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 1
 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, McGraw-
Hill, 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

http://hhud.tvu.edu.vn 2
 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 3
 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),
4
ng phn quang hc
http://hhud.tvu.edu.vn
 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
http://hhud.tvu.edu.vn 5
I.2. ng phn do v tr cc lin kt bi, nhm chc

butene-1 butene-2
C4H8

OH OH OH
OH

OH
OH
1,2- 1,3- 1,4-

dihydroxy benzene

http://hhud.tvu.edu.vn 6
I.3. ng phn c nhm nh chc khc nhau

dimethyl ketone
C3H6O propan-2-one
O acetone

propionaldehyde
CHO propanal
propionic aldehyde

C3H6O2 COOH Propionic acid

O
methyl acetate
O 7
http://hhud.tvu.edu.vn
I.4. ng phn c nhm th khc nhau lin kt vi
nhm nh chc

C4H10O diethyl ether

O

O
methyl propyl ether

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 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

http://hhud.tvu.edu.vn 9
 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 Cl

H H

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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 CH3 H3C H

H H H CH3

cis-butene-2 http://hhud.tvu.edu.vn
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)

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 35 17
Br Cl
(E)-1-Bromo-2-chloro-2-fluoro-1-iodoethene
I F
53 9

Br F
(Z)-1-Bromo-2-chloro-2-fluoro-1-iodoethene
I Cl

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

phi lun trng vi cis, trans

Cl Cl Cl Cl

F H H Br
Z-, cis- E-, cis-

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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 H3C
C N C N
H H OH

anti-acetaldoxime syn-acetaldoxime
(Z)-acetaldoxime http://hhud.tvu.edu.vn (E)-acetaldoxime 14
 i vi ketoxime: Cng 1 cht, c th gi l
syn- hay anti- !!!
H3C H3C

OH
C N C N
OH

anti-phenyl-p-tolylketoxime syn-phenyl-p-tolylketoxime
syn-p-tolyl-phenylketoxime anti-p-tolyl-phenylketoxime

h syn-anti khng chnh xc

chuyn sang h Z-E
http://hhud.tvu.edu.vn 15
 b. aN=Nb

C6H5
N N N N
C6H5 C6H5 C6H5

anti-azobenzene syn-azobenzene

http://hhud.tvu.edu.vn 16
II.1.4. ng phn hnh hc ca hp cht cha C=C
lin hp
CH
6 5 H
a(HC=CH)nb
H
trans,trans-1,4-diphenyl-1,3-butadiene
H
H C6H5

H H
C6H5
cis,cis-1,4-diphenyl-1,3-butadiene
C6H5
H H

H C6H5
C6H5
cis,trans-1,4-diphenyl-1,3-butadiene
H
H H

* 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
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p = (n + 1)/2 nu n l
 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 COOH HOOC H

H H H COOH

cis-cyclopropane-1,2-dicarboxylic acid trans-cyclopropane-1,2-dicarboxylic acid

http://hhud.tvu.edu.vn 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 H H Cl

Cl Cl Cl H
4.7
3.7

http://hhud.tvu.edu.vn 19
 b. Moment lng cc
2 nhm th ging nhau aHC=CHa

H H 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
http://hhud.tvu.edu.vn 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
http://hhud.tvu.edu.vn 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!!!
http://hhud.tvu.edu.vn 22
 II.2.1. Cch biu din
a. Cng thc phi cnh (khng gian 3 chiu)

a a
b b
a c c c a
b b b
c a c

che khut xen k

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

dn ngi quan st

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 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 a
b c

c b c b
c b a

che khut xen k

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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

http://hhud.tvu.edu.vn 25
Xen k: khong cch gia cc H xa nhau nng
lng thp nht bn nht

http://hhud.tvu.edu.vn 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 CH3
CH3 H

H H H H
H H H CH3

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

CH3 CH3
H H H CH3
H H H H
27
CH3 http://hhud.tvu.edu.vnH
http://hhud.tvu.edu.vn 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)

http://hhud.tvu.edu.vn 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 6 1 3
4 3 2.49 4 2
2
2.5 http://hhud.tvu.edu.vn 6 30
 1.84
* Thuyn:
4 1 4 1
5 2.49
6
5 3
3 2

