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Ha
Hc Hu C
TS Phan Thanh Sn NamB
mn
K
Thut Hu C
Khoa K Thut Ha HcTrng i Hc
Bch
Khoa
TP. HCM
in thoi: 8647256 ext. 5681Email:[email protected]
http://hhud.tvu.edu.vn
mailto:[email protected]:[email protected]:[email protected]:[email protected]:[email protected]:[email protected] -
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Ti
liu tham kho
[1] Paula Y. Bruice, Organic chemistry,
fifth edition, Pearson
Prentice Hall, 2007[2] Graham T.W. Solomons, Craig B. Fryhle, Organic chemistry,
eighth edition, John Wiley & Sons, 2004[3] Francis A. Carey, Organic chemistry, fifth edition, McGraw-Hill, 2003[4] Robert T. Morrison, Robert N. Boyd, Oragnic
chemistry,
sixth
edition, Prentice Hall, 1992[5] Trn Th
Vit
Hoa, Phan
Thanh
Sn Nam, Ha
hu c,
NXB
i Hc Quc
Gia
HCM, 2007
[6] Trn Th
Vit Hoa, Trn Vn Thnh, Bi
tp ho hu c, NXB
i Hc Quc
Gia
HCM, 2004
[8] Thi Don Tnh,C
s l
thuyt
ho
hu c, NXB Khoa Hc K
Thut, 2000[9] Trn Quc Sn, C
s
l
thuyt ha hu c,
NXB Gio
Dc,
1979
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NI DUNG CHNH ng
phn
ca hp cht hu c
Hiu
ng
trong
hp cht hu c
C
ch
cc
phn
ng
ca hp cht hu c
Alkane
Alkene
Alkyne
Alkadiene Hp cht
hydrocarbon thm
Dn xut halogen
Alcohol
Phenol
Aldehyde
Ketone
Carboxylic acid Amine Hp cht diazonium
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Chng 1: NG PHNng phn: nhng hp cht hu c ccng thc phn t ging nhau, cng thccu to khc nhau tnh cht ha hc, vtl, 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 hchttp://hhud.tvu.edu.vn
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I. ng phn cu toDo c s sp xp khc nhau ca cc nguyn t trong mch C
I.1.ng phn mch C
C6H12
n-butane
iso-butane
methyl cyclopentane
cyclohexanehttp://hhud.tvu.edu.vn
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I.2.ng phn do v tr cc lin kt bi, nhm chc
OH
OH
OH
OH
OH
OH
C4H8butene-1 butene-2
1,2- 1,3- 1,4-
dihydroxy benzene
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I.3.ng phn c nhm nh chc khc nhau
O
CHO
C3H6O
dimethyl ketone
propan-2-one
acetone
propionaldehyde
propanal
propionic aldehyde
C3H6O2COOH
O
O
Propionic acid
methyl acetate
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I.4.ng phn c nhm th khc nhau lin kt vinhm nh
chc
O
O
C4H10O diethyl ether
methyl propyl ether
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II.ng
phn
lp th
II.1.ng phn hnh hcII.1.1.iu kin xut hin ng phn hnh hc
Xut hin
khi
phn
t
c
1 b
phn cng
nhc
cn trsquay tdo 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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H
Cl Cl
H
Thng
xut hin
cc
hp cht c c ha:
C=C, C=N, N=N, h lin hp, vng phng 3hay 4 cnhabC=Ccd: a b, c d
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II.1.2. Danh php ca ng phn hnh hca. H cis-trans: abC=Cab
Nhm
th
tng
ng
nm
cng
pha
mt phng lin kt cis Khc pha trans
H
H3C CH3
H H
H3C H
CH3
cis-butene-2 trans-butene-2http://hhud.tvu.edu.vn
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b. H Z-E: abC=Ccd a>b c>dQuy tc Kahn-Ingold-Prelog: da theo th t u tin trong bng HTTH ca nhm tha, 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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I
Br Cl
F
I
Br F
Cl
(E)-1-Bromo-2-chloro-2-fluoro-1-iodoethene
35
53
17
9
(Z)-1-Bromo-2-chloro-2-fluoro-1-iodoethene
Lu : Khi dng Z-E, ch Z, E khng phi lun trng vi cis, trans
H
Cl Cl
Br
E-, cis-
F
Cl Cl
H
Z-, cis-
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II.1.3.ng phn hnh hc ca abC=Nd v aN=Nba. 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
C N
H
H3C OH
C N
H
H3C
OH
anti-acetaldoxime(Z)-acetaldoxime
syn-acetaldoxime(E)-acetaldoximehttp://hhud.tvu.edu.vn
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i vi
ketoxime: Cng
1 cht, c
th
gi l
syn- hay anti- !!!
