16 BG HHC Ptsnam

Ha Hc Hu C
TS Phan Thanh Sn Nam

B mn K Thut Hu C
Khoa K Thut Ha Hc
Trng i Hc Bch Khoa TP. HCM
in thoi: 8647256 ext. 5681
Email: ptsnam@hcmut.edu.vn
http://hhud.tvu.edu.vn
Ti liu tham kho

[1] Paula Y. Bruice, Organic chemistry, fifth edition, Pearson
Prentice Hall, 2007
[2] Graham T.W. Solomons, Craig B. Fryhle, Organic chemistry,
eighth edition, John Wiley & Sons, 2004
[3] Francis A. Carey, Organic chemistry, fifth edition, McGrawHill, 2003
[4] Robert T. Morrison, Robert N. Boyd, Oragnic chemistry, sixth
edition, Prentice Hall, 1992
[5] Trn Th Vit Hoa, Phan Thanh Sn Nam, Ha hu c, NXB
i Hc Quc Gia HCM, 2007
[6] Trn Th Vit Hoa, Trn Vn Thnh, Bi tp ho hu c, NXB
i Hc Quc Gia HCM, 2004
[8] Thi Don Tnh, C s l thuyt ho hu c, NXB Khoa Hc
K Thut, 2000
[9] Trn Quc Sn, C s l thuyt ha hu c, NXB Gio Dc,
1979
NI DUNG CHNH
ng phn ca hp cht hu c
Hiu ng trong hp cht hu c
C ch cc phn ng ca hp cht hu c
Alkane
Alkene
Alkyne
Alkadiene
Hp cht hydrocarbon thm
Dn xut halogen
Alcohol Phenol
Aldehyde Ketone
Carboxylic acid
Amine Hp cht diazonium http://hhud.tvu.edu.vn
Chng 1:
NG PHN
ng phn: nhng hp cht hu c c

cng thc phn t ging nhau, cng thc
cu to khc nhau tnh cht ha hc, vt
l, sinh hc khc nhau
Phn loi:
+ ng phn cu to (phng)
+ ng phn lp th: ng phn hnh hc
(cis, trans), ng phn quay (cu dng),
ng phn quang hc
I. ng phn cu to
Do c s sp xp khc nhau ca cc nguyn t
trong mch C
I.1. ng phn mch C
n-butane
iso-butane
C6H12
methyl cyclopentane
cyclohexane
I.2. ng phn do v tr cc lin kt bi, nhm chc

butene-1
C4H8
OH
butene-2
OH
OH
OH
OH
1,2-
1,3-
OH
1,4-
dihydroxy benzene
I.3. ng phn c nhm nh chc khc nhau

dimethyl ketone
C3H6O
propan-2-one
O
acetone
CHO
propionaldehyde
propanal
propionic aldehyde
C3H6O2
COOH
Propionic acid
O
O
methyl acetate
7
I.4. ng phn c nhm th khc nhau lin kt vi

nhm nh chc
C4H10O
diethyl ether
methyl propyl ether
II. ng phn lp th
II.1. ng phn hnh hc
II.1.1. iu kin xut hin ng phn hnh hc
Xut hin khi phn t c 1 b phn cng nhc
cn tr s quay t do ca cc nguyn t
2 nguyn t lin kt vi cng 1 nguyn t ca

b phn cng nhc phi khc nhau
Thng xut hin cc hp cht c cha:

C=C, C=N, N=N, h lin hp, vng phng 3
hay 4 cnh
abC=Ccd: a b, c d
Cl
H
Cl
H
10
II.1.2. Danh php ca ng phn hnh hc

a. H cis-trans: abC=Cab
Nhm th tng ng nm cng pha
mt phng lin kt cis
Khc pha trans
H3C
H
CH3
H3C
cis-butene-2
H
H
CH3
trans-butene-2
11
b. H Z-E: abC=Ccd
a>b c>d
Quy tc Kahn-Ingold-Prelog: da theo th

t u tin trong bng HTTH ca nhm th
a, c cng pha so vi mt phng ni i: Z
(zusammen)
a, c khc pha so vi mt phng ni i: E
(entgegen)
12
35
Br
17
Cl
(E)-1-Bromo-2-chloro-2-fluoro-1-iodoethene
F
9
53
Br
Cl
(Z)-1-Bromo-2-chloro-2-fluoro-1-iodoethene
Lu : Khi dng Z-E, ch Z, E khng

phi lun trng vi cis, trans
Cl
Cl
Cl
Cl
Z-, cis-
Br
E-, cishttp://hhud.tvu.edu.vn
13
II.1.3. ng phn hnh hc ca abC=Nd v

aN=Nb
a. abC=Nd
Trc y, dng h syn-, anti-, nhng
khng chnh xc nn hin nay dng h Z-E
a>b: a, d khc pha so vi mt phng ni
i E, cng pha Z
i vi aldoxime
H3C
OH
C N
H
anti-acetaldoxime
(Z)-acetaldoxime
H3C
C N
OH
H
syn-acetaldoxime
(E)-acetaldoxime
14
i vi ketoxime: Cng 1 cht, c th gi l

syn- hay anti- !!!
H3C
H3C
OH
C N
C N
anti-phenyl-p-tolylketoxime
syn-p-tolyl-phenylketoxime
OH
syn-phenyl-p-tolylketoxime
anti-p-tolyl-phenylketoxime
h syn-anti khng chnh xc

chuyn sang h Z-E
15
b. aN=Nb
C6H5
N N
N N
C6H5
C6H5
C6H5
syn-azobenzene
anti-azobenzene
16
II.1.4. ng phn hnh hc ca hp cht cha C=C

lin hp
a(HC=CH)nb
CH
H
6 5
H
H
C6H5
C6H5
H
H
C6H5
H
C6H5
trans,trans-1,4-diphenyl-1,3-butadiene
cis,cis-1,4-diphenyl-1,3-butadiene
C6H5
H
cis,trans-1,4-diphenyl-1,3-butadiene
* S p hnh hc ca h lin hp C=C

N = 2n-1 + 2p-1
n: s ni i lin hp
p = n/2
nu n chn
p = (n + 1)/2 nu n l
17
II.1.5. ng phn hnh hc ca vng no 3, 4

cnh
c b tr trn 1 mt phng cc nhm th
khng th quay t do xut hin ng phn
hnh hc
* Cc nhm th tng ng cng pha mt phng
cis, khc pha trans
HOOC
H
COOH
HOOC
cis-cyclopropane-1,2-dicarboxylic acid
H
COOH
trans-cyclopropane-1,2-dicarboxylic acid
18
II.1.6. Cch xc nh v so snh cc ng phn

hnh hc
a. xc nh khong cch gia cc nhm th
Khong cch gia 2 nhm th tng ng
trong ng phn cis < trans
H
Cl
H
Cl
H
Cl
Cl
H
4.7
3.7
19
b. Moment lng cc
2 nhm th ging nhau aHC=CHa
H
Cl
Cl
Cl
Cl
H
cis (1.89D) > trans (0D)

2 nhm th khc nhau aHC=CHb (a b)
2 nhm th cng ht hay cng y in t:
cis > trans
2 nhm th c tnh cht in t ngc nhau:
cis < trans
20
c. Nhit nng chy

ng phn trans-: i xng mng li
tinh th cht ch tonc cis < tonc trans
Lu : mi lin h gia to si v ng
phn hnh hc khng cht ch
V d:
CHCl=CHCl tosi ca cis-: 60.3 oC, tosi
ca trans-: 48.4 oC
CH3CH=CHCl tosi ca cis-: 32.8 oC, tosi
ca trans-: 37.4 oC
21
II.2. ng phn cu dng (ng phn quay)

L nhng cu trc khng gian sinh ra do 1 nhm
th quay xung quanh trc C-C (khng lm t C-C)
so vi 1 nhm nguyn t khc
Thng cn nng lng 3-4 Kcal/mol
Ch tn ti nhng cu dng tng i bn
Khng th tch thnh nhng ng phn ring r!!!
ng phn cu dng l cc dng khc nhau trong
khng gian ca cng 1 cu hnh!!!
22
II.2.1. Cch biu din

a. Cng thc phi cnh (khng gian 3 chiu)
a
b
a
b
c
b
c
che khut
a
b
c
xen k
Lin kt C-C: ng cho tri qua phi, xa

dn ngi quan st
23
b. Cng thc Newman

Quan st dc theo C-C 2 nguyn t C
dng che khut, biu din bng vng trn
chiu cc nhm th ln mt phng vung
gc vi C-C
aa
b
c
c
b
b
che khut
c
b
xen k
24
II.2.2. Cu dng ca cc hp cht mch h

a. Ethane
Quay 1 nhm CH3 & c nh nhm cn li
2 ng phn cu dng ti hn
Che khut: khong cch gia cc H gn
nhau nng lng cao nht km bn
nht
25
Xen k: khong cch gia cc H xa nhau nng

lng thp nht bn nht
26
b. n-Butane
Quay cc nhm th quanh trc C2-C3 2 dng
c nng lng cao: che khut ton phn & che 1
phn
CH3
H
CH3
CH3
H
H
H
H
H
H
H
CH3
2 dng c nng lng thp: anti (i) & syn (lch)

CH3
H
H
H
CH3
H
CH3
H
H
H
CH3 http://hhud.tvu.edu.vnH
27
28
II.2.3. Cu dng ca hp cht vng no

Vng no 3,4 cnh khng c ng phn cu dng
Sc cng bayer: do s khc bit ca gc lin kt
so vi gc ha tr bnh thng (109o28)
= (109o28 gc lin kt ca vng)
29
a. Cyclohexane
Cc C khng cng nm trong 1 mt phng
bo m gc lin kt ~ 109o28
Cc nhm th c th quay quanh C-C ng
phn cu dng
C 2 dng c trng: gh (bn) & thuyn
* Gh:
Xem nh 1 t hp ca 6 h thng n-butane
Tt c 6 h thng u dng xen k (syn butane)
5
4
3
2.5
6
2
2.49
2
6
30
* Thuyn:
1.84
5
6
3
4 1
2.49
2.27
4 h thng dng xen k: C1-C2, C3-C4, C4C5, C6-C1

2 h thng dng che khut hon ton: C2C3, C5-C6
Khong cch H C1 & C4 rt nh lc y
km bn hn dng gh
*** Ngoi dng gh & thuyn, cyclohexane cn c dng
xon, dng na gh km bn
(t c)
31
32
b.S b tr cc lin kt C-H

6 C phn b trn 2 mt phng song song (1-3-5
& 2-4-6), cch nhau 0.5
Lin kt C-H gm 2 nhm: lin kt trc a (axial)
& lin kt bin e (equatorial)
a
e
ea
109o28'
e
ae
a
a
33
Cn bng (khng th tch):

a
e
CH3
CH3
Dn xut 1 ln th: e-methyl cyclohexane bn hn

a-methyl cyclohexane
Khi c 2 nhm th khc nhau: nhm ln v tr 34e
II.3. ng phn quang hc

II.3.1. nh sng phn cc
nh sng t nhin: sng in t, dao ng mi
hng vung gc vi phng truyn
nh sng phn cc: ch dao ng trong 1 mt
phng nht nh mt phng phn cc
ASTN qua lng knh Nicol s tr thnh ASPC
35
II.3.2. cht hot ng quang hc

ASPC i qua 1 s hp cht hu c lm mt phng
phn cc quay 1 gc cht hot ng quang hc
Gc quay c xc nh bng phn cc k
36
quay cc ring:
[]t0 = /(l.d)
: gc quay cc quan st c ()
l (dm): b dy dung dch cht quang hc
d (g/ml): nng dung dch cht quang hc
to: nhit o
: bc sng nh sng
37
II.3.3. iu kin xut hin ng phn quang hc

Vt & nh trong gng khng chng kht c 2
ng phn khng chng kht nhng i xng nhau
2 ng phn ny quay mt phng phn cc nhng
gc nh nhau nhng ngc chiu 1 i i
quang
ng phn quang hc thng xut hin khi c C
bt i xng (C*)
Cabcd
* C bt i xng:
a b c d khng c tnh i xng
trong khng gian
38
V d phn t lactic acid 2 ng phn quang hc
COOH
H
C*
OH HO
CH3
(+)
COOH
C* H
CH3
(-)
39
40
Cc nhm th khc nhau v ng phn cu to

ng phn quang hc
n-C3H7
H
C* COOH
iso-C3H7
Cc nhm th khc v ng v
ng phn quang hc
CH3
D C* H
C6H5
41
ng phn quang hc khng cha C*

Phn t b tr cht ch trong khng gian, c cu
to bt i xng trn ton phn t
ng phn allene
C10H7
C10H7
C C C
C6H5
C6H5
HOOC
COOH
ng phn cn quay
Cl Cl
42
II.3.4. Cng thc biu din ng phn quang hc

a. Cng thc t din (3 chiu)
COOH
CH3
OH
khng thun li cho phn t phc tp

43
b. Cng thc chiu Fisher (2 chiu)

Chiu cng thc t din ln mt phng
Cnh nm ngang gn ngi quan st, nm dc
xa ngi quan st
COOH
OH
CH3
C th c nhiu cng thc Fisher khc nhau

c. Cng thc phi cnh & Newman
44
II.3.5. Danh php v cch xc nh cu

hnh ca ng phn quang hc
Cu hnh: s phn b trong khng gian ca
cc nhm th xung quanh C* (khi nim m t
ng phn quang hc)
Cu dng: cc dng khc nhau trong khng
gian ca cng 1 cu hnh!!!
45
a. H danh php D-L: cu hnh tng i

Phi so snh vi 1 cht chun
CHO
H
CHO
OH
CH2OH
D-glyceraldehyde
HO
CH2OH
L-glyceraldehyde
Quy c: cc ng phn cha d t (O, N, S) lin kt

trc tip vi C*, nm bn phi ca cng thc Fisher D,
bn tri L
V d lactic acid c 2 ng phn khi so vi glyceraldehyde
COOH
COOH
H
OH
HO
CH3
CH3
D-lactic acid
L-lactic acid
Rt kh xc nh khi phn t c nhiu C*!
46
b. H danh php R-S:

Cu hnh tuyt i:
L cu hnh thc s, ni ln s phn b cc
nhm th trong khng gian xung quanh C*
Dng quy tc Kahn-Ingold-Prelog xc nh
ln ca nhm th: da theo th t u tin
trong bng HTTH
47
C
H C* O H
H C O H
H
Vng 1: C1 6, C3 6, O 8, H 1
Vng 2 (khi vng 1 khng xc nh c th t):
O-C-O > -C-O
-OH > -CHO > -CH2OH > H
Lu :
C A
C A
A C
C A
A C
C A
A C
-CCH > -C(CH3)3

-CH=CH2http://hhud.tvu.edu.vn
> -CH(CH3)2
HC
C
CH
C
C
48
Lu : cch cng s th t ch p dng

so snh cc nhm th c cha cc nguyn t
ging nhau.
V d -CH(CH3)2 & -CH=CH2
Hoc CHO & -CH2OH
-CH2OH > -CH=CH2

49
Cch xc nh cu hnh: C*abcd,

gi s a>b>c>d
+Theo cng thc t din / phi
cnh (khng gian): t d xa ngi
quan st:
i t a b c: cng chiu kim
ng h: ng phn R
i t a b c: ngc chiu kim
ng h: ng phn S
50
51
+Theo cng thc Fisher:

t d nm di hay trn trong cng thc
Fisher, sau xt th t cc nhm cn li:
i t a b c: cng chiu kim ng h: R
i t a b c: ngc chiu kim ng h: S
Quy c: i v tr 2 cp nhm th cu hnh
khng thay i
Thay i v tr 1 cp nhm th cu hnh s
thay i
Hay l Quay cng thc Fisher 180o cu hnh
khng i, quay 90o hay 270o cu hnh thay
i
52
V d lactic acid:
COOH
H
OH
CH3
a
OH
i H & CH3 (1 cp), OH & COOH (1 cp)
b
COOH
Nu ch i 1 cp H & CH3
c CH3
COOH b
c CH3
H
d
(R)
OH a
H
d
(S)
Lu : R & S ch l i lng l thuyt!!! thc t ch o c d(+)

& l(-)!!! R & S khng lin h vi (+) & (-)!!!
53
II.3.6. Cc hp cht cha nhiu C*

a. Hp cht cha cc C* khng tng ng
CHO
H C* OH
H C* OH
CH2OH
CHO
H C* OH
H C* OH
CH2OH
(2R,3R)-
2 C* khng tng ng v CHO CH2OH

4 ng phn (2 i i quang):
HO
HO
CHO
C* H
C* H
CH2OH
(2S,3S)-
CHO
H C* OH
HO C* H
CH2OH
(2R,3S)-
CHO
HO C* H
H C* OH
CH2OH
(2S,3R)-
threo-aldotetrose
erythro-aldotetrose
S p quang hc: N =
2n
n: s C*
54
b. Hp cht c cha C* tng ng

Tactric acid:
H H
HOOC C* C* COOH
OH OH
COOH
H C* OH
HO C* H
COOH
2 C* tng ng 3 ng phn
COOH
HO C* H
H C* OH
COOH
(2R, 3R)-tactric acid (2S, 3S)-tactric acid
COOH
HO C* H
HO C* H
COOH
meso-tactric acid
55
Trong ng phn meso: quay cc ca 2 C*

trit tiu nhau
khng cn hot tnh quang hc
S ng phn quang hc ca hp cht cha C*
tng ng (tnh c ng phn meso):
N = 2n-1 (n: l)
N = 2n/2-1(2n/2 +1) (n: chn)
56
II.3.7. Hn hp racemic
L hn hp 50% p quay tri + 50% p quay
phi hn hp khng c tnh cht quang
hc v quay cc t b tr nhau
Hn hp racemic: khng ch cc phn t
ring r m l 1 tp hp cc phn t
57
V d: Xc nh cu hnh tuyt i ca 1 s cht
CH2OH
H
OH
CH3
(R)COOH
H
CH3
C6H5
(R)-
CHO
OH
CH3
CH2OH
(S)-
COOH
H2N
H
CH3
(S)-
CH2OH
H
OH
OH
H
CH2OH
(2S, 3S)-
COOH
H2N
H
CH2OH
(S)CH2OH
H
OH
H
OH
CH2OH
(2S, 3R)-
58
Ha Hc Hu C
B mn K Thut Hu C
Khoa K Thut Ha Hc
in thoi: 8647256 ext. 5681
Chng 2: CC LOI HiU NG

* Hiu ng s dch chuyn in t trong phn t
nh hng n c ch phn ng, kh nng phn
ng, tnh acid-base
Chia lm 2 loi:
a. Hiu ng in t:
HU cm ng I (inductive effect)
HU lin hp C (conjugation effect)
HU siu lin hp H (hyperconjugation effect)
b. Hiu ng khng gian:
HU khng gian loi 1
HU khng gian loi 2
HU ortho
I. Hiu ng cm ng
I.1. nh ngha
HU cm ng s dch chuyn in t ca cc
lin kt do cc nguyn t trong phn t c
m in khc nhau phn t phn cc
V d:
C3
C2
C1
Cl
m in Cl > C s dch chuyn t C1-Cl,

3
C2-C1, C3-C2
I.2. Phn loi

a. HU cm ng dng (+I)
Gy ra bi cc nguyn t hay nhm nguyn t
c khuynh hng nhng in t
b. HU cm ng m (-I)
Gy ra bi cc nguyn t hay nhm nguyn t
c khuynh hng ht in t
* Quy c:
C-H c I = 0
Chiu chuyn dch t :
Nhm nguyn t c khuynh hng nhng
4
in t > H cho +I (v ngc li)
I.3. c im ca HU cm ng
Cc nguyn t hay nhm nguyn t mang in
tch + Cho I
Cc nguyn t hay nhm nguyn t mang in

tch - cho +I
in tch cng mnh I cng mnh, nhm
nguyn t mang in tch c I mnh hn trung
ha
-N(+)R3 -O(+)R2 -I
-O-N(-)H +I
-O(+)R2 > -OR
Trong cng 1 chu k trong bng HTTH: -I tng t

tri qua phi
-I:
-NR2 < -OR < -F
Trong cng 1 phn nhm chnh : -I gim t trn
xung di
-I:
-F > -Cl > -Br > -I
-I: -OR > -SR > -SeR
Cc nhm alkyl lun y in t (+I), tng dn t
bc 1 n C bc 3
+I
: -CH3 < -CH2CH3 < -CH(CH3)2 < -C(CH3)3

Cc nhm khng no u mang I, tng dn

theo khng no
-I:
R2C=CR-
<
< RC
HU cm ng gim dn theo mch C nh

hng n tnh cht ca phn t
V d Ka.105 ca cc acid:
CH3CH2CH2COOH
1.5
CH3CH2CH(Cl)COOH 139
CH3CH(Cl)CH2COOH 8.9
ClCH2CH2CH2COOH 3.0
II. Hiu ng lin hp

II.1. nh ngha
H lin hp: l nhng phn t c lin kt &
v tr lun phin nhau
V d: CH2=CH-CH=CH2 hay CH2=CH-CH=CH-CH=CH2
HU lin hp s dch chuyn t trong 1 h lin

hp, lm cho h lin hp tr nn phn cc
V d: CH2=CH-CH=CH2
mt in t phn
b u trn cc C
Tuy nhin: CH2=CH-CH=CH-CHO
m in ca O > C nhm C=O s ht in t
ca h phn t tr nn phn cc ( LH - )
CH2=CH-CH=CH-N(CH3)2
N c i in t t do (p) c xu hng nhng
in t cho h lin hp phn t phn cc (LH -p)
Cl
NH2
Lin hp -p (-Cl, -NH2 ng thi c I!)

