HA HC HU C

VT 2011

CHNG I

NG PHN CA CC
HP CHT HU C

 ng phn hp cht hu c c cng thc phn

t ging nhau, cng thc cu to khc nhau;

Phn loi:
I. ng phn cu to (phng)
II. ng phn lp th: ng phn cu dng, ng
phn cu hnh (ng phn hnh hc, ng phn
quang hc)

Phn loi ng phn

ong phn
khng gian
Cu tao
hnh hoc

Cu hnh
quang hoc

Cu dang

I. NG PHN CU TO
Do c s sp xp khc nhau ca cc nguyn t trong
mch C.
1. ng phn mch C

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

3. ng phn c nhm nh chc khc nhau

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

nhm nh chc

II. NG PHN LP TH
1. ng phn hnh hc
a/ iu kin xut hin
Xut hin khi phn t c 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 nhng hp cht c cha
C=C, C=N, N=N, h lin hp, vng phng 3 hay
4 cnh.

R1R2C=CR3R4
R1 R2 v R3 R4

b/ Danh php ca ng phn hnh hc

b.1. H cis trans: axC=Cay
a nm cng pha vi mt phng cis, khc
pha trans

b.2. H Z-E: axC=Cby (a > x v b > y)

a, b cng pha so vi mt phng Z (zusammen),
khc pha E (entgegen).

Xt tnh hn cp ca nhm th
Da theo th t u tin sau trong bng HTTH ca
nhm th (in tch ht nhn ln)
Br > Cl > S > P > F > O > N > C > H
35 17 16 15 9 8 7 6 1

 Nu cc nguyn t lin kt trc tip ging nhau th xt

lp th 2:
CH(CH3)2 >
CH2CH3 >
CH3
1H+2C=13
2H+1C=8
3H=3
(RO)3C
>
(RO)2CH > ROCH2
3O=24
2O+1H=17
1O+2H=10
CH3 2HC
H 3C

C C

CH3

(E)

CH2CH3

* Nu trong nhm c nguyn t m in hn th s u tin

hn (vd: CH2OH > (CH3)3C)

 Cc nguyn t cha lin kt bi c tnh bi ln:

HC=O > CH2OH

17

10

C6H5 > (CH3)2CH C N > CH2NH2

18

13

21

H3 C 3 C

C 6H 5

C C
N CH3 2
H E

* Ch : khi dng danh php Z-E, Z v E khng

phi lun trng vi danh php cis v trans.

 H c nhiu ni i ring r:
H

C C

C C
H 3C

H2C
C C
H
H

H3 C

H2 C
C C
H
H

CH3

CH3

H
C C
H

H2C
C C
H3 C
H

trans-trans (E-E)

cis-trans (Z-E)

cis-cis (Z-Z)

CH3

H lin hp a(HC=CH)nx:
R

H
C C
R'

C C
H

cis-cis (Z-Z)

R'
C C
H

C C
H

cis-trans (Z-E)

R'
C C
H

C C
R

H
C C
R'

C C
R

trans-trans (E-E) trans-cis (E-Z)

 i vi hp cht axC=Ny
a > x, a v y cng pha so vi mt phng ni i Z
Khc pha E
i vi aldoxime: nu nhm OH v H nm
khc pha => anti. Cng => syn

 i vi ketoxime:
Cng 1 cht c th gi l syn- hay anti- v phi ch
r nhm no syn hay anti vi nhm OH.

 i vi hp cht azo xN=Ny

 i vi cc hp cht vng no:

Cc nhm th tng ng cng pha vi mt
phng vng cis, khc pha trans

c/ Cch xc nh v so snh cc ng phn hnh hc

c.1. Xc nh khong cch gia cc nhm th
Khong cch gia 2 nhm th tng ng trong
ng phn cis < trans

c.2. Moment lng cc

2 nhm th ging nhau aHC=Cha

2 nhm th khc nhau aHC=CHb (a b):

2 nhm th cng ht hay cng y in t:
2 nhm th c tnh cht in t ngc nhau:

c.3. Nhit nng chy

ng phn trans:
do tnh i
xng mng li tinh th cht ch.
Lu : mi lin h gia nhit si v ng
phn hnh hc khng cht ch.