C N
OH
H3C
C NOH
anti-phenyl-p-tolylketoximesyn-p-tolyl-phenylketoxime
syn-phenyl-p-tolylketoximeanti-p-tolyl-phenylketoxime
H3C
h syn-antikhng chnh xcchuyn sang h Z-E
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b. aN=Nb
N NC6H5
C6H5
N NC6H5 C6H5
anti-azobenzene syn-azobenzene
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II.1.4.ng phn hnh hc ca hp cht cha C=Clin
hp
a(HC=CH)n
bHH
C6H5
C6H5
H
H
H
C6H5
H
H
C6H5
H
H
C6
H5
H
C6H5
H
H
trans,trans-1,4-diphenyl-1,3-butadiene
cis,cis-1,4-diphenyl-1,3-butadiene
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 chnp = (n + 1)/2 nu n l
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II.1.5.ng phn hnh hc ca vng no 3, 4cnh c b tr trn 1 mt phng cc nhm thkhng th quay tdo 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 thKhong cch gia 2 nhm th tng ng trong ng phn cis < trans
Cl
H H
Cl Cl
H Cl
H
3.7 4.7
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b. Moment lng cc 2 nhm
th
ging
nhau
aHC=CHa
Cl
H H
Cl Cl
H 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
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c. Nhit nng chyng phn trans-: i xng mng litinh th cht ch tonc cis < tonc trans
Lu : mi lin h gia to
si v ng
phn hnh hc khng cht chV d:CHCl=CHCl t
o
si ca cis-: 60.3o
C, to
si ca trans-: 48.4oC
CH3
CH=CHCl tosi ca cis-: 32.8 oC, tosi ca trans-: 37.4 oChttp://hhud.tvu.edu.vn
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II.2.ng phn cu dng (ng phn quay) L nhng cu trc khng gian sinh ra do 1 nhmth 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!!!http://hhud.tvu.edu.vn
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II.2.1. Cch
biu din
a. Cng thc phi cnh (khng gian 3 chiu)
c
b
c
a
b
a
a
b
c
a
b
c
c
b
a
che
khut
xen
k
Lin kt C-C: ng cho tri qua phi, xa dn ngi
quan
st
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b. Cng thc Newman Quan st dc theo C-C 2 nguyn tC dng che khut, biu din bng vng trn
chiu cc nhm th ln mt phng vung
gc viC-C
a
a
bc
aa
b
b
c
c
cb
che khut xen khttp://hhud.tvu.edu.vn
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II.2.2. Cu dng ca cc hp cht mch ha. Ethane Quay 1 nhm CH3
& c nh nhm cn li2 ng phn cu dng ti hn Che
khut: khong
cch
gia
cc
H gn
nhau nng lng cao nht km bnnht
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Xen
k: khong
cch
gia
cc
H xa
nhau nng
lng thp nht bn nht
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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 1phn
CH3CH3
H
H
H
H
CH3
H
CH3H
H
H
2 dng
c
nng
lng
thp: anti
(i) & syn
(lch)
HH
HH
CH3
CH3
HH
H
CH3
H
CH3
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II.2.3. Cu dng ca hp cht vng noVng 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 ~ 109
o28
Cc
nhm
th
c
th
quay quanh
C-C ng
phn cu dng C 2 dng c trng: gh (bn) & thuyn* Gh:
1
234
5 6
2.5 2.49
Xem nh 1 t hp ca 6 h thng n-butane Tt c
6 h
thng
u
dng
xen
k
(syn
butane)
24
3
6http://hhud.tvu.edu.vn
* Th
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* Thuyn:
1
23
4
56
2.27
1.84
2.49
35
14
4 h thng dng xen k: C1-C2, C3-C4, C4- C5, C6-C1 2 h thng dng che khut hon ton: C2- C3, C5-C6 Khong cch H C1 & C4 rt nh lc ykm bn hn dng gh*** Ngoi dng gh & thuyn, cyclohexane cn c dng xon, dng na ghkm bn (t c)http://hhud.tvu.edu.vn
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b S b li k C H
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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 ktbin e (equatorial)
a e
a
e
a
a
e
e
a
e
a
e
109o28'
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Cn
bng
(khng
th
tch):
a
e
CH3
CH3
Dn xut 1 ln th: e-methyl cyclohexane bn hna-methyl cyclohexane Khi c 2 nhm th khc nhau: nhm ln v tr e
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II.3.ng
phn
quang
hc
II.3.1. nh
sng
phn
cc
nh sng t nhin: sng in t, dao ng mihng
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 ASPChttp://hhud.tvu.edu.vn
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II.3.2. cht hot
