16 BG HHC Ptsnam

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
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
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), 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
methyl acetate
7
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
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
10
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
11
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)
12
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-, cishttp://hhud.tvu.edu.vn
E-, cis-
13
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

14
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

15
b. aN=Nb
C6H5 N N C6H5 anti-azobenzene
N N C6H5 C6H5
syn-azobenzene
16
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 http://hhud.tvu.edu.vn p = (n + 1)/2 nu n l
17
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
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 Cl H Cl 3.7 H Cl Cl H 4.7
19
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
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
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!!!
22
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

23
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
24
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
25
Xen k: khong cch gia cc H xa nhau nng lng thp nht bn nht
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 H H H H H H CH3 H H CH3
2 dng c nng lng thp: anti (i) & syn (lch)

CH3 H H H CH3 H CH3
27
H H H CH3 http://hhud.tvu.edu.vnH
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)
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 4 6 3 2.5 2 1 2.49
3 4 6 2
30
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 b n (t c) http://hhud.tvu.edu.vn
31
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
33
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
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 Gc quay c xc nh bng phn cc k
36
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
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*) Cabcd * C bt i xng: a b c d 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 (-)

39
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
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 C C C C6H5
HOOC
C10H7 C6H5
COOH
ng phn cn quay
Cl Cl
42
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

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
OH CH3
C th c nhiu cng thc Fisher khc nhau c. Cng thc phi cnh & Newman
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!!!
45
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
46
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
47
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
48
-CCH > -C(CH3)3 -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

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
50
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
52
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 (+) & (-)!!!
53
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*
54
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
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)
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
57
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)-
58
Ha Hc Hu C
Chng 2: CC LOI HiU NG * Hiu ng s dch chuyn in t trong phn t nh hng n c ch phn ng, kh nng phn ng, tnh acid-base Chia lm 2 loi: a. Hiu ng in t: HU cm ng I (inductive effect) HU lin hp C (conjugation effect) HU siu lin hp H (hyperconjugation effect) b. Hiu ng khng gian: HU khng gian loi 1 HU khng gian loi 2 HU ortho
I. Hiu ng cm ng
I.1. nh ngha HU cm ng s dch chuyn in t ca cc lin kt do cc nguyn t trong phn t c m in khc nhau phn t phn cc V d:
H H C3 H H C2 H H C1 H Cl
m in Cl > C s dch chuyn t C1-Cl, 3 C2-C1, C3-C2

I.2. Phn loi

a. HU cm ng dng (+I) Gy ra bi cc nguyn t hay nhm nguyn t c khuynh hng nhng in t b. HU cm ng m (-I) Gy ra bi cc nguyn t hay nhm nguyn t c khuynh hng ht in t * Quy c: C-H c I = 0 Chiu chuyn dch t : Nhm nguyn t c khuynh hng nhng 4 in t > H cho +I (v ngc li)
I.3. c im ca HU cm ng
Cc nguyn t hay nhm nguyn t mang in tch + Cho I Cc nguyn t hay nhm nguyn t mang in tch - cho +I in tch cng mnh I cng mnh, nhm nguyn t mang in tch c I mnh hn trung ha -N(+)R3 -O(+)R2 -I -O-N(-)H +I -O(+)R2 > -OR
Trong cng 1 chu k trong bng HTTH: -I tng t tri qua phi -I: -NR2 < -OR < -F Trong cng 1 phn nhm chnh : -I gim t trn xung di -I: -F > -Cl > -Br > -I -I: -OR > -SR > -SeR Cc nhm alkyl lun y in t (+I), tng dn t bc 1 n C bc 3 +I : -CH3 < -CH2CH3 < -CH(CH3)2 < -C(CH3)3
Cc nhm khng no u mang I, tng dn theo khng no -I:

R2C=CR< < RC
C
HU cm ng gim dn theo mch C nh hng n tnh cht ca phn t V d Ka.105 ca cc acid: CH3CH2CH2COOH 1.5 CH3CH2CH(Cl)COOH 139 CH3CH(Cl)CH2COOH 8.9 ClCH2CH2CH2COOH 3.0
II. Hiu ng lin hp

II.1. nh ngha H lin hp: l nhng phn t c lin kt & v tr lun phin nhau V d: CH2=CH-CH=CH2 hay CH2=CH-CH=CH-CH=CH2
HU lin hp s dch chuyn t trong 1 h lin hp, lm cho h lin hp tr nn phn cc V d: CH2=CH-CH=CH2 mt in t phn b u trn cc C Tuy nhin: CH2=CH-CH=CH-CHO m in ca O > C nhm C=O s ht in t ca h phn t tr nn phn cc ( LH - )
CH2=CH-CH=CH-N(CH3)2 N c i in t t do (p) c xu hng nhng in t cho h lin hp phn t phn cc (LH -p)
Cl
NH2
Lin hp -p (-Cl, -NH2 ng thi c I!)

10
II.2. Phn loi

II.2.1. HU lin hp dng (+C) Cc nt hay nhm nguyn t c kh nng y in t t bn thn n ra h lin hp +C c im ca +C: a. Cc nguyn t hay nhm nguyn t c cp in t cha s dng hoc nhng ion mang tch (-) u mang +C -O- -S-H -R SH SR
NH2 NR2 H N C O CH3
-F
-Cl
-Br
-I
11
b. Cc ion mang in tch m c +C mnh hn cc nguyn t trung ha +C: -O- > -OR -S- > -SR c. Trong cng 1 chu k ca bng HTTH: +C gim t tri qua phi +C: -N(R)2 > -OR > -F d. Trong cng 1 phn nhm chnh: +C gim t trn xung di +C: -F > -Cl > -Br > -I +C: -OR > -SR > -SeR
12
II.2.2. HU lin hp m (-C) Cc nguyn t hay nhm nguyn t c kh nng ht in t ca h lin hp v pha n -C c im ca C: a. a s cc nhm nguyn t mang C l nhng nhm khng no -NO2 -CN -CHO -COR
-COOH -CONH2
13
b. Trong cc nhm C=Z: -C ph thuc Z Z c m in cng ln, -C cng mnh -C: C=O > C=NR > C=CR2
c. i vi cc nhm nguyn t tng t: in tch cng ln th C cng mnh -C: C=N+R2 > C=NR
14
II.3. c tnh chung ca HU lin hp a. HU lin hp thay i rt t khi ko di mch lin hp *** HU cm ng: gim nhanh theo mch C !!!
O H CH2 CH CH C H O H CH2 CH CH CH CH C H
linh ng ca H 2 cht ging nhau

15
Tc phn ng ging nhau:

OH
RCHO + H
CH2
CH
CH
C H
OH
O CH2 CH CH C H
C H
RCHO + H
CH2
CH
CH CH
CH
C H OH
OH-
O R C H CH2 CH CH CH CH C H
16
b. Mt s nhm th cha no, du ca HU lin hp s thay i ty thuc vo nhm nt lin kt vi n

-
O N
+
NH2
-C6H5: +C
-C6H5: -C
c. HULH ch c hiu lc trn h lin hp phng
C6H5NH2
H N H
C6H5NR2
R N R
+C ca NR2 gim so vi NH2

17
III. Hiu ng siu lin hp III.1. HU siu lin hp dng (+H)

L s tng tc ca cc in t ca lin kt C-H vi h t (C=C, -C6H5 ), hoc trong carbocation (vd: (CH3)3C+) hay gc t do (vd: (CH3)3C.)
18
Xt phn ng: CH3-CH=CH-CH2-CH3 + HCl Nu xt theo +I: sn phm chnh l: CH3-CH2-CHCl-CH2-CH3 Tuy nhin, thc t, do tc dng ca +H, sn phm chnh l:
H H C H
CH
CH CH2
CH3
HCl
CH3 CHCl
CH2
CH2
CH3
19
+H cng mnh khi s nguyn t H C cng nhiu:
H C
+H:
C H
>
H3C
20
III.2. HU siu lin hp m (-H)

L s tng tc ca cc t ca lkt C-F vi h t (C=C, -C6H5)
F C F F
21
IV. Hiu ng khng gian L nhng loi hiu ng do kch thc ca cc nhm th trong phn t gy nn IV. 1. HU khng gian loi 1 (S1) Do cc nhm th c kch thc ln, chim 1 khong khng gian ng k cn tr khng cho 1 nhm chc no trong phn t tc dng vi phn t hay ion khc
CH3 O O + H2N OH CH3 HO N CH3 O + H2O CH3
22
IV. 2. HU khng gian loi 2 (S2) Do cc nhm th c kch thc ln h lin hp b mt tnh phng khng cho 1 s phn ng Xy ra
R H3C N H3C + Cl-N N+ R H3C N H3C R N N R
R = H: phn ng xy ra R=-CH3: h lin hp mt tnh phng +C ca N(CH3)2 gim mnh phn ng khng xy ra
23
IV. 3. Hiu ng Ortho

Gy ra bi cc nhm th v tr ortho trong vng benzene gy nh hng c bit so vi cc nhm th v tr khc HU ortho: hn hp ca nhiu yu t (S1, S2, I, lin kt H)
24
Xt hng s phn ly (Ka.105) ca dn xut ca benzoic acid C6H4(R)COOH

V tr / R ompOH 10.5 8.3 2.9 F 54.4 13.7 7.2 NO2 67.1 32.1 37.6
Lu : -I ca NO2 > -I ca F
25
Tnh acid:
H O C O H H O > OH OH O C O H O C O
>
o-: OH c I ht t & lin kt H O-H trong COOH phn cc mnh nht p-, m-: OH c I ht in t nhng -I gim dn theo chiu di mch C O-H trong COOH p- t b phn cc nht lu : OH trong o- & p- c +C y in t ln h lin hp p-- C=O trong m-: h lin hp ny b t on do - lin tc !!! cng 26 http://hhud.tvu.edu.vn lm cho tnh acid ca m- > p-
Tnh acid ca C6H4(F)COOH: o- > m- > pdo I gim theo chiu di mch C Kh nng ht (-I) hay y (+C) in t ca F, Cl, Br, I: -I > +C
Tnh acid ca C6H4(NO2)COOH: o- > p- > mhttp://hhud.tvu.edu.vn
27
+O
H O
+O
OH
o-nitrophenol: lin kt H ni phn t tosi thp, khng tan trong nc c th chng li cun hi nc p-nitrophenol: ch c lin kt H ngoi phn t trong nc tan tt trong nc, tosi cao
28
V. nh hng ca cc hiu ng ln tnh acid base v bn ca carbocation

V.1. nh hng ca HU cm ng ln tnh acid Cc R-OH, R-COOH c cha nhm th c +I tnh acid gim Cha nhm th c I: tnh acid tng do O-H cng phn cc
29
Tnh acid ca cc acid: F3C-COOH (pKa 0.23) > Cl2CH-COOH (1.25) > Cl3C-COOH (0.66) >
NO2-CH2-COOH (1.68) >
NC-CH2-COOH (2.47) > F-CH2-COOH (2.57) > Cl-CH2-COOH (2.87) > Br-CH2-COOH (2.90) > HCOOH CH3COOH (3.75) (4.76) > > HO-CH2-COOH CH3CH2COOH (3.83) (4.87) > >
(CH3)3C-COOH (5.03)
30
Nhm th cng xa C nh hng cng yu do I gim mnh: Tnh acid: F3C-COOH > F3C-CH2-COOH > F3C-CH2-CH2-COOH
31
V.2. nh hng ca HU lin hp, HU siu lin hp ln tnh acid Tnh acid ca alcohol < phenol Nhm th c C s lm tng tnh acid & ngc li
-
+O
Tnh acid:
-I, -C > > O H O H +I H H C H >
H H C H +H, +I > O H
+C, -I NH2
O H
O H
32
Thng thng (khng lun lun!) : C > H > I

a. Acid bo khng no: Tnh acid mnh hn acid no cng mch C (do C=C c I) Ni i C=C cng gn COOH th tnh acid cng mnh Tuy nhin: nu C=C lin hp vi C=O trong COOH th tnh acid gim do +C ca C=C!!! Tnh acid: CH3-CH=CH-CH2-COOH (pKa 4.48) > CH2=CH-CH2-CH2-COOH (4.68) > CH3-CH2-CH=CH-COOH (4.83)
33
Ni ba CC cho d v tr lin hp vi C=O th vn lm tng mnh tnh acid (khc C=C): do I ca CC mnh & ch c 1 lkt ca CC cho +C lin hp vi C=O, lkt cn li cho I nhng khng c +C!!!
Tnh acid: CHC-COOH (pKa 1.84) > 34 CH3-CC-COOH (2.60) > CH2=CH-COOH (4.25)
b. Acid c vng thm: Tnh acid H-COOH (pKa 3.75) > C6H5-COOH (4.18) do +C ca C6H5- mnh hn I Tnh acid ty thuc bn cht & v tr nhm th: o-NO2-C6H5-COOH > p- > m Halogen cho I > +C o-Cl-C6H5-COOH > m- > phttp://hhud.tvu.edu.vn
35
V.3. nh hng ln tnh base

Mt in t trn N cng ln tnh base ca amine cng mnh Nhm th y in t (+I) s lm tng tnh base ca amine & ngc li (-I, -C) Tnh base: (CH3)2NH > CH3NH2 > NH3 > C6H5NH2 > p-NO2-C6H4-NH2
36
Tnh base: p-NO2-C6H4-NH2 < m- NO2-C6H4-NH2 < p-Cl-C6H4-NH2 < C6H5-NH2 < p-CH3O-C6H4-NH2 p-NO2: -I, -C mnh nht, m-NO2: -I mnh, -C khng nh hng nhiu do h lin hp b t on -Cl: -I mnh hn +C, -I yu hn -NO2 p-CH3O: +C mnh hn I mt in t trn N cao nht base mnh nht Acid lin hp cng yu th tnh base cng mnh Tnh base: HCC- > (CH3)3CO- > CH3O- > OH- > C6H5O- > CH3COO37
V.4. nh hng ln bn ca cc carbocation

in tch dng trn cc cation cng c gii ta (cng nh) th cation cng bn bn do hiu ng y in t ca +H, +I:
H H C CH2 H
<
H H H H H C H + < H C C H C C+ HH C H HH C H H H 38
bn ca carbocation: (CH3)3C+ < C6H5CH2+ < (C6H5)2CH+ Do +C ca -C6H5 mnh hn +I, +H ca CH3 in tch cng c gii ta carbocation cng bn
39
bn ca carbocation:
H H C CH2 H
<
H3C O CH2 < H3C NH CH2
+C ca NH- > +C ca O- > +H & I ca CH3 -NH- & -O- ng thi c I nhng +C nh hng mnh hn -NH- gii ta tch dng mnh nht bn nht Gc allyl CH2=CH-CH2+ hay C6H5-CH2+ rt bn do +C ca vinyl hay phenyl
40
Ha Hc Hu C
Chng 3: C CH PHN NG CA HP
CHT HU C
I. Phn ng th i nhn nguyn t carbon no I.1. Khi nim chung Phn ng th: 1 nguyn t hay nhm nguyn t ca cht ban u b thay th bi 1 nguyn t hay nhm nguyn t khc CH3-CH2-Cl + OH- CH3-CH2-OH + Cl Tc nhn i nhn: cc tc nhn mang in tch m (hay phn t trung ha cha cp in t t 2 do) tn cng vo trung tm tch in +
Phn ng th i nhn (SN) y- + R-X R-y + Xy-: RO-, OH-, RCOO-, NH3, NH2R, H2O, ROH R: gc hydrocarbon X: Cl, Br, OH, OR, OSO2R V d: CH3-CH2-Cl + OH- CH3-CH2-OH + ClCH3-CH2-Br + CH3O- CH3-CH2-O-CH3 + BrCH3-CH2-Br + NH3 CH3-CH2-NH2 + HBr
I.2. Phn ng th i nhn lng phn t (SN2)

Lng phn t: giai on chm, c s tham gia ca 2 tiu phn
y + R-X
cham
a.C ch:
[y-... R ... X-]
nhanh
R-y + X-
trang thai chuyen tiep

Lin kt gia C & y hnh thnh ng thi vi s yu i & t ca C & X 2 tiu phn tham gia vo giai on chm Nu y- khng d nhiu: r = k[y-].[R-X] phn ng 4 bc 2
Gin nng lng:
R-OH: phn ng th ch xy ra trong mi trng acid v C-O bn Dn xut ca carbon bc 1 ch cho SN2 SN2: carbon bc 1 (ch cho SN2) > carbon bc 2 > carbon bc 3 (ch cho SN1) SN2: CH3-CH2-Cl + OH- CH3-CH2-OH + Cl6
b. Tnh lp th ca SN2 Phn t c cha C*: s c s thay i cu hnh (R S & ngc li) (nghch o Walden)
R1 R1 C* R2 X R1 X R2
y- +
cham
y H
C*
nhanh
C*
H R2
(R)-
(S)-
y- tn cng ngc hng so vi X sn phm c 7 cu hnh ngc vi tc cht