10
II.2. Phn loi

II.2.1. HU lin hp dng (+C)
Cc nt hay nhm nguyn t c kh nng y
in t t bn thn n ra h lin hp +C
c im ca +C:
a. Cc nguyn t hay nhm nguyn t c cp in t
cha s dng hoc nhng ion mang tch (-) u mang
+C
-O- -S-H -R
SH
SR
NH2
NR2
H
N
CH3
-F
-Cl
-Br
-I
11
b. Cc ion mang in tch m c +C mnh hn cc

nguyn t trung ha
+C: -O- > -OR
-S- > -SR
c. Trong cng 1 chu k ca bng HTTH: +C gim
t tri qua phi
+C: -N(R)2 > -OR > -F
d. Trong cng 1 phn nhm chnh: +C gim t
trn xung di
+C: -F > -Cl > -Br > -I
+C: -OR > -SR > -SeR
12
II.2.2. HU lin hp m (-C)

Cc nguyn t hay nhm nguyn t c kh nng
ht in t ca h lin hp v pha n -C
c im ca C:
a. a s cc nhm nguyn t mang C l nhng
nhm khng no
-NO2
-CN -CHO -COR

-COOH -CONH2
13
b. Trong cc nhm C=Z: -C ph thuc Z

Z c m in cng ln, -C cng mnh
-C:
C=O > C=NR > C=CR2
c. i vi cc nhm nguyn t tng t:

in tch cng ln th C cng mnh
-C:
C=N+R2 > C=NR
14
II.3. c tnh chung ca HU lin hp

a. HU lin hp thay i rt t khi ko di mch lin hp
*** HU cm ng: gim nhanh theo mch C !!!
O
H
CH2
CH
CH
C
H
O
CH2
CH
CH CH
CH
C
H
linh ng ca H 2 cht ging nhau

15
Tc phn ng ging nhau:

OH
RCHO + H
CH2
CH
CH
OH
CH2
CH
CH
H
H
O
RCHO + H
CH2
CH
CH CH
CH
OH-
H
OH
O
R
CH2
CH
CH CH
CH
C
H
16
b. Mt s nhm th cha no, du ca HU lin hp s

thay i ty thuc vo nhm nt lin kt vi n
-
O
+
NH2
-C6H5: +C
-C6H5: -C
c. HULH ch c hiu lc trn h lin hp phng
C6H5NH2
C6H5NR2
N
H
+C ca NR2 gim so vi NH2

R
N
R
17
III. Hiu ng siu lin hp

III.1. HU siu lin hp dng (+H)
L s tng tc ca cc in t ca lin kt C-H
vi h t (C=C, -C6H5 ), hoc trong carbocation
(vd: (CH3)3C+) hay gc t do (vd: (CH3)3C.)
18
Xt phn ng:
CH3-CH=CH-CH2-CH3 + HCl
Nu xt theo +I: sn phm chnh l:
CH3-CH2-CHCl-CH2-CH3
Tuy nhin, thc t, do tc dng ca +H, sn phm
chnh l:
H
H
CH
CH CH2
CH3
HCl
CH3 CHCl
CH2
CH2
CH3
H
19
+H cng mnh khi s nguyn t H C cng nhiu:
+H:
>
H3C
H
C
20
III.2. HU siu lin hp m (-H)

L s tng tc ca cc t ca lkt C-F vi h
t (C=C, -C6H5)
F
C
F
F
21
IV. Hiu ng khng gian

L nhng loi hiu ng do kch thc ca cc
nhm th trong phn t gy nn
IV. 1. HU khng gian loi 1 (S1)
Do cc nhm th c kch thc ln, chim 1 khong
khng gian ng k cn tr khng cho 1 nhm
chc no trong phn t tc dng vi phn t
hay ion khc
CH3
O
CH3
O + H2N OH
CH3
HO N
O + H2O
CH3
22
IV. 2. HU khng gian loi 2 (S2)

Do cc nhm th c kch thc ln h lin hp
b mt tnh phng khng cho 1 s phn ng
Xy ra
R
R
H3C
N
H3C
H3C
N
H3C
+ Cl-N N+
R
N N
R
R = H: phn ng xy ra
R=-CH3: h lin hp mt tnh phng +C
ca N(CH3)2 gim mnh phn ng khng
xy ra
23
IV. 3. Hiu ng Ortho

Gy ra bi cc nhm th v tr ortho trong vng
benzene
gy nh hng c bit so vi cc nhm th v
tr khc
HU ortho: hn hp ca nhiu yu t (S1, S2, I, lin
kt H)
24
Xt hng s phn ly (Ka.105) ca dn xut ca

benzoic acid C6H4(R)COOH
V tr / R
OH
NO2
o-
10.5
54.4
67.1
m-
8.3
13.7
32.1
p-
2.9
7.2
37.6
Lu : -I ca NO2 > -I ca F
25
Tnh acid:
H
H
H
O
>
>
OH
OH
o-: OH c I ht t & lin kt H O-H trong COOH phn

cc mnh nht
p-, m-: OH c I ht in t nhng -I gim dn theo chiu di
mch C O-H trong COOH p- t b phn cc nht
lu : OH trong o- & p- c +C y in t ln h lin hp p-- C=O
trong m-: h lin hp ny b t on do - lin tc !!! cng
26
lm cho tnh acid ca m- > p-
Tnh acid ca C6H4(F)COOH: o- > m- > pdo I gim theo chiu di mch C
Kh nng ht (-I) hay y (+C) in t ca
F, Cl, Br, I: -I > +C
Tnh acid ca C6H4(NO2)COOH: o- > p- > mhttp://hhud.tvu.edu.vn
27
+O
H
O
+O
OH
o-nitrophenol: lin kt H ni phn t tosi thp,

khng tan trong nc c th chng li cun hi
nc
p-nitrophenol: ch c lin kt H ngoi phn t trong
nc tan tt trong nc, tosi cao
28
V. nh hng ca cc hiu ng ln tnh

acid base v bn ca carbocation
V.1. nh hng ca HU cm ng ln tnh acid
Cc R-OH, R-COOH c cha nhm th c +I
tnh acid gim
Cha nhm th c I: tnh acid tng do O-H
cng phn cc
29
Tnh acid ca cc acid:

F3C-COOH (pKa 0.23) >
Cl2CH-COOH (1.25) >
Cl3C-COOH (0.66) >
NO2-CH2-COOH (1.68) >
NC-CH2-COOH (2.47) > F-CH2-COOH (2.57) >

Cl-CH2-COOH (2.87) > Br-CH2-COOH (2.90) >
HCOOH
CH3COOH
(3.75)
(4.76)
HO-CH2-COOH
>
>
CH3CH2COOH
(3.83)
>
(4.87)
>
(CH3)3C-COOH (5.03)
30
Nhm th cng xa C nh hng cng

yu do I gim mnh:
Tnh acid: F3C-COOH > F3C-CH2-COOH >
F3C-CH2-CH2-COOH
31
V.2. nh hng ca HU lin hp, HU siu lin hp

ln tnh acid
Tnh acid ca alcohol < phenol
Nhm th c C s lm tng tnh acid & ngc li
-
+O
Tnh acid:
+I
-I, -C
>
>
O
H
O
H
H
H
C
H
>
O
H
H
H C H +H, +I
+C, -I
NH2
>
O
H
O
H
Thng thng (khng lun lun!) : C > H > I

32
a. Acid bo khng no:

Tnh acid mnh hn acid no cng mch C (do
C=C c I)
Ni i C=C cng gn COOH th tnh acid cng
mnh
Tuy nhin: nu C=C lin hp vi C=O trong
COOH th tnh acid gim do +C ca C=C!!!
Tnh acid: CH3-CH=CH-CH2-COOH (pKa 4.48) >
CH2=CH-CH2-CH2-COOH (4.68) >
CH3-CH2-CH=CH-COOH (4.83)
33
Ni ba CC cho d v tr lin hp vi C=O th

vn lm tng mnh tnh acid (khc C=C): do I
ca CC mnh & ch c 1 lkt ca CC cho +C
lin hp vi C=O, lkt cn li cho I nhng
khng c +C!!!
Tnh acid: CHC-COOH (pKa 1.84) >

34
CH3-CC-COOH (2.60) > CH2=CH-COOH (4.25)
b. Acid c vng thm:

Tnh acid H-COOH (pKa 3.75) > C6H5-COOH (4.18)
do +C ca C6H5- mnh hn I
Tnh acid ty thuc bn cht & v tr nhm th:
o-NO2-C6H5-COOH > p- > m Halogen cho I > +C o-Cl-C6H5-COOH > m- > phttp://hhud.tvu.edu.vn
35
V.3. nh hng ln tnh base

Mt in t trn N cng ln tnh base
ca amine cng mnh
Nhm th y in t (+I) s lm tng tnh
base ca amine & ngc li (-I, -C)
Tnh base:
(CH3)2NH > CH3NH2 > NH3 > C6H5NH2 >
p-NO2-C6H4-NH2
36
Tnh base: p-NO2-C6H4-NH2 < m- NO2-C6H4-NH2

< p-Cl-C6H4-NH2 < C6H5-NH2 < p-CH3O-C6H4-NH2
p-NO2: -I, -C mnh nht, m-NO2: -I mnh, -C
khng nh hng nhiu do h lin hp b t on
-Cl: -I mnh hn +C, -I yu hn -NO2
p-CH3O: +C mnh hn I mt in t trn N
cao nht base mnh nht
Acid lin hp cng yu th tnh base cng mnh
Tnh base: HCC- > (CH3)3CO- > CH3O- > OH- >
C6H5O- > CH3COO37
V.4. nh hng ln bn ca cc
carbocation
in tch dng trn cc cation cng c gii
ta (cng nh) th cation cng bn
bn do hiu ng y in t ca +H, +I:
H
H C CH2
H
<
H
H H
H
H
C
H
+
<
H C C
H C C+
HH C H
HH C H
H
H 38
bn ca carbocation:
(CH3)3C+ < C6H5CH2+ < (C6H5)2CH+
Do +C ca -C6H5 mnh hn +I, +H ca CH3
in tch cng c gii ta carbocation cng
bn
39
bn ca carbocation:
H
H C CH2
H
<
H3C O CH2 < H3C NH CH2
+C ca NH- > +C ca O- > +H & I ca CH3

-NH- & -O- ng thi c I nhng +C nh hng
mnh hn -NH- gii ta tch dng mnh
nht bn nht
Gc allyl CH2=CH-CH2+ hay C6H5-CH2+ rt bn
do +C ca vinyl hay phenyl
40
Ha Hc Hu C
B mn K Thut Hu C
Khoa K Thut Ha Hc
in thoi: 8647256 ext. 5681
Chng 3: C CH PHN NG CA HP
CHT HU C
I. Phn ng th i nhn nguyn t carbon no
I.1. Khi nim chung
Phn ng th: 1 nguyn t hay nhm nguyn t
ca cht ban u b thay th bi 1 nguyn t hay
nhm nguyn t khc
CH3-CH2-Cl + OH- CH3-CH2-OH + Cl Tc nhn i nhn: cc tc nhn mang in tch
m (hay phn t trung ha cha cp in t t
2
do) tn cng vo trung tm tch in +
Phn ng th i nhn (SN)

y- + R-X R-y + Xy-: RO-, OH-, RCOO-, NH3, NH2R, H2O, ROH
R: gc hydrocarbon
X: Cl, Br, OH, OR, OSO2R
V d:
CH3-CH2-Cl + OH- CH3-CH2-OH + ClCH3-CH2-Br + CH3O- CH3-CH2-O-CH3 + BrCH3-CH2-Br + NH3 CH3-CH2-NH2 + HBr
I.2. Phn ng th i nhn lng phn t (SN2)

Lng phn t: giai on chm, c s tham gia
ca 2 tiu phn
y + R-X
cham
a.C ch:
[y-... R ... X-]
nhanh
R-y + X-
trang thai chuyen tiep

Lin kt gia C & y hnh thnh ng thi vi s
yu i & t ca C & X 2 tiu phn tham gia
vo giai on chm
Nu y- khng d nhiu: r = k[y-].[R-X] phn ng
4
bc 2
Gin nng lng:
R-OH: phn ng th ch xy ra trong mi trng

acid v C-O bn
Dn xut ca carbon bc 1 ch cho SN2
SN2: carbon bc 1 (ch cho SN2) > carbon bc 2 >
carbon bc 3 (ch cho SN1)
SN2: CH3-CH2-Cl + OH- CH3-CH2-OH + Cl-
b. Tnh lp th ca SN2
Phn t c cha C*: s c s thay i cu hnh (R
S & ngc li) (nghch o Walden)
R1
R1
y- +
C*
R2
cham
R1
C*
H
nhanh
C*
H
R2
R2
(S)-
(R)-
y- tn cng ngc hng so vi X sn phm c

7
cu hnh ngc vi tc cht
I.3. Phn ng th i nhn n phn t (SN1)

n phn t: giai on chm ch c s tham
gia ca 1 tiu phn
a. C ch
R-X
R+
cham
+ y
R+ +
nhanh
X-
R-y
giai on chm: y- khng tham gia

SN1 thng c bc 1 r = k[R-X]
Gin nng lng:
Dn xut ca carbon bc 3 ch cho SN1

V d SN1:
CH3
H3C
CH3
Br
+ OH-
H3C
CH3
OH
+ Br-
CH3
10
Tnh lp th ca SN1
R1
y
R2
C*
C*
-XR2
R3
h
an
nh
R3
cham
R2
R3
nh
an
h
R1
R1
C*
R1
R2
(R1 R2 R3)
C*
R3
Sn phm c th l hn hp racemic
Carbocation c cu trc phng kh nng tn
cng ca y- 2 pha l nh nhau 50% S + 50% 11R
12
I.4. Cc yu t nh hng ln phn ng th

i nhn
a. nh hng ca gc R
Gc R bc cng cao: kh nng SN1 tng & SN2
gim
Do SN1 ph thuc vo bn ca carbocation to thnh:
CH3+
<
H
H C CH2
H
<
H
H H
HH C H
+
<
H C C
H C C+
HH C H
HH C H
H
H13

Bc ca R cng cao y- cng kh tn cng do in tch (+) C

gim & do hiu ng khng gian ca gc alkyl SN2 cng kh
xy ra
14
b. nh hng ca tc nhn i nhn y SN1: khng ph thuc y SN2: ph thuc nhiu vo y- do giai on chm c
y- tham gia
Tc nhn c tnh i nhn cng cao th cng d cho
SN2
Thng thng, tnh i nhn ng bin vi tnh
base
NH2- > (CH3)3CO- > (CH3)2CHO- > C2H5O- > CH3O> OH- > C6H5O- > HCO3- > CH3COO15
Trong cng 1 phn nhm chnh ca bng HTTH:

tnh i nhn nghch bin vi tnh base (phn ng
thc hin trong H2O, ROH):
Tnh base: F- > Cl- > Br- > ITnh i nhn: F- < Cl- < Br- < ITnh i nhn: HS- > OHTnh i nhn: C2H5S- > C2H5OTuy nhin trong pha kh, tnh i nhn: F- > Cl- > Br- > I-
Phn bit tnh base & tnh i nhn: Tnh base v

16
tr cn bng, tnh i nhn tc !!!
c. nh hng ca nhm b th -X
Cc nhm th c tnh base cao rt kh b tch
ra, v d: -OH, -OR, -NH2, -F
V d: R-OH + HBr R-Br + H2O cn xc tc
H2SO4
R-OH khng phn ng vi KBr
Halogen, kh nng tch nhm: F- < Cl- < Br- < I(Do I c bn knh ln C-I d phn cc hn
Nng lng t lin kt: C-I < C-Br < C-Cl < C-F)
17
d. nh hng ca dung mi
Dung mi phn cc c proton nh H2O, ROH,
HCOOH c kh nng solvate ha cao c anion &
cation thun li cho SN1
R1 H
R1
cham
+
R2 C X
- C+ O
-X
R3
R2 R3 H
X- H O
H
Dung mi phn cc khng c proton nh

(CH3)2SO, (CH3)2NCHO khng c kh nng solvate
ha anion thun li cho SN2
18
II. Phn ng tch loi

L phn ng trong c s tch 1nguyn t hay
nhm nguyn t ra khi cht ban u
R
CH2
CH2
CH2
CH2
CH2
Br
OH
CH2 N+R3
ROto
H+
to
HOt
CH
CH2 +
HBr
CH
CH2 +
HOH
CH
CH2 +
HOH + NR3
Nhm b tch cng H: -OH, -OR, -X, -O+(R)2,

-N+(R)3, -OSO2R
19 Base s dng: cc base mnh nh OH-, RO-, NH
2
II. 1. Phn ng tch loi lng phn t (E2)

a. C ch
-
y + R CH2 CH2 X
cham
R
y
C CH2
nhanh
H
trang thai chuyen tiep
H-y + R CH CH2 + X-
giai on chm, c s tham gia ca 2 tiu phn

lng phn t
Tc phn ng r = k[R-X].[y-]
R-CH2-CH2-OH: ch tch loi trong mi trng acid
20
o
t cao (thng l sulfuric acid, acid rn)
b.Tnh lp th ca E2
Cc hydrocarbon khng no tch loi d khi
cc nhm b tch v tr trans vi nhau
(1)
HOOC
Cl
COOH
(2)
OH-
OH-
-HCl
-HCl
COOH
chlorofumaric acid
COOH
HOOC
Cl
HOOC
chloromaleic acid
Tc (1) ln hn (2) 30 ln
21
Cc hydrocarbon no hay vng no tch loi

d khi cc nhm b tch v tr trans, anti vi nhau
Lu : dn xut ca cyclohexane ch tch c
khi nhm b tch v tr trans & phi kiu lin
kt axial (trc)!!!
Br
CH3
H
H
CH3
san pham chnh
CH3
Br
kho
H
H
CH3
CH3
22
II.2. Phn ng tch loi n phn t (E1)