ng
quang
hc
ASPC i qua 1 s hp cht hu c lm mt phngphn
cc
quay 1 gc cht hot ng quang hc
Gc quay c xc nh bng phn cc khttp://hhud.tvu.edu.vn
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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 hcto: nhit
o
: bc sng nh snghttp://hhud.tvu.edu.vn
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II.3.3.iu kin xut hin ng phn quang hcVt & nh trong gng khng chng kht c 2ng phn khng chng kht nhng i xng nhau2 ng phn ny quay mt phng phn cc nhnggc
nh
nhau
nhng
ngc chiu 1 i i
quangng phn quang hc thng xut hin k h i c Cbt
i xng
(C*)
* C bt i xng:Cabcd
a
b
c
d khng c tnh i xng
trong khng gianhttp://hhud.tvu.edu.vn
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V
d
phn
t
lactic acid 2 ng phn quang hc
COOH
H OH
CH3
C*
COOH
H
CH3
C*HO
(+) (-)
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C h th kh h h t
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Cc nhm th khc nhau v ng phn cu tong phn quang hc
n-C3H7 C*H
COOH
iso-C3H7
Cc nhm th khc v ng vng phn quang hc
D C*CH3
H
C6H5http://hhud.tvu.edu.vn
ng phn quang hc khng cha C*
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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 C C CC10H7 C10H7
C6H5 C6H5
ng phn cn quayHOOC COOH
Cl Clhttp://hhud.tvu.edu.vn
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II.3.4. Cng thc biu din ng phn quang hca. Cng thc t din (3 chiu)
COOH
H CH3 OH
khng thun li cho phn tphc tphttp://hhud.tvu.edu.vn
b Cng thc chiu Fisher (2 chiu)
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b. Cng thc chiu Fisher (2 chiu) Chiu cng thc t din l n mt phng Cnh nm ngang gn ngi quan st, nm dc xa
ngi
quan
st
H OHCOOH
CH3 C th c nhiu cng thc Fisher khc nhau
c. Cng thc phi cnh & Newmanhttp://hhud.tvu.edu.vn
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II.3.5. Danh php v cch xc nh cu hnh
ca
ng
phn
quang
hc
Cu hnh: s phn b trong khng gian ca cc
nhm
th
xung
quanh
C* (khi
nim m t
ng phn quang hc) Cu dng: cc dng khc nhau trong khng gian ca cng 1 cu hnh!!!
http://hhud.tvu.edu.vn
H d h h D L h h t i
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a. H danh php D-L: cu hnh tng iPhi
so snh
vi 1 cht chun
H OH
CHO
CH2OH
HO H
CHO
CH2OH
D-glyceraldehyde 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 LV
d
lactic acid c
2 ng
phn
khi
so vi
glyceraldehyde
H OH
COOH
CH3
HO H
COOH
CH3
D-lactic acid L-lactic acid
Rt kh xcnh khi phn tc nhiu C*!
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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
http://hhud.tvu.edu.vn
OH
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H C* OC
C
OH
H
O HHH
Vng 1: C1 6, C3 6, O 8, H 1Vng 2 (khi vng 1 khng xc nh c th t):O-C-O > -C-O -OH > -CHO > -CH2OH > HLu :
C A C AA C
C A CA
AAC
C
CCHHC
CC
-CCH > -C(CH3)3-CH=CH2 > -CH(CH3)2
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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 & -CH2
OH
-CH2OH > -CH=CH2
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Cch
xc
nh
cu hnh: C*abcd,
gi s a>b>c>d+Theo cng
thc t
din / phi
cnh (khng gian): t d xa ngi quan st:i t a b c: cng chiu kimng h: ng phn R
i t a b c: ngc chiu kimng h: ng phn Shttp://hhud.tvu.edu.vn
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+Theo cng thc Fisher:
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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 b c: cng chiu kim ng h: R
i t a b c: ngc chiu kim ng h: SQuy
c: i v
tr
2 cp
nhm
th cu hnh
khng thay iThay i v tr 1 cp nhm th cu hnh sthay i
Hay l Quay cng thc Fisher 180o cu hnh
khng i, quay 90o hay 270o cu hnh thay
ihttp://hhud.tvu.edu.vn
V d lactic acid: COOH
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d
act c ac d
H OH
CH3
i H & CH3 (1 cp), OH & COOH (1 cp) CH3 COOH
OH
H
(R)d
a
bc
Nu ch
i 1 cp
H & CH3
CH3 OH
COOH
H
(S)d
b
ac
Lu : R & S ch l i lng l thuyt!!! thc t ch o c d(+)& l(-)!!! R & S khng lin
h
vi
(+) & (-)!!!