I.3. Phn ng th i nhn n phn t (SN1) n phn t: giai on chm ch c s tham gia ca 1 tiu phn a. C ch
R-X R+
cham
R+ +
X-
+ y
nhanh
R-y
giai on chm: y- khng tham gia SN1 thng c bc 1 r = k[R-X]

Gin nng lng:
Dn xut ca carbon bc 3 ch cho SN1 SN1: carbon bc 3 (ch cho SN1) > carbon bc 2 > carbon bc 1 (ch cho SN2) V d SN1:
CH3 H3C C CH3

CH3 Br
+ OH-
H3C
C CH3
OH
+ Br-
10
Tnh lp th ca SN1
R1 y R1 R2 R3 C* X C* R2 R3
cham -XR2
C*
nh an h h an nh
R2
R1
R3
R1 C* R3 y
(R1 R2 R3)
Sn phm c th l hn hp racemic Carbocation c cu trc phng kh nng tn cng ca y- 2 pha l nh nhau 50% S + 50% 11 R
12
I.4. Cc yu t nh hng ln phn ng th i nhn

a. nh hng ca gc R Gc R bc cng cao: kh nng SN1 tng & SN2 gim SN1: carbon bc 3 (ch cho SN1) > carbon bc 2 > carbon bc 1 (ch cho SN2) Do SN1 ph thuc vo bn ca carbocation to thnh:
CH3+ < H H C CH2 H < H H H HH C H + < H C C H C C+ HH C H HH C H H 13 H
Bc ca R cng cao y- cng kh tn cng do in tch (+) C gim & do hiu ng khng gian ca gc alkyl SN2 cng kh xy ra
SN2: carbon bc 1 (ch cho SN2) > carbon bc 2 > carbon bc 3 (ch cho SN1)
14
b. nh hng ca tc nhn i nhn y SN1: khng ph thuc y SN2: ph thuc nhiu vo y- do giai on chm c y- tham gia Tc nhn c tnh i nhn cng cao th cng d cho SN2 Thng thng, tnh i nhn ng bin vi tnh base NH2- > (CH3)3CO- > (CH3)2CHO- > C2H5O- > CH3O> OH- > C6H5O- > HCO3- > CH3COO15
Trong cng 1 phn nhm chnh ca bng HTTH: tnh i nhn nghch bin vi tnh base (phn ng thc hin trong H2O, ROH): Tnh base: F- > Cl- > Br- > ITnh i nhn: F- < Cl- < Br- < ITnh i nhn: HS- > OHTnh i nhn: C2H5S- > C2H5OTuy nhin trong pha kh, tnh i nhn: F- > Cl- > Br- > I-
Phn bit tnh base & tnh i nhn: Tnh base v 16 tr cn bng, tnh i nhn tc !!!
c. nh hng ca nhm b th -X Cc nhm th c tnh base cao rt kh b tch ra, v d: -OH, -OR, -NH2, -F V d: R-OH + HBr R-Br + H2O cn xc tc H2SO4 R-OH khng phn ng vi KBr Halogen, kh nng tch nhm: F- < Cl- < Br- < I(Do I c bn knh ln C-I d phn cc hn Nng lng t lin kt: C-I < C-Br < C-Cl < C-F)
17
d. nh hng ca dung mi Dung mi phn cc c proton nh H2O, ROH, HCOOH c kh nng solvate ha cao c anion & cation thun li cho SN1
R1 H R1 cham + R2 C X - C+ O -X R3 R2 R3 H
X- H O H
Dung mi phn cc khng c proton nh (CH3)2SO, (CH3)2NCHO khng c kh nng solvate ha anion thun li cho SN2 18
II. Phn ng tch loi

L phn ng trong c s tch 1nguyn t hay nhm nguyn t ra khi cht ban u
R CH2 CH2 Br
ROto H+ to HOt
o
CH
CH2 +
HBr HOH HOH + NR3
CH2
CH2
OH
CH
CH2 +
CH2
CH2 N+R3
CH
CH2 +
Nhm b tch cng H: -OH, -OR, -X, -O+(R)2, -N+(R)3, -OSO2R 19 Base s dng: cc base mnh nh OH-, RO-, NH 2
II. 1. Phn ng tch loi lng phn t (E2) a. C ch

y + R CH2 CH2 X
-
cham
R y
C CH2
nhanh
H trang thai chuyen tiep H-y + R CH CH2 + X-
giai on chm, c s tham gia ca 2 tiu phn lng phn t Tc phn ng r = k[R-X].[y-] R-CH2-CH2-OH: ch tch loi trong mi trng acid 20 o t cao (thng l sulfuric acid, acid rn)
b.Tnh lp th ca E2 Cc hydrocarbon khng no tch loi d khi cc nhm b tch v tr trans vi nhau
(1)
HOOC Cl COOH
(2) OH-HCl
HOOC
Cl
OH-HCl
COOH COOH
HOOC
chlorofumaric acid
chloromaleic acid
Tc (1) ln hn (2) 30 ln
21
Cc hydrocarbon no hay vng no tch loi d khi cc nhm b tch v tr trans, anti vi nhau Lu : dn xut ca cyclohexane ch tch c khi nhm b tch v tr trans & phi kiu lin kt axial (trc)!!!
Br CH3 H H CH3
+
CH3
san pham chnh

Br
kho
H H CH3
CH3
22
II.2. Phn ng tch loi n phn t (E1) C ch:
H C C X
cham
H C C+
X-
H C C
nhanh
H+
Thng cc dn xut ca hydrocarbon carbon bc 3 bao gi cng cho E1 Carbocation cng bn, cng d cho E1 Tc r = k [R-X] Nhng yu t lm thun li SN1 cng lm thun li 23 cho E1
V d:
CH3 H3C C Br CH3 H HH C H H C C+ HH C H H
cham
H HH C H H C C+ HH C H H
nhanh
+ Br-
+ C2H5O-
CH3 + H2C C CH3
C2H5OH
24
II.3. Hng ca phn ng tch loi

a. Quy tc Zaitsev Dn xut bc 1 thng ch cho 1 sn phm duy nht khi tch loi CH3-CH2-CH2-Br ch cho CH3-CH=CH2 Dn xut bc 2, bc 3: cho nhiu hn 1 sn phm
H H H H3C C C C H H Br H OHH3C CH CH CH3 (Zaitsev)
H3C CH2 CH CH2
(Hofmann)
Sn phm Zaitsev : bn hn (do +H) thng thng, phn ng tch loi cho sn phm Zaitsev Quy tc: phn ng tch loi s cho sn phm m 25 carbon ca ni i lkt vi nhiu nhm alkyl nht
b. Quy tc Hofmann Khi gc R (bc 1 & 2) ca R-X cha nhiu nhm th kch thc ln, tc nhn base c kch thc ln (vd (CH3)3CO-) hoc X l nhm th mang in tch dng c kch thc ln (vd N+R3, S+R2, SO2R) sn phm Hofmann chim ch yu (E2)
CH3 H2C C CH2 CH3 (CH3)3COCH3 H3C C CH CH3
CH3 H3C C CH2 CH3 Br
72%
28%
26 Nu base l C2H5O- th sn phm chnh l Zaitsev!!!
H H3C C CH2 CH3 N+(CH3)3
OH(E2)
CH2=CH-CH2-CH3
CH3CHCH2CH2CH3 SO2CH3
OH(E2)
CH2=CH-CH2-CH2-CH3
Lu : Nu trong phn t c sn 1 ni i (C=C, C=O), sn phm lin hp thng l sn phm chnh (bn hn) 27
II. 4. Quan h gia phn ng th i nhn & tch loi

Nhit phn ng cng cao phn ng tch loi cng chim u th
<140oC CH3-CH2-OH H2SO4 >170oC

C2H5-O-C2H5
CH2=CH2 + H2O
28
Gc R c bc cng cao, hay base cng mnh th tch loi cng chim u th
CH3-CH2-CH2-Br
+ C 2 H5 O -
to thng
CH3-CH2-CH2-O-C2H5
CH3 H3C C Br CH3
C2H5Oto cao
CH3 H2C C CH3

29
III. Phn ng cng hp

III. 1. Phn ng cng hp i in t (AE) Phn ng cng hp vo ni i ca hydrocarbon khng no nh alkene, alkyne vi cc hp cht nh X2 (halogen), HX, H2O, HOX, H2SO4
C C
+ X-Y
X C C Y
30
a. C ch: Giai on 1:
C C + X+-Y dung moi xuc tac nhanh cham C C X+ Y phc khong ben C+ C X ben hoa C C X+
Giai on chm: X+ tn cng vo C=C i in t
Giai on 2:
Y-
C C X+
nhanh
Y C C X
31
Y-
tn cng vo pha i lp vi X
Chng minh AE c 2 giai on: Phn ng cng hp ca CH2=CH2 vi Br2 vi s c mt ca NaCl, NaNO3, sn phm thu c l 1 hn hp: Br-CH2-CH2-Br + Br-CH2-CH2-Cl + Br-CH2-CH2-ONO2 Nu phn ng thc hin trong dung mi l CH3OH, sn phm chnh l Br-CH2-CH2-OCH3 !!!
32
H2C CH2 + Br2
CCl4
H2C CH2 Br Br
H2C CH2 + Br2
CH3OH
H2C CH2 Br OCH3
H2C CH2 + Br2
H2O
H2C CH2 Br OH
33
b. Quy lut cng hp Quy tc Markonikov (dnh cho C=C khng i xng): H+ s tn cng vo C cha nhiu H CH3-CH=CH2 + H+ CH3-C+H-CH3 (bn hn) + CH3-CH2-C+H2 Quy tc Zaitsev-Wagner: H+ s tn cng vo pha to thnh carbocation trung gian bn nht
HBr
CH3-CH=CH-CH2-CH3
CH3-CH-CH-CH2-CH3 34 Br
c. Ha lp th ca phn ng AE Phn ng cng hp AE xy ra theo kiu trans ph thuc vo tc cht ban u m c cc ng phn lp th khc nhau ng phn cis sn phm threo (nhm th tng ng khc pha)
C2H5 Br C2H5 H CH3 H Br2 C2H5 Br+ CH3 H BrC2H5
Br H
CH3
CH3 Br H H Br C2H5
Br
CH3 Br
CH3 H Br Br H C2H5 threo-
35
ng phn trans sn phm erythro (nhm th tng ng cng pha)
C2H5 H
H CH3
Br2
CH3 Br H Br H C2H5
CH3 H Br H Br C2H5 erythro
36
d. nh hng ca nhm th lin kt vi ni i Nhm th y in t tng mt in t ca C=C tng kh nng phn ng AE Nhm th ht in t gim kh nng AE Cc nhm th nh phenyl nu c kh nng cho +C vi carbocation bn ha cation thun li cho AE
37
Kh nng AE:
O2N H H HOOC < H H Cl < H H H H H3C < H H H H3C < H CH3 H H3C < H CH3 H3C < CH3 H3C CH3 CH3
Phenyl gy nh hng mnh hn 1 nhm methyl nhng yu hn 2 nhm methyl CH3CH=CH2 < C6H5CH=CH2
< (CH3)2 C=CH2

38
III.2. Phn ng cng hp i nhn vo C=O (AN)
C O + X -Y
OX C Y
X-Y c th l H-OH, H-OR, H-CN, H-SO3Na, Li-R, BrMg-R
39
a. C ch: 2 giai on, lng phn t Giai on 1:
+ Y
cham
C OY carbanion
Giai on chm: Y- tn cng vo C+ i nhn

40
Giai on 2:
-
C OX C O Y Y Phn ng AN c th khng cn xc tc. Tuy nhin, pH c nh hng V d: Trong acid yu (pH 4) + X+
nhanh
C O
H+
C+ OH
in tch (+) ca carbon c tng cng AN cng thun li Tuy nhin, acid qu mnh: R-NH2 + H+ R-N+ H3 41 Kh nng phn ng vi C=O gim
b. nh hng ca nhm th lin kt vi C=O Nguyn t C trong C=O c in tch dng cng ln AN cng thun li Nhm th y in t (+C, +I, +H) lm gim kh nng phn ng Nhm th ht in t (-C, -I) lm tng kh nng phn ng
NO2 CH2 C O H > Cl CH2 C O H > CH3 C O H > H3C C CH3 o
> H3C C OR o
> H3C C NH2 o
> H3C C Oo http://hhud.tvu.edu.vn
42
IV. Phn ng th i in t vo nhn thm (SE)

X + X+ acid + H+
Xc tc: cc acid v c: H2SO4, H3PO4, HF hay Lewis acid: FeCl3, AlCl3, ZnCl2 V d: C6H6 + (CH3)3C-Br /AlBr3 C6H5-C(CH3)3 + HBr
43
C ch phn ng: 2 giai on, lng phn t Giai on 1: to phc ( benzonium cation)
xt nhanh
H + + + X H
+ X -Y
X+-Y
phc
X cham
H +
phc
Trong phc : X khng lin kt trc tip vi C no c Phc : X c lin kt trc tip vi 1 C ca benzene
44
Giai on 2: tch proton
X +
H nhanh
X + HY
45
+++ Nhm th y in t (+C, +H, +I) SE tng V d: * alkyl +I, +H *-NR2 (R: H hay gc alkyl), -OH, -OCH3, -NH-CO-CH3 (+C > -I) Anion: -O- : +C, +I mnh +++ Nhm th ht in t (-C, -I) SE gim V d: -N+N, -NO2, -CN, -CHO, -COR, -COCl, -COOH, -CO-NH2 (-I, -C) Cation: -N+R3 (-I mnh) * halogen (-I > +C)
46
Ha Hc Hu C
Chng 4: Alkane I. Gii thiu chung Alkane hydrocarbon no mch h, nguyn t carbon lai ha sp3 Cng thc tng qut: CnH2n+2
methane
Gc ha tr 109o5, lin kt C-H: 1.09, C-C: 1.53 2 ng phn: cu to, cu dng (quay)
II. Danh php IUPAC

II.1. Alkane khng phn nhnh: 4 alkane u: gi theo tn thng thng methane, ethane, n-propane, n-butane Cc alkane t C5: da theo cch m s ca Hy Lp hoc Latin. V d: pentane, hexane, heptane, octane(t c)
II. 2. Alkane phn nhnh Chn mch di nht lm mch chnh nh s sao cho mch nhnh c ch s nh nht Dng ch s & gch (-) ch v tr nhnh, nhm cui cng phi vit lin vi tn mch chnh Nu c nhiu nhnh tng ng: dng tip u ng di-, tri-, tetra- ch s lng nhm tng ng
Nu c nhiu nhm th khc nhau: sp xp theo th t alphabetical. Lu : b qua cc tip u ng di-, tri-, tetra- khi xt th t alphabetical. Tuy nhin khng b qua iso!!! sec- & tert- c b qua khi xt th t vi cc nhm khc, nhng vn dng so snh gia chng vi nhau. V d: dimethyl hoc methyl s i sau ethyl hay diethyl isopropyl i trc methyl tert-butyl i trc isobutyl sec-butyl i trc tert-butyl
V d (H vit tt):
C C C C C C C C C C 4-Ethyl-2,2-dimethylhexane
C C C C C C C C C C C C C C C C 3,3-Diethyl-5-isopropyl-4-methyloctane
C C C C C C C C C C C C 5-Ethyl-2,3,5-trimethylheptane
C C C C C C C C C C C C C C C 2-methyl-5-(1,2-dimethylpropyl)nonane
6
II.3. Tn gc alkyl c ly 1 H t alkane, gi theo tn alkane nhng i ane yl CH3-: methyl CH3-CH2-: ethyl CH3-CH2-CH2-: n-propyl
CH3CHCH3
: isopropyl
CH3CH2CHCH3
: sec-butyl (CH3)2CHCH2-: isobutyl (CH3)3C-: tert-butyl 7
III. Cc phng php iu ch alkane III.1. Kh cc dn xut ca halogen, alcohol, carbonyl: a. Kh bng HI 80%, 180oC:
CH3-CH2-OH + HI P o CH3-CH3 + I2 + H2O
CH3I + HI
P o
CH4 + I2
b. Kh bng Zn/HCl
R C R' O
(Kh Clemmensen)
Zn(Hg)/HCl
R-CH2-R'
8
III.2. Hydro ha alkene

