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
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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
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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
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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 butene-2

C4H8

OH OH

OH

OH

OH 1,21,3dihydroxy benzene OH 1,4-

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

dimethyl ketone C3H6O O propan-2-one acetone

CHO

propionaldehyde propanal propionic aldehyde

C3H6O2

COOH

Propionic acid

O O methyl acetate
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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
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 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

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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 H

CH3 H

H3C H

H CH3
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cis-butene-2

trans-butene-2

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 Br I 53 Br I

17 Cl F 9 F Cl (E)-1-Bromo-2-chloro-2-fluoro-1-iodoethene

(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 F Cl H

Cl H

Cl 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 C N H anti-acetaldoxime (Z)-acetaldoxime H3C C N OH H syn-acetaldoxime (E)-acetaldoxime
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 i vi ketoxime: Cng 1 cht, c th gi l syn- hay anti- !!!

H3C OH C N H3C

C N

OH

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

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

h syn-anti khng chnh xc chuyn sang h Z-E

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b. aN=Nb

C6H5 N N C6H5 anti-azobenzene

N N C6H5 C6H5

syn-azobenzene

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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

trans,trans-1,4-diphenyl-1,3-butadiene

H C6H5 H H

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

H C6H5 H H

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

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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 H HOOC H H COOH

cis-cyclopropane-1,2-dicarboxylic acid

trans-cyclopropane-1,2-dicarboxylic acid

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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 3.7 H Cl Cl H 4.7

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b. Moment lng cc 2 nhm th ging nhau aHC=CHa

H Cl H Cl H 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

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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

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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!!!
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II.2.1. Cch biu din a. Cng thc phi cnh (khng gian 3 chiu)
a b a b c a c c b b c b c a a

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 b c c b b c

c b

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

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Xen k: khong cch gia cc H xa nhau lng thp nht bn nht

nng

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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 H H H H H H CH3 H H CH3

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

CH3 H H H H CH3 CH3 H CH3 H H H
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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)

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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 6 3 2.5 2 1 2.49

3 4 6 2
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1.84

* Thuyn:
1

4 5 6 3 2
2.27

4 1
2.49

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)
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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 e ae a a
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ea e

109o28'

 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 34 e

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
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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
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 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
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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: abcd khng c tnh i xng trong khng gian 38

V d phn t lactic acid

2 ng phn quang hc

COOH H C*

COOH C* H CH3 (-)

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OH HO

CH3 (+)

40

 Cc nhm th khc nhau v ng phn cu to ng phn quang hc

H C* COOH

n-C3H7

iso-C3H7

Cc nhm th khc v ng v ng phn quang hc

CH3 D C* H C6H5

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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 C C C C6H5
HOOC

C10H7 C6H5
COOH

ng phn cn quay
Cl Cl
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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

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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
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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!!!
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a. H danh php D-L: cu hnh tng i Phi so snh vi 1 cht chun

CHO H OH CH2OH D-glyceraldehyde HO CHO H

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 H OH CH3 D-lactic acid HO COOH H CH3 L-lactic acid
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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

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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 HC C CH C C
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-CCH > -C(CH3)3 -CH=CH2 > -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

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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
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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 i t a b b c: cng chiu kim ng h: R 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
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V d lactic acid:
H

COOH OH CH3

a OH c CH3 H d (R) COOH b

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

b COOH

Nu ch i 1 cp H & CH3

c CH3 H d (S)

OH a

Lu : R & S ch l i lng l thuyt!!! thc t ch o c d(+) & l(-)!!! R & S khng lin h vi (+) & (-)!!!

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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

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

CHO H C* OH H C* OH CH2OH (2R,3R)-

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)-

erythro-aldotetrose

threo-aldotetrose

S p quang hc: N =

2n

n: s C*

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b. Hp cht c cha C* tng ng Tactric acid:

H H HOOC C* C* COOH OH OH
2 C* tng ng 3 ng phn

COOH H C* OH HO C* H COOH

COOH HO C* H H C* OH COOH

COOH HO C* H HO C* H COOH meso-tactric acid

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

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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)

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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

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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)-

COOH H2N H CH2OH (S)CH2OH H OH H OH CH2OH (2S, 3R)-

CH2OH H OH OH H CH2OH (2S, 3S)-

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