http://hhud.tvu.edu.vn
II.3.6. Cc hp cht cha nhiu C*
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II.3.6. Cc hp cht cha nhiu Ca. Hp cht cha
cc
C* khng
tng
ng
H C* OH
CHO
C*H OH
CH2OH
2 C* khng tng ng v CHO CH2OH
4 ng phn (2 i i quang):
H C* OH
CHO
C*HO H
CH2OH
OH
CHO
C*H OH
CH2OH
H C*
HO
HO C* H
CHO
C* H
CH2OH
HO
H
C* H
CHO
C* OH
CH2OH
threo-aldotetroseerythro-aldotetrose
(2R,3R)- (2S,3S)- (2R,3S)- (2S,3R)-
S p quang hc: N = 2n n: s C*http://hhud.tvu.edu.vn
b. Hp cht c c ha C* tng ng
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b. Hp cht c c ha C tng ngTactric
acid:
HOOC C* C* COOHH
OH
H
OH2 C* tng ng 3 ng phn
H C* OH
COOH
C*HO HCOOH
HOH
C* H
COOH
C* OHCOOH
HOHO C* H
COOH
C* H
COOH(2R, 3R)-tactric acid (2S, 3S)-tactric acid meso-tactric acid
http://hhud.tvu.edu.vn
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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)
http://hhud.tvu.edu.vn
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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 quanghc 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
http://hhud.tvu.edu.vn
V d: Xc nh cu hnh tuyt i ca 1 s cht
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V
d: Xc
nh
cu hnh tuyt
i ca 1 s
cht
(R)-
(R)-
H OHCH2OH
CH3
H CH3
COOH
C6H5
(S)-
OH CH3
CHO
CH2OH
H OHCH2OH
OH H
CH2OH
H2N HCOOH
CH3(S)-
H OHCH2OH
H OHCH
2OH
H2N HCOOH
CH2OH(S)-
(2S, 3S)- (2S, 3R)-
http://hhud.tvu.edu.vn
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1
Ha Hc Hu CTS Phan Thanh Sn NamB mn K Thut Hu CKhoa K Thut Ha H cTrng i Hc Bch Khoa TP. HCMin thoi: 8647256 ext. 5681
Email:[email protected]
http://hhud.tvu.edu.vn
Chng 2: CC LOI HiU NG
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Chng 2: CC LOI HiU NG* Hiu
ng s dch chuyn in t trong phn tnh 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 http://hhud.tvu.edu.vn
I. Hiu ng cm ng
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I. Hiu ng cm ngI.1.nh ngha HU cm ng sdch chuyn in tca cclin ktdo cc nguyn ttrong phn tc
m in khc nhau phn tphn cc V d:
H C3 C2 C1 Cl
H
H
H
H
H
H
m in Cl > C sdch chuyn tC1-Cl,C2-C1, C3-C2http://hhud.tvu.edu.vn
I.2. Phn loi
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I.2. Phn loia. 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 in t > H cho +I (v ngc li)http://hhud.tvu.edu.vn
I 3 c im ca HU cm ng
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I.3.c im ca HU cm ng Cc nguyn t hay nhm nguyn t mang intch + Cho I Cc nguyn t hay nhm nguyn t mang intch - cho +I
in tch cng mnh I cng mnh, nhmnguyn t mang in tch c I mnh hn trungha
-N(+)R3-O(+)R2 -I
-O- -N(-)H +I-O(+)R2 > -ORhttp://hhud.tvu.edu.vn
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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 trnxung di-I:
-F > -Cl > -Br > -I
-I: -OR > -SR > -SeR
Cc nhm alkyl lun y in t (+I), tng dn tbc 1 n C bc 3+I : -CH3 < -CH2 CH3 < -CH(CH3 )2 < -C(CH3 )3http://hhud.tvu.edu.vn
Cc nhm khng no u mang I, tng dn
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Cc nhm khng no u mang I, tng dn theo
khng
no
-I: R2C=CR- CRC< C nhm C=O s ht in t
ca h phn t tr nn phn cc ( LH - )
http://hhud.tvu.edu.vn
CH2=CH-CH=CH-N(CH3)2
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2
( 3
)2
N c i in t t do (p) c x u hng nhngin tcho h lin hp phn tphn cc (LH -p)
Cl NH2
Lin hp -p (-Cl, -NH2 ng thi c I!)http://hhud.tvu.edu.vn
II.2. Phn loi
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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
HN C
O
CH3 -F -Cl -Br -I
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b. Cc ion mang in tch m c +C mnh hn ccnguyn t trung ha+C:
-O-
> -OR
-S-
> -SR
c. Trong cng 1 chu k ca bng HTTH: +C gimt
tri
qua phi
+C: -N(R)2 > -OR > -Fd. Trong
cng
1 phn
nhm
chnh: +C gim t
trn xung di+C: -F > -Cl > -Br > -I+C: -OR > -SR > -SeRhttp://hhud.tvu.edu.vn
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II.2.2. HU lin hp m (-C)
Cc nguyn t hay nhm nguyn t c kh nnght 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
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b. Trong cc nhm C=Z: -C ph thuc ZZ 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
http://hhud.tvu.edu.vn
II.3. c tnh chung ca HU lin hp
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II.3.c tnh chung ca HU lin hpa. HU lin hp thay i rt t khi ko di mch lin hp
*** HU cm
ng: gim nhanh theo mch
C !!!
