vi nguyn t carbon
thiu ht electron
A Nhm b t ra (leaving group) c thay th bi
mt tc nhn nucleophile







R X
Nu
-
R
X
-
Nu
873
Chapter 1-73
Cc nhm chuyn ha trong phn ng S
N
2
874
Chapter 1-74
Phn ng th i nhn ( th nucleophin) SN
875
Chapter 1-75
Phn ng th i nhn SN
876
Chapter 1-76
Phn ng th i nhn SN
877
Chapter 1-77
C ch phn ng th Nu







Ph v v hnh thnh lin kt
ng thi: S
N
2
Tng bc: S
N
1
C X
Nu
-
o- o+
878
Chapter 1-78
C ch phn ng th S
N
2







A transition state (trng thi chuyn tip): nng lng
cao
Km bn v ch tn ti trong thi gian ngn(10
-12
s)
Lin kt trng thi hnh thnh v ph v
C chlorometan v hydroxit lin quan n trng thi
chuyn tip

879
Chapter 1-79
Gin nng lng phn ng S
N
2
880
Chapter 1-80
Tnh khng gian (ha lp th) ca phn ng S
N
2
Tc nhn Nucleophile tn cng t pha sau cho
nn dn n vic quay cu hnh ca sn phm
cui cng





881
Chapter 1-81
C ch phn ng th Nu SN
1
Reactions
Bc 1 xc nh tc phn ng
To thnh hp cht ionic km bn gi cacbocation
water molecules help stabilize the ionic products
882
Chapter 1-82
C ch phn ng th Nu S
N
1 Reactions
Cacbocation cng b th nhiu th cng bn , khi
cng bn th cacboccation cng d to ra
883
Chapter 1-83
Tnh khng gian (ha lp th) ca phn ng S
N
1
Trong phn ng S
N
1

trong trng hp l tng
s xut hin bin th raxemic

884
Chapter 1-84
Tnh khng gian ca phn ng S
N
1








885
Chapter 1-85
So snh S
N
1 v. S
N
2
Cc yu t lin quan ti tc ca phn ng S
N
1 and S
N
2
Cu trc ca tc cht
Trong phn ng S
N
2 : Methyl > primary > secondary >> tertiary
(unreactive)
Yu t khng gian: S sp xp cc nguyn t hay nhm trong khng
gian lm cho cc tc nhn tn cng vo v tr t nh hng khng
gian nht
tertiary halogen thc hin phn ng S
N
1 (carbocations bn)

886
Chapter 1-86
nh hng ca nng
nh hng ca nng v kh nng ca tc nhn Nucleophin
S
N
1
Tc phn ng khng ph thuc nng nucleophin
S
N
2 Reaction
Tc phn ng lin quan trc tip ti nng nucleophin
Cc tc nhn nucleophin mnh phn ng nhanh hn ( cc tc
nhn mang in tch m phn ng nhanh hn tc nhn mang in
tch m)
V d