C ch:
H C C X
H C C
cham
nhanh
H C C+
H+
X-
Thng cc dn xut ca hydrocarbon carbon

bc 3 bao gi cng cho E1
Carbocation cng bn, cng d cho E1
Tc r = k [R-X]
Nhng yu t lm thun li SN1 cng lm thun li
23
cho E1
V d:
CH3
H3C C Br
CH3
H
HH C H
H C C+
HH C H
H
cham
+ C2H5O-
H
HH C H
H C C+
HH C H
H
nhanh
+ Br-
CH3
+
H2C C
CH3
C2H5OH
24
II.3. Hng ca phn ng tch loi

a. Quy tc Zaitsev
Dn xut bc 1 thng ch cho 1 sn phm duy
nht khi tch loi
CH3-CH2-CH2-Br ch cho CH3-CH=CH2
Dn xut bc 2, bc 3: cho nhiu hn 1 sn phm
H H H
H3C C C C H
H Br H
OH-
H3C CH CH CH3
H3C CH2 CH CH2
(Zaitsev)
(Hofmann)
Sn phm Zaitsev : bn hn (do +H) thng

thng, phn ng tch loi cho sn phm
Zaitsev
Quy tc: phn ng tch loi s cho sn phm m
25
carbon ca ni i lkt vi nhiu nhm alkyl nht
b. Quy tc Hofmann
Khi gc R (bc 1 & 2) ca R-X cha nhiu nhm th
kch thc ln, tc nhn base c kch thc ln (vd
(CH3)3CO-) hoc X l nhm th mang in tch dng
c kch thc ln (vd N+R3, S+R2, SO2R) sn
phm Hofmann chim ch yu (E2)
CH3
H3C C CH2 CH3
Br
CH3
H2C C CH2 CH3
72%
CH3
H3C C CH CH3
28%
(CH3)3CO-
26
Nu base l C2H5O- th sn phm chnh l Zaitsev!!!
H
H3C C CH2 CH3
N+(CH3)3
CH3CHCH2CH2CH3
SO2CH3
OH(E2)
OH-
CH2=CH-CH2-CH3
CH2=CH-CH2-CH2-CH3
(E2)
Lu : Nu trong phn t c sn 1 ni i (C=C,

C=O), sn phm lin hp thng l sn phm
chnh (bn hn)
27
II. 4. Quan h gia phn ng th i nhn &

tch loi
Nhit phn ng cng cao phn ng tch loi
cng chim u th
<140oC
CH3-CH2-OH
C2H5-O-C2H5
H2SO4
>170oC
CH2=CH2 + H2O
28
Gc R c bc cng cao, hay base cng mnh th

tch loi cng chim u th
CH3-CH2-CH2-Br
+ C 2 H5 O -
CH3
H3C C Br
CH3
to thng
C2H5Oto cao
CH3-CH2-CH2-O-C2H5
CH3
H2C C
CH3
29
III. Phn ng cng hp

III. 1. Phn ng cng hp i in t (AE)
Phn ng cng hp vo ni i ca hydrocarbon
khng no nh alkene, alkyne vi cc hp cht nh
X2 (halogen), HX, H2O, HOX, H2SO4
C C
+ X-Y
X C C Y
30
a. C ch:
Giai on 1:
C C
dung moi
xuc tac
+ X+-Y
nhanh
cham
C C
X+
Y
phc
khong ben
C+ C
X
ben hoa C C
X+
Giai on chm: X+ tn cng vo C=C i in t
Giai on 2:
Y-
C C
nhanh
X+
Y-
tn cng vo pha i lp vi X
Y
C C
X
31
Chng minh AE c 2 giai on:

Phn ng cng hp ca CH2=CH2 vi Br2 vi s
c mt ca NaCl, NaNO3, sn phm thu c l 1
hn hp:
Br-CH2-CH2-Br + Br-CH2-CH2-Cl +
Br-CH2-CH2-ONO2
Nu phn ng thc hin trong dung mi l CH3OH,
sn phm chnh l Br-CH2-CH2-OCH3 !!!
32
H2C CH2 + Br2
H2C CH2 + Br2
H2C CH2 + Br2
CCl4
CH3OH
H2O
H2C CH2
Br Br
H2C CH2
Br OCH3
H2C CH2
Br OH
33
b. Quy lut cng hp

Quy tc Markonikov (dnh cho C=C khng i
xng): H+ s tn cng vo C cha nhiu H
CH3-CH=CH2 + H+ CH3-C+H-CH3 (bn hn) +
CH3-CH2-C+H2
Quy tc Zaitsev-Wagner: H+ s tn cng vo pha
to thnh carbocation trung gian bn nht
CH3-CH=CH-CH2-CH3
HBr
CH3-CH-CH-CH2-CH3
34
Br
c. Ha lp th ca phn ng AE
Phn ng cng hp AE xy ra theo kiu trans
ph thuc vo tc cht ban u m c cc ng
phn lp th khc nhau
ng phn cis sn phm threo (nhm th tng
ng khc pha)
C2H5
CH3
Br
C2H5
H
CH3
H
Br2
Br
CH3
Br
H
H
Br
C2H5
C2H5 Br+ CH3

H
Br
BrC2H5
CH3
Br
CH3
H
Br
Br
H
C2H5
35
threo-
ng phn trans sn phm erythro (nhm th

tng ng cng pha)
C2H5
H
H
CH3
Br2
CH3
Br
H
Br
H
C2H5
CH3
H
Br
H
Br
C2H5
erythro
36
d. nh hng ca nhm th lin kt vi ni i

Nhm th y in t tng mt in t ca
C=C tng kh nng phn ng AE
Nhm th ht in t gim kh nng AE
Cc nhm th nh phenyl nu c kh nng cho
+C vi carbocation bn ha cation thun li
cho AE
37
Kh nng AE:
O2N
H
H HOOC
<
Cl
H3C
<
H3C
<
<
CH3
H
H3C
<
H
CH3 H3C
<
CH3 H3C
CH3
CH3
Phenyl gy nh hng mnh hn 1 nhm

methyl nhng yu hn 2 nhm methyl
CH3CH=CH2 < C6H5CH=CH2
< (CH3)2 C=CH2

38
III.2. Phn ng cng hp i nhn vo C=O (AN)
C O + X -Y
OX
C
Y
X-Y c th l H-OH, H-OR, H-CN, H-SO3Na, Li-R,

BrMg-R
39
a. C ch:
2 giai on, lng phn t
Giai on 1:
+ Y
cham
C OY
carbanion
Giai on chm: Y- tn cng vo C+ i nhn

40
Giai on 2:
nhanh
C OX
C O
Y
Y
Phn ng AN c th khng cn xc tc. Tuy nhin,
pH c nh hng
V d:
Trong acid yu (pH 4)
+ X+
C O
H+
C+ OH
in tch (+) ca carbon c tng cng AN cng

thun li
Tuy nhin, acid qu mnh: R-NH2 + H+ R-N+ H3
41
Kh nng phn ng vi C=O gim
b. nh hng ca nhm th lin kt vi C=O

Nguyn t C trong C=O c in tch dng cng
ln AN cng thun li
Nhm th y in t (+C, +I, +H) lm gim kh nng
phn ng
Nhm th ht in t (-C, -I) lm tng kh nng phn
ng
NO2
CH2 C
> H3C C OR
o
O
H
> Cl CH2 C
> H3C C NH2

o
O
H
> CH3 C
> H3C C Oo
O
H
> H3C C CH3

o
42
IV. Phn ng th i in t vo nhn thm (SE)

X
+ X+
acid
+ H+
Xc tc: cc acid v c: H2SO4, H3PO4, HF

hay Lewis acid: FeCl3, AlCl3, ZnCl2
V d: C6H6 + (CH3)3C-Br /AlBr3 C6H5-C(CH3)3 +
HBr
43
C ch phn ng: 2 giai on, lng phn t

Giai on 1: to phc ( benzonium cation)
+ X -Y
X
cham
H
+
xt
X+-Y
nhanh
phc
+
+
phc
Trong phc : X khng lin kt trc tip vi C no c

Phc : X c lin kt trc tip vi 1 C ca benzene
44
Giai on 2: tch proton
H
nhanh
+
+ HY
45
+++ Nhm th y in t (+C, +H, +I) SE tng

V d:
* alkyl +I, +H
*-NR2 (R: H hay gc alkyl), -OH, -OCH3, -NH-CO-CH3
(+C > -I)
Anion: -O- : +C, +I mnh
+++ Nhm th ht in t (-C, -I) SE gim
V d:
-N+N, -NO2, -CN, -CHO, -COR, -COCl, -COOH,
-CO-NH2 (-I, -C)
Cation: -N+R3 (-I mnh)
* halogen (-I > +C)
46
Ha Hc Hu C
B mn K Thut Hu C
Khoa K Thut Ha Hc
in thoi: 8647256 ext. 5681
Chng 4: Alkane
I. Gii thiu chung
Alkane hydrocarbon no mch h, nguyn t
carbon lai ha sp3
Cng thc tng qut: CnH2n+2
methane
Gc ha tr 109o5, lin kt C-H: 1.09, C-C: 1.53

2
ng phn: cu to, cu dng (quay)
II. Danh php IUPAC

II.1. Alkane khng phn nhnh:
4 alkane u: gi theo tn thng thng
methane, ethane, n-propane, n-butane
Cc alkane t C5: da theo cch m s ca Hy
Lp hoc Latin.
V d: pentane, hexane, heptane, octane(t c)
II. 2. Alkane phn nhnh

Chn mch di nht lm mch chnh
nh s sao cho mch nhnh c ch s nh nht
Dng ch s & gch (-) ch v tr nhnh, nhm
cui cng phi vit lin vi tn mch chnh
Nu c nhiu nhnh tng ng: dng tip u
ng di-, tri-, tetra- ch s lng nhm tng
ng
Nu c nhiu nhm th khc nhau: sp xp theo

th t alphabetical. Lu : b qua cc tip u
ng di-, tri-, tetra- khi xt th t alphabetical.
Tuy nhin khng b qua iso!!! sec- & tert- c
b qua khi xt th t vi cc nhm khc, nhng
vn dng so snh gia chng vi nhau.
V d: dimethyl hoc methyl s i sau ethyl hay
diethyl
isopropyl i trc methyl
tert-butyl i trc isobutyl
sec-butyl i trc tert-butyl
V d (H vit tt):
C
C
C
C C C C C C
C
C
C C
C C C C C C C C
C
C
C
C
C
4-Ethyl-2,2-dimethylhexane
3,3-Diethyl-5-isopropyl-4-methyloctane
C
C
C C C C C C C
C
C
C
5-Ethyl-2,3,5-trimethylheptane
C
C C C C C C C C
C
C
C C C
C
2-methyl-5-(1,2-dimethylpropyl)nonane
II.3. Tn gc alkyl
c ly 1 H t alkane, gi theo tn alkane nhng
i ane yl
CH3-: methyl
CH3-CH2-: ethyl
CH3-CH2-CH2-: n-propyl
CH3CHCH3
: isopropyl
CH3CH2CHCH3
: sec-butyl
(CH3)2CHCH2-: isobutyl
(CH3)3C-: tert-butyl 7
III. Cc phng php iu ch alkane

III.1. Kh cc dn xut ca halogen, alcohol,
carbonyl:
a. Kh bng HI 80%, 180oC:
CH3-CH2-OH + HI
CH3I + HI
b. Kh bng Zn/HCl
R C R'
O
P o
CH3-CH3 + I2 + H2O
P o
CH4 + I2
(Kh Clemmensen)
Zn(Hg)/HCl
R-CH2-R'
8
III.2. Hydro ha alkene

R-CH=CH2
H2
Ni, Pd, Pt
R-CH2-CH3
alkene c th iu ch t alcohol (H2SO4/toC)

III.3. Thy phn hp cht c kim
(CH3)2Zn + H2O CH4
+ Zn(OH)2
C2H5-MgBr + H2O C2H6 + Mg(OH)Br

iu ch hp cht c magnesium (Grignard):
C2H5-Br + Mg/ether khan C2H5-MgBr
III.4. Phn ng Wurtz

CH3CH2Br + Na CH3CH2CH2CH3
+ NaBr
Ch c hiu qu khi iu ch alkane i xng:

CH3CH2Br + CH3Br CH3CH2CH3 + CH3CH3 +
CH3CH2CH2CH3
khng c tnh chn lc t s dng
Ch hiu qu cho R-Br & R-I
Hiu sut: bc 1 (60%) > bc 2 (40%) > bc 3 (10%)
10
III.5. in phn mui ca carboxylic acid

CH3COONa
CH3COO. CH3. CH3-CH3
III.6. Nhit phn mun natri ca carboxylic acid

CH3COONa + NaOH CH4 + Na2CO3
IV. Tnh cht vt l (t c)
Alkane khng phn cc ch tan trong dung mi
khng phn cc
to si ca alkane nhnh < thng
11
V. Tnh cht ha hc
Alkane tr khng c phn ng cng, c trng
l phn ng th H
V.1. Phn ng th H bng halogen
Ch xy ra nhit cao hoc khi c nh sng
R-H
+ X2
to
h
R-X
HX
12
a. C ch phn ng (gc t do SR )
Khi mo:
X-X
to
2X
Truyn mch:
R-H
R
+ X
+
X2
RX
HX
+ X
Phn ng c th tip tc to sn phm di-, tri-,

tetra V d chlor ha CH4 c th thu c CH3Cl,
CH2Cl2, CHCl3, CCl4
CH4 + Cl2 CH3Cl
HCl H = -25Kcal/mol
13
Ngt mch:
+ X
X-X
+ R
R-R
+ X
R-X
14
Giai on to CH3. kh hn giai on to CH3Cl

giai on to CH3. (hay R. ni chung) s quyt nh
tc phn ng chung
15
b. So snh kh nng thay th H

H bc 1 & bc 2:
25 oC
CH3-CH2-CH3
+ Cl2
h
CH3-CH2-CH2-Cl
CH3-CHCl-CH3
45%
55%
Vn tc tng i khi thay th H bc 1: 45 / 6 = 7.5

Thay th H bc 2: 55 / 2 =27.5
t l vn tc tng i H bc 1/ H bc 2 = 7.5/27.5 ~
16
H bc 1 & bc 3:
CH3
H3C C CH3 + Cl2
H
25 oC
h
CH3
H3C C CH2Cl
H
64%
CH3
+ H3C C CH3
Cl
36%
Vn tc tng i khi thay th H bc 1: 64 / 9 ~7

Thay th H bc 2: 36 / 1 ~ 36
t l vn tc tng i H bc 1/ H bc 3 = 7/36 ~ 1/5
T l vn tc tng i bc 1/bc 2/bc 3 = 1/4/5

nhit thng, kh nng thay th H C bc 3
cao nht
Lu : 600oC: t l ny l 1/1/1
17
c. Kh nng phn ng ca dy halogen

F2 > Cl2 > Br2 > I2
F ha: mnh lit, t lin kt t dng
I ha: rt kh xy ra (H = + 13 Kcal/mol), ch xy
ra khi loi HI trong qu trnh
18
d. Tnh chn lc ca phn ng

Phn ng Br ha c tc chm hn Cl ha
nhng c chn lc cao
T l vn tc tng i 127 oC ca Br ha: bc
1/bc 2/bc 3 = 1/82/1000
CH3
H3C C CH3 + Cl2
H
CH3
H3C C CH3 + Br2
H
25 oC
h
CH3
H3C C CH2Cl
H
64%
127 oC
h
CH3
H3C C CH2Br
H
1%
CH3
+ H3C C CH3
Cl
36%
CH3
+ H3C C CH3
Br
99%
127 oC
CH3-CH2-CH3
+ Br2
h
CH3-CH2-CH2-Br
3%
CH3-CHBr-CH3
97%
19
V.2. Phn ng nitro ha alkane

R-H
+ HNO3 R-NO2
+ H2O
Phn ng xy ra nhit cao,c ch gc t do

Thng xy ra phn ng t mch carbon
CH3-CH2-CH3 + HNO3 CH3-CH2-CH2-NO2 (25%) +
CH3-CHNO2-CH3 (40%) + CH3-CH2-NO2 (25%) +
CH3-NO2 (10%)
20
V.3. Phn ng ng phn ha

Chuyn cc alkane mch thng thnh alkane mch
nhnh di tc dng ca xc tc nhit cao
Xc tc thng dng: acid Lewis nh AlCl3, xc
tc acid trn c s zeolite
V d:
CH3-CH2-CH2-CH3
AlCl3
to
CH3
H3C C CH3
H
21
C ch:
CH3-CH-CH2-CH3
H
AlCl3
HAlCl3
+
CH3-C-CH2-CH3
H
-HAlCl3
CH3
H3C C CH3
H
to
H
HH C H
H C C+
HH C H
H
+ AlCl3
Xu hng: to carbocation bn hn chuyn v

22
V.4. Phn ng cracking

To alkane c mch carbon ngn hn di tc
dng ca xc tc & nhit
Km theo phn ng tch loi hydrogen & phn
ng ng vng
Cracking nhit: 800oC 1000oC, cracking xc tc
(thng l zeolite): 500oC -600oC
S dng trong sn xut nhin liu (khng dng
iu ch alkane hay alkene v khng chn lc)
23
V.5. Phn ng oxy ha alkane

Alkane bn vi tc nhn oxy ha nhit
thng
nhit cao hoc c mt xc tc c th
phn ng vi oxygen, KMnO4, K2Cr2O7
phn ng t mch to alcohol (ROH),
aldehyde (RCHO), ketone (RCOR), carboxylic
acid (RCOOH)
Phn ng quan trng:
2CnH2n+2 + (3n + 1)O2 2nCO2 + (2n+2) H2O
ta nhit mnh, -341 kcal/mol alkane c dng
24
lm nhin liu
Ha Hc Hu C
B mn K Thut Hu C
Khoa K Thut Ha Hc
in thoi: 8647256 ext. 5681
Chng 5: ALKENE
I. Gii thiu chung
Alkene: hydrocarbon mch h, cha 1 lin kt i
C=C (CnH2n, n2)
Trong C=C: 1 & 1, hnh thnh do lin kt ca
orbital sp2
Lin kt vung gc vi mt phng phn t

Alkene n gin nht l ethylene CH2=CH2
121.7o
116.6o
1.08
1.33
II. H danh php

II.1. Tn thng thng
Tn alkane tng ng, i ane ylene
t dng, tr 3 alkene thng dng:
CH2=CH2 ethylene
CH2=CH-CH2 propylene
(CH3)2C=CH2 isobutylene
II.2. Danh php IUPAC

Tn alkane tng ng, i ane ene
Chn mch carbon di nht & cha C=C lm mch
chnh
nh s sao cho C=C c ch s nh nht
Ch s ca C=C chn theo v tr C gn C1 nht, vit cch
tn mch chnh 1 gch ngang
CH3-CH-CH=CH2
CH3
CH3
CH3-C-CH=CH-CH3
H
3-methyl-1-butene
4-methyl-2-pentene (c cis & trans)
II.3. Tn gc ca alkene
Alkenyl
CH2=CH- 1-ethenyl (vinyl)
CH2=CH-CH2- 2-propenyl (allyl)
CH3-CH=CH- 1-propenyl
III. Cc phng php iu ch

III.1. Tch nc t alcohol
Phn ng c th pha lng (xc tc acid H2SO4,
H3PO4, 100-170oC) hay pha kh (xc tc Al2O3,
zeolite, 350-400oC)
C C
H OH
to
xt
C C
+ H 2O
Kh nng tch nc: alcohol bc 3 > bc 2 > bc 1
CH3CH2CH2CH2-OH
H2SO4 75%
140 oC
CH3CH=CHCH3
CH3-CH-CH2-CH3 H2SO4 50-60%

CH3-CH=CH-CH3
o
100 C
OH
(CH3)3C-OH
H2SO4 20%
80 oC
CH2=C(CH3)2
III.2. Tch HX t dn xut ca halogen