H CH2 CH CH C
O
H
H CH2
CH CH CH CH C
O
H
linh ng ca H 2 cht ging nhauhttp://hhud.tvu.edu.vn
T h i h
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Tc phn ng ging nhau:
RCHO
RCHO H CH2
CH CH C
O
H
H CH2 CH CH CH CH C
O
H
OH-
OH
-
C CH2 CH CH CH CH C
O
H
R
OH
H
C CH2 CH CH C
O
HR
OH
H
+
+
http://hhud.tvu.edu.vn
b. Mt s nhm th cha no, du ca HU lin hp s
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thay
i ty thuc
vo
nhm
nt
lin
kt vi n
N+
-O ONH2
-C6H5: +C -C6H5: -C
c. HULH ch c hiu lc trn h lin hp phngN
H
H
C6H5NH2 N
R
R
C6H5NR2
+C ca NR2 gim so vi NH2http://hhud.tvu.edu.vn
III. Hiu ng siu lin hp
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III.1. HU siu lin hp dng (+H)
L s tng tc ca cc in t ca lin kt C-Hvi h t (C=C, -C6 H5), hoc trong carbocation(vd: (CH3
)3
C+) hay gc t
do (vd: (CH3
)3
C.)
http://hhud.tvu.edu.vn
Xt phn ng:
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p gCH3
-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 phmchnh l:
C CH CH CH2 CH3H
H
H
HClCH3 CHCl CH2 CH2 CH3
http://hhud.tvu.edu.vn
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CH
H
H
CH3C
H H
>+H:
+H cng mnh khi s nguyn t H C cng nhiu:
http://hhud.tvu.edu.vn
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III.2. HU siu
lin
hp
m
(-H)
L s tng tc ca cc t ca lkt C-F vi ht (C=C, -C6
H5
)
C F
F
F
http://hhud.tvu.edu.vn
IV. Hiu ng khng gian
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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 trkhng cho 1 nhmchc no trong phn ttc dng vi phn t hay ion khc
OO
CH3
CH3
H2N OH+ ON
CH3
CH3
HO + H2O
http://hhud.tvu.edu.vn
IV. 2. HU khng gian loi 2 (S2)
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Do cc nhm th c kch thc ln h lin hpbmt tnh phng khng cho 1 sphn ng
Xy ra
N
H3C
H3C
N+N
R
R
+ N
H3C
H3C
R
R
N NCl-
R = H: phn ng xy ra R=-CH3 : h lin hp mt tnh phng +Cca N(CH
3)2 gim m
nh
phn ng khngxy rahttp://hhud.tvu.edu.vn
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IV. 3. Hiu ng OrthoGy 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, linkt H)http://hhud.tvu.edu.vn
Xt hng s phn ly (Ka.105) ca dn xut ca
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25
Xt hng s phn ly (Ka.10 ) ca dn xut ca benzoic acid C6
H4
(R)COOH
V
tr
/ R OH F NO2
o- 10.5 54.4 67.1
m- 8.3 13.7 32.1
p- 2.9 7.2 37.6
Lu : -I ca NO2> -I ca Fhttp://hhud.tvu.edu.vn
Tnh acid:
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C
O OH
OH
>
C
O OH
OH
CO O
H
OH
>
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 !!! cnglm cho tnh acid ca m- > p-http://hhud.tvu.edu.vn
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Tnh acid ca C6 H4 (F)COOH: o- > m- > p-do I gim theo chiu d i mch
C
Kh nng ht (-I) hay y (+C) in t caF, Cl, Br, I: -I > +C
Tnh acid ca C6 H4
(NO2
)COOH: o- > p- > m-
http://hhud.tvu.edu.vn
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N+
-O O
OH
N+-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 caohttp://hhud.tvu.edu.vn
V nh hng ca cc hiu ng ln tnh
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V. nh
hng
ca
cc
hiu
ng
ln
tnh
acid base v bn ca carbocationV.1. nh hng ca HU cm ng ln tnh acid Cc R-OH, R-COOH c cha nhm th c +Itnh acid gim
Cha
nhm
th
c
I: tnh
acid tng
do O-H
cng phn cchttp://hhud.tvu.edu.vn
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Tnh acid ca cc acid:F3
C-COOH (pKa 0.23) > Cl3
C-COOH (0.66) >
Cl2 CH-COOH (1.25) > 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 (3.75) >HO-CH2
-COOH (3.83) >
CH3
COOH (4.76) > CH3 CH2
COOH (4.87) >
(CH3 )3 C-COOH (5.03)
http://hhud.tvu.edu.vn
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Nhm
th
cng
xa
C nh hng cng
yu do I gim mnh:
Tnh acid: F3 C-COOH > F3 C-CH2 -COOH >F
3 C-CH
2 -CH
2 -COOH
http://hhud.tvu.edu.vn
V.2. nh hng ca HU lin hp, HU siu lin hpln tnh acid
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ln
tnh
acid
Tnh acid ca alcohol < phenol Nhm th c C s lm tng tnh acid & ngc li
Tnh
acid:
N+
-O O
O
C
OO
H
H H
H HH
-I, -C +H, +I
> >
NH2
O
H
>
+C, -I
O
H
>
CH
HH
+I
Thng thng (khng lun lun!) : C > H > Ihttp://hhud.tvu.edu.vn
a.Acid bo khng no:
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g Tnh acid mnh hn acid no cng mch C (doC=C c I) Ni i C=C cng gn COOH th tnh acid cngmnh 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)http://hhud.tvu.edu.vn
Ni b a CC cho d v tr lin hp vi C=O th
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vn lmtng mnh tnh acid (khc C=C): do Ica CC mnh & ch c 1 lkt ca CC cho +Clin hp vi C=O, lkt cn li cho I nhng khng c +C!!!