2.27

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

C5, C6-C1
2 h thng dng che khut hon ton: C2-
C3, 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)
http://hhud.tvu.edu.vn 31
http://hhud.tvu.edu.vn 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
ea 109o28'
a
e
e e
e
a
ae a
http://hhud.tvu.edu.vn 33
 Cn bng (khng th tch):
a

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
http://hhud.tvu.edu.vn
 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

http://hhud.tvu.edu.vn 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
36
Gc quay c xc nh bng phn cc k
http://hhud.tvu.edu.vn
 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

http://hhud.tvu.edu.vn 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*)

* C bt i xng:
Cabcd a b c d khng c tnh i xng
trong khng gian 38
http://hhud.tvu.edu.vn
V d phn t lactic acid 2 ng phn quang hc

COOH COOH

H C* C* H
OH HO
CH3 CH3
(+) (-)

http://hhud.tvu.edu.vn 39
http://hhud.tvu.edu.vn 40
 Cc nhm th khc nhau v ng phn cu to
ng phn quang hc

H
n-C3H7 C* COOH

iso-C3H7

Cc nhm th khc v ng v
ng phn quang hc

CH3
D C* H
C6H5
http://hhud.tvu.edu.vn 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

http://hhud.tvu.edu.vn 42
Cl Cl
II.3.4. Cng thc biu din ng phn quang hc

a. Cng thc t din (3 chiu)

COOH

CH3
H OH

khng thun li cho phn t phc tp

http://hhud.tvu.edu.vn 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

H OH
CH3
C th c nhiu cng thc Fisher khc nhau

c. Cng thc phi cnh & Newman

http://hhud.tvu.edu.vn 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!!!

http://hhud.tvu.edu.vn 45
 a. H danh php D-L: cu hnh tng i
Phi so snh vi 1 cht chun
CHO CHO
H OH HO H
CH2OH CH2OH
D-glyceraldehyde 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 H
CH3 CH3
D-lactic acid L-lactic acid 46
http://hhud.tvu.edu.vn

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

 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

http://hhud.tvu.edu.vn 47
 H O
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 :
A C
C A C A C A C
C A HC CH
A C C
A C C

-CCH > -C(CH3)3

48
-CH=CH2http://hhud.tvu.edu.vn
> -CH(CH3)2
 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

http://hhud.tvu.edu.vn 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

http://hhud.tvu.edu.vn 50
http://hhud.tvu.edu.vn 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
http://hhud.tvu.edu.vn 52
V d lactic acid: COOH
H OH
CH3
a
OH

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

H
d
b (R)
COOH

Nu ch i 1 cp H & CH3 c CH3 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 (+) & (-)!!!
http://hhud.tvu.edu.vn 53
 II.3.6. Cc hp cht cha nhiu C*
a. Hp cht cha cc C* khng tng ng

CHO
H C* OH
2 C* khng tng ng v CHO CH2OH
H C* OH
4 ng phn (2 i i quang):
CH2OH

CHO CHO CHO CHO

H C* OH HO C* H H C* OH HO C* H
H C* OH HO C* H HO C* H H C* OH
CH2OH CH2OH CH2OH CH2OH
(2R,3R)- (2S,3S)- (2R,3S)- (2S,3R)-
erythro-aldotetrose threo-aldotetrose

http://hhud.tvu.edu.vn 54
S p quang hc: N = 2n n: s C*
 b. Hp cht c cha C* tng ng
Tactric acid:
H H
HOOC C* C* COOH 2 C* tng ng 3 ng phn
OH OH

COOH COOH COOH

H C* OH HO C* H HO C* H
HO C* H H C* OH HO C* H
COOH COOH COOH
(2R, 3R)-tactric acid (2S, 3S)-tactric acid meso-tactric acid

http://hhud.tvu.edu.vn 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)

http://hhud.tvu.edu.vn 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

http://hhud.tvu.edu.vn 57
V d: Xc nh cu hnh tuyt i ca 1 s cht

CH2OH CHO COOH COOH

H OH OH CH3 H2N H H2N H
CH3 CH2OH CH3 CH2OH
(R)- (S)- (S)- (S)-

CH2OH CH2OH
COOH
H OH H OH
H CH3
OH H H OH
C6H5
CH2OH CH2OH
(R)-
(2S, 3S)- (2S, 3R)-

http://hhud.tvu.edu.vn 58