II. ng phn khng

gian
D .Cch
biu din cu trc khng gian ca phn t
1

a. Cng thc phi cnh:

Qui c biu din:
Lin kt nm trong mt phng c biu din bng
ng lin tc
Lin kt hng ra pha trc biu din bng ng
m
Lin kt pha sau biu din bng
H ng t on
a
C

C
b

d
c

H
H

Metan

 Theo cch khc: biu din phn t c 2 nguyn t C

th lin kt gia 2 C c biu din bng ng thng t
tri sang phi v xa dn ngi quan st, cc nguyn t
v nhm nguyn t lin kt vi c cng c biu din
trong khng gian bng on thng xut pht t C1 v
C2
V d Cabc-Cabc

c'
a'

b'

a
b
c

xen ke

b'

a'

b
c

che khuat

c'

b. Cng thc chiu Niumen

Qui c: Nhn phn t dc theo 1 lin kt no ,
(Newman)

thng l lin kt C-C

Nguyn t C u lin kt xa mt (b che
khut C2) c th hin bng hnh trn v
nguyn t gn mt quan st (C1) c biu
din bng tm ca hnh trn.
Cc lin kt t C1 c nhn thy ton b v
xut pht t tm hnh trn (C1).
Cc lin kt t C2 ch nhn thy c phn l ra
t chu vi ca hnh trn C2.
H
H

H
H

Newman

c. Cng thc Fischer

Qui c:
Cu trc KG ca phn t c biu din trn mt
phng bng cch chiu ln mt phng giy
t cng thc phi cnh ca phn t sao cho
nguyn t C c chn nm trong mt phng
trang giy, hai nhm th gn mt ngi quan st
khi chiu ln mt phng th nm bn phi v
bn tri nguyn t C, 2 nhm nguyn t cn li xa
mt ngi quan st khi chiu ln nm trn trc
dc ca cng thc Fis (Fischer)
CHO
C
H

CHO

OH
CH2OH

CHO

OH

CH2OH

Cng thc phi cnh

HO

CH2OH

Cng thc Fis

 Nu phn t c nhiu nguyn

t C th trc dc l trc ca
nguyn t C
Nu hai nguyn t C u
mch c s oxi ho nh nhau
th pha trn l nhm th c
H
s th t nh hn trong tn gi
Lu
Thng thng ngi ta biu
din cng thc Fischer ch
cc nguyn t C bt i, cn
khi khng c C bt i th ngi
ta thng biu din dng cng
thc rt gn cng thc t
phc tp

CH3-CHCl-CH2-CH3
CH3

CH3
Cl

C2 H 5

Cl

H
C2H5

Cacbon bt i xng:
Phn t Cabcd vi a b c d khng c
tnh i xng trong khng gian

Phn t lactic acid

 i ch bt k 2 nhm th no nguyn t carbon

bt i cng lm quay cu hnh v s sinh ra dng
ng phn khc.
CHO (2)
H

OH(1)
(3) CH2OH
R

CHO
HO

OH
H

CH2OH
S

HOC

H
CH2OH
R

Nu dch chuyn ng thi c 3 nhm th theo chiu

kim ng h hay theo chiu ngc li th cng thc
Fisher vn gi nguyn ngha.
Khng c quay cng thc Fisher trn mt phng
mt gc 900 hay 2700 v s lm quay cu hnh nhng
c th quay mt gc 1800.

2. ng phn cu dng (ng phn quay)

ng phn cu dng l cc dng khc nhau trong
khng gian ca cng 1 cu hnh
Khng th tch thnh nhng ng phn ring l
L nhng cu trc khng gian sinh ra do 1 nhm
th quay xung quanh trc C C so vi 1 nhm
nguyn t khc
Ch tn ti nhng cu dng tng i bn
Thng cn nng lng 3-4 kcal/mol.

a/ Cch biu din

a.1. Cng thc phi cnh (khng gian 3 chiu)

Lin kt C C: ng cho i qua phi, xa dn ngi

quan st

a.2. Cng thc Newman

Quan st dc theo trc C C 2 nguyn t
dng che khut hay xen k
Biu din bng vng trn
Chiu cc nhm th ln mt phng vung gc vi
trc C C.