Tnh acid: CHC-COOH (pKa 1.84) >CH3-CC-COOH (2.60) > CH2=CH-COOH (4.25)http://hhud.tvu.edu.vn
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b. Acid c vng thm:Tnh acid H-COOH (pKa 3.75) > C6
H5
-COOH (4.18)
do +C ca C6 H5
- mnh hn ITnh acid ty thuc bn cht & v tr nhm th:o-NO2
-C6
H5
-COOH >p-
> m-
Halogen cho I > +C o-Cl-C6H5-COOH > m- > p-
http://hhud.tvu.edu.vn
V.3. nh hng ln tnh base
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V.3. nh hng ln tnh base
Mtin t trn N cng ln tnh baseca amine cng mnh Nhm thy in t (+I) s lm tng tnhbase ca amine & ngc li (-I, -C)
Tnh base:
(CH3
)2
NH > CH3
NH2
> NH3 > C6
H5
NH2
>
p-NO2
-C6
H4
-NH2http://hhud.tvu.edu.vn
Tnh base:p-NO2-C6H4-NH2 < m- NO2-C6H4-NH2
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p 2 6 4 2 2 6 4 2
CH3
O-
> OH-
>
C6H5O- > CH3COO- http://hhud.tvu.edu.vn
V.4. nh hng ln bn ca cc
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g 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 C CH2
H
H
C C+
H
C
H
H
H H
H
HC C
+
C
C
H
H
H H
H
H
H
HH
< +C ca O- > +H & I ca CH3-NH- & -O- ng thi c I nhng +C nh hngmnh hn -NH- gii ta tch dng mnhnht bn nht
Gc allyl CH2
=CH-CH2
+ hay
C6
H5
-CH2
+
rt bn
do +C ca vinyl hay phenylhttp://hhud.tvu.edu.vn
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1
Ha Hc Hu CTS Phan Thanh Sn NamB mn K Thut Hu CKhoa
K
Thut Ha H c
Trng i Hc Bch Khoa TP. HCMin thoi: 8647256 ext. 5681Email:[email protected]
http://hhud.tvu.edu.vn
Chng 3: C CH PHN NG CA HPCHT HU C
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CHT HU CI. Phn ng th i nhn nguyn t carbon noI.1. Khi
nim
chung
Phn ng th: 1 nguyn t hay nhm nguyn tca cht ban u b
thay
th
bi
1 nguyn
t
hay
nhm nguyn t khcCH
3 -CH
2 -Cl + OH- CH
3-CH
2-OH + Cl-
Tc
nhn
i
nhn:
cc
tc
nhn
mang
in tch
m (hay phn t trung ha cha cp in t t do) tn cng vo trung tm tch in +http://hhud.tvu.edu.vn
Phn ng th i nhn (SN)
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y- + R-X R-y + X-y-: RO-, OH-, RCOO-, NH3, NH2R, H2O, ROHR: gc
hydrocarbon
X: Cl, Br, OH, OR, OSO2
R
V
d:
CH3
-CH2
-Cl + OH- CH3-CH2-OH + Cl
-
CH3
-CH2
-Br + CH3
O- CH3-CH2-O-CH3 + Br
-
CH3 -CH2
-Br + NH3 CH3-CH2-NH2 + HBrhttp://hhud.tvu.edu.vn
I.2. Phn ng th i nhn lng phn t(SN2)
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Lng phn t: giai on chm, c s tham giaca 2 tiu phn
a.C ch:chamy- + R-X [y
-... R ... X -] nhanh R-y + X-
trang thai chuyen tiep
Lin kt gia C & y hnh thnh ng thi vi syu i & t ca C & X 2 tiu phn tham giavo giai on chm Nu y- khng d nhiu: r = k[y-].[R-X] phn ngbc 2 http://hhud.tvu.edu.vn
Gin nng lng:
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5
http://hhud.tvu.edu.vn
R OH h th h t i t
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R-OH: phn
ng
th
ch
xy ra trong mi trng
acid v C-O bn
Dn xut ca carbon bc 1 ch cho SN 2
SN
2: carbon bc 1 (ch cho SN
2) > carbon bc 2 >carbon bc 3 (ch cho SN
1)
SN
2: CH3
-CH2
-Cl + OH- CH3-CH2-OH + Cl
-
http://hhud.tvu.edu.vn
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I.3. Phn ng th i nhn n phn t(SN1)
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8
n phn t: giai on chm ch c s tham gia ca 1 ti u phna. C
ch
R+
R-X R+ X-
cham+
+ y-nhanh R-y
giai on chm: y-
khng tham gia
SN1 thng c bc 1 r = k[R-X]http://hhud.tvu.edu.vn
Gin nng lng:
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9
http://hhud.tvu.edu.vn
Dn xut ca carbon bc 3 ch cho SN1
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SN