C C
H X
to
KOH/ethanol
C C
+ H2O + KX
Kh nng tch HX: RX bc 3 > bc 2 > bc 1

to
CH3CH2CH=CH2
CH3CH2CH2CH2Cl
KOH/ethanol
CH3CH2CHCH3
Cl
to
KOH/ethanol
CH3CH2CH=CH2
20%
CH3CH=CHCH3
80%
Lu : tch R-X bc 1 khng c chuyn v R-OH bc 1
CH3CH2CH2CH2-OH
H2SO4 75%
o
140 C
CH3CH=CHCH3
III.3. Kh dn xut 2 ln th ca halogen

Zn
C C
X X
C C
to
H H
H3C C C CH3
Br Br
Zn
+ ZnX2
CH3CH=CHCH3 + ZnX2
to
III.4. Hydro ha alkyne

t
, x ar
H 2 dl
Lin )
(Pd
R'
R'
R C C R'
Na
,N
10
III.5. Nhit phn ester

CnH2n+1-O-COR CnH2n
+ RCOOH
Nhit phn ester ca ru bc 1 < bc 2 < bc 3

Ester bc 1 1 sn phm, bc 2 & bc 3 nhiu
sn phm
Ch tan trong dung mi khng phn cc hay t phn cc
V. Tnh cht ha hc
Lin kt (E phn ly = 60 kcal/mol) yu hn lin kt
(E = 80 kcal/mol)
11
o
Xc tc, t ... lin kt d b t
V.1. Phn ng cng hp i in t

V.1.1. C ch:
Giai on 1:
C C
+ X+-Y
dung moi
xuc tac
nhanh
cham
C C
X+
Y
phc
khong ben
C+ C
X
ben hoa C C
X+
Giai on chm: X+ tn cng vo C=C i in t

12
Giai on 2:
Y-
C C
nhanh
X+
Y
C C
X
Y- tn cng vo pha i lp vi X
Nhm th y in t (+C, +I, +H) tng mt
in t ca C=C tng kh nng phn ng AE
13
V.1.2. Phn ng cng hp halogen

Phn ng cng hp ca CH2=CH2 vi Br2 vi s c
mt ca NaCl, NaNO3, sn phm thu c l 1 hn
hp:
Br-CH2-CH2-Br + Br-CH2-CH2-Cl +
Br-CH2-CH2-ONO2
Nu phn ng thc hin trong dung mi l CH3OH,
sn phm chnh l Br-CH2-CH2-OCH3 !!!
14
H2C CH2 + Br2
H2C CH2 + Br2
H2C CH2 + Br2
CCl4
CH3OH
H2O
H2C CH2
Br Br
H2C CH2
Br OCH3
H2C CH2
Br OH
15
***Lp th ca phn ng cng X2:

Cng hp trans (anti)
cis sn phm l hn hp racemic (1 i i
quang)
trans sn phm c th l meso (1 sn phm)
H
H
C
C
H3C
H
CH3
Br2
CH3
C
C
H
CH3
Br2
CH3
H C Br
Br C H
CH3
CH3
H C Br
H C Br
CH3
meso
CH3
Br C H
H C Br
CH3
rac-
16
V.1.3. Phn ng cng HX

a. Quy tc Markonikov (dnh cho C=C khng i
xng): H+ s tn cng vo carbon cha nhiu H
CH3-CH=CH2 + HBr
CH3-CH-CH3
Br
Br
CH3-C-CH3
CH3
CH3-C=CH2 + HBr
CH3
b. Quy tc Zaitsev-Wagner: H+ s tn cng vo

pha to thnh carbocation trung gian bn nht
CH3-CH=CH-CH2-CH3
HBr
CH3-CH-CH-CH2-CH3
Br
17
c. Quy tc Kharasch: khi c mt peroxide, phn

ng s i theo hng ngc vi Markonikov &
theo c ch cng hp gc t do
CH3-CH=CH2 + HBr CH3-CH2-CH2-Br
Cc peroxide: H2O2, acetyl peroxide CH3CO-O-OCO-CH3, benzoylperoxide C6H5CO-O-O-COC6H5
18
C ch: Theo hng to gc t do bn

to
CH3-C-O-O-C-CH3
O
O
CH3-CO-O
Br
+ HBr
CH3-CH=CH2
CH3-CH-CH2Br
CH3 + CH3-CO-O
Br
+ CH3COOH
CH3-CH-CH2
Br
HBr
+ CO2
+ CH3-CH-CH2Br
CH3-CH2-CH2Br + Br
Lu : HI & HCl khng tham gia phn ng cng

19
gc t do nh HBr!!!
V.1.4. Phn ng cng hp nc

Cn xc tc acid: H2SO4, H3PO4 (khng dng HX)
CH3-CH=CH2 + H2O
H2SO4
CH3-CH-CH3
OH
Tun theo quy tc Markonikov

C ch:
CH3-CH=CH2
+ H+
-H
+
CH3-CH-CH3
+ H2O
-H2O
H
H3 C C O
CH3
-H+
+ H+
CH3-CH-CH3
OH
Nu dng nhiu H2SO4:

CH3-CH=CH2 + H2SO4 (CH3)2CH-OSO3H
(CH3)2CH-OSO3H + H2O (CH3)2CH-OH + H2SO4
20
V.1.5. Phn ng cng hp B2H6

Phn ng quan trng iu ch alcohol bc 1 & 2
t alkene, ngc vi sn phm Markonikov
CH3-CH=CH2
1. B2H6
CH3-CH2-CH2-OH
2. H2O2 / NaOH
C ch: B2H6 BH3

CH3-CH=CH2
BH3
(Lewis acid)
H
+
CH3-CH-CH2-B H
H
CH3-CH2-CH2-BH2
H-
[CH3-CH2-CH2]3B
CH3-CH2-CH2-OH
H2O2
OH[CH3-CH2-CH2-O]3B
21
V.2. Phn ng hydro ha

V.2.1. C ch:
C C
+ H2
Ni
C C
H H
Xc tc thng dng: Ni, Pd, Pt

C ch: gc t do (AR), 2 H gn vo cng pha
ni i (khc phn ng +X2) cng hp cis
C C
H H
+ H2
H H
C C
H H
22
V.2.2. Tnh lp th
Phn ng cng hp cis (syn)
ng phn cis c th thu sn phm meso (1 sn
phm)
ng phn trans sn phm l hn hp racemic (1
i i quang)
H
H
C
C
D2
Ni
COOH
H C D
H C D
COOH
meso
D2
Ni
COOH
H C D
D C H
COOH
COOH
COOH
maleic acid
H
HOOC
C
C
COOH
H
fumaric acid
COOH
D C H
H C D
COOH
rac-
23
V.3. Phn ng oxy ha

V.3.1. Tc nhn oxy ha peracid
R-C-O-O-H
O
C C
O
C C
OH
H2O
C C
(H+, OH-)
OH
O
C C
+ RCOOH
Cng hp trans, to -diol

Phn ng khng gy ct mch C=C
24
V.3.2. Oxy ha bng ddch KMnO4 long (pH 7, 0oC )

Cng hp cis, to diol
OH-
C C
MnO4
0 oC
pH 7
C
O
O
C
O
Mn
H2O
+
C C
OH OH
+ MnO3-
O-
Phn ng khng ct mch C=C

25
V.3.3. Oxy ha bng ddch KMnO4 m c, to cao

Phn ng gy ct mch C=C
Sn phm l carboxylic acid
CH3-CH=CH-CH3 + KMnO4 / to 2 CH3COOH
(CH3)2CH=CH-CH3 + K2Cr2O7 /H2SO4/to
(CH3)2C=O + CH3COOH
26
V.3.4. Oxy ha bng ozone

Phn ng gy ct mch C=C
Sn phm l carbonyl (khc KMnO4 )
H
O
CO
C C
O3
C
O
C
O
O
molozonide
CH3-C=CH-CH2-CH3
CH3
1. O3
2. H2O
C
C
O O
ozonide
CH2-C-CH3 +
O
H3
C
/
Zn
H2/Pt
H
2O
(H +
)
C O + H2O
C O + H2O
C O + H2O2
CH3-CH2-CHO + H2O2
Lu : H2O2 d dng oxy ha carbonyl thnh

27
carboxylic acid sn phm cui l acid!!!
V.4. Phn ng polymer ha

Phn ng to polymer di tc dng ca nh
sng, to cao, xc tc
C th xy ra theo c ch gc t do (xc tc
peroxide), c ch cation (xc tc H2SO4, AlCl3,
BF3) hay anion (xc tc LiNH2)
CH3
H2C C
CH3
nCH2=CH
Cl
H+
CH3
H3C C CH2
CH3
peroxide
CH3
C CH2
CH3
CH3
C
CH3
--CH2-CH- CH2-CH- CH2-CH-Cl

Cl
Cl
polyvinyl chloride
28
Ha Hc Hu C
B mn K Thut Hu C
Khoa K Thut Ha Hc
in thoi: 8647256 ext. 5681
Chng 6: ALKADIENE
I. Phn loi
I.1. Hai ni i ng lin nhau (allene)
CH2=C=CH2 propadiene
CH3-CH2=C=CH2 1,2-butadiene
I.2. Hai ni i lin hp

C cu to c bit c tnh cht ha hc quan
trng ch trng cc hp cht ny
CH2=CH-CH=CH2 1,3-butadiene
CH2=C(CH3)-CH=CH2 2-methyl-1,3-butadiene
(isoprene)
I.3. Hai ni i xa nhau

Tnh cht ging nh alkene
CH2=CH-CH2-CH=CH2
1,4-pentadiene
II. Cc phng php iu ch

II.1. Tch nc t 1,3-butadiol
i t acetylene
HC CH + H2O
O
H3C C + +
H
O
H2C C
H H
OH
H3C C CH2 CH2OH
H
HgSO4
H2SO4
-
OH
CH3-CHO
OH
O
H3C C CH2 C
H
H
Al2O3
o
350 C
CH2=CH-CH=CH2
H2/Ni
+ 2H2O
5
II.2. T ethanol
2 CH3-CH2-OH
ZnO/Al2O3
o
450-500 C
CH2=CH-CH=CH2
II.3. T 1,4-butadiol
HC CH + HCHO
HO-CH2-C
HO-CH2-CH2 CH2-CH-OH
Al2O3
350 oC
C-CH2-OH
H2/Ni
CH2=CH-CH=CH2
6
III. Tnh cht ha hc

Cc in t c gii ta u trn ton b phn t
linh ng
C1-C2: 1.38 (C=C bnh thng: 1.34)

C2-C3: 1.46 (C-C bnh thng: 1.54)
Khi c mt tc nhn khc, h lin hp s phn cc:
CH2=CH-CH=CH2
+
CH2-CH=CH-CH2
+
CH2-CH-CH=CH2
khc alkene bnh thng
III.1. Phn ng cng halogen

Thu c 2 sn phm cng 1,2 & 1,4
CH2=CH-CH-CH2
Br Br
CH2=CH-CH=CH2 + Br-Br
CH2-CH=CH-CH2
Br
C ch:
CH2=CH-CH=CH2
+
+ Br-Br
Br
+
CH2=CH-CH-CH2 Br
+
CH2-CH=CH-CH2 Br
Br-
Br-
CH2=CH-CH-CH2
Br Br
CH2-CH=CH-CH2
Br
Br8
III.2. Phn ng cng HX

Ty theo nhit m thu c hn hp sn phm
khc nhau
CH2=CH-CH=CH2 + HBr
-80 oC
CH2=CH-CH-CH2
Br H
CH2-CH=CH-CH2
Br
40 oC
80%
CH2=CH-CH-CH2
Br H
40 oC
CH2-CH=CH-CH2
20%
Br
H
20%
80%
H
9
III.3. Phn ng Diels-Alder

Phn ng cng hp & ng vng ca1,3butadiene
hay dn xut ca n vi cc hydrocarbon khng no
khc (i diene)
H
H
C
C
H
C
C
H
H
H
H
H
C
C
O
C
O
CH3
H
to
CH3
10
Cc hp cht i diene phi mang nhm th ht

in t, ethylene phn ng rt chm
CH2=CH-CHO acrolein
CH2=CH-CN acrylonitrile
(CN2)C=C(CN)2 tetracyan ethylene
C6H5-CH=CH-COOH cinnamic acid
O
O
O
maleic anhydride
O
benzoquinone
11
III.4. Phn ng trng hp
--CH2-CH=CH-CH2--
n CH2=CH-CH=CH2
Trng hp isoprene cha 94% cis ~ cao su

thin nhin
--CH2-C=CH-CH2--
n CH2=C-CH=CH2
CH3
CH3
n
12
Ha Hc Hu C
B mn K Thut Hu C
Khoa K Thut Ha Hc
in thoi: 8647256 ext. 5681
Chng 7: ALKYNE
I. Gii thiu chung
Hp cht hydrocarbon khng no, mch h, cha
lin kt ba CC
Cng thc chung: CnH2n-2
180o
1.06
1.2
II. Danh php

II.1. Tn thng thng
Alkyne n gin nht l HCCH acetylene
Cc alkyne n gin khc c xem l dn xut
ca acetylene
HCC-CH2-CH3 ethylacetylene
CH3-CC-CH(CH3)2 isopropylmethylacetylene
II. 2. Tn IUPAC
Cch gi tn ging nh alkene, ch i ene
thnh yne
Mch chnh phi cha CC
Nhng hp cht cha nhiu hn 1 ni ba
diyne, triyne
Hp cht va c ni i va c ni ba enyne
6-methyl-3-octyne
4-methyl-7-nonene-1-yne
1-heptene-6-yne

III.1. Thy phn calcium carbide CaC2
CaO + 3C
2000 oC
CaC2 + 2H2O
CaC2 + CO
HC CH + Ca(OH)2
III.2. Oxy ha methane
6CH4 + O2
1500 oC 2 HC CH + 2CO + 10H

2
III.3. i t dn xut dihalogen

H2C CH2 KOH/EtOH
to
Br Br
CH3-CH2-CHCl2
Cl
CH3-CH2-C-CH3
Cl
HC CH
KOH/EtOH
t
H
O
t
/E
H
KO
to
Na
NH
to 2
CH3-CH
CH3-C
CH
C CH3
CH3-CH2-C
CH
7
III.4. Alkyl ha dn xut natri hay c magnesium

ca acetylene
HCCNa
HCC-MgX
+ R-X HCC-R
+ NaX
+ R-X HCC-R + MgX2
iu ch dn xut ca acetylene
HCCH
HCCH
+ NaNH2 HCCNa
+ CH3MgX HCC-MgX
+ NH3
+ CH4

V. Tnh cht ha hc
V.1. Phn ng th H u mch
H u mch th hin tnh acid
HCC-H + NaNH2 HCCNa
+ NH3
HCC-H + [Ag(NH3)2]+NO3- Ag-CC-Ag +
NH4NO3 + NH3
C trong CC-H trng thi sp, m in ln
hn sp2 hay sp3 ht in t ca lin kt C-H
H+ d tch ra
Alkene & alkane khng c tnh cht ny
V.2. Phn ng cng hydrogen

R C C R'
+ H2
Ni hay Pt
R-CH2-CH2-R'
R-CH2-CH2-R'
/C
d
P
R C C R'
+ H2
Pd
/Ca
Pd
CO
/B
aS 3
O
4
R C C R' + Na/NH3
H
H
C C
R
R'
H
R'
C C
R
H
10
V.3. Phn ng cng halogen
H3C C CH
+ Br-Br
Br
H3C C CH
Br
Br2
Br
H3C C CHBr2
Br
Sn phm trans trong ln cng th nht

Lu : nu ni i & ni ba khng lin hp, X2 s
cng vo ni i!!!
CH2=CH-CH2-CCH + Br2 BrCH2-CHBr-CH2-CCH
11
V.4. Phn ng cng HX
H
H C C CH
H
H-Br
H
H-Br
H C C CH2
H Br
H Br
H C C CH3
H Br

12
V.5. Phn ng cng nc

HC CH + H2O
R C CH + H2O
HgSO4
H2SO4
HC CH2
OH
enol
HgSO4 R C CH2
H2SO4
OH
enol
CH3CHO
R C CH3
O
Ch c acetylene mi to thnh aldehyde

13
V.6. Phn ng cng hp alkylborane
H +
H
H C C C C CH3
H
H
BHR2
H3C C C CH2 CH3 CH3COOH

H BR2
C2H5
H3C
C C
H
H
H2O2/OHH3C C C CH2 CH3

H OH
H3C CH2 C CH2 CH3

O
To alken: cng cis

14
V.7. Phn ng cng hp cht carbonyl

Cng hp i nhn
+
H C C H
H
C O
+
H
H C C H
H C C CH2-OH HCHO
R
+ 2 C O
R
HO-H2C C C CH2-OH
R
R
HO-C C C C-OH
R
R
15
V.8. Phn ng cng hp i nhn

R-OH, R-SH, R-COOH, H-CN, amine monomer quan trng
HC CH
RO150 oC
ROCH CH-
C6H5CO C CH
C6H5C CH
CH2 CH C CH
ROH
C6H5
OC2H5
C C
H
H
C2H5ONa
+ RO-
C6H5CO
NR2
C C
H
H
R2NH
ROH
ROCH CH2
CH2 CH CH CHOR
RO
150 oC
16
V.9. Phn ng oxy ha

Oxy ha alkyne bng KMnO4 hay ozone to
carboxylic acid
R-CC-R + KMnO4 hay ozone RCOOH +
RCOOH
R-CC-H + KMnO4 hay ozone RCOOH +CO2
V. 10. Phn ng trng hp
2H C C H
CuCl
to
CH2=CH-C
CH HCl
CH2=CH-C
CH2
Cl
chloroprene
CH2-CH=C CH2
Cl
cao su neoprene
17
Ha Hc Hu C
B mn K Thut Hu C
Khoa K Thut Ha Hc
in thoi: 8647256 ext. 5681
Chng 6:
HYDROCARBON THM
I. Cu to ca benzene
Kkul a ra cng thc cu to ca benzene

nm 1865
6C, 6H vng 6 cnh c 3 ni i nhng khng
th l cyclotriene
H
H
H
C
C
C
C
C
C
H
H
2
H
Kkul chng minh rng v tr 3 Lin kt i khng

c nh m c th thay i
Phn ng th 2 ln Br ch cho 1 sn phm

Br
Br
+ Br2
Br
Br
Cu to thc t: h in t phn b u cho 6C

(khng phi ca ring 3 cp C=C)
6C nm trong cng 1 mt phng, trng thi

lai ha sp2
120
120
120
1.39
1.09
121.7o
116.6o
1.08
1.33
II. Tnh thm

Hydrocarbon thm (arene) nhng hp cht vng
lin hp c cu to phng, c cu to in t ging
benzene, kh cho phn ng cng, d cho phn ng
th
H
Br2
CCl4
Br
Br
H
Br2
H
KMnO4 L
H2O
H
CCl4
OH
OH
KMnO4 L
H2O
Arene thng l vng phng 5, 6, 7 cnh, c h

in t lin hp, s t tun theo quy tc Hkel
4n + 2, n = 0,1,2,3,4
V d cc hp cht arene thng dng
n=1
n=2
n=3
Mt s trng hp c bit
cyclopentadienyl 6 in t (i t ca anion
tham gia h lin hp) n=1 c tnh thm
(-)
(+)
cycloheptatrienyl 6 in t (C+ tham gia

orbital trng p vo h lin hp) c tnh
thm
4 in t khng c tnh thm
(+)
2 in t c tnh thm
(+)

(.)
(.)
(-)
N
H
Pyrrole
O
Furan
6 in t (i in t
p tham gia h lin hp)
c tnh thm
Thiophene
III. Danh php