Che khut

Xen k

b/ Cu dng ca cc hp cht mch h

b.1. Etan
Quay 1 nhm CH3 v 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
Xen k: khong cch gia cc H xa nhau nng
lng thp nht bn nht.

Gin m t mc nng lng khc nhau ty

thuc vo tng loi cu dng ca etan

b.2. n Butan
Quay cc nhm th quanh trc C2 C3:
2 dng c nng lng cao: che khut ton phn
v che khut 1 phn

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

syn).

Gin m t mc nng lng khc nhau ty thuc

vo tng loi cu dng ca n-butan

b.3. Cu dng ca hp cht vng no

Vng no 3, 4 cnh khng c ng phn cu dng
b.3.1. Cyclohexane
C 2 dng c trng: gh (bn) v thuyn.
Gh
Xem nh 1 t hp ca 6 h thng n-butan
Tt c 6 h thng u dng xen k.

 Thuyn
4 h thng dng xen k: C1-C2, C3-C4, C4-C5 v
C6-C1
2 h thng dng che khut hon ton: C2-C3, C5-C6
Khong cch H C1 v C4 rt nh lc y km
bn hn dng gh.

2. ng phn quang hc
a/ nh sng phn cc
nh sng phn cc: ch dao ng trong 1 mt
phng nht nh mt phng phn cc
ASPC i qua 1 s hp cht hu c lm mt phng
phn cc quay 1 gc cht hot ng quang hc
ASTN i qua lng knh Nicol s tr thnh ASPC.

b/ iu kin xut hin ng phn quang hc

C yu t khng trng vt nh: Phn t c vt v
nh trong gng khng chng kht
2 ng phn ny quay mt phng phn cc nhng
gc nh nhau nhng ngc chiu 1 i i
quang:
ng phn quay mt phng sang tri ng
phn quay tri, k hiu (-)
Ngc li l ng phn quay phi, k hiu (+)
2 ng phn ny c tnh cht l ha ging nhau.

 ng phn quang hc thng xut hin khi c

C bt i xng C*
Cacbon bt i xng:
Phn t Cabcd vi a b c d khng c
tnh i xng trong khng gian

Phn t lactic acid

AS
phn
cc

Cl

AS
phn
cc

Br

Br
H

H
F

Phn t ( ng
phn quay tri).

Cl

Phn t( ng
Gng phng

phn quay phi)

COOH

H3C

C
H

HO

CH3
OH

Axit L (-)-lactic
tonc

26

tos

122/14 mmHg

COOH

+3.8o

Axit D (+)-lactic
26
122/14 mmHg
-3.8o

Axit lactic c 2 i quang l ng phn quay phi

v ng phn quay tri.
Hn hp 50% ng phn quay phi v 50% ng
phn quay tri gi l hn hp raxemic

d/ Cng thc biu din ng phn quang hc

d.1. Cng thc t din (3 chiu)

Khng thun li cho phn t phc tp

d.2. 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

C th c nhiu cng thc Fisher khc nhau

d.3. Cng thc phi cnh v Newman

 Hp cht c nhiu trung tm bt i

Xt phn t: aldotetroz, nu ta gi gc quay ca
cacbon bt i th nht l (a), gc quay cacbon th hai
l (b) th gc quay ca phn t s bng tng i s ca
cc gc quay cc ca tng nguyn t cacbon bt i.