1: carbon bc 3 (ch cho SN 1) > carbon bc 2 >carbon bc 1 (ch cho SN
2)
V d SN 1:
H3C C
CH3
Br
CH3
+ OH- H3C C
CH3
OH
CH3
+ Br-
http://hhud.tvu.edu.vn
Tnh lp th ca SN1
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11
C* X
R3
R2
R1
C*
R3R2
R1
cham
C*
R3
R2
R1
y
nhanh
-X- nhanh
C* y
R3
R2
R1
(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 nhnhau 50% S + 50% Rhttp://hhud.tvu.edu.vn
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12http://hhud.tvu.edu.vn
I.4. Cc yu t nh hng ln phn ng thi nhn
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13
i
nhn
a. nh hng ca gc R
Gc R bc
cng
cao: kh nng SN1 tng & SN2
gim SN
1: carbon bc 3 (ch cho SN
1) > carbon bc 2 >
carbon bc 1 (ch
cho
S
N 2)
Do SN
1 ph thuc vo bn ca carbocation to thnh:
H C C H2
H
H
C C+H
C
H
H
H H
H
HC C+
C
C
HH
H H
H
H
H
HH< carbon bc 3 (ch cho SN1)
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14
( N )
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 khxy ra
http://hhud.tvu.edu.vn
b. nh hng ca tc nhn i nhn y-
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15
SN
1: khng ph thuc y-
SN
2: ph
thuc
nhiu
vo
y-
do giai
on chm c
y-
tham giaTc
nhn
c
tnh
i
nhn
cng
cao
th
cng
d
cho
SN
2
Thng
thng, tnh
i
nhn
ng
bin vi tnh
base
NH2-
> (CH3
)3
CO-
>
(CH3
)2
CHO-
> C2
H5
O-
>
CH3
O-
> OH-
> C6H5O
-
> HCO3
-
> CH3COO
-http://hhud.tvu.edu.vn
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c nh hng ca nhm b th X
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17
c. nh
hng
ca
nhm
b
th
-X
Cc nhm th c tnh base cao rt kh b tchra, v d: -OH, -OR, -NH2, -FV d: R-OH + HBr R-Br + H2O cn xc tcH
2
SO4R-OH khng phn ng vi KBr
Halogen, kh nng tch nhm: F- < Cl- < Br- < I-(Do I c bn knh ln C-I dphn cc hnNng
lng
t lin kt: C-I < C-Br < C-Cl
< C-F)
http://hhud.tvu.edu.vn
d. nh hng ca dung mi
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18
Dung mi phn cc c proton nh H2 O, ROH,HCOOH c kh nng solvate ha cao c anion &cation thun li cho SN1
C XR3
R2
R1
C+R3R2
R1
-X-cham
O
H
H+ X
-
H OH
Dung mi phn cc khng c proton nh (CH3
)2
SO, (CH3
)2
NCHO
khng c kh
nng
solvate
ha anion thun li cho SN2http://hhud.tvu.edu.vn
II. Phn ng tch loiL phn ng trong c s tch 1nguyn t hay
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19
L
phn
ng
trong
c s
tch
1nguyn t
hay
nhm nguyn t ra khi cht ban uR CH
2CH
2Br
RO-
R CH2 CH2 OHH+
R CH2 CH2 N+R3
HO-
R CH CH2
R CH CH2
R CH CH2
+ HBr
+ HOH
to
to
+ HOH + NR3
t
o
Nhm b tch cng H: -OH, -OR, -X, -O+(R)2
,
-N
+
(R)3 , -OSO2 R Base sdng: cc base mnh nh OH-, RO-, NH2-http://hhud.tvu.edu.vn
II. 1. Phn ng tch loi lng phn t(E2)a. C ch
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20
y- + R CH2 CH2 X H C CH2
R
H
y Xcham nhanh
H-y + R CH CH2 + X-
trang thai chuyen tiep
giai on chm, c s tham gia ca 2 ti u phnlng phn t Tc
phn
ng
r = k[R-X].[y-]
R-CH2 -CH2 -OH: ch tch loi trong mi trng acid to cao (thng l sulfuric acid, acid rn)http://hhud.tvu.edu.vn
b.Tnh lp th ca E2
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21
p
2
Cc hydrocarbon khng no tch loi d khicc nhm b tch v trtrans vi nhauHOOC Cl
COOHH
OH-
-HCl
COOH
COOH
OH-
-HCl
HOOC Cl
HHOOC
(1) (2)
chlorofumaric acid chloromaleic acid
Tc (1) ln hn (2) 30 lnhttp://hhud.tvu.edu.vn
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II.2. Phn ng tch loi n phn t (E1)C ch:
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23
H C C X H C C+ + X-
H C C+ H+ +
cham
nhanh
Thng cc dn xut ca hydrocarbon carbonbc 3 bao gi cng cho E1 Carbocation cng bn, cng d cho E1 Tc
