NG PHN LP TH

TS. BI TH BU HU KHOA KHOA HC T NHIN

NG PHN

NG PHN PHNG
ng phn khng i quang ng phn Cis-trans

NG PHN LP TH
ng phn i quang

ng phn Cu trng

NG PHN CIS-TRANS
L loi ng phn xut hin do s gii hn quay ca lin kt gy ra bi: Mt lin kt i Cu trc mch vng

Quy tc CahnIngoldPrelog Bc nguyn t cng ln th t u tin cng ln: I > Br > Cl > H Nguyn t u tin ging nhau: Xt tip nguyn t k tip cho n khi thy c s khc bit: CH2OH > CH(CH3)2 > CH3 Lin kt i: bng hai lin kt n, COOH > CHO > CH2OH

Th t u tin ?

DANH PHP EZ

CU HNH E HAY Z ?

HP CHT MCH VNG

HP CHT NH VNG

NG PHN

NG PHN PHNG

NG PHN LP TH

NG PHN CIS-TRANS

NG PHN CHA TM CARBON BT I XNG

CHIRALITY: TNH CHT BN TAY Dng bn tay tri khc vi dng bn tay phi Khng th xp tay tri trng kht ln tay phi Vt c tnh cht ca bn tay c gi l chiral Vt chiral c nh khng trng kht vi chnh n Ngc li gi l achiral

PHN T BT I XNG Carbon bt i xng (Asymmetric Carbon): Carbon mang 4 nhm th khc nhau Mt phn t c mt tm carbon bt i xng l chiral

PHN T BT I XNG

Phn t c tm carbon bt i xng?

C bao nhiu tm C* trong phn t ?

C bao nhiu tm C* trong phn t ?

Tm C* trong phn t ?

PHN T BT I XNG
Phn t c gi l bt i xng (chiral) khi khng th xp trng kht ln nh ca n Ngc li c gi l i xng (achiral)

Hai cht khc nhau: Enantiomers

Hai cht trng nhau

TNH I XNG TRONG PHN T ACHIRAL

Phn t i xng (achiral) khi c cha mt phng i xng hoc tm i xng Mt phng i xng: mt phng chia phn t lm 2 phn nh nhau, phn ny l nh ca phn kia qua gng.

Chlorodifluoromethane

E-1,2-Dichloroethene

NG PHN TRONG TRNG HP PHN T C MT TM C*

Hai ng phn khc nhau ca 2-bromobutane l nh ca nhau qua gng v khng th xp trng kht ln nhau c gi l ng phn i quang (Enantiomers)

NG PHN I QUANG

Enantiomers

Hai ng phn i quang ch khc nhau v hot tnh quang hc

TNH CHT CA PHN T BT I XNG: HOT TNH QUANG HC

Hot tnh quang hc: Kh nng ca mt phn t bt i xng (Chiral) lm quay mt phng ca nh sng phn cc. Phn cc k: Thit b o quay cc ca phn t

TNH CHT CA PHN T BT I XNG: HOT TNH QUANG HC

Cht hot ng quang hc: lm quay mt phng ca nh sng phn cc Cht hu trin (+): lm quay mt phng nh sng phn cc v pha tay phi Cht t trin (-): lm quay mt phng nh sng phn cc v pha tay tri

TNH CHT CA PHN T BT I XNG: HOT TNH QUANG HC

quay cc ring, []: c: Nng dd (g/100mL) l: Chiu di ng nghim : Gi tr quay cc o c

TNH CHT CA PHN T BT I XNG: HOT TNH QUANG HC

Hn hp tiu trin: cha 2 dng ng phn quang hc vi lng bng nhau Khi mt trong 2 dng ng phn hin din nhiu hn: % tinh khit quang hc (ee) ee = % tinh khit quang hc = % ca mt dng ng phn - % ca dng cn li V d: Mt mu c ee = 50% gm 70% mt dng ng phn + 20% dng i quang.

