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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
C4H8
OH OH
OH
OH
CHO
C3H6O2
COOH
Propionic acid
O O methyl acetate
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C4H10O
diethyl 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
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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C N
OH
anti-phenyl-p-tolylketoxime syn-p-tolyl-phenylketoxime
syn-phenyl-p-tolylketoxime anti-p-tolyl-phenylketoxime
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b. aN=Nb
N N C6H5 C6H5
syn-azobenzene
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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
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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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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
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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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
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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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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'
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.3.2. 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
2 ng phn quang hc
COOH H C*
OH HO
CH3 (+)
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n-C3H7
iso-C3H7
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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
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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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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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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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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
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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+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
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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HO HO
erythro-aldotetrose
threo-aldotetrose
S p quang hc: N =
2n
n: s C*
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COOH H C* OH HO C* H COOH
COOH HO C* H H C* OH COOH
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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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