R-CH=CH2 + H2 Ni, Pd, Pt R-CH2-CH3
alkene c th iu ch t alcohol (H2SO4/toC) III.3. Thy phn hp cht c kim (CH3)2Zn + H2O CH4 + Zn(OH)2
C2H5-MgBr + H2O C2H6 + Mg(OH)Br iu ch hp cht c magnesium (Grignard): C2H5-Br + Mg/ether khan C2H5-MgBr
III.4. Phn ng Wurtz CH3CH2Br + Na CH3CH2CH2CH3 + NaBr
Ch c hiu qu khi iu ch alkane i xng: CH3CH2Br + CH3Br CH3CH2CH3 + CH3CH3 + CH3CH2CH2CH3 khng c tnh chn lc t s dng Ch hiu qu cho R-Br & R-I Hiu sut: bc 1 (60%) > bc 2 (40%) > bc 3 (10%)
10
III.5. in phn mui ca carboxylic acid CH3COONa CH3COO. CH3. CH3-CH3
III.6. Nhit phn mun natri ca carboxylic acid CH3COONa + NaOH CH4 + Na2CO3 IV. Tnh cht vt l (t c) Alkane khng phn cc ch tan trong dung mi khng phn cc to si ca alkane nhnh < thng
11
V. Tnh cht ha hc Alkane tr khng c phn ng cng, c trng l phn ng th H V.1. Phn ng th H bng halogen Ch xy ra nhit cao hoc khi c nh sng
R-H
+ X2
to h
R-X
HX
12
a. C ch phn ng (gc t do SR ) Khi mo:

X-X to h 2X
R-H R + + X X2 R RX + HX
Truyn mch:
+ X
Phn ng c th tip tc to sn phm di-, tri-, tetra V d chlor ha CH4 c th thu c CH3Cl, CH2Cl2, CHCl3, CCl4 CH4 + Cl2 CH3Cl + HCl H = -25Kcal/mol
13
Ngt mch:
X R R
+ X + R + X
X-X R-R R-X

14
Giai on to CH3. kh hn giai on to CH3Cl giai on to CH3. (hay R. ni chung) s quyt nh tc phn ng chung
15
b. So snh kh nng thay th H H bc 1 & bc 2:

25 oC CH3-CH2-CH3 + Cl2 h CH3-CH2-CH2-Cl 45% + CH3-CHCl-CH3 55%
Vn tc tng i khi thay th H bc 1: 45 / 6 = 7.5 Thay th H bc 2: 55 / 2 =27.5 t l vn tc tng i H bc 1/ H bc 2 = 7.5/27.5 ~ 16

H bc 1 & bc 3:
CH3 H3C C CH3 + Cl2 H 25 oC h CH3 H3C C CH2Cl H 64% CH3 + H3C C CH3 Cl 36%
Vn tc tng i khi thay th H bc 1: 64 / 9 ~7 Thay th H bc 2: 36 / 1 ~ 36 t l vn tc tng i H bc 1/ H bc 3 = 7/36 ~ 1/5
T l vn tc tng i bc 1/bc 2/bc 3 = 1/4/5

nhit thng, kh nng thay th H C bc 3 cao nht Lu : 600oC: t l ny l 1/1/1
17
c. Kh nng phn ng ca dy halogen F2 > Cl2 > Br2 > I2 F ha: mnh lit, t lin kt t dng I ha: rt kh xy ra (H = + 13 Kcal/mol), ch xy ra khi loi HI trong qu trnh
18
d. Tnh chn lc ca phn ng Phn ng Br ha c tc chm hn Cl ha nhng c chn lc cao T l vn tc tng i 127 oC ca Br ha: bc 1/bc 2/bc 3 = 1/82/1000
CH3 H3C C CH3 + Cl2 H
CH3 H3C C CH3 + Br2 H
25 oC h
CH3 H3C C CH2Cl H 64%
CH3 + H3C C CH3 Cl 36%

CH3 + H3C C CH3 Br 99%
127 oC h
CH3 H3C C CH2Br H 1%
127 oC CH3-CH2-CH3 + Br2 h CH3-CH2-CH2-Br

CH3-CHBr-CH3 97%
19
3%
V.2. Phn ng nitro ha alkane R-H + HNO3 R-NO2 + H2O
Phn ng xy ra nhit cao,c ch gc t do Thng xy ra phn ng t mch carbon CH3-CH2-CH3 + HNO3 CH3-CH2-CH2-NO2 (25%) + CH3-CHNO2-CH3 (40%) + CH3-CH2-NO2 (25%) + CH3-NO2 (10%)
20
V.3. Phn ng ng phn ha Chuyn cc alkane mch thng thnh alkane mch nhnh di tc dng ca xc tc nhit cao Xc tc thng dng: acid Lewis nh AlCl3, xc tc acid trn c s zeolite V d:
AlCl3 to
CH3-CH2-CH2-CH3
CH3 H3C C CH3 H

21
C ch:
H HH C H H C C+ HH C H H
CH3-CH-CH2-CH3 H AlCl3
+ CH3-C-CH2-CH3 H -HAlCl3 to
HAlCl3
CH3 H3C C CH3 H
+ AlCl3
Xu hng: to carbocation bn hn chuyn v

22
V.4. Phn ng cracking To alkane c mch carbon ngn hn di tc dng ca xc tc & nhit Km theo phn ng tch loi hydrogen & phn ng ng vng Cracking nhit: 800oC 1000oC, cracking xc tc (thng l zeolite): 500oC -600oC S dng trong sn xut nhin liu (khng dng iu ch alkane hay alkene v khng chn lc)
23
V.5. Phn ng oxy ha alkane Alkane bn vi tc nhn oxy ha nhit thng nhit cao hoc c mt xc tc c th phn ng vi oxygen, KMnO4, K2Cr2O7 phn ng t mch to alcohol (ROH), aldehyde (RCHO), ketone (RCOR), carboxylic acid (RCOOH) Phn ng quan trng: 2CnH2n+2 + (3n + 1)O2 2nCO2 + (2n+2) H2O ta nhit mnh, -341 kcal/mol alkane c dng 24 lm nhin liu
Ha Hc Hu C
Chng 5: ALKENE I. Gii thiu chung Alkene: hydrocarbon mch h, cha 1 lin kt i C=C (CnH2n, n2) Trong C=C: 1 & 1, hnh thnh do lin kt ca orbital sp2
Lin kt vung gc vi mt phng phn t Alkene n gin nht l ethylene CH2=CH2

121.7o 116.6o 1.08 1.33
II. H danh php

II.1. Tn thng thng Tn alkane tng ng, i ane ylene t dng, tr 3 alkene thng dng: CH2=CH2 ethylene CH2=CH-CH2 propylene (CH3)2C=CH2 isobutylene
II.2. Danh php IUPAC Tn alkane tng ng, i ane ene Chn mch carbon di nht & cha C=C lm mch chnh nh s sao cho C=C c ch s nh nht Ch s ca C=C chn theo v tr C gn C1 nht, vit cch tn mch chnh 1 gch ngang
CH3-CH-CH=CH2 CH3
CH3 CH3-C-CH=CH-CH3 H
3-methyl-1-butene
4-methyl-2-pentene (c cis & trans)
II.3. Tn gc ca alkene Alkenyl CH2=CH- 1-ethenyl (vinyl) CH2=CH-CH2- 2-propenyl (allyl) CH3-CH=CH- 1-propenyl
III. Cc phng php iu ch

III.1. Tch nc t alcohol Phn ng c th pha lng (xc tc acid H2SO4, H3PO4, 100-170oC) hay pha kh (xc tc Al2O3, zeolite, 350-400oC)
C C H OH
to xt
C C
+ H 2O
Kh nng tch nc: alcohol bc 3 > bc 2 > bc 1
CH3CH2CH2CH2-OH
H2SO4 75% 140 oC
CH3CH=CHCH3
CH3-CH-CH2-CH3 H2SO4 50-60% CH3-CH=CH-CH3 o 100 C OH (CH3)3C-OH H2SO4 20% 80 oC CH2=C(CH3)2
III.2. Tch HX t dn xut ca halogen

C C H X to KOH/ethanol C C + H2O + KX
Kh nng tch HX: RX bc 3 > bc 2 > bc 1

to CH3CH2CH=CH2 CH3CH2CH2CH2Cl KOH/ethanol CH3CH2CHCH3 Cl to KOH/ethanol CH3CH2CH=CH2 20% CH3CH=CHCH3 80%
Lu : tch R-X bc 1 khng c chuyn v R-OH bc 1
CH3CH2CH2CH2-OH
H2SO4 75%
140 C
CH3CH=CHCH3
III.3. Kh dn xut 2 ln th ca halogen

C C X X
H H H3C C C CH3 Br Br
Zn to
Zn to
C C
+ ZnX2
CH3CH=CHCH3 + ZnX2
III.4. Hydro ha alkyne

t , x ar H 2 dl Lin ) (Pd
R H
R' H
R C C R'
Na ,N H
3
R H
H R'
10
III.5. Nhit phn ester CnH2n+1-O-COR CnH2n + RCOOH
Nhit phn ester ca ru bc 1 < bc 2 < bc 3 Ester bc 1 1 sn phm, bc 2 & bc 3 nhiu sn phm IV. Tnh cht vt l (t c)
Ch tan trong dung mi khng phn cc hay t phn cc
V. Tnh cht ha hc Lin kt (E phn ly = 60 kcal/mol) yu hn lin kt (E = 80 kcal/mol) 11 o Xc tc, t ... lin kt d b t
V.1. Phn ng cng hp i in t V.1.1. C ch: Giai on 1:

dung moi xuc tac nhanh
C C
+ X+-Y
cham C C X+ Y phc khong ben
C+ C X
ben hoa C C X+
Giai on chm: X+ tn cng vo C=C i in t

12
Giai on 2:
Y-
C C X+
nhanh
Y C C X
Y- tn cng vo pha i lp vi X Nhm th y in t (+C, +I, +H) tng mt in t ca C=C tng kh nng phn ng AE
13
V.1.2. Phn ng cng hp halogen Phn ng cng hp ca CH2=CH2 vi Br2 vi s c mt ca NaCl, NaNO3, sn phm thu c l 1 hn hp: Br-CH2-CH2-Br + Br-CH2-CH2-Cl + Br-CH2-CH2-ONO2 Nu phn ng thc hin trong dung mi l CH3OH, sn phm chnh l Br-CH2-CH2-OCH3 !!!
14
H2C CH2 + Br2
CCl4
H2C CH2 Br Br
H2C CH2 + Br2
CH3OH
H2C CH2 Br OCH3
H2C CH2 + Br2
H2O
H2C CH2 Br OH
15
***Lp th ca phn ng cng X2: Cng hp trans (anti) cis sn phm l hn hp racemic (1 i i quang) trans sn phm c th l meso (1 sn phm)
H H C C CH3 CH3 Br2 CH3 H C Br Br C H CH3 CH3 H C Br H C Br CH3 http://hhud.tvu.edu.vn meso CH3 Br C H H C Br CH3 rac-
H3C H
C C
H CH3
Br2
16
V.1.3. Phn ng cng HX a. Quy tc Markonikov (dnh cho C=C khng i xng): H+ s tn cng vo carbon cha nhiu H
CH3-CH=CH2 + HBr CH3-CH-CH3 Br Br CH3-C-CH3 CH3
CH3-C=CH2 + HBr CH3
b. Quy tc Zaitsev-Wagner: H+ s tn cng vo pha to thnh carbocation trung gian bn nht

CH3-CH=CH-CH2-CH3 CH3-CH-CH-CH2-CH3 http://hhud.tvu.edu.vn Br HBr
17
c. Quy tc Kharasch: khi c mt peroxide, phn ng s i theo hng ngc vi Markonikov & theo c ch cng hp gc t do CH3-CH=CH2 + HBr CH3-CH2-CH2-Br Cc peroxide: H2O2, acetyl peroxide CH3CO-O-OCO-CH3, benzoylperoxide C6H5CO-O-O-COC6H5
18
C ch: Theo hng to gc t do bn

CH3-C-O-O-C-CH3 O O CH3-CO-O + HBr Br to CH3 + CH3-CO-O + CO2
Br
+ CH3COOH + CH3-CH-CH2Br
CH3-CH=CH2
CH3-CH-CH2 Br
CH3-CH-CH2Br
HBr
CH3-CH2-CH2Br + Br
Lu : HI & HCl khng tham gia phn ng cng 19 gc t do nh HBr!!!

V.1.4. Phn ng cng hp nc Cn xc tc acid: H2SO4, H3PO4 (khng dng HX)

CH3-CH=CH2 + H2O H2SO4 CH3-CH-CH3 OH
Tun theo quy tc Markonikov C ch:

CH3-CH=CH2 + H+ -H
+
+ CH3-CH-CH3
+ H2O -H2O
H H3 C C O CH3
H H
-H+ + H+
CH3-CH-CH3 OH
Nu dng nhiu H2SO4: CH3-CH=CH2 + H2SO4 (CH3)2CH-OSO3H (CH3)2CH-OSO3H + H2O (CH3)2CH-OH + H2SO4
20
V.1.5. Phn ng cng hp B2H6 Phn ng quan trng iu ch alcohol bc 1 & 2 t alkene, ngc vi sn phm Markonikov
CH3-CH=CH2 1. B2H6 2. H2O2 / NaOH CH3-CH2-CH2-OH
C ch: B2H6 BH3

CH3-CH=CH2 BH3 (Lewis acid) H + CH3-CH-CH2-B H H HOH[CH3-CH2-CH2-O]3B
21
CH3-CH2-CH2-BH2
[CH3-CH2-CH2]3B
H2O2
CH3-CH2-CH2-OH
V.2. Phn ng hydro ha V.2.1. C ch:

C C + H2 Ni C C H H
Xc tc thng dng: Ni, Pd, Pt C ch: gc t do (AR), 2 H gn vo cng pha ni i (khc phn ng +X2) cng hp cis
C C C C H H
22
H H + H2
H H
V.2.2. Tnh lp th Phn ng cng hp cis (syn) ng phn cis c th thu sn phm meso (1 sn phm) ng phn trans sn phm l hn hp racemic (1 i i quang)
H H C C COOH COOH D2 Ni COOH H C D H C D COOH meso COOH H C D D C H COOH COOH D C H H C D COOH rac-
maleic acid H HOOC COOH H D2 Ni
C C
fumaric acid
23
V.3. Phn ng oxy ha V.3.1. Tc nhn oxy ha peracid
C C O C C
R-C-O-O-H O
O C C
+ RCOOH
OH H2O C C (H+, OH-) OH
Cng hp trans, to -diol Phn ng khng gy ct mch C=C

24
V.3.2. Oxy ha bng ddch KMnO4 long (pH 7, 0oC ) Cng hp cis, to diol
OH0 oC pH 7 C O O C O OH2O H
+
C C
MnO4
Mn
C C OH OH
+ MnO3-
Phn ng khng ct mch C=C

25
V.3.3. Oxy ha bng ddch KMnO4 m c, to cao Phn ng gy ct mch C=C Sn phm l carboxylic acid CH3-CH=CH-CH3 + KMnO4 / to 2 CH3COOH (CH3)2CH=CH-CH3 + K2Cr2O7 /H2SO4/to (CH3)2C=O + CH3COOH
26
V.3.4. Oxy ha bng ozone Phn ng gy ct mch C=C Sn phm l carbonyl (khc KMnO4 )
C O C O
H3 C / Zn H2/Pt H
2O
H O CO
C O + H2O C O + H2O C O + H2O2
C C
O3
O molozonide
C C O O ozonide
(H + )
CH3-C=CH-CH2-CH3 CH3
1. O3 2. H2O
CH2-C-CH3 + O
CH3-CH2-CHO + H2O2
Lu : H2O2 d dng oxy ha carbonyl thnh 27 carboxylic acid sn phm cui l acid!!!
V.4. Phn ng polymer ha Phn ng to polymer di tc dng ca nh sng, to cao, xc tc C th xy ra theo c ch gc t do (xc tc peroxide), c ch cation (xc tc H2SO4, AlCl3, BF3) hay anion (xc tc LiNH2)
CH3 H2C C CH3
nCH2=CH Cl
H+
CH3 H3C C CH2 CH3

Cl
CH3 C CH2 CH3
CH3 C CH3
peroxide
--CH2-CH- CH2-CH- CH2-CH-Cl Cl polyvinyl chloride

28
Ha Hc Hu C
Chng 6: ALKADIENE I. Phn loi I.1. Hai ni i ng lin nhau (allene) CH2=C=CH2 propadiene CH3-CH2=C=CH2 1,2-butadiene
I.2. Hai ni i lin hp C cu to c bit c tnh cht ha hc quan trng ch trng cc hp cht ny CH2=CH-CH=CH2 1,3-butadiene CH2=C(CH3)-CH=CH2 2-methyl-1,3-butadiene (isoprene)
I.3. Hai ni i xa nhau Tnh cht ging nh alkene CH2=CH-CH2-CH=CH2 1,4-pentadiene
II. Cc phng php iu ch II.1. Tch nc t 1,3-butadiol i t acetylene