CHO

C HO

CHO

HO

OH

HO

OH

HO

CH2OH

CH2OH

Hai o
i quang erytro

CHO

OH
H
CH2OH

HO

OH

C H2OH

Hai o
i quang treo

C 4 cu hnh, 4 ng phn quang hc

o
ng pha
n quang hoc aldotetrazo

 Xt Acid tartric (HOOC CHOHCHOH_

COOH), c hai C* nhng ch c 3 ng phn
quang hc. Trong c mt ng phn
meso to thnh do mt phng i xng
trong phn t,
COOH

OH

OH
COOH

meso
Enantiomer

2 hot ng quang hc gi enantiomer

v 1 khng hot ng quang hc gi meso

e/ 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*
Cu dng cc dng khc nhau trong khng gian
ca cng 1 cu hnh

e.1. H danh php D-L: cu hnh tng i

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

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

Danh php ng phn quang

hc
a. Danh php D,L: gi theo tn ca cht
chun l D v L glyxerandehit

CHO

CHO
H

OH
CH2OH

D- glyxerandehit

HO

H
CH2OH

L- glyxerandehit

Lu : khi gi tn theo D,L th cng thc dng Fischer

ca cht nghin cu phi dng chun

e.2. 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
hn cp ca nhm th
-OH > -CHO > -CH2OH

 Cch xc nh cu hnh: C*abcd

a>b>c>d
Theo cng thc t din/phi cnh (khng gian):
t d xa ngi quan st
i t abc: ngc chiu kim ng h ng
phn S
Cng chiu kim ng h ng phn R

 Theo cng thc Fisher

t d nm di hay trn trong cng thc Fisher, sau
xt th t cc nhm cn li
i t abc: ngc chiu kim ng h ng phn S
Cng chiu kim ng h ng phn R
Quy c:
i v tr 2 cp nhm th (quay CT Fisher 180o) cu
hnh khng thay i
Thay i v tr 1 cp nhm th (quay CT Fisher 90o hay
270o) cu hnh s thay i

 V d lactic acid:

i H & CH3 (cp 1),

OH & COOH (cp 2):
i 1 cp H & CH3:
* Lu : R & S ch l i lng
l thuyt, thc t ch o c
(+) & (-), R & S khng lin h vi (+) & (-)

 Quy tc ny da trn c s tng s u

tin ca nhm th nh vi trung tm
bt i xng theo th t u tin t ln
nht (1) cho n nhm nh nht (4)
vi iu kin nhm nh nht phi xa
vj tr ngi quan st v sau mt phng
Nu nhn t C bt i n nhm c
hn cp (u tin) nh nht m t
123 theo chiu kim ng h l R ,
ngc chiu l S

c tn cu hnh R, S

Kinh nghim: Nu c theo R,S t cng thc Fischer c

nhm th c hn cp nh nht nm trc ngang, t
123 theo kim ng h l S , ngc kim ng h l R

f/ Cc hp cht cha nhiu C*

f.1. Hp cht cha cc C* khng tng ng

S ng phn quang hc: N=2n, n s C* khng tng ng

f.2. Hp cht cha C* tng ng

Tactric acid

 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 - chn)

g/ Hn hp racemic

L hn hp 50% (+) v 50% (-) hn hp

khng c tnh cht quang hc v quay cc t
b tr nhau

Tm nhng trung tm bt i
xng ca cc phn t sau?
a.

b.
CH3
CH2CH2CHCH2OH

d.
H

Cl
Br

Cl
Br

Vit cc ng phn quang hc ca cc

hp cht : a.HO-CH2CHOH-CHOH-CHO; b.
HOOC-CHOH-CHOH-COOH, ch r nhng
cht i quang, ng phn meso ?

a
C 4 ng phn quang hc :Cp cht I &II;
III&IV l cc cp i quang
CHO
H

OH

OH

H
HO

CHO

CHO

CHO
OH

OH

OH

OH

OH

OH

OH

OH

OH

II

III

IV

C 4 ng phn quang hc :Cp cht I &II; III&IV l cc cp i quang

CHO
H

OH

OH HO

CHO

CHO

CHO
OH

OH

OH

OH

OH

OH

OH

OH

OH

II

III

IV

Xc nh cu hnh R/S ca mt s
cht?
CHO

COOH

C
H

OH
CH3CH2

Br
H2N

COOH

COOH

OH
CH3

OH

OH

OH
CH3

Qui tc Can, Ingon v Preloc cho h danh

php R-S

VD
xc nh cu hnh tuyt i ca mt s cht:

CHO
H
NH2
CH3

COOH
Cl OH

Br

H
CH3

COOH
H
OH

COOH

OH OH

OH

COOH

COOH