Hu ht cc arene u c tn thng thng, 1 s
tn thng thng c chp nhn lm tn IUPAC
Tn IUPAC: benzene c chn lm tn gc, tn
cc nhm th t trc, nhm th c nh s
theo nguyn tc tng ch s nh nht, xp theo
alphabetical
10
III.1. Dn xut ca benzene
11
12
I
NO2
CH3
NO2
Cl
Br
p-bromoiodobenzene m-chloronitrobenzene
o-nitrotoluene
OH
COOH
NH2
I
Br
4-bromophenol
NO2
m-nitrobenzoic acid
o-iodoaniline
HC CH2
HC CH2
1,4-divinylbenzene
hay p-divinylbenzene
khohttp://hhud.tvu.edu.vn
ng goi la p-vinylstyrene
13
NH2
NO2
Cl
Br
Br
Br
Br
1,2,4-tribromobenzene
Br
Cl
Br
3-bromo-5-chloronitrobenzene
Br
OH
2,4,6-tribromoaniline
Cl
2,4,6-trichlorophenol
OH
Cl
Cl
CH3
O2N
NO2
NO2
2-chloro-4-nitrophenol
2,6-dinitrotoluene
14
III.2. Vng a ngng t
8
7
6
9
10
8
2
5
4
Naphthalene
1
2
3
10
4
Anthracene
15
III.3. Cc arene c d t trong vng
N
Pyridine
N
H
Pyrrole
CH3
2-methylpyridine
Furan
Thiophene
16
IV. Cc phng php iu ch

IV.1. Chng ct mui ca benzoic acid
COONa
+ NaOH
to
+ Na2CO3
IV.2. i t acetylene
3HC CH Cu hay phc Ni

to
17
IV.3. Alkyl ha benzene

R
+ R-Cl
AlCl3
+ HCl
IV.4. ng vng & dehydro ha phn on du m

C6-C8
CH3(CH2)4CH3
Cr2O3 / Al2O3
V. Tnh cht vt l (t c)
18
V. Tnh cht ha hc
V.1. Phn ng th i in t
V.1.1. C ch phn ng
X
+ X+
acid
+ H+
Xc tc: H2SO4, H3PO4, HF

hay Lewis acid: FeCl3, AlCl3, ZnCl2
C6H6 + (CH3)3C-Br /AlBr3 C6H5-C(CH3)3 + HBr
19
C ch phn ng: 2 giai on, lng phn t

Giai on 1: to phc ( benzonium cation)
+ X -Y
X
cham
H
+
xt
X+-Y
nhanh
phc
+
+
phc
Trong phc : X khng lin kt trc tip vi C no c

Phc : X c lin kt trc tip vi 1 C ca benzene
20
Giai on 2: tch proton
H
nhanh
+
+ HY
21
V.1.2. Kh nng phn ng v quy lut th

a. Kh nng phn ng:
Nhm th y in t (+I, +C, +H) mt
in t trong nhn thm tng tc nhn i
in t cng d tn cng tc phn ng
tng
Cc nhm th y in t (tng hot) thng
gp:
* alkyl ( +I, +H)
*-NR2 (R: H hay gc alkyl), -OH, -OCH3
-NH-CO-CH3 (+C > -I)
* anion: -O- (+C, +I mnh)
22
Nhm th ht in t (-C, -I) mt in t ca

nhm thm gim khng thun li cho tc nhn i
in t gim tc phn ng
Cc nhm th ht in t (gim hot) thng gp:
* -N+N, -NO2, -CN, -CHO, -COR, -COCl, -COOH,
-CO-NH2 (-I, -C)
* cation: -N+R3 (-I mnh)
* halogen (-I > +C)
V d: kh nng th i in t:
NO2
Cl
OH
>
>
>
23
b. Tnh chn la quy lut th

Nhm th y in t nh hng nhm th
th 2 vo v tr o- hay p Nhm th ht in t nh hng nhm th
th 2 vo m Ring dy halogen gim hot, nhng vn nh
hng nhm th 2 vo o-, p-
24
Nhn thm c nhm th y in t:

Y
mt t o-, p- cao nht nhm th th 2 (i in

t) s vo o-, p Nhn thm cha nhm th ht in t:
Y
mt t o-, p- thp nht nhm th th 2

25
s vo mhttp://hhud.tvu.edu.vn
C th gii thch da vo bn ca phc

Y
+ X+
Th o-:
Y
Th p-:
X
H http://hhud.tvu.edu.vn
26
Th m-:
Y
Y
H
H
X
H
X
khi Y y in t: trong th o-& p-: c 2 trng thi

cation bn (+ gn Y nht) d to thnh nhm
th th 2 s vo o-, p khi Y ht in t: trong th o-, p-: c 2 trng thi
rt km bn (+ gn Y) nhm th 2 s khng vo o27
, p- m vo mhttp://hhud.tvu.edu.vn
c. Nhn thm c 2 nhm th:

Nhm th th 3 s nh hng da theo nh hng
ca nhm th tng hat nht
V d:
-I>+C
Cl
NH2
+C>-I
+C>-I
OH
+C>-I
OH
CH3
+I, +H
HN C CH3
O
+C>-I
+C>-I
NH2
NO2
-C, -I
28
d. T l 2 ng phn o-/p-:
D on: o-/p- = 2/1
Thc t o-/p- <2
Nguyn nhn 1: hiu ng khng gian
nhm th hay tc nhn i t c kch thc ln
s gim t l o-/p-
29
R
NO2
+
HNO3 /H2SO4
R
Br
Br2 /AlCl3
NO2
Br
R -CH3
Phn ng
-CH2CH3
-CH(CH3)2 -C(CH3)3
Nitro ha
1.37
0.93
0.48
0.22
Brom ha
0.69
0.22
0.12
30
Nguyn nhn 2: Hiu ng in t

X
X
HNO3 /H2SO4
NO2
+
NO2
t l o-/p-:
X=F: 0.14 Cl: 0.43
Br: 0.60 I: 0.69
-I cng mnh, v tr o- cng b phn hot ha
sn phm o- cng t
31
V.2. Cc phn ng th i in t tiu biu

V.2.1. Phn ng nitro ha
H ca nhn thm c thay th bng NO2+
Tc nhn nitro ha ch yu: HNO3 hay
HNO3/H2SO4
NO2
+ HNO3
H2SO4
+ H2O
NO2+ to thnh do:

HNO3 + 2H2SO4
HNO3
+ HNO3
O
N
+ H3O+ + HSO4-
O
N
+ H2 O
+ NO3-
32
Nitro ha 1 ln: 50-60 oC

Nitro ha 2 ln (m-): 70-80 oC
Nitro ha 3 ln: phi i t toluene
COOH
NO2
CH3
CH3
HNO3
H2SO4
O2N
NO2
[O]
O2N
O2N
-CO2
NO2
NO2
T.N.T
NO2
NO2
Nitroha phenol: khng cn H2SO4

OH
OH
OH
NO2
HNO3
+
NO2
65%
35%
33
V.2.2. Phn ng sulfo ha

H ca nhn thm c thay bng SO3H
Tc nhn sulfo ha: H2SO4 , oleum, Cl-SO2OH
SO3H
+
H2SO4
20 oC
+ H2O
benzenesulfonic acid
Tc nhn i in t c th l SO3 hay S+O2OH

+ HSO4-
2 H2SO4
SO3
2 H2SO4
HOSO2+
+ H3O+
+ HSO4-
+ H2O
34
Tnh cht ca sulfonic acid:

SO3H
+ H2O
to
H2SO4
SO3Na
SO3H
+ H2O
+ NaOH L
ONa
SO3H
+ NaOH R
300 oC
+ Na2SO3
H+
OH
phng php kim chy, iu ch phenol

35
Nhm SO3H d b thay th bi nhm NO-2

OH
OH
OH
SO3H
H2SO4
HNO3
O2 N
NO2
NO2
picric acid
SO3H
* iu ch sulfanilic acid
NH3+HSO4-
NH2
H2SO4
NHSO3H
NH2
to
-H2O
H
SO3H
sulfanilic acid 36
Sulfo ha naphthalene
SO3H
H2SO4 80 oC
> 170 oC
170-180 oC
SO3H
37
V.2.3. Phn ng halogen ha
X
+ X2
xt
+ HX
Xc tc: AlCl3, FeBr3, ZnCl2

Flor ha: mnh lit, t mch t s dng
Iodo ha: thun nghch
38
C ch phn ng:
+ Cl - Cl
FeCl3
nhanh
Cl -Cl
cham
FeCl3
Cl
H
+
FeCl4-
Cl
+ FeCl3 + HCl
39
iu ch C6H5I:
I
+ NO2 + H2O
+ I2 + HNO3
H+
I+
+ I2 + HNO3
+ NO2 + H2O
Tc nhn i in t I+ tn cng nhn thm

theo c ch nh trn
40
Halogen ha mch nhnh ca arene:

Nu c xc tc & nhit thp phn ng th i
in t (SE)
Nhit cao, nh sng hay peroxide: th vo mch
nhnh (SR)
CH3
CH2Cl
Cl2
130 oC
CHCl2
Cl2
140-160 oC
CCl3
Cl2
>180 oC
Kh nng chlor ha SR: C bc 3 > C bc 2 > bc 1

41
V.2.4. Phn ng alkyl ha Friedel-Crafts

a. Alkyl ha vi R-X, xc tc Lewis acid (AlCl3,
FeBr3)
R
AlCl3
+ R-Cl
+ HCl
C ch:
+
+ R - Cl
AlCl3
nhanh
R -Cl
cham
AlCl3
R
AlCl4-
R
+ AlCl3 + HCl
+
42
b. Alkyl ha vi alkene, xc tc Lewis acid hay

Bronsted acid (HF, H3PO4)
R-CH=CH2
H+
+
R-CH-CH3
Carbocation tn cng nhn thm theo c ch th

i in t nh trn, to thnh
H
R C CH3
43
c. Alkyl ha vi alcohol, xc tc Lewis acid hay

Bronsted acid (HF, H3PO4)
R-OH
+ H
R-O
H
R+ + H2O
Carbocation tn cng nhn thm theo c ch th

i in t nh trn, to C6H5-R
44
d. Cc im cn lu ca phn ng alkyl ha
Friedel-Crafts
C6H5-X khng th to tc nhn i in t
Tc phn ng alkyl ha ca R-X: bc 1 < bc 2
< bc 3 < dn xut benzyl hay allyl carbocation
cng bn, phn ng cng d
Alkyl ha khng dng li sn phm monohttp://hhud.tvu.edu.vn
45
Carbocation lun c chuyn v to cao:

CH3-CH2-CH2-Cl
AlCl3
+
CH3-CH-CH3
+
CH3-CH2-CH2
H
H3C C CH3
CH3-CH2-CH2-Cl
AlCl3
CH2-CH2-CH3
+
70%
30%
Alkyl ha phenol, khng dng AlCl3 (to phc

phi tr vi OH), phi dng H2SO4, H3PO4 lm xc
tc
Vng thm c nhm th ht in t mnh hn
46
halogen khng tham gia phn ng akyl ha
Sn phm c th b ng phn ha hay d ha khi

xc tc d:
CH3
CH3
Lewis acid
to
CH3
CH3
CH2CH3
2
CH2CH3
Lewis acid
to
+
CH2CH3
47
V.2.5. Phn ng acyl ha Friedel-Crafts

R-CO-Cl
R C O
(R-CO)2O
Lewis acid
a.C ch:
R C Cl
O
+
R-C
O
+ AlCl3
+ AlCl4-
R C
O
R C
O
+ AlCl3
R-C+
O
+ [RCOOAlCl3]
Tc nhn i in t RC+=O tn cng nhn thm

48
theo c ch th i in t nh trn
b. c im quan trng
Lng xc tc AlCl3 rt nhiu, do:
O
C
AlCl3
AlCl3
O
C+
R
HCl
O
C
R
49
iu ch alkyl benzene bc 1 hoc mono-
CH2CH2CH3
C O
CH3CH2CH2COCl
CH2CH2CH2CH3
Zn(Hg)/HCl
AlCl3
Kh nng phn ng: RCOI > RCOBr > RCOCl >

RCOF
HCOCl khng bn phi dng CO/HCl/AlCl3 lm
tc nhn acyl ha
50
Nhm th phn hat ha khng thun li cho

phn ng:
O2N
C
O
AlCl3
AlCl3
O2N
O2N
+ ClOC
COCl
51
V.3. Phn ng th i nhn ca vng thm (SN)

Vng thm giu in t SN ca benzene hay dn
xut rt kh xy ra
X
Y
+ X-
+ Y
Cl
OH
+ KOH
300 oC
280 atm
+ KCl
Khng xy ra iu kin thng

52
Trng hp c bit: nhm th th 2 ht in t

mnh & v tr o-, p- th i nhn ca nhm th 1
c th xy ra
Cc nhm th ht in t mnh: -N+N, -NO2, -CN, CHO, -COR
V d:
OH
Cl
+ Na2CO3 L
NO2
NO2
53
NO2
NO2
Cl
NO2
OH
NaOH
to
OH
NaOH
to
CH3ONa
NaNH2
N
NO2
to
NH2
Cl
OCH3
C ch: th i nhn lng phn t

O
O-
O + ON
cham
HO-
Cl
O-
nhanh
-ClCl
OH
OH
54
Cc mui diazonium ca arene c kh nng cho

phn ng th i nhn n phn t
N+ NCl-
to
cham
+ N2 + Clnhanh YY
Y- : H2O, HOCH3, I-, CNhttp://hhud.tvu.edu.vn
55
V.4. Phn ng oxy ha

Nhn thm thng tr vi tc nhn oxy ha k
c KMnO4, K2Cr2-O7
Trong iu kin nghim ngt:
O
O2/ V2O5
HC COOH
450-500 oC HC COOH
O2/ V2O5
450-500 oC
O
56
Nhnh alkyl ca vng thm rt d b oxy ha bi

CrO3, K2Cr2O7/H2SO4, KMnO4/H2O, KMnO4/KOH
-COOH
CH3
COOH
KMnO4
H2O, to
NO2
NO2
57
Gc alkyl mch di ct mch, vn to COOH
CH2CH2CH2CH3
KMnO4
H2O
COOH
Nu khng c H benzyl, khng phn ng:

H3C
CH3
C
CH3
KMnO4
H2O
58
Ha Hc Hu C
B mn K Thut Hu C
Khoa K Thut Ha Hc
in thoi: 8647256 ext. 5681
Chng 9:
CC DN XUT HALOGEN
I.Phn loi
Cc hydrocarbon trong 1 hay nhiu H c thay

bng nguyn t halogen
Halogenoalkane: v d CH3-CH2-CH2-Cl
Halogenoalkene: v d CH2=CH-CH2-CH2-Cl
Halogenoalkyne: v d CHC-Cl
Halogenoarene: v d C6H5-Cl
Halogenocycloalkane: v d
Cl
2
II. Danh php

II.1. Tn thng thng (dnh cho dn xut n
gin)
Gc alkyl + halide (halogenua)
CH3-CH2-CH2-CH2-Br
V d:
n-butyl bromide (bromua)
(CH3)2CH-Cl isopropyl chloride

(CH3)2CH-CH2-Cl isobutyl chloride
C6H5-CH2-Cl benzyl chloride
II.2. Tn IUPAC
Halogen c xem l nhm th halo: chloro-,
bromo-, iodo-, fluoro Chn mch di nht cha halogen lm mch chnh
nh s sao cho nhm th c ch s nh nht, bt
k l halo- hay alkyl Khi c nhiu nhm th ging nhau, dng cc tip
u ng di-, tri-, tetrahttp://hhud.tvu.edu.vn
Nu c nhiu nhm th halo khc nhau, sp xp

theo th t alphabetical
Nu mch chnh c th nh s t 2 u, u tin
nhm ng trc theo th t alphabetical
H3C CH3
CH3 CH3
CH3-CH2-C-CH2-CH-CH3
Br
CH3-C-C-CH3
ClBr
4-bromo-2,4-dimethylhexane
2-bromo-3-chloro-2,3-dimethylbutane

III.1. Halogen ha alkane
CH3
H3C C CH3 + Cl2
H
CH3
H3C C CH3 + Br2
H
25 oC
h
CH3
H3C C CH2Cl
H
64%
127 oC
h
CH3
H3C C CH2Br
H
1%
CH3
+ H3C C CH3
Cl
36%
CH3
+ H3C C CH3
Br
99%
127 oC
CH3-CH2-CH3
+ Br2
h
CH3-CH2-CH2-Br
3%
CH3-CHBr-CH3
97%
III.2. Cng hp halogen hay HX vo alkene, alkyne

H2C CH2 + Br2
H2C CH2 + Br2
H2C CH2 + Br2
CH3-CH=CH-CH2-CH3
CCl4
H2C CH2
Br Br
CH3OH
H2O
HBr
H2C CH2
Br OCH3
H2C CH2
Br OH
CH3-CH-CH-CH2-CH3
Br
C mt peroxide: CH3-CH=CH2 + HBr

CH3-CH2-CH2-Br
III.3. Halogen ha arene

X
+ X2
xt
+ HX
Xc tc: AlCl3, FeBr3, ZnCl2

CH3
CH2Cl
Cl2
130 oC
CHCl2
Cl2
140-160 oC
CCl3
Cl2
>180 oC
8
III.4. i t alcohol
a.Tc nhn HX
CH3-CH2-OH
CH3-CH2-OH
+ HBr
+ HCl
H2SO4
ZnCl2
CH3-CH2-Br + H2O
CH3-CH2-Cl + H2O
b. Tc nhn PX3, PX5, SOCl2

R-OH
R-OH
R-OH
+
+
+
PCl3
PCl5
SOCl2
pyridine
pyridine
pyridine
R-Cl
+ H3PO3
R-Cl
+ POCl3
R-Cl
+ SO2
+ HCl
+ HCl
9

To s ca R-X bc 1 > bc 2 > bc 3
Ch tan tt trong dung mi hu c & khng tan
trong nc
V. Tnh cht ha hc
V.1. c im chung
+
R-CH2-CH2
Cl
m in ca Cl >> C C-Cl phn cc mnh

R-Cl c hot tnh cao
Trong dy halogen, kh nng tch X:
-I > -Br > -Cl > -F
Nng lng phn ly lin kt C-I nh nht, bn knh
10
nguyn t I ln nht
Dn xut R-X c chia thnh 3 nhm :

a. R-X hot ng mnh nht
Dn xut bc 3, dn xut m C-X lin kt vi nhm
vinyl hay aryl carbocation bn nht
CH3
H3C C Br
CH3
-Br-
C Br
-Br
CH3
H3C C+
CH3
+I, +H
C+
+C > -I
CH2=CH-CH-Br
-Br-
+
CH2=CH-CH
+C > -I
11
a.Nhm hot ng yu hn nhm a

R-X bc 1: CH3-CH2-CH2-CH2-Br
Nhm khng no nm xa nt halogen:
CH3-CH=CH-CH2-CH2-Br
a.Nhm hot ng yu
Nguyn t halogen lin kt trc tip vi lin kt
i, lin kt ba, vng thm
H3C CH CH Cl
+C>-I
Cl
+C>-I
+C ca X lm cho C-X bn kh phn cc, kh tch

12
V.2. Phn ng th i nhn

R-X
+ Y- R-Y + X-
Dn xut bc 1 SN2
Dn xut bc 3 SN1
Phn ng thy phn R-X
R-X + OH- R-OH
+ X-
CH3-CH2-Br + OH- CH3-CH2-OH + Brhttp://hhud.tvu.edu.vn
13
Phn ng to ether (Williamson)

R-X + R-O- R-O-R + XCH3-CH2-Br + CH3-O- CH3-CH2-O-CH3
Phn ng to amine
R-X + NH3 R-NH2 + HX
CH3-CH2-Br + NH3 CH3-CH2-NH2 + HBr
CH3-CH2-CH2-CH2-NH2 + CH3-CH2-Br
CH3-(CH2)3-NH-C2H5 + HBr
14
Phn ng to nitrile
R-X + KCN R-CN + KX
CH3-CH2-Br + CN- CH3-CH2-CN + BrLu : R-CN d b thy phn trong nc to
R-COOH
15
V.3. Phn ng tch loi