HC CH + H2O HgSO4 H2SO4
-
CH3-CHO
O H3C C + + H
O H2C C H H
OH
OH O H3C C CH2 C H H
H2/Ni
OH H3C C CH2 CH2OH H
Al2O3 350 C
CH2=CH-CH=CH2
+ 2H2O
5
II.2. T ethanol
2 CH3-CH2-OH ZnO/Al2O3 450-500 C
o
CH2=CH-CH=CH2
II.3. T 1,4-butadiol
HC CH + HCHO HO-CH2-CH2 CH2-CH-OH
HO-CH2-C Al2O3 350 oC

C-CH2-OH
H2/Ni
CH2=CH-CH=CH2
6
III. Tnh cht ha hc Cc in t c gii ta u trn ton b phn t linh ng
C1-C2: 1.38 (C=C bnh thng: 1.34) C2-C3: 1.46 (C-C bnh thng: 1.54) Khi c mt tc nhn khc, h lin hp s phn cc:
CH2=CH-CH=CH2 + CH2-CH=CH-CH2 + CH2-CH-CH=CH2
khc alkene bnh thng

7
III.1. Phn ng cng halogen Thu c 2 sn phm cng 1,2 & 1,4
CH2=CH-CH-CH2 CH2=CH-CH=CH2 + Br-Br Br Br CH2-CH=CH-CH2
C ch:
CH2=CH-CH=CH2 + + Br-Br
Br
Br
+ CH2=CH-CH-CH2 Br BrCH2=CH-CH-CH2
+ CH2-CH=CH-CH2 Br BrCH2-CH=CH-CH2 Br Br 8
Br Br
III.2. Phn ng cng HX Ty theo nhit m thu c hn hp sn phm khc nhau

CH2=CH-CH=CH2 + HBr -80 oC CH2=CH-CH-CH2 Br H CH2-CH=CH-CH2 Br H
40 oC 80% CH2=CH-CH-CH2 40 oC Br H CH2-CH=CH-CH2 Br H

9
20% 80%
20%
III.3. Phn ng Diels-Alder Phn ng cng hp & ng vng ca1,3butadiene hay dn xut ca n vi cc hydrocarbon khng no khc (i diene)
H H
C C
H C C H
H H
H H
C C
O C H
O CH3 to CH3
10
Cc hp cht i diene phi mang nhm th ht in t, ethylene phn ng rt chm CH2=CH-CHO acrolein CH2=CH-CN acrylonitrile (CN2)C=C(CN)2 tetracyan ethylene C6H5-CH=CH-COOH cinnamic acid
O O O
maleic anhydride
O
benzoquinone
11
III.4. Phn ng trng hp
n CH2=CH-CH=CH2
--CH2-CH=CH-CH2--
Trng hp isoprene cha 94% cis ~ cao su thin nhin
n CH2=C-CH=CH2 CH3
--CH2-C=CH-CH2-CH3
n
12
Ha Hc Hu C
Chng 7: ALKYNE I. Gii thiu chung Hp cht hydrocarbon khng no, mch h, cha lin kt ba CC Cng thc chung: CnH2n-2
180o
1.06
1.2
II. Danh php

II.1. Tn thng thng Alkyne n gin nht l HCCH acetylene Cc alkyne n gin khc c xem l dn xut ca acetylene HCC-CH2-CH3 ethylacetylene CH3-CC-CH(CH3)2 isopropylmethylacetylene
II. 2. Tn IUPAC Cch gi tn ging nh alkene, ch i ene thnh yne Mch chnh phi cha CC Nhng hp cht cha nhiu hn 1 ni ba diyne, triyne Hp cht va c ni i va c ni ba enyne
6-methyl-3-octyne
4-methyl-7-nonene-1-yne
1-heptene-6-yne
III. Cc phng php iu ch III.1. Thy phn calcium carbide CaC2

CaO + 3C 2000 oC CaC2 + CO HC CH + Ca(OH)2
CaC2 + 2H2O
III.2. Oxy ha methane

1500 oC 2 HC CH + 2CO + 10H 2
6CH4 + O2
III.3. i t dn xut dihalogen

H2C CH2 KOH/EtOH to Br Br CH3-CH2-CHCl2
o
HC CH
KOH/EtOH t
CH3-CH
CH
Cl CH3-CH2-C-CH3 Cl
H O t /E H KO to Na NH to 2
CH3-C
C CH3
CH3-CH2-C
CH
7
III.4. Alkyl ha dn xut natri hay c magnesium ca acetylene HCCNa HCC-MgX + R-X HCC-R + NaX
+ R-X HCC-R + MgX2
iu ch dn xut ca acetylene HCCH HCCH + NaNH2 HCCNa + CH3MgX HCC-MgX IV. Tnh cht vt l (t c)
+ NH3 + CH4
V. Tnh cht ha hc V.1. Phn ng th H u mch H u mch th hin tnh acid HCC-H + NaNH2 HCCNa + NH3 HCC-H + [Ag(NH3)2]+NO3- Ag-CC-Ag + NH4NO3 + NH3 C trong CC-H trng thi sp, m in ln hn sp2 hay sp3 ht in t ca lin kt C-H H+ d tch ra Alkene & alkane khng c tnh cht ny
V.2. Phn ng cng hydrogen

R C C R' + H2 Ni hay Pt R-CH2-CH2-R'
R-CH2-CH2-R'
/C d P
R C C R'
+ H2
Pd /Ca Pd CO /B aS 3 O
4
H H C C R R'
H R' C C R H
R C C R' + Na/NH3
10
V.3. Phn ng cng halogen
H3C C CH
+ Br-Br
Br H3C C CH Br
Br2
Br H3C C CHBr2 Br
Sn phm trans trong ln cng th nht Lu : nu ni i & ni ba khng lin hp, X2 s cng vo ni i!!! CH2=CH-CH2-CCH + Br2 BrCH2-CHBr-CH2-CCH
11
V.4. Phn ng cng HX
H H C C CH H
H-Br
H H-Br H C C CH2 H Br
H Br H C C CH3 H Br
Tun theo quy tc Markonikov

12
V.5. Phn ng cng nc

HC CH + H2O HgSO4 H2SO4 HC CH2 OH enol CH3CHO
R C CH + H2O
HgSO4 R C CH2 H2SO4 OH enol
R C CH3 O
Ch c acetylene mi to thnh aldehyde

13
V.6. Phn ng cng hp alkylborane
H + H H C C C C CH3 H H BHR2
H3C C C CH2 CH3 CH3COOH H BR2 H2O2/OHH3C C C CH2 CH3 H OH
C2H5 H3C C C H H
H3C CH2 C CH2 CH3 O
To alken: cng cis

14
V.7. Phn ng cng hp cht carbonyl Cng hp i nhn
+ H C C H
H C O + H
H C C CH2-OH HCHO
HO-H2C C C CH2-OH
H C C H
R + 2 C O R
R R HO-C C C C-OH R R
15
V.8. Phn ng cng hp i nhn

R-OH, R-SH, R-COOH, H-CN, amine monomer quan trng
HC CH RO150 oC ROCH CHR2NH
ROH
ROCH CH2
C6H5CO NR2 C C H H
+ RO-
C6H5CO C CH
C6H5C CH
C2H5ONa
C6H5 OC2H5 C C H H
CH2 CH C CH
ROH
-
RO http://hhud.tvu.edu.vn 150 oC
CH2 CH CH CHOR
16
V.9. Phn ng oxy ha Oxy ha alkyne bng KMnO4 hay ozone to carboxylic acid R-CC-R + KMnO4 hay ozone RCOOH + RCOOH R-CC-H + KMnO4 hay ozone RCOOH +CO2 V. 10. Phn ng trng hp
2H C C H CuCl to CH2=CH-C CH HCl CH2=CH-C CH2
Cl chloroprene cao su neoprene

CH2-CH=C CH2 Cl n
17
Ha Hc Hu C
Chng 6:
HYDROCARBON THM
I. Cu to ca benzene
Kkul a ra cng thc cu to ca benzene nm 1865 6C, 6H vng 6 cnh c 3 ni i nhng khng th l cyclotriene H H H C C C C C C H H 2 H
Kkul chng minh rng v tr 3 Lin kt i khng c nh m c th thay i
Phn ng th 2 ln Br ch cho 1 sn phm

Br Br + Br2 Br Br
Cu to thc t: h in t phn b u cho 6C (khng phi ca ring 3 cp C=C)
6C nm trong cng 1 mt phng, trng thi lai ha sp2

120
120
120 1.09
1.39
121.7o 116.6o 1.08 1.33

II. Tnh thm

Hydrocarbon thm (arene) nhng hp cht vng lin hp c cu to phng, c cu to in t ging benzene, kh cho phn ng cng, d cho phn ng th
H Br2 CCl4 Br Br2 CCl4 Br H
H KMnO4 L H2O H KMnO4 L H2O
OH OH
Arene thng l vng phng 5, 6, 7 cnh, c h in t lin hp, s t tun theo quy tc Hkel 4n + 2, n = 0,1,2,3,4 V d cc hp cht arene thng dng
n=1
n=2
n=3
7
Mt s trng hp c bit
cyclopentadienyl 6 in t (i t ca anion tham gia h lin hp) n=1 c tnh thm cycloheptatrienyl 6 in t (C+ tham gia orbital trng p vo h lin hp) c tnh thm
(-)
(+)
4 in t khng c tnh thm
(+)
2 in t c tnh thm
(+)

(.)
(.)
(-)
8 in t khng c tnh thm 6 in t (i in t p tham gia h lin hp) c tnh thm

9
N H Pyrrole
O Furan
http://hhud.tvu.edu.vn Thiophene
III. Danh php

Hu ht cc arene u c tn thng thng, 1 s tn thng thng c chp nhn lm tn IUPAC Tn IUPAC: benzene c chn lm tn gc, tn cc nhm th t trc, nhm th c nh s theo nguyn tc tng ch s nh nht, xp theo alphabetical
10
III.1. Dn xut ca benzene
11
12
I NO2 CH3 NO2 Br Cl
p-bromoiodobenzene m-chloronitrobenzene
o-nitrotoluene
OH COOH NH2 I Br NO2
4-bromophenol
m-nitrobenzoic acid
o-iodoaniline
HC CH2
HC CH2
1,4-divinylbenzene hay p-divinylbenzene khohttp://hhud.tvu.edu.vn ng goi la p-vinylstyrene
13
NO2
NH2 Br Br Br Cl
OH Cl
Cl
Br
Cl
3-bromo-5-chloronitrobenzene
2,4,6-tribromoaniline
2,4,6-trichlorophenol
Br Br
OH Cl O2N
CH3 NO2
Br
NO2
1,2,4-tribromobenzene
2-chloro-4-nitrophenol
2,6-dinitrotoluene
14
III.2. Vng a ngng t
8 7 6
9 10
8 2 3 7 6 5
1 2 3
5 4 Naphthalene
10 4 Anthracene
15
III.3. Cc arene c d t trong vng
N Pyridine
CH3
2-methylpyridine
N H Pyrrole
O Furan
S Thiophene
16
IV. Cc phng php iu ch

IV.1. Chng ct mui ca benzoic acid
COONa + NaOH to + Na2CO3
IV.2. i t acetylene
3HC CH Cu hay phc Ni to

17
IV.3. Alkyl ha benzene

R + R-Cl AlCl3 + HCl
IV.4. ng vng & dehydro ha phn on du m C6-C8
CH3(CH2)4CH3
Cr2O3 / Al2O3
V. Tnh cht vt l (t c)
18
V. Tnh cht ha hc
V.1. Phn ng th i in t V.1.1. C ch phn ng X
+ X+ acid + H+
Xc tc: H2SO4, H3PO4, HF hay Lewis acid: FeCl3, AlCl3, ZnCl2 C6H6 + (CH3)3C-Br /AlBr3 C6H5-C(CH3)3 + HBr 19
C ch phn ng: 2 giai on, lng phn t Giai on 1: to phc ( benzonium cation)
xt nhanh
H + + + X H
+ X -Y
X+-Y
phc
X cham
H +
phc
Trong phc : X khng lin kt trc tip vi C no c Phc : X c lin kt trc tip vi 1 C ca benzene
20
Giai on 2: tch proton
X +
H nhanh
X + HY
21
V.1.2. Kh nng phn ng v quy lut th

a. Kh nng phn ng: Nhm th y in t (+I, +C, +H) mt in t trong nhn thm tng tc nhn i in t cng d tn cng tc phn ng tng Cc nhm th y in t (tng hot) thng gp: * alkyl ( +I, +H) *-NR2 (R: H hay gc alkyl), -OH, -OCH3 -NH-CO-CH3 (+C > -I) * anion: -O- (+C, +I mnh)
22
Nhm th ht in t (-C, -I) mt in t ca nhm thm gim khng thun li cho tc nhn i in t gim tc phn ng Cc nhm th ht in t (gim hot) thng gp: * -N+N, -NO2, -CN, -CHO, -COR, -COCl, -COOH, -CO-NH2 (-I, -C) * cation: -N+R3 (-I mnh) * halogen (-I > +C)
OH Cl > > >
23
NO2
V d: kh nng th i in t:
b. Tnh chn la quy lut th Nhm th y in t nh hng nhm th th 2 vo v tr o- hay p Nhm th ht in t nh hng nhm th th 2 vo m Ring dy halogen gim hot, nhng vn nh hng nhm th 2 vo o-, p-
24
Nhn thm c nhm th y in t:

Y Y Y Y
mt t o-, p- cao nht nhm th th 2 (i in t) s vo o-, p Nhn thm cha nhm th ht in t:

Y Y Y Y
mt t o-, p- thp nht nhm th th 2 25 s vo mhttp://hhud.tvu.edu.vn
C th gii thch da vo bn ca phc

Y + X+
Th o-:
Y X H Y X H Y X H
Th p-:
X H http://hhud.tvu.edu.vn X H X
26
Th m-:
Y H X X Y H X Y H
khi Y y in t: trong th o-& p-: c 2 trng thi cation bn (+ gn Y nht) d to thnh nhm th th 2 s vo o-, p khi Y ht in t: trong th o-, p-: c 2 trng thi rt km bn (+ gn Y) nhm th 2 s khng vo o27 , p- m vo mhttp://hhud.tvu.edu.vn
c. Nhn thm c 2 nhm th: Nhm th th 3 s nh hng da theo nh hng ca nhm th tng hat nht V d:
-I>+C Cl +C>-I OH
+C>-I OH
+C>-I NH2
NH2 +C>-I
CH3 +I, +H
HN C CH3 O +C>-I
NO2 -C, -I
28
d. T l 2 ng phn o-/p-: D on: o-/p- = 2/1 Thc t o-/p- <2 Nguyn nhn 1: hiu ng khng gian nhm th hay tc nhn i t c kch thc ln s gim t l o-/p-
29
R HNO3 /H2SO4
R NO2 +
R Br2 /AlCl3
R Br +
NO2
Br
R -CH3 Phn ng
-CH2CH3
-CH(CH3)2 -C(CH3)3
Nitro ha
1.37
0.93
0.48
0.22
Brom ha
0.69
0.22
0.12
0
30
Nguyn nhn 2: Hiu ng in t

X HNO3 /H2SO4 X NO2 + NO2 X
t l o-/p-: X=F: 0.14 Cl: 0.43 Br: 0.60 I: 0.69 -I cng mnh, v tr o- cng b phn hot ha sn phm o- cng t
31
V.2. Cc phn ng th i in t tiu biu V.2.1. Phn ng nitro ha H ca nhn thm c thay th bng NO2+ Tc nhn nitro ha ch yu: HNO3 hay HNO3/H2SO4
NO2 + HNO3 H2SO4 + H2O
NO2+ to thnh do:

HNO3 + 2H2SO4 O N O + H3O+ + HSO4-
HNO3
+ HNO3
O
+ H2 O
+ NO3-
32
Nitro ha 1 ln: 50-60 oC Nitro ha 2 ln (m-): 70-80 oC Nitro ha 3 ln: phi i t toluene
CH3 HNO3 H2SO4 CH3 O2N NO2 [O] O2N COOH NO2 O2N NO2
NO2 T.N.T
NO2
-CO2
NO2
Nitroha phenol: khng cn H2SO4

OH HNO3 NO2
OH +
OH NO2
65%
35%
33
V.2.2. Phn ng sulfo ha H ca nhn thm c thay bng SO3H Tc nhn sulfo ha: H2SO4 , oleum, Cl-SO2OH
SO3H + H2SO4 20 oC + H2O benzenesulfonic acid
Tc nhn i in t c th l SO3 hay S+O2OH

2 H2SO4 2 H2SO4 SO3 + HSO4+ H3O+ + H2O
34
HOSO2+
+ HSO4-
Tnh cht ca sulfonic acid:

SO3H + H2O SO3H + NaOH L SO3H + NaOH R 300 oC ONa + Na2SO3 H+ OH to + SO3Na + H2O H2SO4
phng php kim chy, iu ch phenol