V CU TRC NG PHN I QUANG: CNG THC PHI CNH

Hai ng phn i quang ca 2-bromobutane

DANH PHP R, S
HOOC

H C

H C COOH

OH CH3

HO H3C

(R)()-Lactic acid []D= 3.82o

(S)-(+)-Lactic acid []D= + 3.82o

OH C COOH CH3 COOH C OH CH3

CH3 3 2 HOOC H C OH
1 1

HO

H C CH3 3

COOH

LU !!!
Khng c mi lin h gia cu hnh R hay S vi c
tnh hu trin hay t trin Cu hnh R hay S c xc nh t cu trc ca ha cht c tnh hu trin hay t trin c xc nh bng phn cc k

(R)-(+)-4-Methylcyclohexene

Cu trc ca (+)-2-butanol hay (-)-2-butanol ?

ng phn i quang hay ca cng mt cht?

v

V CU TRC NG PHN I QUANG: CNG THC FISCHER

Tng ng vi

(R)-Bromochlorofluoromethane

W Y

C Z

X Z Z Y C X Z Z C Y COOH X

PHP CHIU FISCHER

HOOC

H C OH CH3

COOH

C CH3

OH

H CH3

OH

(R)()-Lactic acid H C

Fischer projection (R)()-Lactic acid COOH COOH

HO H3C

COOH

HO

C CH3

HO CH3

(S)-(+)-Lactic acid

Fischer projection
(S)(+)-Lactic acid

180 COOH H C OH COOH CH3 CH3 H COOH

H CH3

OH

HO

HO

CH3 (R)()-Lactic acid 90 COOH H Hold steady Gi c nh COOH H C CH3 (R)()-Lactic acid OH C CH3 OH

COOH

H H3C OH COOH

H3C OH

COOH

(S)(+)-Lactic acid

COOH

COOH

COOH

HO

C H

CH3

H3C

C OH

C CH3

OH

2 1

COOH H
3 4

COOH

H
4

H2N CH3

H2N
3

H CH3

HOOC
3

NH2 CH3

Alanine
4

Hold steady Gi c nh H
2

HOOC
3

NH2 CH3

=
CHO

HOOC

H C CH3
3

NH2

(S)-Alanine

CHO H OH HO

HO H

2 3

C C

H (2S,3R)-2,3,4-Trihydroxybutanal OH

4 CH OH 2

CH2OH

Cu hnh R hay S ?

Cu hnh R hay S ?

Cu hnh R hay S ?

Cu hnh R hay S ?

Cp ng phn i quang?

Mirror CHO
R

CHO HO H CS CH2OH CHO HO H CH2OH CHO HO H CH2OH L-()-Glyceraldehyde

[]D = 13.5

HOH2C

OH H

DANH PHP D, L

CHO H OH CH2OH CHO H OH CH2OH D-(+)-Glyceraldehyde

[]D = + 13.5

CHO (CHOH) n H C

CHO (CHOH) n

OH

HO

CH2OH D series

CH2OH L series CHO CH2OH O HO H H H OH

CHO H CHO H H H OH OH

H HO H H

OH H OH

OH
CH2OH

OH
CH2OH D-ribose

OH
CH2OH

OH
CH2OH D-fructose

D-glyceraldehyde

D-glocose

CHO HO CHO H H OH H CH2OH L-Xylose O HO

CH2OH

H H CH2OH

HO

H CH2OH

HO

HO

L-glyceraldehyde CO2H H2N D-Valine H

L-Ribulose CO2H H2N H

L-Valine

NG PHN TRONG TRNG HP PHN T C NHIU TM C*

S ng phn lp th = 2n

2S,3R

2R,3S

2S,3S

2R,3R

ng phn lp th ca 2-chloro-3-hexanol ?
2

CH3

CH Cl

CH OH

CH2

CH2

CH3

ng phn lp th ca 2-chloro-3-hexanol
HO
3

C3H7 H

C3H7
3

OH

C3H7
3

OH

HO
3

C3H7 H

H3 C
2

H Cl
2

H H3 C
2

Cl H H

CH3

Cl H H

Cl
2

CH3

H H C3H7 Cl C3H7 Cl
R R

H H OH Cl HO Cl
S R

HO H3 C

S S

OH CH3

C3H7 H3C

R S

C3H7 CH3

H (1)

H (2)

H (3)

H (4)

Tng s ng phn lp th?

HP CHT MESO

CH3 H Br Br H CH3
CH3 H H Br Br CH3

CH3 Br H H Br CH3

CH3

H H

Br Br CH3

HP CHT MESO

Hp cht meso c mt tm C* hoc nhiu hn v mt mt phng i xng Hp cht meso l mt achiral Hp cht meso khng hot ng quang hc

HP CHT MESO

HP CHT MESO

TNH CHT VT L

PHN NG CA HP CHT CHA TM C*

Nu phn ng khng lin quan n s t bt k lin kt xung quanh tm C*: S phn b tng i ca cc nhm th xung quanh tm C* l khng i.

Lu : Cu hnh tng i ca tc cht v sn phm khng i khng c ngha l cu hnh tuyt i ca chng s lun ging nhau!

HOT TNH SINH HC