CH3-CH-CH-CH3 KOH/ethanol CH3-CH=CH-CH3
o
t
H Br
Gc R c bc cng cao, hay base cng mnh th

tch loi cng chim u th
CH3-CH2-CH2-Br
+ C2 H5 O -
CH3
H3C C Br
CH3
to thng
C 2H 5 O to cao
CH3-CH2-CH2-O-C2H5
H 2C C
CH3
CH3
16
V.4. Phn ng vi kim loi-Hp cht Grignard

CH3-CH2-Br + Na CH3-CH2-CH2-CH3 + NaBr
Quan trng: phn ng vi magnesium
R-X
+
C Mg Br
+ Mg
ether khan
R-Mg-X
C-MgX phn cc rt mnh, rt d

to R- base rt mnh & tc nhn i
nhn rt mnh
17
V.4.1. Phn ng vi H linh ng

CH3-CH2-MgBr + HOH CH3-CH3 + HO-MgBr
CH3-CH2-MgBr + ROH CH3-CH3 + RO-MgBr
CH3-CH2-MgBr + RNH2 CH3-CH3 + RNH-MgBr
CH3-CH2-MgBr + RCOOH CH3-CH3
+ RCOO-MgBr
CH3-CH2-MgBr + RCCH CH3-CH3
+ R-CC-MgBr
18
V.4.2. Phn ng vi carbonyl
+
O
CH3-CH2-MgBr + H C C H
3
+
OH
H3C C H
C2H5
O-MgBr
H2O /H+
H3C C H
C2H5
+ HO-MgBr
Phn ng vi HCHO alcohol bc 1

Vi aldehyde alcohol bc 2
Vi ketone alcohol bc 3
19
V.4.3. Phn ng vi CO2

+
+
CH3-CH2-MgBr O C O
C2H5-C-O-MgBr
O
H2O /H+
C2H5-COOH + HO-MgBr
V.4.4. Phn ng vi nitrile

+
CH3-CH2-MgBr
+
+ R-C N
R C N MgBr
C2H5
H2O /H+
R C NH
H2O /H+ R C O
C2H5
C2H5
Kh nng phn ng: nitrile > ketone ch khi d

Grignard phn ng tip vi ketone to alcohol
20
bc 3
V.4.5. Phn ng vi dn xut ca carboxylic acid
+
O
CH3-CH2-MgBr + H C C Cl
3
+
-HCl
O-MgBr
OH
H2O /H+
H3C C Cl
H3C C Cl
C2H5
C2H5
H3C C O
C2H5
Kh nng phn ng: dn xut acid > ketone ch

khi d Grignard phn ng tip vi ketone to
alcohol bc 3
Tng t cho phn ng vi anhydride
21
Phn ng vi ester:
+
O
CH3-CH2-MgBr + H C C OCH
3
3
+
-CH3OH
H3C C O
C2H5
O-MgBr
OH
H2O /H+
H3C C OCH3
H3C C OCH3
C2H5
C2H5
1. C2H5-MgBr
2.H2O /H+
C2H5
H3C C OH
C2H5
Kh nng phn ng: ester < ketone khng th

22
tch ketone trung gian
V.4.5. Phn ng vi oxide
CH3-CH2-MgBr +
ether khan
CH2
CH2
CH3-CH2-CH2-CH2-OMgBr
O
H2O /H+
CH3-CH2-CH2-CH2-OH
OH
CH2CHCH3
MgBr
+
CHCH3
CH2
O
1. ether khan
2. H2O / H+
60%
23
V.4.6. Phn ng ghp i Kumada

Kharash
RMgX
R'X
CoCl2
R R'
MgX2
Kumada: t sn phm ph hn Kharash

L2NiX2
RMgX' + R'X''
or L2PdX2
R-R' + MgX'X''
24
Ha Hc Hu C
B mn K Thut Hu C
Khoa K Thut Ha Hc
in thoi: 8647256 ext. 5681
Chng 10: ALCOHOL-PHENOL

Chng 10A: Alcohol
R-OH trong :
R: no hay khng no
CH3-CH2-OH
CH2=CH-CH2-OH
R: nhnh ca arene
C6H5-CH2-OH
I. Danh php
I.1. Tn thng thng (dng cho alcohol n gin)
Gc alkyl + alcohol
CH3-CH -OH
(CH3)2CH-OH
(CH3)2CH-CH2-OH
(CH3)3C-OH
C6H5-CH2-OH
CH2=CH-CH2-OH
ethyl alcohol
isopropyl alcohol
isobutyl alcohol
tert-butyl alcohol
benzyl alcohol
allyl alcohol
C th gi CH3-OH l carbinol, cc alcohol khc l

dn xut ca carbinol, v d: methyl carbinol
3
(ethyl alcohol)
I.2. Tn IUPAC
Chn mch di nht c cha nhm OH lm mch
chnh
Ly tn alkane, i ane anol
nh s mch chnh t u gn nhm OH nht
Khi c nhiu nhm th, sp xp theo th t alphabetical
CH3-OH
CH3-CH2-OH
methanol
ethanol
4
CH3
H3C C CH2-OH
CH3
CH3
CH3-CH-CH-CH3
OH
OH
C6H5-CH2-OH
2,2-dimethyl-1-propanol
3-methyl-2-butanol
7-ethyl-8,9-dimethyl-5-dodecanol
phenylmethanol

II.1. Cng hp nc vo alkene
Phn ng cn xc tc acid: H2SO4, H3PO4 (khng
dng HX)
CH3-CH=CH2 + H2O
H2SO4
CH3-CH-CH3
OH

Phn ng quan trng iu ch alcohol bc 1 & 2 t

alkene, ngc vi sn phm Markonikov:
CH3-CH=CH2
1. B2H6
2. H2O2 / NaOH
CH3-CH2-CH2-OH
II.2. Kh ha carbonyl, carboxylic acid v dn xut

Kh bng H2
R C R'
O
+ H2
Ni
H
R C R'
OH
aldehyde alcohol bc 1
ketone alcohol bc 2
Kh bng LiAlH4, NaBH4

R-CHO + LiAlH4
R-CH2-OH
R-COOH + LiAlH4
+ R-CH2-OH
Kh bng [(CH3)2CH-O]3Al trong (CH3)2CH-OH

R-CHO + [(CH3)2CH-O]3Al/(CH3)2CH-OH
R-CH2-OH + (CH3)2CO
II.3. i t hp cht Grignar
+
O
3
+
OH
H3C C H
C2H5
O-MgBr
H2O /H+
H3C C H
C2H5
+ HO-MgBr
II.4. Thy phn R-X, dn xut ca ester

O
R C
OR'
+ H2 O
OH-
R-COO-
R-X + OH- R-OH + Xhttp://hhud.tvu.edu.vn
+ R'-OH
10
III. Tnh cht vt l

R-OH to lin kt H to si cao hn cc dn
xut ca hydrocarbon c khi lng phn t
tng ng
C1-C3: tan tt trong nc
C4-C7: tan 1 phn trong nc
>C7: khng tan trong nc
11
IV. Tnh cht ha hc

IV.1. Gii thiu chung
a. Kh nng t lin kt C-O
Ch xy ra trong mi trng acid
R OH
+ H
+ H
R O
H
R+
+ H2 O
Kh nng phn ng: bc 1 < bc 2 < bc 3

C-OH cha nhiu nhm th y in t thun12 li
b. Kh nng t lin kt O-H

Ch xy ra trong mi trng base mnh
R OH
R-O
+ H+
Kh nng phn ng: bc 1> bc 2> bc 3

R cha nhiu nhm y in t khng thun li
13
IV.2. Tnh acid-base

Tnh acid ca alcohol rt yu
Tnh acid: C2H5-OH (Ka 1.3x10-18) < H2O
(1.3x10-14) < C6H5-OH (1.3x10-10) < CH3COOH
(1.8x10-5)
Alcohol hu nh khng phn ng vi NaOH
R OH
+ NaOH
R-ONa + H2O
14
Alcohol ch tc dng vi Na hay NaNH2

R OH
+ Na
R OH
+ NaNH2
R-ONa + H2
R-ONa + NH3
Mui alkoxide l base rt mnh

Tnh base:
(CH3)3C-O- > (CH3)2CH-O- > CH3-CH2-O> CH3-O- > OHhttp://hhud.tvu.edu.vn
15
IV.3. Phn ng to ether

2 CH3-CH2-OH
2 CH3-CH2-OH
H2SO4
Al2O3
o
350-400 C
CH3-CH2-O-CH2-CH3
+ H2O
CH3-CH2-O-CH2-CH3
+ H2O
Alcohol bc 1: SN2
Alcohol bc 3: SN1
***Danh php ca ether:
tn gc alkyl + ether
C2H5-O-C2H5
diethyl ether
CH3-O-C(CH3)3 tert-butyl methyl ether

16
Nu gc alkyl phc tp, c th xem l nhm th

alkoxy
CH3-CH2-CH2-CH-CH2-CH3
3-methoxyhexane
OCH3
CH2
OH
H3C
CH2
OC2H5
2-ethoxyethanol
CH3
CH3-CH-CH CH3
OC2H5
2-ethoxy-2,3-dimethylbutane
17
IV.4. Phn ng ester ha

R C OH
O
+ R'-OH
R C Cl
O
+ R'-OH
O
R C
O
R C
O
+ R'-OH
H2SO4
R C O-R'
O
+ H2O
R C O-R'
O
+ HCl
R C O-R'
O
+ RCOOH
Kh nng phn ng: RCO-Cl (khng cn xc tc) >

(RCO)2O (khng cn xc tc) > RCOOH
18
R'-OH
C ch phn ng:
+
R C OH
O
+ H
+
H O R'
R C OH
OH
O R'
R C OH
+
+
R C OH
OH
O R'
R C OH
OH2
+
HSO4-H+
-H2O
O R'
R C O
Kh nng phn ng: alcohol bc 1> bc 2> bc 3

HCOOH > CH3COOH > RCH2COOH > R2CHCOOH >
19
R3CCOOH
IV.5. Phn ng th -OH bi halogen

a.Tc nhn HX
CH3-CH2-OH
+ HBr
CH3-CH2-OH + HCl
H2SO4
ZnCl2
CH3-CH2-Br + H2O
CH3-CH2-Cl + H2O
Kh nng phn ng: HI > HBr > HCl > HF

HCl kh phn ng, cn xc tc ZnCl2 Lewis acid
tn cng vo O lin kt C-O d t
Kh nng thay th: bc 3 > bc 2 > bc 1
20
b. Tc nhn PX3, PX5, SOCl2
R-OH
R-OH
R-OH
+
+
+
PCl3
PCl5
SOCl2
pyridine
R-Cl
+ H3PO3
R-Cl
+ POCl3
R-Cl
+ SO2
pyridine
pyridine
+ HCl
+ HCl
21
IV.6. Phn ng dehydro ha v oxy ha

a. Phn ng dehydro ha
R-CH2OH
R
R C H
OH
Cu
R-CHO + H2
200-300 oC
Cu
R C R
O
200-300 C
CH3
CH3-C-CH2-CH3
OH
Cu
200-300 oC
+ H2
CH3
CH3-C=CH-CH3
+ H2O
22
b. Phn ng oxy ha
Tc nhn oxy ha: KMnO4, K2Cr2O7, CrO3
Alcohol bc 1 aldehyde carboxylic acid
Rt kh dng li giai on aldehyde thng i
thng n RCOOH
R-CH2OH + KMnO4
R-COOK
+ MnO2 + KOH
H+
RCOOH
23
Mun dng li giai on aldehyde: phi dng

pyridinium chlorocromate C5H5NH+CrO3Cl- (PCC):
C5H5NH+CrO3Cl-
R-CH2OH
CH2Cl2
RCHO + Cr3+
Alcohol bc 2 ketone
(H3C)3C
OH
Na2Cr2O7
CH3COOH, H2O
to
(H3C)3C
Alcohol bc 3 ch b oxy ha trong acid (tch

nc thnh alkene oxy ha ct mch alkene)
CH3
CH3-C-CH2-CH3
OH
KMnO4
H3C C CH3
H2SO4, to http://hhud.tvu.edu.vn
O
+ CH3-COOH
24
Chng 10B:
Phenol
-OH lin kt trc tip vi nhn thm

o
1,36 A
109 o
25
I. Danh php
OH
OH
OH
OH
CH3
phenol
CH3
o-cresol
CH3
m-cresol
p-cresol
OH
OH
OH
OH
O2N
OH
Tn
thng
thng
NO2
OH
NO2
OH
catechol
resorcinol
OH
hydroquinone
OH
OCH3
OH
picric acid
OH
CH(CH3)2
H3C
CH2CH CH2
eugenol
Thymol
26
-naphthol
-naphthol
Tn IUPAC
OH
OH
OH
CH3
Cl
Br
OCH3
4-methoxyphenol
Cl
3-bromo-4-chlorophenol 5-chloro-2-methylphenol
OH
OH
OH
OH
OH
1,2-benzenediol
1,3-benzenediol
OH
1,4-benzenediol
27

II.1. Chng ct nha than
Ly phn on 170-240 oC
Tch phenol bng cch chuyn thnh phenolate
ha tan
Hon nguyn phenol
C6H5ONa + CO2 + H2O C6H5OH + NaHCO3
28
II.2. Thy phn chlorobenzene

Cl
OH
300 oC
+ KOH
+ KCl
280 atm
Khng xy ra iu kin thng

II.3. Phng php kim chy
ONa
SO3H
+ NaOH R
300 oC
+ Na2SO3
H+
OH
29
II.4. Oxy ha cumene (dng trong cng nghip)
OH
O
H3C C CH3
CH(CH3)2
O2
OH
H2O, H+
H3C C CH3
O
cumene hydroperoxide
30
II.5. Thy phn mui diazonium (phng TN)

N+ N Cl-
OH
+ H2O
40-50 oC
+ N2 + HCl
iu ch mui diazonium:
NH2
N+ N Cl+ NaCl
+ NaNO2 + HCl
+ H2O
31
III. Tnh cht vt l

+C ca OH vi nhn thm O-H phn cc mnh
kh nng to lin kt H ca phenol > alcohol
to si , to nng chy, ha tan trong nc >
alcohol tng ng
phenol
tosi (oC)
180
tonc
41
ha tan (g/100g H2O)9.3
cyclohexanol
161
25.5
3.6
32
IV. Tnh cht ha hc
O H
IV.1. Tnh acid

O-H phn cc tnh acid > HOH > alcohol
OH
ONa
NaOH
OH
+ H2O
ONa
Na
+ H2
Tnh acid: phenol < H2CO3 :

H2O C6H5OH + NaHCO3
C6H5ONa + CO2 + http://hhud.tvu.edu.vn
33
So snh tnh acid ca 1 s phenol:

OH
NO2
>
pKa
OH
OH
>
NO2
NO2
7.15
OH
OH
10.08
8.4
7.23
OH
>
>
CH3
10.14
CH3
CH3
OH
OH
OH
10.28
OCH3
>
>
OCH3
9.65
OCH3
10.21
9.98
OH
OH
OH
Cl
>
>
Cl
8.48
9.02
Cl
34
9.38
IV.2. Phn ng to ether

Khc vi alcohol
OH
+ C2H5OH
H+
OH
OH
+
H+
35
Gii thch:
CH3-CH2-OH
H+
+ + H
CH2-CH2-O
H
O H
+C ca OH lm gim mt in t ca O
khng c kh nng tn cng vo oxonium
cation khng c SN2
36
Ngoi l:
OH
+ CH3OH
O-CH3
H2SO4
+ H2O
methyl ethyl ether /nerolin
Mt in t O trn naphthol > trn phenol

iu ch ether ca phenol bng phng php
Williamson:
O C2H5
ONa
+ NaBr
+ C2H5-Br
37
O CH2
ONa
CH
+ CH2=CH-CH2-I
+ NaBr
O CH3
ONa
H3C O O
S
H3C O O
CH2
Na O O
S
H3C O O
ONa
O
+
+ NaI
38
Lu : iu ch C6H5-O-C2H5 , cn i t
C6H5ONa+ C2H5-Br
nhng khng i t
C6H5-Br + C2H5ONa
Ether ca phenol c th b ct mch:
OH
OCH3
57% HI
120-130 oC
+ CH3I
39
IV.3. Phn ng ester ha

Khc vi alcohol
OH
+ CH3COOH
H+
Phi dng dn xut chloride hay anhydride

ca carboxylic acid
O C CH3
O
OH
+
H3C C Cl
O
acetyl chloride
+ HCl
40
O C C6H5
O
OH
+
C6H5 C Cl
O
+ HCl
benzoyl chloride
OH
+
O C CH3
O
O
H3C C
O
H3C C
O
+ CH3COOH
Lu :
O C C2H5
O
AlCl3
t
OH O
C
o
OH
C2H5
+
O
C2H5
41
IV.4. Phn ng th nhm OH

Khc vi alcohol
OH
+
X-
Ngoi l:
OH
O2N
Cl
NO2
O2N
NO2
+ PCl5
+ POCl3
NO2
+ HCl
NO2
OH
Zn
o
400 C
+ ZnO
42
IV.5. Phn ng th i in t
-OH (+C>-I) vng thm tham gia SE d dng, sn
phm o-, p Halogen ha
OH
OH
+ Br2
H2O
Br
Br
-HBr
Br
OH
OH
OH
+ Br2
CS2
Br
+
-HBr
Br
43
Nitro ha phenol:
Khng cn H2SO4, xy ra to thng, ng phn od tch bng chng ct li cun hi nc
OH
OH
OH
NO2
HNO3
+
NO2
35%
65%
44
Sulfo ha
OH
SO3H
15-20 oC
OH
H2SO4
H2SO4
100 oC
100 oC
OH
SO3H
Friedel-Crafts: thng cho hiu sut thp (cn

dng xc tc HF, H3PO4)
45
IV.6. Phn ng Kolbe (trong cng nghip)

O-Na+
O
+
+ O C O
OH O
C
ONa
H+
125 oC
4-7 atm
OH O
C
O
H
C
ONa
OH
Sn phm ph l p-hydroxybenzoic acid, c th

tch khi salicylic acid bng chng ct li cun
hi nc
46
IV.7. Phn ng vi formaldehyde

Trong mi trng base:
O-
O-
O+
H +
C O
H
SE
CH2OH
HOCH2OH
OH
OH
H+
CH2OH
Trong mi trng acid:
CH2OH
OH
OH
OH
H +
C O
H
H+
H+
C OH
H
+
SE
CH2OH
CH2OH
47
Ha Hc Hu C
B mn K Thut Hu C
Khoa K Thut Ha Hc
in thoi: 8647256 ext. 5681
Chng 9: ALDEHYDE-KETONE
I. Gii thiu chung
R-CHO aldehyde
RCOR ketone
C O
Ty theo cu to ca R, s c hp cht carbonyl

mch h (no + khng no) & carbonyl thm
CH3-CH2-CH2-CHO
CH2=CH-CH2-CHO
O
C
CH3-CH2-C-CH3
O
O
C
CH3
3
II. Danh php