35
Nhm SO3H d b thay th bi nhm NO-2

OH H2SO4 OH SO3H HNO3 O2 N OH NO2
SO3H
NO2 picric acid
* iu ch sulfanilic acid
NH2 H2SO4 NH3+HSO4to -H2O H
NHSO3H
NH2
SO3H sulfanilic acid 36
Sulfo ha naphthalene
SO3H H2SO4 80 oC > 170 oC 170-180 oC
SO3H
37
V.2.3. Phn ng halogen ha
X + X2 xt + HX
Xc tc: AlCl3, FeBr3, ZnCl2 Flor ha: mnh lit, t mch t s dng Iodo ha: thun nghch
38
C ch phn ng:
+ Cl - Cl
FeCl3 nhanh Cl
Cl -Cl
cham
FeCl3 Cl + H FeCl4-
+ FeCl3 + HCl
39
iu ch C6H5I:
I + I2 + HNO3 H+ + I2 + HNO3 I+ + NO2 + H2O + NO2 + H2O
Tc nhn i in t I+ tn cng nhn thm theo c ch nh trn

40
Halogen ha mch nhnh ca arene: Nu c xc tc & nhit thp phn ng th i in t (SE) Nhit cao, nh sng hay peroxide: th vo mch nhnh (SR)
CH3 Cl2 130 oC CH2Cl Cl2 140-160 oC CHCl2 Cl2 >180 oC CCl3
Kh nng chlor ha SR: C bc 3 > C bc 2 > bc 1

41
V.2.4. Phn ng alkyl ha Friedel-Crafts a. Alkyl ha vi R-X, xc tc Lewis acid (AlCl3, FeBr3)
R + R-Cl AlCl3 + HCl
C ch:
+ R - Cl
+
AlCl3 nhanh R
R -Cl
cham
AlCl3 R +
AlCl4-
+ AlCl3 + HCl
42
b. Alkyl ha vi alkene, xc tc Lewis acid hay Bronsted acid (HF, H3PO4)

R-CH=CH2 H+ + R-CH-CH3
Carbocation tn cng nhn thm theo c ch th i in t nh trn, to thnh

H R C CH3
43
c. Alkyl ha vi alcohol, xc tc Lewis acid hay Bronsted acid (HF, H3PO4)
R-OH
+ H R-O H
R+ + H2O
Carbocation tn cng nhn thm theo c ch th i in t nh trn, to C6H5-R

44
d. Cc im cn lu ca phn ng alkyl ha Friedel-Crafts C6H5-X khng th to tc nhn i in t Tc phn ng alkyl ha ca R-X: bc 1 < bc 2 < bc 3 < dn xut benzyl hay allyl carbocation cng bn, phn ng cng d Alkyl ha khng dng li sn phm monohttp://hhud.tvu.edu.vn
45
Carbocation lun c chuyn v to cao:

CH3-CH2-CH2-Cl AlCl3 + CH3-CH2-CH2 H H3C C CH3 CH3-CH2-CH2-Cl AlCl3 70% + 30% + CH3-CH-CH3 CH2-CH2-CH3
Alkyl ha phenol, khng dng AlCl3 (to phc phi tr vi OH), phi dng H2SO4, H3PO4 lm xc tc Vng thm c nhm th ht in t mnh hn 46 halogen khng tham gia phn ng akyl ha
Sn phm c th b ng phn ha hay d ha khi xc tc d:

CH3 Lewis acid to CH3 CH2CH3 2 Lewis acid to
CH3
CH3
CH2CH3 + CH2CH3
47
V.2.5. Phn ng acyl ha Friedel-Crafts

R-CO-Cl (R-CO)2O Lewis acid R C O
a.C ch:
R C Cl O R C O R C O O + AlCl3 R-C+ O + [RCOOAlCl3]
_
+ AlCl3
+ R-C O
+ AlCl4-
Tc nhn i in t RC+=O tn cng nhn thm 48 theo c ch th i in t nh trn

b. c im quan trng Lng xc tc AlCl3 rt nhiu, do:

O C AlCl3 O C+ R
AlCl3
HCl O C
R
49
iu ch alkyl benzene bc 1 hoc mono-
CH2CH2CH3 C O CH3CH2CH2COCl AlCl3 Zn(Hg)/HCl
CH2CH2CH2CH3
Kh nng phn ng: RCOI > RCOBr > RCOCl > RCOF HCOCl khng bn phi dng CO/HCl/AlCl3 lm tc nhn acyl ha
50
Nhm th phn hat ha khng thun li cho phn ng:
O2N C O AlCl3 O2N + ClOC + AlCl3 O2N COCl
51
V.3. Phn ng th i nhn ca vng thm (SN) Vng thm giu in t SN ca benzene hay dn xut rt kh xy ra
X + Y
-
Y + X-
Cl + KOH 300 oC 280 atm

OH + KCl
Khng xy ra iu kin thng
52
Trng hp c bit: nhm th th 2 ht in t mnh & v tr o-, p- th i nhn ca nhm th 1 c th xy ra Cc nhm th ht in t mnh: -N+N, -NO2, -CN, CHO, -COR V d:
Cl + Na2CO3 L NO2
OH
NO2
53
NO2 Cl NaOH to NaNH2 N to
NO2 OH
NO2 NaOH to CH3ONa
NO2 OH
NH2
Cl
OCH3
C ch: th i nhn lng phn t

O N Ocham HOCl OH
-
O + ON nhanh -Cl-
O-
Cl
OH
54
Cc mui diazonium ca arene c kh nng cho phn ng th i nhn n phn t

N+ NClto cham + + N2 + Clnhanh YY Y- : H2O, HOCH3, I-, CNhttp://hhud.tvu.edu.vn
55
V.4. Phn ng oxy ha Nhn thm thng tr vi tc nhn oxy ha k c KMnO4, K2Cr2-O7 Trong iu kin nghim ngt:
O O2/ V2O5 450-500 oC O
O2/ V2O5
HC COOH 450-500 oC HC COOH
56
Nhnh alkyl ca vng thm rt d b oxy ha bi CrO3, K2Cr2O7/H2SO4, KMnO4/H2O, KMnO4/KOH -COOH
CH3 KMnO4 H2O, to NO2
COOH
NO2
57
Gc alkyl mch di ct mch, vn to COOH
CH2CH2CH2CH3 KMnO4 H2O
COOH
Nu khng c H benzyl, khng phn ng:

H3C CH3 C CH3 KMnO4 H2O
58
Ha Hc Hu C
Chng 9:
CC DN XUT HALOGEN
I.Phn loi
Cc hydrocarbon trong 1 hay nhiu H c thay bng nguyn t halogen Halogenoalkane: v d CH3-CH2-CH2-Cl Halogenoalkene: v d CH2=CH-CH2-CH2-Cl Halogenoalkyne: v d CHC-Cl Halogenoarene: v d C6H5-Cl Halogenocycloalkane: v d
Cl
2
II. Danh php II.1. Tn thng thng (dnh cho dn xut n gin) Gc alkyl + halide (halogenua) CH3-CH2-CH2-CH2-Br V d: n-butyl bromide (bromua)
(CH3)2CH-Cl isopropyl chloride (CH3)2CH-CH2-Cl isobutyl chloride C6H5-CH2-Cl benzyl chloride

II.2. Tn IUPAC Halogen c xem l nhm th halo: chloro-, bromo-, iodo-, fluoro Chn mch di nht cha halogen lm mch chnh nh s sao cho nhm th c ch s nh nht, bt k l halo- hay alkyl Khi c nhiu nhm th ging nhau, dng cc tip u ng di-, tri-, tetrahttp://hhud.tvu.edu.vn
Nu c nhiu nhm th halo khc nhau, sp xp theo th t alphabetical Nu mch chnh c th nh s t 2 u, u tin nhm ng trc theo th t alphabetical
CH3 CH3 CH3-CH2-C-CH2-CH-CH3 Br 4-bromo-2,4-dimethylhexane
H3C CH3 CH3-C-C-CH3 ClBr
2-bromo-3-chloro-2,3-dimethylbutane
5
III. Cc phng php iu ch III.1. Halogen ha alkane

CH3 H3C C CH3 + Cl2 H 25 oC h CH3 H3C C CH2Cl H 64% CH3 + H3C C CH3 Cl 36%
CH3 H3C C CH3 + Br2 H
127 oC h
CH3 H3C C CH2Br H 1%
CH3 + H3C C CH3 Br 99%
127 oC CH3-CH2-CH3 + Br2 h CH3-CH2-CH2-Br

CH3-CHBr-CH3 97%
6
3%
III.2. Cng hp halogen hay HX vo alkene, alkyne

H2C CH2 + Br2 CCl4 H2C CH2 Br Br
H2C CH2 + Br2
CH3OH
H2C CH2 Br OCH3
H2C CH2 + Br2
H2O
H2C CH2 Br OH
CH3-CH-CH-CH2-CH3 Br
CH3-CH=CH-CH2-CH3
HBr
C mt peroxide: CH3-CH=CH2 + HBr CH3-CH2-CH2-Br

III.3. Halogen ha arene

X + X2 xt + HX
Xc tc: AlCl3, FeBr3, ZnCl2

CH3 Cl2 130 oC CH2Cl Cl2 140-160 oC
CHCl2 Cl2 >180 oC
CCl3
III.4. i t alcohol a.Tc nhn HX

CH3-CH2-OH CH3-CH2-OH + HBr + HCl H2SO4 ZnCl2 CH3-CH2-Br + H2O CH3-CH2-Cl + H2O
b. Tc nhn PX3, PX5, SOCl2

R-OH R-OH R-OH + + + PCl3 PCl5 SOCl2 pyridine pyridine pyridine R-Cl R-Cl R-Cl + H3PO3 + POCl3 + SO2 + HCl
+ HCl
9
IV. Tnh cht vt l (t c) To s ca R-X bc 1 > bc 2 > bc 3 Ch tan tt trong dung mi hu c & khng tan trong nc V. Tnh cht ha hc V.1. c im chung
+ R-CH2-CH2 Cl
m in ca Cl >> C C-Cl phn cc mnh R-Cl c hot tnh cao Trong dy halogen, kh nng tch X: -I > -Br > -Cl > -F Nng lng phn ly lin kt C-I nh nht, bn knh 10 nguyn t I ln nht
Dn xut R-X c chia thnh 3 nhm : a. R-X hot ng mnh nht Dn xut bc 3, dn xut m C-X lin kt vi nhm vinyl hay aryl carbocation bn nht
CH3 H3C C Br CH3 -BrCH3 H3C C+ CH3 +I, +H
C Br
-Br
C+
+C > -I CH2=CH-CH-Br -Br+ CH2=CH-CH +C > -I

11
a.Nhm hot ng yu hn nhm a R-X bc 1: CH3-CH2-CH2-CH2-Br Nhm khng no nm xa nt halogen: CH3-CH=CH-CH2-CH2-Br a.Nhm hot ng yu Nguyn t halogen lin kt trc tip vi lin kt i, lin kt ba, vng thm
H3C CH CH Cl +C>-I Cl +C>-I
+C ca X lm cho C-X bn kh phn cc, kh tch

12
V.2. Phn ng th i nhn R-X + Y- R-Y + X-
Dn xut bc 1 SN2 Dn xut bc 3 SN1 Phn ng thy phn R-X R-X + OH- R-OH + X-
CH3-CH2-Br + OH- CH3-CH2-OH + Brhttp://hhud.tvu.edu.vn
13
Phn ng to ether (Williamson) R-X + R-O- R-O-R + XCH3-CH2-Br + CH3-O- CH3-CH2-O-CH3 Phn ng to amine R-X + NH3 R-NH2 + HX CH3-CH2-Br + NH3 CH3-CH2-NH2 + HBr CH3-CH2-CH2-CH2-NH2 + CH3-CH2-Br CH3-(CH2)3-NH-C2H5 + HBr
14
Phn ng to nitrile R-X + KCN R-CN + KX CH3-CH2-Br + CN- CH3-CH2-CN + BrLu : R-CN d b thy phn trong nc to R-COOH
15
V.3. Phn ng tch loi

CH3-CH-CH-CH3 KOH/ethanol CH3-CH=CH-CH3 o t H Br
Gc R c bc cng cao, hay base cng mnh th tch loi cng chim u th
CH3-CH2-CH2-Br + C2 H5 O to thng CH3-CH2-CH2-O-C2H5
CH3 H3C C Br CH3
C 2H 5 O to cao
H 2C C
CH3 CH3
16
V.4. Phn ng vi kim loi-Hp cht Grignard CH3-CH2-Br + Na CH3-CH2-CH2-CH3 + NaBr Quan trng: phn ng vi magnesium
R-X
+ Mg
ether khan
R-Mg-X
+ C Mg Br
C-MgX phn cc rt mnh, rt d to R- base rt mnh & tc nhn i nhn rt mnh

17
V.4.1. Phn ng vi H linh ng CH3-CH2-MgBr + HOH CH3-CH3 + HO-MgBr CH3-CH2-MgBr + ROH CH3-CH3 + RO-MgBr CH3-CH2-MgBr + RNH2 CH3-CH3 + RNH-MgBr CH3-CH2-MgBr + RCOOH CH3-CH3 + RCOO-MgBr CH3-CH2-MgBr + RCCH CH3-CH3 + R-CC-MgBr
18
V.4.2. Phn ng vi carbonyl

+ O CH3-CH2-MgBr + H C C H 3 + OH H3C C H C2H5 O-MgBr H2O /H+ H3C C H C2H5
+ HO-MgBr
Phn ng vi HCHO alcohol bc 1 Vi aldehyde alcohol bc 2 Vi ketone alcohol bc 3

19
V.4.3. Phn ng vi CO2

+ + CH3-CH2-MgBr O C O C2H5-C-O-MgBr O H2O /H+ C2H5-COOH + HO-MgBr
V.4.4. Phn ng vi nitrile

+ CH3-CH2-MgBr + + R-C N R C N MgBr C2H5 H2O /H+
R C NH H2O /H+ R C O C2H5 C2H5
Kh nng phn ng: nitrile > ketone ch khi d Grignard phn ng tip vi ketone to alcohol 20 bc 3
V.4.5. Phn ng vi dn xut ca carboxylic acid

+ O CH3-CH2-MgBr + H C C Cl 3 + O-MgBr OH H2O /H+ H3C C Cl H3C C Cl C2H5 C2H5
-HCl
H3C C O C2H5
Kh nng phn ng: dn xut acid > ketone ch khi d Grignard phn ng tip vi ketone to alcohol bc 3 Tng t cho phn ng vi anhydride
21
Phn ng vi ester:
+ O CH3-CH2-MgBr + H C C OCH 3 3 +
O-MgBr OH H2O /H+ H3C C OCH3 H3C C OCH3 C2H5 C2H5 C2H5 H3C C OH C2H5
-CH3OH
H3C C O C2H5
1. C2H5-MgBr 2.H2O /H+
Kh nng phn ng: ester < ketone khng th 22 tch ketone trung gian
V.4.5. Phn ng vi oxide
CH3-CH2-MgBr +
CH2 O
CH2
ether khan
CH3-CH2-CH2-CH2-OMgBr
H2O /H+
CH3-CH2-CH2-CH2-OH
MgBr + CH2 O CHCH3 1. ether khan 2. H2O / H+

OH CH2CHCH3 60%
23
V.4.6. Phn ng ghp i Kumada Kharash

RMgX + R'X CoCl2 R R' + MgX2
Kumada: t sn phm ph hn Kharash

L2NiX2 RMgX' + R'X'' or L2PdX2 R-R' + MgX'X''
24
Ha Hc Hu C
Chng 10: ALCOHOL-PHENOL Chng 10A: Alcohol

R-OH trong : R: no hay khng no CH3-CH2-OH CH2=CH-CH2-OH R: nhnh ca arene C6H5-CH2-OH
I. Danh php
I.1. Tn thng thng (dng cho alcohol n gin) Gc alkyl + alcohol CH3-CH -OH (CH3)2CH-OH (CH3)2CH-CH2-OH (CH3)3C-OH C6H5-CH2-OH CH2=CH-CH2-OH ethyl alcohol isopropyl alcohol isobutyl alcohol tert-butyl alcohol benzyl alcohol allyl alcohol
C th gi CH3-OH l carbinol, cc alcohol khc l dn xut ca carbinol, v d: methyl carbinol 3 (ethyl alcohol)
I.2. Tn IUPAC Chn mch di nht c cha nhm OH lm mch chnh Ly tn alkane, i ane anol nh s mch chnh t u gn nhm OH nht Khi c nhiu nhm th, sp xp theo th t alphabetical CH3-OH CH3-CH2-OH
methanol ethanol
4
CH3 H3C C CH2-OH CH3
2,2-dimethyl-1-propanol
CH3 CH3-CH-CH-CH3 OH
3-methyl-2-butanol
OH
7-ethyl-8,9-dimethyl-5-dodecanol
C6H5-CH2-OH
phenylmethanol
II. Cc phng php iu ch

II.1. Cng hp nc vo alkene Phn ng cn xc tc acid: H2SO4, H3PO4 (khng dng HX)
CH3-CH=CH2 + H2O
H2SO4
CH3-CH-CH3 OH
Tun theo quy tc Markonikov

Phn ng quan trng iu ch alcohol bc 1 & 2 t alkene, ngc vi sn phm Markonikov:
CH3-CH=CH2
1. B2H6 2. H2O2 / NaOH
CH3-CH2-CH2-OH
II.2. Kh ha carbonyl, carboxylic acid v dn xut Kh bng H2
R C R' O
+ H2
Ni
H R C R' OH
aldehyde alcohol bc 1 ketone alcohol bc 2

Kh bng LiAlH4, NaBH4 R-CHO + LiAlH4 R-COOH + LiAlH4 R-CH2-OH + R-CH2-OH
Kh bng [(CH3)2CH-O]3Al trong (CH3)2CH-OH R-CHO + [(CH3)2CH-O]3Al/(CH3)2CH-OH R-CH2-OH + (CH3)2CO

II.3. i t hp cht Grignar

+ O CH3-CH2-MgBr + H C C H 3 + OH H3C C H C2H5 O-MgBr H2O /H+ H3C C H C2H5
+ HO-MgBr
II.4. Thy phn R-X, dn xut ca ester

O R C OR' + H2 O OHR-COO+ R'-OH
R-X + OH- R-OH + Xhttp://hhud.tvu.edu.vn
10
III. Tnh cht vt l

R-OH to lin kt H to si cao hn cc dn xut ca hydrocarbon c khi lng phn t tng ng C1-C3: tan tt trong nc C4-C7: tan 1 phn trong nc >C7: khng tan trong nc
11
IV. Tnh cht ha hc

IV.1. Gii thiu chung a. Kh nng t lin kt C-O Ch xy ra trong mi trng acid
R OH + H
+
+ H R O H
R+
+ H2 O
Kh nng phn ng: bc 1 < bc 2 < bc 3

12 C-OH cha nhiu nhm th y in t thun li
b. Kh nng t lin kt O-H Ch xy ra trong mi trng base mnh
R OH
R-O
+ H+
Kh nng phn ng: bc 1> bc 2> bc 3 R cha nhiu nhm y in t khng thun li
13
IV.2. Tnh acid-base Tnh acid ca alcohol rt yu Tnh acid: C2H5-OH (Ka 1.3x10-18) < H2O (1.3x10-14) < C6H5-OH (1.3x10-10) < CH3COOH (1.8x10-5) Alcohol hu nh khng phn ng vi NaOH
R OH
+ NaOH
R-ONa + H2O
14
Alcohol ch tc dng vi Na hay NaNH2

R OH R OH + Na + NaNH2 R-ONa + H2 R-ONa + NH3
Mui alkoxide l base rt mnh Tnh base: (CH3)3C-O- > (CH3)2CH-O- > CH3-CH2-O> CH3-O- > OHhttp://hhud.tvu.edu.vn
15
IV.3. Phn ng to ether

2 CH3-CH2-OH H2SO4 CH3-CH2-O-CH2-CH3 + H2O
2 CH3-CH2-OH
Al2O3 350-400 C
o
CH3-CH2-O-CH2-CH3
+ H2O
Alcohol bc 1: SN2 Alcohol bc 3: SN1 ***Danh php ca ether: tn gc alkyl + ether C2H5-O-C2H5 diethyl ether
16
CH3-O-C(CH3)3 tert-butyl methyl ether

Nu gc alkyl phc tp, c th xem l nhm th alkoxy

CH3-CH2-CH2-CH-CH2-CH3 OCH3
3-methoxyhexane
CH2 OH
H3C CH3
CH2 OC2H5
2-ethoxyethanol
CH3-CH-CH CH3 OC2H5
2-ethoxy-2,3-dimethylbutane
17
IV.4. Phn ng ester ha

R C OH O R C Cl O O R C O R C O + R'-OH H2SO4 R C O-R' O R C O-R' O + H2O
+ R'-OH
+ HCl
+ R'-OH
R C O-R' O
+ RCOOH
Kh nng phn ng: RCO-Cl (khng cn xc tc) > (RCO)2O (khng cn xc tc) > RCOOH 18
R'-OH + R C OH O + H O R' R C OH OH O R' R C OH + HSO4-H+
C ch phn ng:
+ H
+ R C OH OH
O R' R C OH OH2 + O R' R C O
-H2O
Kh nng phn ng: alcohol bc 1> bc 2> bc 3 HCOOH > CH3COOH > RCH2COOH > R2CHCOOH > 19 R3CCOOH
IV.5. Phn ng th -OH bi halogen a.Tc nhn HX

CH3-CH2-OH + HBr H2SO4 ZnCl2 CH3-CH2-Br + H2O CH3-CH2-Cl + H2O
CH3-CH2-OH + HCl
Kh nng phn ng: HI > HBr > HCl > HF HCl kh phn ng, cn xc tc ZnCl2 Lewis acid tn cng vo O lin kt C-O d t Kh nng thay th: bc 3 > bc 2 > bc 1
20
b. Tc nhn PX3, PX5, SOCl2
R-OH R-OH R-OH
+ + +
PCl3 PCl5 SOCl2
pyridine pyridine pyridine
R-Cl R-Cl R-Cl
+ H3PO3 + POCl3 + SO2 + HCl
+ HCl
21
IV.6. Phn ng dehydro ha v oxy ha a. Phn ng dehydro ha

R-CH2OH Cu 200-300 oC R-CHO + H2
R R C H OH
Cu 200-300 C
o
R C R O
+ H2
CH3 CH3-C-CH2-CH3 OH
Cu 200-300 oC
CH3 CH3-C=CH-CH3
+ H2O
22
b. Phn ng oxy ha Tc nhn oxy ha: KMnO4, K2Cr2O7, CrO3 Alcohol bc 1 aldehyde carboxylic acid Rt kh dng li giai on aldehyde thng i thng n RCOOH
R-CH2OH + KMnO4 R-COOK H+
+ MnO2 + KOH
RCOOH
23
Mun dng li giai on aldehyde: phi dng pyridinium chlorocromate C5H5NH+CrO3Cl- (PCC):
R-CH2OH C5H5NH+CrO3ClCH2Cl2 RCHO + Cr3+
Alcohol bc 2 ketone
(H3C)3C OH Na2Cr2O7 CH3COOH, H2O to (H3C)3C O
Alcohol bc 3 ch b oxy ha trong acid (tch nc thnh alkene oxy ha ct mch alkene)
CH3 CH3-C-CH2-CH3 OH H3C C CH3 H2SO4, to http://hhud.tvu.edu.vn O KMnO4 + CH3-COOH
24
Chng 10B:
Phenol
-OH lin kt trc tip vi nhn thm

o
1,36 A
109 o
25
I. Danh php
OH OH CH3 CH3 OH OH
phenol
o-cresol
m-cresol
CH3
p-cresol
OH OH OH OH O2N OH OH NO2 OH NO2
Tn thng thng
catechol
OH OCH3
resorcinol
hydroquinone
OH CH(CH3)2
picric acid
OH
OH
H3C CH2CH CH2
eugenol
26
Thymol
-naphthol
-naphthol
Tn IUPAC
OH OH OH CH3 Br OCH3 Cl Cl
4-methoxyphenol
3-bromo-4-chlorophenol 5-chloro-2-methylphenol
OH OH
OH
OH
OH
OH
1,2-benzenediol
http://hhud.tvu.edu.vn 1,3-benzenediol
1,4-benzenediol
27
II. Cc phng php iu ch

II.1. Chng ct nha than Ly phn on 170-240 oC Tch phenol bng cch chuyn thnh phenolate ha tan Hon nguyn phenol C6H5ONa + CO2 + H2O C6H5OH + NaHCO3
28
II.2. Thy phn chlorobenzene

Cl + KOH 300 oC 280 atm OH + KCl
Khng xy ra iu kin thng II.3. Phng php kim chy

SO3H + NaOH R 300 oC ONa + Na2SO3 H+ OH
29
II.4. Oxy ha cumene (dng trong cng nghip)
CH(CH3)2 O2
OH O H3C C CH3 H2O, H+ cumene hydroperoxide
OH + H3C C CH3 O
30
II.5. Thy phn mui diazonium (phng TN)

N+ N Cl+ H2O 40-50 oC OH + N2 + HCl
iu ch mui diazonium:
NH2 + NaNO2 + HCl N+ N Cl+ NaCl + H2O
31
III. Tnh cht vt l +C ca OH vi nhn thm O-H phn cc mnh kh nng to lin kt H ca phenol > alcohol to si , to nng chy, ha tan trong nc > alcohol tng ng phenol tosi (oC) 180 tonc 41 ha tan (g/100g H2O)9.3
cyclohexanol 161 25.5 3.6

32
IV. Tnh cht ha hc
O H
IV.1. Tnh acid

O-H phn cc tnh acid > HOH > alcohol
OH NaOH OH Na ONa + H2 ONa + H2O
Tnh acid: phenol < H2CO3 : H2O C6H5OH + NaHCO3 C6H5ONa + CO2 + http://hhud.tvu.edu.vn
33
So snh tnh acid ca 1 s phenol:

OH > pKa NO2 7.15 OH > 10.08 CH3 CH3 OH NO2 > NO2 7.23 OH > 10.14 8.4 OH CH3 OH
OH
10.28
OH > OCH3 OCH3 >
OH
9.65 OH Cl >
9.98 OH > Cl 9.02
OCH3 10.21 OH
8.48
Cl 34
9.38
IV.2. Phn ng to ether Khc vi alcohol
OH + C2H5OH H+
OH +
OH H+
35
Gii thch:
CH3-CH2-OH H+ + + H CH2-CH2-O H
O H
+C ca OH lm gim mt in t ca O khng c kh nng tn cng vo oxonium cation khng c SN2

36
Ngoi l:
OH + CH3OH O-CH3 + H2O methyl ethyl ether /nerolin
H2SO4
Mt in t O trn naphthol > trn phenol iu ch ether ca phenol bng phng php Williamson:
ONa + C2H5-Br
O C2H5 + NaBr
37
ONa + CH2=CH-CH2-I
O CH2
CH
CH2 + NaBr
ONa +
O CH3 H3C O O S H3C O O I O +

Na O O S H3C O O
ONa
+ NaI
38
Lu : iu ch C6H5-O-C2H5 , cn i t C6H5ONa+ C2H5-Br nhng khng i t C6H5-Br + C2H5ONa Ether ca phenol c th b ct mch:
OCH3 57% HI 120-130 oC
OH + CH3I
39
IV.3. Phn ng ester ha Khc vi alcohol

OH + CH3COOH H+
Phi dng dn xut chloride hay anhydride ca carboxylic acid

OH + H3C C Cl O
http://hhud.tvu.edu.vn acetyl chloride
O C CH3 O + HCl
40
OH + C6H5 C Cl O benzoyl chloride OH +
O C C6H5 O + HCl
O H3C C O H3C C O
O C CH3 O + CH3COOH
Lu :
O C C2H5 O OH O C OH C2H5 + O C C2H5
41
AlCl3 t
o
IV.4. Phn ng th nhm OH Khc vi alcohol

OH + X-
Ngoi l:
OH O2N NO2 + PCl5 NO2 NO2 O2N Cl NO2 + POCl3 + HCl
OH Zn 400 C
http://hhud.tvu.edu.vn o
+ ZnO
42
IV.5. Phn ng th i in t -OH (+C>-I) vng thm tham gia SE d dng, sn phm o-, p Halogen ha
OH + Br2 H2O -HBr Br OH + Br2 CS2 -HBr
OH Br Br
OH Br +
OH
Br
43
Nitro ha phenol: Khng cn H2SO4, xy ra to thng, ng phn od tch bng chng ct li cun hi nc
OH HNO3 OH NO2 + NO2 35%
OH
65%
44
Sulfo ha
OH SO3H OH H2SO4 15-20 oC H2SO4 100 oC OH
100 oC
SO3H
Friedel-Crafts: thng cho hiu sut thp (cn dng xc tc HF, H3PO4)
45
IV.6. Phn ng Kolbe (trong cng nghip)

O-Na+ + + O C O 125 oC 4-7 atm O O H C
ONa
OH O C
ONa
H+
OH O C
OH
Sn phm ph l p-hydroxybenzoic acid, c th tch khi salicylic acid bng chng ct li cun hi nc 46
IV.7. Phn ng vi formaldehyde Trong mi trng base:

O+ H + C O H SE HOCH2OH OH H+ + CH2OH OH CH2OH O+ OCH2OH
Trong mi trng acid:
OH OH H + C O H H+ H+ C OH H +
OH CH2OH
SE
CH2OH
47
Ha Hc Hu C
Chng 9: ALDEHYDE-KETONE
I. Gii thiu chung
C O
R-CHO aldehyde RCOR ketone

Ty theo cu to ca R, s c hp cht carbonyl mch h (no + khng no) & carbonyl thm CH3-CH2-CH2-CHO CH2=CH-CH2-CHO
O C
CH3-CH2-C-CH3 O
O C
CH3
3
II. Danh php

II.1. Aldehyde *Tn thng thng Da theo tn carboxylic acid tng ng, thay ic acid bng aldehyde Aldehyde mch nhnh xem nh l dn xut ca mch thng, dng , , ... ch v tr nhnh Mt s tn thng thng c chp nhn lm tn IUPAC
* Tn IUPAC Mch chnh di nht & cha CHO Gi theo tn hydrocarbon tng ng thay ne nal HCHO formaldehyde / methanal CH3CHO acetaldehyde / ethanal C6H5CHO benzaldehyde /phenylmethanal C6H5CH2CHO phenylacetaldehyde / phenylethanal
CH3-CH2-CH-CH2-CHO CH3
-methylvaleraldehyde / 3-methylpentanal
II.2. Ketone
Tn thng thng Tn 2 gc alkyl + ketone Nu nhm carbonyl gn trc tip vng thm phenone Tn IUPAC Mch chnh di nht cha nhm carbonyl nh s nhm carbonyl c ch s nh nht Gi theo tn hydrocarbon, thay ne none
H3C C CH3 acetone / propanone O CH3-CH2-CH2-C-CH3
O
methyl n-propyl ketone / 2-pentanone
CH2 C CH3 O
benzyl methyl ketone / 1-phenyl-2-propanone
C CH3 O
acetophenone / 1-phenylethanone / methyl phenyl ketone
H3C C CH CH2 O methyl vinyl ketone / 3-butane-2-one

III. Cc phng php iu ch III.1. Oxy ha hydrocarbon

CH4 NO 600-700 C CuCl2 50 C
o o
+ O2
HCHO
+ H2O
H2C CH2 + O2
CH3-CHO
CH3 + O2 Co2+
CHO
III.2. i t alkyne
HC CH + H2O HgSO4 H2SO4 HC CH2 OH enol CH3CHO
R C CH + H2O
HgSO4 R C CH2 H2SO4 OH enol
R C CH3 O
H + H H C C C C CH3 H H BHR2
H3C C C CH2 CH3 CH3COOH H BR2 H2O2/OHH3C C C CH2 CH3 http://hhud.tvu.edu.vn H OH
H3C C2H5 C C H H
H3C CH2 C CH2 CH3 9 O
III.3. Ozone ha alkene

OH O C
C C
O3
C O
C O
O molozonide
C C O O ozonide
H3 C / Zn H2/Pt H
2O
C O + H2O C O + H2O C O + H2O2
(H + )
CH3-C=CH-CH2-CH3 CH3
1. O3 2. H2O
CH2-C-CH3 + O
CH3-CH2-CHO + H2O2
Lu : H2O2 d dng oxy ha aldehyde thnh carboxylic acid sn phm cui l acid!!! 10
III.4. i t alcohol Dehydro ha alcohol bc 1, bc 2

R-CH2OH Cu 200-300 oC R-CHO + H2
R R C H OH
Cu 200-300 C
o
R C R O
+ H2
CH3 CH3-C-CH2-CH3 OH
Cu 200-300 oC
CH3 CH3-C=CH-CH3
+ H2O
11
Oxy ha alcohol: Tc nhn oxy ha: KMnO4, K2Cr2O7, CrO3 Alcohol bc 1 aldehyde carboxylic acid Rt kh dng li giai on aldehyde thng i thng n RCOOH Mun dng li giai on aldehyde, phi dng pyridinium chlorocromate C5H5NH+CrO3Cl- (PCC):
R-CH2OH
C5H5NH+CrO3ClCH2Cl2
RCHO + Cr3+
12
Alcohol bc 2 ketone
Na2Cr2O7 CH3COOH, H2O to
(H3C)3C
OH
(H3C)3C
OH
Na2Cr2O7 H2SO4 / H2O
O 85%
OH H2C CHCHCH2CH2CH2CH2CH3
PCC CH2Cl2
O H2C CHCCH2CH2CH2CH2CH3 80%