II.1. Aldehyde
*Tn thng thng
Da theo tn carboxylic acid tng ng, thay ic
acid bng aldehyde
Aldehyde mch nhnh xem nh l dn xut ca
mch thng, dng , , ... ch v tr nhnh
Mt s tn thng thng c chp nhn lm tn
IUPAC
* Tn IUPAC
Mch chnh di nht & cha CHO
Gi theo tn hydrocarbon tng ng
thay ne nal
HCHO
formaldehyde / methanal
CH3CHO acetaldehyde / ethanal
C6H5CHO benzaldehyde /phenylmethanal
C6H5CH2CHO phenylacetaldehyde / phenylethanal
CH3-CH2-CH-CH2-CHO
CH3
-methylvaleraldehyde / 3-methylpentanal
II.2. Ketone
Tn thng thng
Tn 2 gc alkyl + ketone
Nu nhm carbonyl gn trc tip vng thm phenone
Tn IUPAC
Mch chnh di nht cha nhm carbonyl
nh s nhm carbonyl c ch s nh nht
Gi theo tn hydrocarbon, thay ne none
H3C C CH3 acetone / propanone

O
CH3-CH2-CH2-C-CH3
O
methyl n-propyl ketone / 2-pentanone
CH2
C CH3
O
benzyl methyl ketone / 1-phenyl-2-propanone
C CH3
O
acetophenone / 1-phenylethanone /
methyl phenyl ketone
H3C C CH CH2
O
methyl vinyl ketone / 3-butane-2-one

III.1. Oxy ha hydrocarbon
CH4
NO
+ O2
600-700 C
CuCl2
H2C CH2 + O2
50 C
HCHO
+ H2O
CH3-CHO
CHO
CH3
+ O2
Co2+
III.2. i t alkyne
HC CH + H2O
R C CH + H2O
H +
H
H C C C C CH3
H
H
BHR2
HgSO4
H2SO4
HC CH2
OH
enol
HgSO4 R C CH2
H2SO4
OH
enol
CH3CHO
R C CH3
O
H3C C C CH2 CH3 CH3COOH

H BR2
H3C
C2H5
C C
H
H
H2O2/OHH3C C C CH2 CH3

H OH
H3C CH2 C CH2 CH3

9
O
III.3. Ozone ha alkene

OH
O
C
C C
O3
C
O
C
O
O
molozonide
CH3-C=CH-CH2-CH3
CH3
1. O3
2. H2O
C
C
O O
ozonide
H3
C
/
Zn
H2/Pt
H
CH2-C-CH3 +
O
2O
(H +
)
C O + H2O
C O + H2O
C O + H2O2
CH3-CH2-CHO + H2O2
Lu : H2O2 d dng oxy ha aldehyde thnh

carboxylic acid sn phm cui l acid!!! 10
III.4. i t alcohol
Dehydro ha alcohol bc 1, bc 2
R-CH2OH
R
R C H
OH
Cu
R-CHO + H2
200-300 oC
Cu
R C R
O
200-300 C
CH3
CH3-C-CH2-CH3
OH
Cu
200-300 oC
+ H2
CH3
CH3-C=CH-CH3
+ H2O
11
Oxy ha alcohol:
Tc nhn oxy ha: KMnO4, K2Cr2O7, CrO3
Alcohol bc 1 aldehyde carboxylic acid
Rt kh dng li giai on aldehyde thng
i thng n RCOOH
Mun dng li giai on aldehyde, phi dng
pyridinium chlorocromate C5H5NH+CrO3Cl- (PCC):
R-CH2OH
C5H5NH+CrO3ClCH2Cl2
RCHO + Cr3+
12
Alcohol bc 2 ketone
(H3C)3C
OH
OH
Na2Cr2O7
CH3COOH, H2O
to
Na2Cr2O7
85%
H2SO4 / H2O
OH
H2C CHCHCH2CH2CH2CH2CH3
(H3C)3C
PCC
CH2Cl2
O
H2C CHCCH2CH2CH2CH2CH3
80%
13
III.5. i t dn xut ca carboxylic acid

O
R C
Cl
Pd/BaSO4
H2
R-CHO
+ HCl
CHO
COCl
LiAlH(O-tBu)3
NO2
NO2
(RCOO)2Ca
to
R C R
O
+ CaCO3
14

+
O
CH3-CH2-MgBr + H C C Cl
3
+
-HCl
O-MgBr
OH
H2O /H+
H3C C Cl
H3C C Cl
C2H5
C2H5
H3C C O
C2H5
Kh nng phn ng: dn xut acid > ketone ch

khi d Grignard phn ng tip vi ketone to
alcohol bc 3
Tuy nhin, thc t kh tch ketone vi hiu sut
cao
15
III.6. iu ch hp cht carbonyl ca arene

R-CO-Cl
R C O
(R-CO)2O
Lewis acid
HCOCl khng bn phi dng CO/HCl/AlCl3 lm

tc nhn acyl ha (Phng php GattermannKoch)
H3C
+ CO + HCl
AlCl3
H3C
CHO + HCl
[H-C-Cl]
O
16
C th thay CO bng HCN khan (phng php

Gattermann)
H3C O
+ HCN + HCl
AlCl3
[H-C-Cl]
NH
H2O
-NH4Cl
H3C O
H3C O
+
NH2
ClC
H
CHO
Thay HCN bng R-CN iu ch ketone thm

17
IV. Tnh cht vt l

Khng to lin kt H nh alcohol to si < alcohol
tng ng
Phn cc mnh, d tan trong nc (C1-C5)
+
sp2 C O
V. Tnh cht ha hc
Cu to phng
Gc lin kt ~ 120o
Moment lng cc = 2.7 D (CH3CHO)
di lin kt C-O 1.23
18
V.1. Phn ng cng hp i nhn (AN)
+
C O
+ X -Y
OX
Y
X-Y c th l H-OH, H-OR, H-CN, H-SO3Na, Li-R,

BrMg-R
19
a. C ch: 2 giai on, lng phn t

Giai on 1:
+
+ Y
cham
C OY
carbanion
Giai on chm: Y- tn cng vo C+ i nhn

Giai on 2:
-
C O
Y
+ X+
nhanh
C OX
Y
20
b. nh hng ca nhm th lin kt vi C=O

Nguyn t C trong C=O c in tch dng cng
ln AN cng thun li
Nhm th y t (+C, +I, +H) lm gim kh nng
phn ng
Nhm th ht t (-C, -I) lm tng kh nng phn ng
R C R
NO2-CH2-CHO > H-CHO > R-CHO >
O
R C O-R
R C NH2
>
O
O
R
C
O
R
C
NHR
>
>
21
O
O
V.2. Phn ng vi tc nhn i nhn carbon

Phn ng vi hp cht Grignard
+
O
3
+
OH
H3C C H
C2H5
O-MgBr
H2O /H+
H3C C H
C2H5
+ HO-MgBr
22
O
C
CH3CH2
CH3
O
C
1. ether khan
O
C
CH3CH2CH2CH2MgBr
CH2CH2CH3
CH3CH2CH2
O
C
CH3CH2CH2MgBr
2. H3O+
1. ether khan
2. H3O+
1. ether khan
CH3CH2MgBr
2. H3O+
MgBr
1. ether khan
H
2. H3O+
CH3CH2CH2CH2CH2OH
OH
CH3CH2CHCH2CH2CH3
OH
CH3CCH2CH2CH3
CH2CH3
OH
CH3CH2CH2CH
23
Phn ng vi acetylide anion
CH3C CH
CH3C CH
CH3CH2
O
C
CH3C CNa
Na
CH3C C
H
CH3C CNa
NaNH2
OCH3CH2CHC CCH3
N
H+
NH3
H2
OH
CH3CH2CHC CCH3
24
Phn ng vi hydrogen cyanide
H3C
O
C
CH3
CH3CH2
C N
OH3C C C N
CH3
OH
C C N
CH2CH3
CH3CH2CH2
OH
C C N
H
HCl / H2O
t
H2
Pt
HCN
OH
H3C C C N
CH3
CH3CH2
C N
OH
C COOH
CH2CH3
CH3CH2CH2
OH
C CH2NH2
H
25
V.3. Phn ng vi tc nhn i nhn oxygen

Phn ng vi nc gem-diol
O
C
CH3
H2O
CH3
CH3
0,2%
99,8%
CH3
O
C
OH
C CH3
OH
+
H
H2O
CH3
OH
C H
OH
42%
58%
O
C
OH
H C H
OH
99,9%
+
H
0,1%
H2O
26
Phn ng vi alcohol
O
R C
H
R'-OH/H
OH
R C OR'
H
OR'
R C OR'
H
R'-OH/H
-H2O
acetal
hemiacetal
O
R C
H
+H
-H+
+H+
-H+
+
-H
+ H+
OH
R C+
H
+
OH2
R C OR'
H
+ R'-OH
- R'-OH
- H2O
+ H2O
OH
+
R C OR'
H H
+
R C OR'
H
- H+
+ H+
+ R'-OH
- R'-OH
OH
R C OR'
H
hemiacetal
H
+ OR'
R C OR'
H
OR'
R C OR'
H
acetal
27
Acetal bo v nhm chc
O
C
O
OCH3
HOCH2CH2OH
O
C
LiAlH4
OCH3
HCl
O
CH2O-
CH2OH
H2O / HCl
HOCH2CH2OH
H
HCl
O
H
O
1. CH3MgBr
2. H2O / HCl
OH
28
V.4. Phn ng vi tc nhn i nhn nitrogen

Phn ng vi amine bc 1
O
+
R C
H
NH2-R'
O- H
R C N R'
+
H H
OHH
R C N R'
H
carbinolamine
+ H+
H
H O H
R C N R'
H
- H2O
H
R C N R'
H
-H+
R C N R'
H
29
Phn ng vi amine bc 2
RCH2
O
+
C
H
NHR2
RCH2
O- H
C N R
+
H R
RCH2
OHR
C N R
H
carbinolamine
+ H+
H
H O R
RCH2 C N R
H
- H2O
RCH2
R
C N R
H
-H+
R
RCH C N R
H
30
Phn ng hnh thnh imine

+
CHO
H2NOH
CH NOH
H2O
oxime
C O
H3C
H2NNH2
C NNH2
H3C
H2O
hydrazone
O
O
H2NNHCNH2
O
NHNCNH2
semicarbazone
H2O
31
V.5. Phn ng vi tc nhn i nhn lu hunh

O
+
R C
H
ONa
:S O
OH
OH
R C SO3Na
H
ONa
R C SO3H
H
OH
R C SO3Na
H
HCl
OH
R C SO3Na
H
NaOH
R-CHO + SO2 + H2O + NaCl
R-CHO
Na2SO3
+ H2O
32
V.6. Phn ng ngng t aldol

Trong mi trng base (NaOH, Ba(OH)2, Na2CO3,
CH3COONa) , aldehyde hay ketone c H c th
phn ng vi nhau ngng t aldol
a. Phn ng gia aldehyde v aldehyde
CH3-CHO + CH3-CHO
to
OH-
CH3-CH=CH-CHO
CH3-CH-CH2-CHO
OH
+ H2O
33
C ch:
Giai on 1 to carbanion
H CH2
O
C
H
O
_
CH2 C
H
+ OH-
+ H2O
Giai on 2 cng hp i nhn

O
H3C C
H
O
_
CH2 C
H
OCH3-CH-CH2-CHO
Giai on 3 proton ha, ti to OHOCH3-CH-CH2-CHO
OH
CH3-CH-CH2-CHO
OH
CH3-CH-CH2-CHO + OH-
+ H2O
OH-
O
CH3-CH=CH2-C
H
34
Sn phm tch nc bn do lin hp gia C=C v C=O
b. Phn ng gia aldehyde v ketone

C ch tng t nh trn, trong aldehyde
ng vai tr tc nhn carbonyl, ketone ng vai
tr tch H to carbanion
CH3-CHO + H3C C CH3
O
-H2O
OH
OH
CH3-CH-CH2-C-CH3
O
CH3-CH=CH-C-CH3
O
35
c. Phn ng gia ketone v ketone

Hiu sut rt thp
O
2 CH3CCH3
OH
OH O
CH3CCH2CCH3
CH3
OH
to
O
CH3C CHCCH3
CH3
+ H2O
36
d. Phn ng gia 2 carbonyl khc nhau (crossed

aldol )
C th thu c 1 hn hp 4 sn phm
Thng ch hiu qu khi 1 carbonyl khng c
H & carbonyl c H c thm t t vo phn
ng 1 sn phm
CHO + CH3CH2CH2CHO
OH-
OH H
CH C CHO
CH2CH3
CH C CHO
CH2CH3
+ H2O
37
Phn ng aldol ha ni phn t

O
O
CH3CCH2CH2CCH3
OH-
O
O
CH3CCH2CH2CH2CH2CCH3
O
O
CH3CCH2CH2CCH2
OH-
O
O
CH3CCH2CH2CH2CHCCH3
O
O
OHCH3CCH2CH2CH2CCH3
HO
H3C
COCH3
HO
H3C
O
O
CH3CCH2CH2CH2CCH2
HO
O
O
OHCH3CCH2CH2CH2CH2CH2CCH3
O
O
CH3CCH2CH2CH2CH2CHCCH3
COCH3
HO
Vng 5, 6 cnh bn hn 3,4,7 cnh
CH3
CH3
38
V.7. Phn ng Cannizzaro

Trong mi trng kim, aldehyde khng c H s
t oxy ha kh to 1 carboxylic acid + 1 alcohol
CHO
COONa
CH2OH
35% NaOH
+
NO2
NO2
p-nitrobenzaldehyde
HCHO
NO2
p-nitrobenzyl alcohol sodium p-nitrobenzoate
50% NaOH
CH3OH
+ HCOONa
39
1 hn hp 2 aldehyde khng c H c kh nng to

4 sn phm. Nu 1 aldehyde l formaldehyde th ~
ch c formate & alcohol ca aldehyde kia
CHO
CH2OH
35% NaOH
HCHO +
+
OCH3
HCOONa
OCH3
anisaldehyde
p-methoxybenzaldehyde
p-methoxybenzyl alcohol
40
C ch:
H-
O
C6H5 C
+ H
C6H5
OC H
OH
O
C6H5 C
+ H
C6H5 C OH
O
C6H5 CH2
O-
OH-
C6H5 C OO
C6H5 CH2OH
41
V.8. Phn ng oxy ha
CH3CH2CH2CH2CH2CHO
CH3CH2CH2CH2CHO
K2Cr2O7
H2SO4
Ag(NH3)2+
NH3
CH3CH2CH2CH2CH2COOH
CH3CH2CH2CH2COOH
Mun bo ton C=C:

RCH CHCHO
Ag(NH3)2+
NH3
RCH CHCOOH
42
Ketone ch b oxy ha bi tc nhn oxy mnh,

ct mch, to carboxylic acid
CH3-CH2-C-CH2-CH3
O
[O]
CH3-CH2-COOH
+ CH3-COOH
c th phn bit aldehyde & ketone

Ring methyl ketone, c phn ng haloform:
R C CH3
O
NaOI
RCOONa + CHI3
nhn bit methyl ketone

Lu : R-CH(OH)-CH3 + NaOI R-CO-CH3 vn
cho phn ng haloform!!!
43
V.9. Phn ng kh
Kh thnh hydrocarbon
NH2NH2
O
C
CH2CH3
OH-, to
CH3
Zn(Hg)
CH2CH3
HCl
44
CH2CH3
COCH3
NH2NH2
OH-, to
OH
Zn(Hg)
OH
CH2CH3
HCl
Cl
45
Kh thnh alcohol
CH3O
CHO
H2 / Pt
CH3O
C2H5OH
CH2OH
O2N
O2N
CHO
O
CH3CCH2C(CH3)3
O
(CH3)2C CHCH2CH2CCH3
NaBH4
CH3OH
NaBH4
C2H5OH
1. LiAlH4 / ether
2. H O+
3
CH2OH
OH
CH3CHCH2C(CH3)3
OH
(CH3)2C CHCH2CH2CHCH3
46
Ha Hc Hu C
B mn K Thut Hu C
Khoa K Thut Ha Hc
in thoi: 8647256 ext. 5681
Chng 12:
CARBOXYLIC ACID
I. Gii thiu chung

L nhng hp cht hu c cha nhm carboxyl
O
C
O-H
trong phn t
Ty theo gc hydrocarbon m phn loi thnh

carboxylic acid no, khng no, thm
V d:
CH3-COOH
CH2=CH-COOH
C6H5-COOH
II. Danh php

II.1. Tn thng thng
HCOOH
CH3COOH
CH3CH2COOH
formic acid
acetic acid
propionic acid
CH3(CH2)2COOH
CH3(CH2)3COOH
butyric acid
valeric acid
CH3(CH2)10COOH
CH3(CH2)16COOH
C6H5COOH
lauric acid
stearic acid
benzoic acid
Acid c nhnh xem nh l dn xut ca acid

mch thng, dng , , , ch v tr nhnh
CH2-CH2-CH-COOH
CH3
Cl
-chloro--methylbutyric acid
Ar-COOH xem nh l dn xut ca benzoic acid

COOH
NO2
NO2
2,4-Dinitrobenzoic acid
C th xem cc acid l dn xut th H ca acetic

acid
4
C6H5-CH2-COOH
phenylacetic acid
II.2. Tn IUPAC
Mch chnh di nht cha nhm COOH (C1)
Gi theo tn hydrocarbon tng ng, i ne
noic acid
CH3
CH-CH2-COOH
CH3-CH2-CH-COOH
CH3
Cl
2-methylbutanoic acid
3-(p-chlorophenyl)butanoic acid
CH3-CH=CH-COOH
2-butenoic acid

III.1. Dng tc nhn Grignard
CH3CH2CH2CH2Cl
Mg
CH3CH2CH2CH2MgCl
ether
CH3
H3C C Cl
CH3
Cl
Mg
ether
Mg
ether
CH3
H3C C MgCl
CH3
MgCl
1. CO2
+
2. H3O
1. CO2
2. H3O+
1. CO2
2. H3O+
CH3CH2CH2CH2COOH
CH3
H3C C COOH
CH3
COOH
6
III.2. Thy phn cc dn xut polyhalogen,

cc dn xut ca acid
Cl
R-CH2-C Cl
Cl
O
R C
O-R'
O
R C
NH2
R CN
O
R C
Cl
+ H2O
+ H2O
+ H2O
+ H2O
+ H2O
to
H+ (OH-)
H+ (OH-)
H+ (OH-)
H+ (OH-)
R-CH2-COOH
R-COOH
+ HCl
+ R'-OH
R-COOH
+ NH3
R-COOH
+ NH3
R-COOH
+ HCl
III.3. Carboxyl ha alkene

Dng trong cng nghip, sn xut acid > 3C
R-CH=CH2 + CO + H2O
Ni(CO)4
o
250 C
200 atm
R CH2
CH2-COOH
III.4. Phng php oxy ha
R-CH2OH + KMnO4
R-COOK
+ MnO2 + KOH
H+
RCOOH
CH3
COOH
KMnO4
H2O, to
NO2
NO2
CH2CH2CH2CH3
KMnO4
H2O, to
COOH
IV. Tnh cht vt l
O
R C
O H
O-H phn cc mnh hn ROH

Kh nng to lin kt H > ca alcohol
To si > cc hp cht khc c cng C
10
V. Tnh cht ha hc
Theo hiu ng:
+C ca O trong OH O-H phn cc mnh H d
tch ra dng H+
tnh acid mnh hn alcohol, phenol
Theo cng thc cng hng:
O
R C
O-H
O
+ R C
O-
OR C
O
O
R C O
carboxylate anion bn cn bng chuyn dch v

11
pha to H+
V.1. Tnh acid

Gc R cha nhm th ht in t tnh acid tng
Gc R cha nhm th y in t tnh acid gim
Tnh acid:
CH3
H3C C COOH
CH3
<
CH3
H3C C COOH
H
H
H
O
H
H3C C COOH
H
<
>
CH3-COOH
<
>
OH
OH
12
Tnh acid ca cc acid:

F3C-COOH (pKa 0.23) >
Cl2CH-COOH (1.25) >
Cl3C-COOH (0.66) >
NO2-CH2-COOH (1.68) >
NC-CH2-COOH (2.47) > F-CH2-COOH (2.57) >