13
III.5. i t dn xut ca carboxylic acid

O R C Cl Pd/BaSO4
H2
R-CHO
+ HCl
COCl LiAlH(O-tBu)3
CHO
NO2
NO2
(RCOO)2Ca
to
R C R O
+ CaCO3
14
+ O CH3-CH2-MgBr + H C C Cl 3 +
O-MgBr OH H2O /H+ H3C C Cl H3C C Cl C2H5 C2H5
-HCl
H3C C O C2H5
Kh nng phn ng: dn xut acid > ketone ch khi d Grignard phn ng tip vi ketone to alcohol bc 3 Tuy nhin, thc t kh tch ketone vi hiu sut
cao
15
III.6. iu ch hp cht carbonyl ca arene

R-CO-Cl (R-CO)2O Lewis acid R C O
HCOCl khng bn phi dng CO/HCl/AlCl3 lm tc nhn acyl ha (Phng php GattermannKoch)
H3C + CO + HCl [H-C-Cl] O
AlCl3
H3C
CHO + HCl
16
C th thay CO bng HCN khan (phng php Gattermann)

+ NH2 ClC H
H3C O
+ HCN + HCl [H-C-Cl] NH
AlCl3
H3C O
H2O -NH4Cl
H3C O
CHO
Thay HCN bng R-CN iu ch ketone thm 17

IV. Tnh cht vt l

Khng to lin kt H nh alcohol to si < alcohol tng ng Phn cc mnh, d tan trong nc (C1-C5)
+ sp2 C O
V. Tnh cht ha hc
Cu to phng Gc lin kt ~ 120o Moment lng cc = 2.7 D (CH3CHO) di lin kt C-O 1.23
18
V.1. Phn ng cng hp i nhn (AN)
+ C O
+ X -Y
OX Y
X-Y c th l H-OH, H-OR, H-CN, H-SO3Na, Li-R, BrMg-R

19
a. C ch: 2 giai on, lng phn t Giai on 1:

C
+
+ Y
cham
C OY carbanion
Giai on chm: Y- tn cng vo C+ i nhn Giai on 2:
C O Y
+ X+
nhanh
C OX Y
20
b. nh hng ca nhm th lin kt vi C=O Nguyn t C trong C=O c in tch dng cng ln AN cng thun li Nhm th y t (+C, +I, +H) lm gim kh nng phn ng Nhm th ht t (-C, -I) lm tng kh nng phn ng
R C R NO2-CH2-CHO > H-CHO > R-CHO > O R C O-R R C NH2 > O O
R C O R C NHR > > 21 O O
V.2. Phn ng vi tc nhn i nhn carbon

Phn ng vi hp cht Grignard
+ O CH3-CH2-MgBr + H C C H 3 + OH H3C C H C2H5
O-MgBr H2O /H+ H3C C H C2H5
+ HO-MgBr
22
O C
1. ether khan CH3CH2CH2CH2MgBr 2. H3O+ CH3CH2CH2CH2CH2OH
CH3CH2
O C
CH3CH2CH2MgBr
1. ether khan 2. H3O+
OH CH3CH2CHCH2CH2CH3
CH3
O C
CH2CH2CH3
1. ether khan CH3CH2MgBr 2. H3O+
OH CH3CCH2CH2CH3 CH2CH3
CH3CH2CH2
O C
MgBr 1. ether khan H +

2. H3O+
OH CH3CH2CH2CH
23
Phn ng vi acetylide anion
CH3C CH
NaNH2
CH3C CNa
NH3
CH3C CH
Na
CH3C CNa
H2
CH3CH2
O C
CH3C C H
OCH3CH2CHC CCH3
N H+
OH CH3CH2CHC CCH3
24
Phn ng vi hydrogen cyanide

O C
-
H3C
CH3
C N
OH3C C C N CH3
HCN
OH H3C C C N CH3
C N
CH3CH2
OH C C N CH2CH3
HCl / H2O t
o
CH3CH2
OH C COOH CH2CH3
CH3CH2CH2
OH C C N H
H2 Pt
CH3CH2CH2
OH C CH2NH2 H
25
V.3. Phn ng vi tc nhn i nhn oxygen

Phn ng vi nc gem-diol
CH3 O C + CH3 H2O CH3 OH C CH3 OH 0,2% OH C H OH 58% OH H C H OH 99,9%
99,8%
CH3
O C
+ H
H2O
CH3
42% O C
+ H
H2O
0,1%
26
Phn ng vi alcohol
O R C H R'-OH/H
+
OH R C OR' H hemiacetal
R'-OH/H -H2O
OR' R C OR' H acetal
O R C H
+H
-H+
OH R C+ H
+ R'-OH - R'-OH
OH + R C OR' H H
- H+ + H+
OH R C OR' H hemiacetal H + OR' R C OR' H
+H+ -H+
+
+ OH2 R C OR' H OR' R C OR' H acetal
- H2O + H2O
+ R C OR' H
+ R'-OH - R'-OH
-H
+ H+
27
Acetal bo v nhm chc
O C
O OCH3 HOCH2CH2OH HCl
O C
OCH3
LiAlH4
O CH2OH2O / HCl CH2OH
O H O
O HOCH2CH2OH HCl O
O H
1. CH3MgBr 2. H2O / HCl OH
28
V.4. Phn ng vi tc nhn i nhn nitrogen

Phn ng vi amine bc 1
O + R C H
NH2-R'
O- H R C N R' + H H
OHH R C N R' H
carbinolamine
H H O H R C N R' H
+ H+
- H2O
H R C N R' H
-H+
R C N R' H
29
Phn ng vi amine bc 2
RCH2
O + C H
NHR2
RCH2
O- H C N R + H R
RCH2
OHR C N R H
carbinolamine
H H O R RCH2 C N R H
+ H+
- H2O
RCH2
R C N R H
-H+
R RCH C N R H
30
Phn ng hnh thnh imine

CHO + H2NOH CH NOH + H2O
oxime
C O H3C
H2NNH2
C NNH2 H3C
H2O
hydrazone
O O + H2NNHCNH2
O NHNCNH2
H2O
31
semicarbazone
V.5. Phn ng vi tc nhn i nhn lu hunh

O + R C H ONa :S O OH ONa R C SO3H H OH R C SO3Na H
OH R C SO3Na H
HCl
R-CHO + SO2 + H2O + NaCl
OH R C SO3Na H
NaOH
R-CHO
Na2SO3
+ H2O
32
V.6. Phn ng ngng t aldol

Trong mi trng base (NaOH, Ba(OH)2, Na2CO3, CH3COONa) , aldehyde hay ketone c H c th phn ng vi nhau ngng t aldol a. Phn ng gia aldehyde v aldehyde
CH3-CHO + CH3-CHO
OH-
CH3-CH-CH2-CHO OH
to
CH3-CH=CH-CHO
+ H2O
33
C ch: Giai on 1 to carbanion

H CH2 O C H + OHO _ CH2 C H + H2O
Giai on 2 cng hp i nhn

O H3C C H + O _ CH2 C H OCH3-CH-CH2-CHO
Giai on 3 proton ha, ti to OHOCH3-CH-CH2-CHO + H2O OH CH3-CH-CH2-CHO + OH-
OH CH3-CH-CH2-CHO
OH-
O CH3-CH=CH2-C H
34
Sn phm tch nc bn do lin hp gia C=C v C=O
b. Phn ng gia aldehyde v ketone C ch tng t nh trn, trong aldehyde ng vai tr tc nhn carbonyl, ketone ng vai tr tch H to carbanion
CH3-CHO + H3C C CH3 O -H2O OH
-
OH CH3-CH-CH2-C-CH3 O
CH3-CH=CH-C-CH3 O
35
c. Phn ng gia ketone v ketone Hiu sut rt thp
O 2 CH3CCH3
OH
OH O CH3CCH2CCH3 CH3
OH to
O CH3C CHCCH3 CH3
+ H2O
36
d. Phn ng gia 2 carbonyl khc nhau (crossed aldol ) C th thu c 1 hn hp 4 sn phm Thng ch hiu qu khi 1 carbonyl khng c H & carbonyl c H c thm t t vo phn ng 1 sn phm
CHO + CH3CH2CH2CHO OHOH H CH C CHO CH2CH3
CH C CHO CH2CH3
+ H2O
37
Phn ng aldol ha ni phn t

O O CH3CCH2CH2CCH3 OHO O CH3CCH2CH2CCH2 HO H3C O
O O CH3CCH2CH2CH2CH2CCH3
OH-
O O CH3CCH2CH2CH2CHCCH3
HO H3C
COCH3
O O OHCH3CCH2CH2CH2CCH3
O O CH3CCH2CH2CH2CCH2 HO
CH3
COCH3
O O OHCH3CCH2CH2CH2CH2CH2CCH3
O O CH3CCH2CH2CH2CH2CHCCH3 HO
CH3
38
Vng 5, 6 cnh bn hn 3,4,7 cnh
V.7. Phn ng Cannizzaro

Trong mi trng kim, aldehyde khng c H s t oxy ha kh to 1 carboxylic acid + 1 alcohol
CHO 35% NaOH + NO2 p-nitrobenzaldehyde NO2 NO2
CH2OH
COONa
p-nitrobenzyl alcohol sodium p-nitrobenzoate
HCHO
50% NaOH
CH3OH
+ HCOONa
39
1 hn hp 2 aldehyde khng c H c kh nng to 4 sn phm. Nu 1 aldehyde l formaldehyde th ~ ch c formate & alcohol ca aldehyde kia
CHO HCHO + OCH3 anisaldehyde p-methoxybenzaldehyde

CH2OH 35% NaOH + OCH3 p-methoxybenzyl alcohol

40
HCOONa
C ch:
HO C6H5 C + H
O C6H5 C + H OH-
C6H5
OC H OH
C6H5 C OH O
C6H5 CH2 O-
C6H5 C OO
C6H5 CH2OH
41
V.8. Phn ng oxy ha

K2Cr2O7 H2SO4 Ag(NH3)2+ NH3 CH3CH2CH2CH2CH2COOH
CH3CH2CH2CH2CH2CHO
CH3CH2CH2CH2CHO
CH3CH2CH2CH2COOH
Mun bo ton C=C:

RCH CHCHO Ag(NH3)2+
NH3
RCH CHCOOH
42
Ketone ch b oxy ha bi tc nhn oxy mnh, ct mch, to carboxylic acid

CH3-CH2-C-CH2-CH3 O [O] CH3-CH2-COOH + CH3-COOH
c th phn bit aldehyde & ketone Ring methyl ketone, c phn ng haloform:
R C CH3 O NaOI RCOONa + CHI3
nhn bit methyl ketone Lu : R-CH(OH)-CH3 + NaOI R-CO-CH3 vn cho phn ng haloform!!!
43
V.9. Phn ng kh Kh thnh hydrocarbon
NH2NH2 O C OH-, to CH3 Zn(Hg) HCl
CH2CH3
CH2CH3
44
CH2CH3
COCH3
NH2NH2 OH-, to
OH
Zn(Hg) OH HCl CH2CH3
Cl
45
Kh thnh alcohol
CH3O CHO H2 / Pt C2H5OH CH3O CH2OH
O2N CHO NaBH4 CH3OH
O2N CH2OH
O CH3CCH2C(CH3)3
O (CH3)2C CHCH2CH2CCH3
NaBH4 C2H5OH
1. LiAlH4 / ether
http://hhud.tvu.edu.vn 3
OH CH3CHCH2C(CH3)3
OH (CH3)2C CHCH2CH2CHCH3
46
2. H O+
Ha Hc Hu C
Chng 12:
CARBOXYLIC ACID
I. Gii thiu chung

L nhng hp cht hu c cha nhm carboxyl
O C O-H
trong phn t
Ty theo gc hydrocarbon m phn loi thnh carboxylic acid no, khng no, thm V d: CH3-COOH CH2=CH-COOH C6H5-COOH
II. Danh php

II.1. Tn thng thng HCOOH CH3COOH CH3CH2COOH CH3(CH2)2COOH CH3(CH2)3COOH CH3(CH2)10COOH CH3(CH2)16COOH C6H5COOH formic acid acetic acid propionic acid butyric acid valeric acid lauric acid stearic acid benzoic acid
Acid c nhnh xem nh l dn xut ca acid mch thng, dng , , , ch v tr nhnh

CH2-CH2-CH-COOH CH3 Cl -chloro--methylbutyric acid
Ar-COOH xem nh l dn xut ca benzoic acid

COOH NO2
NO2 2,4-Dinitrobenzoic acid
C th xem cc acid l dn xut th H ca acetic acid 4 C6H5-CH2-COOH phenylacetic acid

II.2. Tn IUPAC Mch chnh di nht cha nhm COOH (C1) Gi theo tn hydrocarbon tng ng, i ne noic acid
CH3-CH2-CH-COOH CH3 2-methylbutanoic acid CH3 CH-CH2-COOH
Cl
3-(p-chlorophenyl)butanoic acid
CH3-CH=CH-COOH
2-butenoic acid
5
III. Cc phng php iu ch

III.1. Dng tc nhn Grignard
CH3CH2CH2CH2Cl Mg ether CH3CH2CH2CH2MgCl 1. CO2 2. H3O
+
CH3CH2CH2CH2COOH
CH3 H3C C Cl CH3
Mg ether
CH3 H3C C MgCl CH3
1. CO2 2. H3O+
CH3 H3C C COOH CH3
Cl
Mg ether
MgCl
1. CO2 2. H3O+
COOH
6
III.2. Thy phn cc dn xut polyhalogen, cc dn xut ca acid

Cl R-CH2-C Cl Cl + H2O to R-CH2-COOH + HCl
O R C O-R' O R C NH2
R CN O R C Cl
+ H2O
H+ (OH-)
R-COOH
+ R'-OH
+ H2O
H+ (OH-)
R-COOH
+ NH3
+ H2O
H+ (OH-)
R-COOH
+ NH3
+ H2O
H+ (OH-)
R-COOH
+ HCl
III.3. Carboxyl ha alkene Dng trong cng nghip, sn xut acid > 3C
R-CH=CH2 + CO + H2O Ni(CO)4 250 C 200 atm
o
R CH2
CH2-COOH
III.4. Phng php oxy ha
R-CH2OH + KMnO4
R-COOK H+ RCOOH
+ MnO2 + KOH
CH3 KMnO4 H2O, to NO2
COOH
NO2
CH2CH2CH2CH3
KMnO4 H2O, to
COOH
IV. Tnh cht vt l
O R C O H
O-H phn cc mnh hn ROH Kh nng to lin kt H > ca alcohol To si > cc hp cht khc c cng C
10
V. Tnh cht ha hc
Theo hiu ng: +C ca O trong OH O-H phn cc mnh H d tch ra dng H+ tnh acid mnh hn alcohol, phenol Theo cng thc cng hng:
O R C O-H H
+
O + R C O-
OR C O
O R C O
carboxylate anion bn cn bng chuyn dch v 11 pha to H+

V.1. Tnh acid Gc R cha nhm th ht in t tnh acid tng Gc R cha nhm th y in t tnh acid gim Tnh acid:
CH3 H3C C COOH CH3 < CH3 H3C C COOH H < H H3C C COOH H < CH3-COOH
H H O >
> OH
OH
12
Tnh acid ca cc acid: F3C-COOH (pKa 0.23) > Cl2CH-COOH (1.25) > Cl3C-COOH (0.66) >
NO2-CH2-COOH (1.68) >
NC-CH2-COOH (2.47) > F-CH2-COOH (2.57) > Cl-CH2-COOH (2.87) > Br-CH2-COOH (2.90) > HCOOH CH3COOH (3.75) (4.76) > > HO-CH2-COOH CH3CH2COOH (3.83) (4.87) > >
(CH3)3C-COOH (5.03)
13
* Acid bo khng no: Tnh acid mnh hn acid no cng mch C (do C=C c I) Ni i C=C cng gn COOH th tnh acid cng mnh Tuy nhin: nu C=C lin hp vi C=O trong COOH th tnh acid gim do +C ca C=C!!! Tnh acid: CH3-CH=CH-CH2-COOH (pKa 4.48) > CH2=CH-CH2-CH2-COOH (4.68) > CH3-CH2-CH=CH-COOH (4.83)
14
Ni ba CC cho d v tr lin hp vi C=O th vn lm tng mnh tnh acid (khc C=C): do I ca CC mnh & ch c 1 lkt ca CC cho +C lin hp vi C=O, lkt cn li cho I nhng khng c +C!!!
Tnh acid: CHC-COOH (pKa 1.84) > 15 CH3-CC-COOH (2.60) > CH2=CH-COOH (4.25)
* Acid c vng thm: Tnh acid H-COOH (pKa 3.75) > C6H5-COOH (4.18) do +C ca C6H5- mnh hn I Tnh acid ty thuc bn cht & v tr nhm th: o-NO2-C6H5-COOH > p- > m Halogen cho I > +C o-Cl-C6H5-COOH > m- > phttp://hhud.tvu.edu.vn
16
V.2. Phn ng th nhm OH ca acid a. Phn ng to acid chloride
O H3C C O-H O H3C C O-H
+ PCl3
+ PCl5
O + H3PO3 H3C C Cl O + POCl3 + HCl H3C C Cl O H3C C Cl

O H3C C + SOCl2 O-H
+ SO2
+ HCl
17
b. Phn ng to amide
O H3C C O-H O H3C C O-NH4+ to O H3C C NH2
+ NH3
+ H2O
c. Phn ng tch nc to anhydride
O + H3C C O-H
O H3C C O-H
P2O5
O H3C C O H3C C O
+ H2O
18
d. Phn ng to ester
R C OH O R C Cl O O R C O R C O + R'-OH H2SO4 R C O-R' O R C O-R' O + H2O
+ R'-OH
+ HCl
+ R'-OH
R C O-R' O
+ RCOOH
Kh nng phn ng: RCO-Cl (khng cn xc tc) > (RCO)2O (khng cn xc tc) > RCOOH Kh nng phn ng: alcohol bc 1> bc 2> bc 3 HCOOH > CH3COOH > RCH2COOH > R2CHCOOH > 19 R3CCOOH
V.3. Phn ng th H (Hell-Vohard-Zelinsky)

H O H C C H O-H
H linh ng c th tham gia phn ng th (xc tc PBr3, PCl3, P)

R O R' C C H O-H R O R' C C Br O-H
+ Br2
PBr3
+ HBr
O H3C C O-H
Cl2 P
O Cl2 ClH2C C P O-H
O Cl2HC C O-H
Cl2 P
O Cl3C C O-H
20
CH3CH2COOH
Cl2 P
CH3CHClCOOH
Cl2 P
CH3CCl2COOH
Cl2 P
Cc dn xut ny vn tham gia phn ng th i nhn v tch loi:
R-CH-COOH Br
NaOH
R-CH-COONa OH
H+
R-CH-COOH OH -hydroxy acid

-
R-CH2-CH-COOH Br
KOH/C2H5OH t
o
R-CH=CH-COO
H+
R-CH=CH-COOH
21
V.4. Phn ng kh thnh alcohol Tn dng c ngun acid bo thin nhin

4R-COOH + 3LiAlH4 4H2 + 2LiAlO2 + (R-CH2-O)4AlLi H2O 4 R-CH2-OH
Hiu sut cao, tuy nhin LiAlH4 mt tin dng trong PTN Trong cng nghip, chuyn thnh ester, kh bng H2/CuO.CuCr2O4 p sut cao
CH3(CH2)10COOCH3 methyl laurate H2, CuO.CuCr2O4 150 oC
CH3(CH2)10CH2OH + lauryl alcohol
CH3OH
22
Ha Hc Hu C
Chng 13: AMINE
- DIAZONIUM
I. Gii thiu chung L hp cht hu c m phn t cha 1 hay nhiu nhm NH2 (hay NHR, -NR2) lin kt vi C Amine c phn loi da trn s nhm alkyl hay aryl lin kt vi N
H R N H
amine bc 1
R' R N H
amine bc 2
R' R N R
amine bc 3
II. Danh php

II.1. Tn thng thng Tn gc hydrocarbon + amine
CH3NH2
CH3NHCH2CH2CH3
CH3CH2NHCH2CH3
methylamine
CH3 CH3NCH3
methylpropylamine
CH3 CH3NCH2CH2CH2CH3
diethylamine
CH3 CH3CH2NCH2CH2CH3
trimethylamine
butyldimethylamine
ethylmethylpropylamine
II.2. Tn IUPAC Amine khng cha COOH, -CHO, -OH: alkanamine

CH3CH2CH2CH2NH2 CH3CH2CHCH2CH2CH3 NHCH2CH3 CH3 CH3CH2NCH2CH2CH3
butanamine
N-ethyl-3-hexanamine
N-ethyl-N-methyl-1-propanamine
CH3CHCH2CH2NHCH3 Cl
CH3 CH3CH2CHCH2CHCH3 NHCH2CH3
3-chloro-N-methyl-1-butanamine
N-ethyl-5-methyl-3-hexanamine
CH3 N CH3 CH3CHCH2CHCH3 Br

CH2CH3 NHCH2CH2CH3
4
4-bromo-N,N-dimethyl-2-pentanamine 2-ethyl-N-propylcyclohexanamine
Cha nhiu nhm amine:

CH3CHCH2NH2 NH2 H2NCH2(CH2)4CH2NH2
1,2-propandiamine
1,6-hexandiamine
Trt t u tin: -COOH > -CHO > >C=O > -OH > -NH2
HOCH2CH2NH2 CH3CCH2CH2NH2 O COOH H2N
2-aminoethanol
4-amino-2-butanone
4-aminobenzoic acid
5
III. Cc phng php iu ch III.1. Alkyl ha NH3 a. Alkyl ha bng dn xut halogen
R RX R N H -HX CH3Cl -HCl CH3Cl -HCl R R N R R R N+ R XR
NH3
RX -HX
R-NH2
RX -HX
RX -HX
CH3-CH2-Cl
NH3 -HCl NH3 -HCl
CH3-CH2-NH2
C2H5
H N CH3
CH2Cl
CH2-NH2
CH2-NH-CH3
6
Aryl halide ch phn ng nu nhn thm cha nhm th ht in t mnh nh -NO2 v tr o-, phoc iu kin khc nghit
Cl NO2 CH3-NH2 NHCH3 NO2
NO2 2,4-dinitrochlorobenzene
NO2 N-methyl-2,4-dinitroaniline
Cl + NH3 Cu2O 200 oC
NH2
b. Alkyl ha bng alcohol

R-OH + NH3 Al2O3 400-450 oC R-NH2 + H2O
III.2. Phn ng chuyn v Hofmann ca amide

R C NH2 O + OBrR-NH2 + CO32-
Ar C NH2 O
+ OBrhttp://hhud.tvu.edu.vn
Ar-NH2
+ CO328
III.3. Kh ha hp cht nitro Kh bng H mi sinh t Fe, Sn/H+ C6H5-NO2 + 3Fe + 6HCl C6H5-NH2 + 3FeCl2 + 2H2O C6H5-NO2 + 3Sn + 6HCl C6H5-NH2 + 3SnCl2 + 2H2O
Kh bng H2 dng xc tc Pt, Ni, Pd

NO2 + 3H2 Pt NH2 + 2H2O
Kh bng tc nhn kh yu nh Na2S, (NH4)2S nu c nhiu nhm NO2 th ch kh 1 nhm

NO2 + Na2S + H2O NO2
NO2 + Na2SO3 NH2

10
III.4. Kh ha nitrile
CH2Cl NaCN
CH2CN H2, Ni 140 oC
H2C CH2NH2
Cl-CH2-CH2-CH2-CH2-Cl
NaCN
NC-(CH2)4-CN
H2, Ni
NH2-CH2-(CH2)4-CH2-NH2
11
III.5. i t hp cht carbonyl

H R C O H R C NH imine H2/Ni
+ NH3
R CH2 NH2
C th thay H2/Ni bng NaBH3CN

CHO + NH3 H2/Ni
CH2NH2
12
IV. Tnh cht vt l Kh nng to lin kt H < alcohol To si < ca alcohol tng ng V. Tnh cht ha hc V.1. Tnh base
R-NH2 NH2 + HCl
HCl
R-NH3+ClNH3+Cl-
13
Trong H2O:
R-NH2 + H2O R-NH3+ + OH-
Tnh base ca amine trong H2O ph thuc vo mt in t trn N & kh nng hydrate ha ca cation alkylammonium R y in t (+I) lm tng tnh base R ht in t (-C, -I) lm gim tnh base amine bo c tnh base > amine thm
14
*** Tuy nhin trong H2O, tnh base: (CH3)2NH > CH3NH2 > (CH3)3N > NH3
Gii thch: trong H2O, cation ca amine bc 3 c kh nng hydrate ha yu (1H)

H O H R H H N+ H O H R R H R N+ H O H R
Lu : trong dung mi khng phn cc nh benzene hay trong pha kh, amine bc 3 c tnh 15 base mnh nht
Amine thm: bc cng cao, tnh base cng gim (do +C ca N)

NH2 > N H > N
Nhm th trong nhn thm y in t tnh base tng v ngc li Tnh base: p-NO2-C6H4-NH2 < m- NO2-C6H4-NH2 < p-Cl-C6H4-NH2 < C6H5-NH2 < p-CH3O-C6H4-NH2
16
V.2. Phn ng alkyl ha
NH3
RX -HX
R-NH2
RX -HX
R RX R N H -HX CH3Cl -HCl
R R N R
RX -HX
R R N+ R XR
CH3-CH2-Cl
NH3 -HCl NH3 -HCl
CH3-CH2-NH2
C2H5
H N CH3
CH2Cl
CH2-NH2
CH3Cl -HCl
CH2-NH-CH3
17
V.3. Phn ng acyl ha nhm NH2 Phn ng c trng ca amine thm

H N C CH3 + H2O O H N C CH3 + HCl O H N C CH3 + CH3-COOH O
NH2 + CH3-COOH
NH2 +
O H3C C Cl
NH2
O H3C C + O H3C C O
18
C ch:
O + H3C C + O H H ON+ C OH H CH3
NH2
OH N C OH H CH3
H N C CH3 + H2O O
19
c dng bo v nhm NH2 khi nitro ha aniline

H N C CH3 + H2O O HNO3 / H2SO4
NH2 + CH3-COOH
NO2
NH2
H2O / H+ t
o
NO2
H N C CH3 O
20
Gim hot nhm NH2 & nh hng para
NH2 + CH3-COOH
H N C CH3 + H2O O AlCl3 Br2
Br
NH2
H2O / H+ t
o
Br
H N C CH3 O
21
V.4. Phn ng vi HNO2

Thc t: NaNO2 + HCl hay H2SO4 a. Phn ng ca amine bc 1 Amine thm bc 1 s cho mui diazonium
NH2 + NaNO2 + HCl 0-5 oC N+ N Cl+ NaCl + 2H2O
Amine bo bc 1 mui diazonium khng bn phn hy thnh alcohol

R CH2NH2 + NaNO2 + HCl
0-5 oC
R-OH + N2
H2 O
22
b. Phn ng ca amine bc 2 C amine bo & amine thm u cho Nnitrosoamines

CH3 N N O 0-5 oC + NaCl + H2O
NHCH3 + NaNO2 + HCl
N-nitroso-N-methylaniline
R NHCH3 + NaNO2 + HCl
0-5 oC
CH3 R N N O
NaCl + H2O
23
c. Phn ng ca amine bc 3 Amine bo bc 3 khng tham gia phn ng Amine thm bc 3 s cho phn ng th i in t
N(CH3)2 + NaNO2 + HCl 0-5 oC N O p-nitroso-N,N-dimethylaniline
N(CH3)2 + NaCl + H2O
24
VI. Mui diazonium VI.1. iu ch mui diazonium

NH2 +
+
HN N O N O cham -H+
+ N N O H H
chuyen v
N N OH H+
H2O
N+ N Clhttp://hhud.tvu.edu.vn
N+ N Cl
25
VI.2. Phn ng th nhm diazonium Phn ng th i nhn n phn t, tch N2 C6H5-N+NCl- + y- C6H5-y + N2 + ClC ch tng t SN1 thng thng, giai on chm to carbocation C6H5+ a. Phn ng vi H2O
N+ N Cl + H2O H+ 40-50 C
OH + N2 + HCl
26
b. Phn ng vi alcohol C 2 phn ng cnh tranh Phn ng th

N+ N Cl + C2H5-OH OC2H5 + N2 + HCl
Phn ng kh Xy ra khi c mt alcohol khan, H3PO2, hay NaBH4

N+ N Cl + C2H5-OH khan
CH3CHO +
N2
+ HCl
27
Phn ng kh cng tt khi nhn thm c cha nhm th ht in t o-, p Alcohol mch cng di, cng u tin phn ng kh CH3OH 90% SN1 CH3CH2OH 60% SN1 CH3CH2CH2OH 30% SN1
28
S dng cho cc trng hp khng th tng hp bng con ng trc tip

CH3 HNO3 H2SO4 CH3 NO2 l + NO2 r CH3
Fe/HCl
CH3 NaNO2 /HCl 0-5 oC NH2 CH3 H3PO2 Br N2+Clhttp://hhud.tvu.edu.vn
CH3 Br2/CS2 Br NH2 CH3
Br
29
c. Phn ng vi KI C6H5-N2+Cl- + KI C6H5-I + N2 + KCl Mun thu c dn xut ca Br, Cl cn xc tc CuCl, CuBr (Sandmeyer), c ch gc t do
N+ N Cl CuCl + N2 Cl
30
NH2 CH3 NaNO2 / HCl H2O 0-5 oC NH2 NaNO2 / H2SO4 NH2 NH2 NaNO2 / HBr Cl H2O 0-10 oC CH3COOH 30 oC
N2+ClCH3
Cl CuCl 15-60 oC CH3
N2+HSO4CuCl N2 HSO4 N2+BrCuBr Cl 100 oC

+ -
Cl
40-100 oC
Cl Br
Cl
31
Ar N N BF4-
to
Ar F
N2
BF3
NH2 1. HNO2 CH3 2.HBF4
N2+BF4to CH3
CH3
NH2
1. NaNO2 / HCl H2O CCH2CH3 O 2.HBF4
N2+BF4to CCH2CH3 O
CCH2CH3 O
32
d. Phn ng nitrile ha
N+ N Cl + KCN to
C N + KCl + N2
H+, H2O
COOH
33
C th nitrile ha bng CuCN

NO2 HNO3 H2SO4 CH3 CH3 CN CuCN H2O H+ CH3 CH3
NH2 Fe HCl CH3 COOH NaNO2 HCl
N2+ Cl-
CH3
34
VI.2. Phn ng ghp i diazonium Hp cht diazonium + arene c nhm tng hot phm mu azo
N2+ Cl+ OH 0 oC pH = 8-9 N N OH
p-(phenylazo)phenol
N2+ Cl+
N(CH3)2 0 oC pH = 5-7
N N
N(CH3)2
35
N,N-dimethyl-p-(phenylazo)aniline
Hp cht diazonium cha nhm th ht in t cng mnh th phn ng ghp i xy ra cng d
N2+ O2N NO2 > NO2
N2+ NO2 > NO2
N2+ > NO2
N2+
36

16 BG HHC Ptsnam

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

16 BG HHC Ptsnam

Uploaded by

Copyright:

Available Formats

Ha Hc Hu C

TS Phan Thanh Sn Nam

Ti liu tham kho

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

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

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

propionaldehyde propanal propionic aldehyde

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

methyl propyl ether

Lu : Khi dng Z-E, ch Z, E khng phi lun trng vi cis, trans

H3C C N OH H syn-acetaldoxime (E)-acetaldoxime

i vi ketoxime: Cng 1 cht, c th gi l syn- hay anti- !!!

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

C6H5 N N C6H5 anti-azobenzene

II.1.4. ng phn hnh hc ca hp cht cha C=C lin hp a(HC=CH)nb CH H

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

Lin kt C-C: ng cho tri qua phi, xa dn ngi quan st

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

Cn bng (khng th tch):

II.3. ng phn quang hc

V d phn t lactic acid 2 ng phn quang hc

COOH C* H CH3 (-)

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

Cc nhm th khc v ng v ng phn quang hc

khng thun li cho phn t phc tp

II.3.5. Danh php v cch xc nh cu hnh ca ng phn quang hc

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

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

-CCH > -C(CH3)3 -CH=CH2http://hhud.tvu.edu.vn > -CH(CH3)2

-CH2OH > -CH=CH2

a OH c CH3 H d (R) COOH b

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

II.3.6. Cc hp cht cha nhiu C* a. Hp cht cha cc C* khng tng ng

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)-

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)-

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

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

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

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)-

m in Cl > C s dch chuyn t C1-Cl, 3 C2-C1, C3-C2

I.2. Phn loi

Cc nhm khng no u mang I, tng dn theo khng no -I:

II. Hiu ng lin hp

Lin hp -p (-Cl, -NH2 ng thi c I!)

II.2. Phn loi

linh ng ca H 2 cht ging nhau

Tc phn ng ging nhau:

b. Mt s nhm th cha no, du ca HU lin hp s thay i ty thuc vo nhm nt lin kt vi n

c. HULH ch c hiu lc trn h lin hp phng

+C ca NR2 gim so vi NH2

III. Hiu ng siu lin hp III.1. HU siu lin hp dng (+H)

+H cng mnh khi s nguyn t H C cng nhiu:

III.2. HU siu lin hp m (-H)

IV. 3. Hiu ng Ortho

Xt hng s phn ly (Ka.105) ca dn xut ca benzoic acid C6H4(R)COOH