Cl-CH2-COOH (2.87) > Br-CH2-COOH (2.90) >
HCOOH
CH3COOH
(3.75)
(4.76)
HO-CH2-COOH
>
>
CH3CH2COOH
(3.83)
>
(4.87)
>
(CH3)3C-COOH (5.03)
13
* Acid bo khng no:

Tnh acid mnh hn acid no cng mch C (do
C=C c I)
Ni i C=C cng gn COOH th tnh acid cng
mnh
Tuy nhin: nu C=C lin hp vi C=O trong
COOH th tnh acid gim do +C ca C=C!!!
Tnh acid: CH3-CH=CH-CH2-COOH (pKa 4.48) >
CH2=CH-CH2-CH2-COOH (4.68) >
CH3-CH2-CH=CH-COOH (4.83)
14
Ni ba CC cho d v tr lin hp vi C=O th

vn lm tng mnh tnh acid (khc C=C): do I
ca CC mnh & ch c 1 lkt ca CC cho +C
lin hp vi C=O, lkt cn li cho I nhng
khng c +C!!!
Tnh acid: CHC-COOH (pKa 1.84) >

15
CH3-CC-COOH (2.60) > CH2=CH-COOH (4.25)
* Acid c vng thm:

Tnh acid H-COOH (pKa 3.75) > C6H5-COOH (4.18)
do +C ca C6H5- mnh hn I
Tnh acid ty thuc bn cht & v tr nhm th:
o-NO2-C6H5-COOH > p- > m Halogen cho I > +C o-Cl-C6H5-COOH > m- > phttp://hhud.tvu.edu.vn
16
V.2. Phn ng th nhm OH ca acid

a. Phn ng to acid chloride
O
H3C C
O-H
+ PCl3
O
H3C C
O-H
+ PCl5
O
H3C C
+ SOCl2
O-H
O
+ H3PO3
H3C C
Cl
O
+ POCl3 + HCl
H3C C
Cl
O
H3C C
Cl
+ SO2
+ HCl
17
b. Phn ng to amide
O
H3C C
O-H
+ NH3
O
H3C C
O-NH4+
to
O
H3C C
NH2
+ H2O
c. Phn ng tch nc to anhydride
O
+
H3C C
O-H
O
H3C C
O-H
P2O5
O
H3C C
O
H3C C
O
+ H2O
18
d. Phn ng to ester
R C OH
O
+ R'-OH
R C Cl
O
+ R'-OH
O
R C
O
R C
O
+ R'-OH
H2SO4
R C O-R'
O
+ H2O
R C O-R'
O
+ HCl
R C O-R'
O
+ RCOOH
Kh nng phn ng: RCO-Cl (khng cn xc tc)

> (RCO)2O (khng cn xc tc) > RCOOH
Kh nng phn ng: alcohol bc 1> bc 2> bc 3
HCOOH > CH3COOH > RCH2COOH > R2CHCOOH >
19
R3CCOOH
V.3. Phn ng th H (Hell-Vohard-Zelinsky)

H O
H C C
H O-H
H linh ng c th tham gia phn ng th

(xc tc PBr3, PCl3, P)
R O
R' C C
H O-H
O
H3C C
O-H
Cl2
P
+ Br2
R O
R' C C
Br O-H
PBr3
O
Cl2
ClH2C C
P
O-H
O
Cl2HC C
O-H
+ HBr
Cl2
P
O
Cl3C C
O-H
20
CH3CH2COOH
Cl2
P
CH3CHClCOOH
Cl2
P
CH3CCl2COOH
Cl2
P
Cc dn xut ny vn tham gia phn ng th i

nhn v tch loi:
R-CH-COOH
Br
NaOH
R-CH2-CH-COOH
Br
R-CH-COONa
OH
KOH/C2H5OH
t
H+
R-CH-COOH
OH
-hydroxy acid
-
R-CH=CH-COO
H+
R-CH=CH-COOH
21
V.4. Phn ng kh thnh alcohol

Tn dng c ngun acid bo thin nhin
4R-COOH + 3LiAlH4
4H2 + 2LiAlO2 + (R-CH2-O)4AlLi
H2O
4 R-CH2-OH
Hiu sut cao, tuy nhin LiAlH4 mt tin dng

trong PTN
Trong cng nghip, chuyn thnh ester, kh bng
H2/CuO.CuCr2O4 p sut cao
CH3(CH2)10COOCH3
methyl laurate
H2, CuO.CuCr2O4
150 oC
CH3(CH2)10CH2OH +
lauryl alcohol
CH3OH
22
Ha Hc Hu C
B mn K Thut Hu C
Khoa K Thut Ha Hc
in thoi: 8647256 ext. 5681
Chng 13: AMINE
- DIAZONIUM
I. Gii thiu chung

L hp cht hu c m phn t cha 1 hay nhiu
nhm NH2 (hay NHR, -NR2) lin kt vi C
Amine c phn loi da trn s nhm alkyl
hay aryl lin kt vi N
H
R N H
amine bc 1
R'
R N H
amine bc 2
R'
R N R
amine bc 3
II. Danh php

II.1. Tn thng thng
Tn gc hydrocarbon + amine
CH3NH2
CH3NHCH2CH2CH3
methylamine
methylpropylamine
CH3
CH3NCH3
CH3
CH3NCH2CH2CH2CH3
trimethylamine
butyldimethylamine
CH3CH2NHCH2CH3
diethylamine
CH3
CH3CH2NCH2CH2CH3
ethylmethylpropylamine
II.2. Tn IUPAC
Amine khng cha COOH, -CHO, -OH: alkanamine
CH3CH2CH2CH2NH2
butanamine
CH3
CH3CH2NCH2CH2CH3
CH3CH2CHCH2CH2CH3
NHCH2CH3
N-ethyl-3-hexanamine
N-ethyl-N-methyl-1-propanamine
CH3
CH3CH2CHCH2CHCH3
CH3CHCH2CH2NHCH3
Cl
NHCH2CH3
3-chloro-N-methyl-1-butanamine
N-ethyl-5-methyl-3-hexanamine
CH2CH3
CH3 N CH3
CH3CHCH2CHCH3
Br
NHCH2CH2CH3
4-bromo-N,N-dimethyl-2-pentanamine 2-ethyl-N-propylcyclohexanamine
Cha nhiu nhm amine:

CH3CHCH2NH2
NH2
H2NCH2(CH2)4CH2NH2
1,2-propandiamine
1,6-hexandiamine
Trt t u tin: -COOH > -CHO > >C=O > -OH > -NH2
HOCH2CH2NH2
2-aminoethanol
CH3CCH2CH2NH2
O
4-amino-2-butanone
COOH
H2N
4-aminobenzoic acid
5

III.1. Alkyl ha NH3
a. Alkyl ha bng dn xut halogen
NH3
RX
-HX
CH3-CH2-Cl
CH2Cl
R-NH2
RX
-HX
NH3
-HCl
NH3
-HCl
R
RX
R N H
-HX
CH3-CH2-NH2
CH3Cl
R
R N R
C2H5
RX
-HX
R
R N+ R XR
H
N CH3
-HCl
CH2-NH2
CH3Cl
-HCl
CH2-NH-CH3
6
Aryl halide ch phn ng nu nhn thm cha

nhm th ht in t mnh nh -NO2 v tr o-, phoc iu kin khc nghit
Cl
NO2
NHCH3
NO2
CH3-NH2
NO2
NO2
2,4-dinitrochlorobenzene
N-methyl-2,4-dinitroaniline
Cl
NH2
+ NH3
Cu2O
200 oC
b. Alkyl ha bng alcohol

R-OH
+ NH3
Al2O3
400-450 oC
R-NH2 + H2O
III.2. Phn ng chuyn v Hofmann ca amide

R C NH2
O
+ OBr-
R-NH2
+ CO32-
Ar C NH2
O
+ OBr-
Ar-NH2
+ CO32-
III.3. Kh ha hp cht nitro

Kh bng H mi sinh t Fe, Sn/H+
C6H5-NO2 + 3Fe + 6HCl C6H5-NH2 + 3FeCl2 +
2H2O
C6H5-NO2 + 3Sn + 6HCl C6H5-NH2 + 3SnCl2 +
2H2O
Kh bng H2 dng xc tc Pt, Ni, Pd

NO2
NH2
+ 3H2
Pt
+ 2H2O
Kh bng tc nhn kh yu nh Na2S, (NH4)2S

nu c nhiu nhm NO2 th ch kh 1 nhm
NO2
NO2
+ Na2S + H2O
NO2
+ Na2SO3
NH2
10
III.4. Kh ha nitrile
CH2Cl
H2C CH2NH2
CH2CN
NaCN
H2, Ni
140 oC
Cl-CH2-CH2-CH2-CH2-Cl
NaCN
NC-(CH2)4-CN
H2, Ni
NH2-CH2-(CH2)4-CH2-NH2
11
III.5. i t hp cht carbonyl

H
R C O
H
R C NH
+ NH3
H2/Ni
R CH2 NH2
imine
C th thay H2/Ni bng NaBH3CN

CHO
CH2NH2
+ NH3
H2/Ni
12
IV. Tnh cht vt l

Kh nng to lin kt H < alcohol
To si < ca alcohol tng ng
V. Tnh cht ha hc
V.1. Tnh base
R-NH2
HCl
NH2
R-NH3+ClNH3+Cl-
HCl
13
Trong H2O:
R-NH2
+ H2O
R-NH3+ + OH-
Tnh base ca amine trong H2O ph thuc vo

mt in t trn N & kh nng hydrate ha ca
cation alkylammonium
R y in t (+I) lm tng tnh base
R ht in t (-C, -I) lm gim tnh base
amine bo c tnh base > amine thm
14
*** Tuy nhin trong H2O, tnh base:

(CH3)2NH
> CH3NH2 > (CH3)3N > NH3
Gii thch: trong H2O, cation ca amine bc 3 c

kh nng hydrate ha yu (1H)
H
O
H
R
H
H N+ H O
H
R
R
H
R N+ H O
H
R
Lu : trong dung mi khng phn cc nh

benzene hay trong pha kh, amine bc 3 c tnh
15
base mnh nht
Amine thm: bc cng cao, tnh base cng gim

(do +C ca N)
NH2 >
N
H
>
Nhm th trong nhn thm y in t tnh

base tng v ngc li
Tnh base: p-NO2-C6H4-NH2 < m- NO2-C6H4-NH2
< p-Cl-C6H4-NH2 < C6H5-NH2
< p-CH3O-C6H4-NH2
16
V.2. Phn ng alkyl ha
NH3
RX
-HX
CH3-CH2-Cl
CH2Cl
R-NH2
RX
-HX
NH3
-HCl
NH3
-HCl
R
RX
R N H
-HX
CH3-CH2-NH2
CH3Cl
R
R N R
C2H5
RX
-HX
R
R N+ R XR
H
N CH3
-HCl
CH2-NH2
CH3Cl
-HCl
CH2-NH-CH3
17
V.3. Phn ng acyl ha nhm NH2

Phn ng c trng ca amine thm
H
N C CH3 + H2O
O
NH2 + CH3-COOH
NH2 +
NH2
O
H3C C
Cl
O
H3C C
+
O
H3C C
O
H
N C CH3 + HCl
O
H
N C CH3 + CH3-COOH
O
18
C ch:
NH2
O
+ H3C C +
O H
OH
N C OH
H CH3
H ON+ C OH
H CH3
H
N C CH3 + H2O
O
19
c dng bo v nhm NH2 khi nitro ha

aniline
H
N C CH3 + H2O
O
NH2 + CH3-COOH
HNO3 / H2SO4
NO2
NH2
H2O / H+
t
NO2
H
N C CH3
O
20
Gim hot nhm NH2 & nh hng para
H
N C CH3 + H2O
O
NH2 + CH3-COOH
AlCl3 Br2
Br
NH2
H2O / H+
o
Br
H
N C CH3
O
21
V.4. Phn ng vi HNO2

Thc t: NaNO2 + HCl hay H2SO4
a. Phn ng ca amine bc 1
Amine thm bc 1 s cho mui diazonium
NH2
N+
+ NaNO2 + HCl
0-5 oC
N Cl+
NaCl
+ 2H2O
Amine bo bc 1 mui diazonium khng bn

phn hy thnh alcohol
R CH2NH2 + NaNO2 + HCl
0-5 oC
R-OH + N2
H2 O
22
b. Phn ng ca amine bc 2
C amine bo & amine thm u cho Nnitrosoamines
CH3
N N O
NHCH3
+ NaNO2 + HCl
0-5 oC
NaCl + H2O
N-nitroso-N-methylaniline
R NHCH3 + NaNO2 + HCl
0-5 oC
CH3
R N N O
NaCl + H2O
23
c. Phn ng ca amine bc 3
Amine bo bc 3 khng tham gia phn ng
Amine thm bc 3 s cho phn ng th i in t
N(CH3)2
+ NaNO2 + HCl
N(CH3)2
0-5 oC
NaCl + H2O
N O
p-nitroso-N,N-dimethylaniline
24
VI. Mui diazonium

VI.1. iu ch mui diazonium
HN N O
NH2
+
N O
cham
chuyen v
-H+
N N OH
H+
N+ N
+
N N O H
H
H2O
N+ N Cl
Clhttp://hhud.tvu.edu.vn
25
VI.2. Phn ng th nhm diazonium

Phn ng th i nhn n phn t, tch N2
C6H5-N+NCl- + y- C6H5-y + N2 + ClC ch tng t SN1 thng thng, giai on chm to
carbocation C6H5+
a. Phn ng vi H2O
N+ N Cl
OH
+ H2O
H+
o
40-50 C
N2
+ HCl
26
b. Phn ng vi alcohol
C 2 phn ng cnh tranh
Phn ng th
N+ N Cl
OC2H5
+ C2H5-OH
N2
+ HCl
Phn ng kh
Xy ra khi c mt alcohol khan, H3PO2, hay NaBH4
N+ N Cl
+ C2H5-OH
khan
+
CH3CHO +
N2
+ HCl
27
Phn ng kh cng tt khi nhn thm c cha

nhm th ht in t o-, p Alcohol mch cng di, cng u tin phn ng
kh
CH3OH 90% SN1
CH3CH2OH 60% SN1
CH3CH2CH2OH 30% SN1
28
S dng cho cc trng hp khng th tng hp

bng con ng trc tip
CH3
CH3
CH3
NO2
HNO3
H2SO4
r
NO2
Fe/HCl
CH3
CH3
NaNO2 /HCl
Br2/CS2
0-5 oC
Br
NH2
NH2
CH3
CH3
H3PO2
Br
N2+Cl-
Br
29
c. Phn ng vi KI
C6H5-N2+Cl- + KI C6H5-I + N2 + KCl
Mun thu c dn xut ca Br, Cl cn xc tc
CuCl, CuBr (Sandmeyer), c ch gc t do
N+ N Cl
Cl
CuCl
+
N2
30
NH2
CH3
NaNO2 / HCl
N2+ClCH3
H2O
0-5 oC
Cl
15-60 oC
N2+HSO4-
NH2
Cl
NaNO2 / H2SO4
NH2
CH3COOH
30 oC
CuCl
+
N2 HSO4
40-100 oC
N2+Br-
NH2
NaNO2 / HBr
Cl
H2O
0-10 oC
CH3
CuCl
Cl
Br
CuBr
Cl
100 oC
Cl
31
Ar N N BF4-
to
Ar F
N2+BF4-
NH2
1. HNO2
2.HBF4
CH3
NH2
N2
1. NaNO2 / HCl
H2O
CCH2CH3
O
2.HBF4
BF3
F
to
CH3
CH3
N2+BF4-
F
to
CCH2CH3
O
CCH2CH3
O
32
d. Phn ng nitrile ha
N+ N Cl
C N
+
KCN
to
+ KCl + N2
H+, H2O
COOH
33
C th nitrile ha bng CuCN

NO2
NH2
N2+ Cl-
HNO3
Fe
NaNO2
H2SO4
HCl
HCl
CH3
CH3
CN
CuCN
CH3
CH3
COOH
H2O
H+
CH3
CH3
34
VI.2. Phn ng ghp i diazonium

Hp cht diazonium + arene c nhm
tng hot phm mu azo
N2+ Cl-
OH
0 oC
N N
pH = 8-9
OH
p-(phenylazo)phenol
N2+ Cl-
N(CH3)2
+
0 oC
N N
pH = 5-7
N(CH3)2
35
N,N-dimethyl-p-(phenylazo)aniline
Hp cht diazonium cha nhm th ht in

t cng mnh th phn ng ghp i xy ra
cng d
N2+
O2N
N2+
NO2
NO2
>
NO2
N2+
>
NO2
N2+
>
NO2
36

16 BG HHC Ptsnam

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16 BG HHC Ptsnam

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Ha Hc Hu C

TS Phan Thanh Sn Nam

Ti liu tham kho

ng phn: nhng hp cht hu c c

I.2. ng phn do v tr cc lin kt bi, nhm chc

I.3. ng phn c nhm nh chc khc nhau

I.4. ng phn c nhm th khc nhau lin kt vi

methyl propyl ether

2 nguyn t lin kt vi cng 1 nguyn t ca

Thng xut hin cc hp cht c cha:

II.1.2. Danh php ca ng phn hnh hc

Quy tc Kahn-Ingold-Prelog: da theo th

Lu : Khi dng Z-E, ch Z, E khng

II.1.3. ng phn hnh hc ca abC=Nd v

i vi ketoxime: Cng 1 cht, c th gi l

h syn-anti khng chnh xc

II.1.4. ng phn hnh hc ca hp cht cha C=C

* S p hnh hc ca h lin hp C=C

II.1.5. ng phn hnh hc ca vng no 3, 4

II.1.6. Cch xc nh v so snh cc ng phn

cis (1.89D) > trans (0D)

c. Nhit nng chy

II.2. ng phn cu dng (ng phn quay)

II.2.1. Cch biu din

Lin kt C-C: ng cho tri qua phi, xa

b. Cng thc Newman

II.2.2. Cu dng ca cc hp cht mch h

Xen k: khong cch gia cc H xa nhau nng

2 dng c nng lng thp: anti (i) & syn (lch)

II.2.3. Cu dng ca hp cht vng no

4 h thng dng xen k: C1-C2, C3-C4, C4C5, C6-C1

b.S b tr cc lin kt C-H

Cn bng (khng th tch):

Dn xut 1 ln th: e-methyl cyclohexane bn hn

II.3. ng phn quang hc

II.3.2. cht hot ng quang hc

II.3.3. iu kin xut hin ng phn quang hc

V d phn t lactic acid 2 ng phn quang hc

Cc nhm th khc nhau v ng phn cu to

ng phn quang hc khng cha C*

II.3.4. Cng thc biu din ng phn quang hc

khng thun li cho phn t phc tp

b. Cng thc chiu Fisher (2 chiu)

C th c nhiu cng thc Fisher khc nhau

II.3.5. Danh php v cch xc nh cu

a. H danh php D-L: cu hnh tng i

Quy c: cc ng phn cha d t (O, N, S) lin kt

Rt kh xc nh khi phn t c nhiu C*!

b. H danh php R-S:

-CCH > -C(CH3)3

Lu : cch cng s th t ch p dng

-CH2OH > -CH=CH2

Cch xc nh cu hnh: C*abcd,

+Theo cng thc Fisher:

i H & CH3 (1 cp), OH & COOH (1 cp)

Lu : R & S ch l i lng l thuyt!!! thc t ch o c d(+)

II.3.6. Cc hp cht cha nhiu C*

2 C* khng tng ng v CHO CH2OH

b. Hp cht c cha C* tng ng

(2R, 3R)-tactric acid (2S, 3S)-tactric acid

Trong ng phn meso: quay cc ca 2 C*

V d: Xc nh cu hnh tuyt i ca 1 s cht

Chng 2: CC LOI HiU NG