r = k [R-X]
Nhng yu t lm thun li SN 1 cng lm thun licho E1 http://hhud.tvu.edu.vn
Vd:
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24
H3C C B r
CH3
CH3
cham C C+C
C
H
H
H H
H
H
H
HH
+ Br-
C C+C
C
H
H
H HH
H
H
HH
+ C2H5O- nhanh H2C C
CH3
CH3
+ C2H5OH
http://hhud.tvu.edu.vn
II.3. Hng ca phn ng tch loia. Quy tc Zaitsev
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25
Dn xut bc 1 thng ch cho 1 sn phm duynht khi tch loiCH3
-CH2
-CH2
-Br ch
cho
CH3
-CH=CH2
Dn xut bc 2, bc 3: cho nhiu hn 1 sn phm
H3C C C C H
H
BrH
H
H
OH-H3C CH CH CH3 (Zaitsev)
H3C CH2 CH CH2(Hofmann)
H
Sn phm Zaitsev : bn hn (do +H) thngthng, phn ng tch loi cho sn phmZaitsev
Quy tc: phn ng tch loi s cho sn phm mcarbon ca nii lkt vi nhiu nhm alkyl nhthttp://hhud.tvu.edu.vn
b. Quy tc Hofmann
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26
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
)3
CO-)
hoc
X l
nhm
th
mang
in tch dng
c kch thc ln (vd N +
R3 , S+
R2 , SO2
R) snphm Hofmann chim ch yu (E2)
H3C C CH
2CH
3
CH3
Br
(CH3)3CO-
H3C C
CH3
CH CH3
H2C C CH2 CH3CH3 72%
28%
Nu base l C2H5O- th sn phm chnh l Zaitsev!!!http://hhud.tvu.edu.vn
H3CHC CH2 CH3
+
OH- CH2=CH-CH2-CH3(E2)
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27
N
+
(CH3)3
(E2)
CH3CHCH2CH2CH3
SO2CH3
OH- 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)
(E2)
http://hhud.tvu.edu.vn
II. 4. Quan h gia phn ng th i nhn &tch loi
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28
tch
loi
Nhit phn ng cng cao phn ng tch loicng chim u th
CH3-CH2-OH H2SO4
CH2=CH2
C2H5-O-C2H5170o
C + H2Ohttp://hhud.tvu.edu.vn
Gc R c bc cng cao, hay base cng mnh thtch loi cng chim u th
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29
CH3-CH2-CH2-Br + C
2H
5O- CH3-CH2-CH2-O-C2H5
to thng
H3C C B r
CH3
CH3to cao
H2C C
CH3
CH3
C2H5O
-
http://hhud.tvu.edu.vn
III. Phn ng cng hp
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30
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, H2
O, HOX, H2
SO4
C C + X-Y X C C Y
http://hhud.tvu.edu.vn
a. C ch: Giai on 1
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31
Giai on 2: C CX+
Y-nhanh C C
X
Y
Y- tn cng vo pha i lp vi X
Giai
on 1:
C C + X -Ydung moi
xuc tac C C
X
Yphc
khong ben
nhanh
C+ C
X
cham C Cben hoa
X+
Giai
on chm: X+ tn
cng
vo
C=C i in t
http://hhud.tvu.edu.vn
Chng minh AE c 2 giai on:
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32
g
E
g
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 CH3 OH,
sn phm chnh l Br-CH2 -CH2
-OCH3
!!!
http://hhud.tvu.edu.vn
H2C CH2CCl4
H C CH+ Br2
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33
H2C CH2
H2C CH2
H2C CH2H2O
CH3OH
H2C CH2
Br Br
H2C CH2
Br OH
H2C CH2
Br OCH3
+ Br2
+ Br2
+ Br2
http://hhud.tvu.edu.vn
b. Quy lut cng hp
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34
Quy tc Markonikov (dnh cho C=C khng ixng): 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 phato
thnh
carbocation
trung
gian
bn nht
CH3-CH=CH-CH2-CH3HBr
CH3-CH-CH-CH2-CH3
Brhttp://hhud.tvu.edu.vn
c. Ha lp th ca phn ng AE
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35
Phn ng cng hp AE xy ra theo kiu transph thuc vo tc cht ban u m c cc ngphn lp th khc nhau
ng phn cis sn phm threo (nhm th tngng khc pha)
H
CH3C2H5
H
Br2
H
CH3C2H5
H
Br+
Br-
C2H5
C2H5
H
Br
Br
CH3
H Br
BrCH3
H
H
Br H
CH3
H Br
C2H5
H Br
CH3
Br H
C2H5
threo-http://hhud.tvu.edu.vn
ng phn trans sn phm erythro (nhm thtng ng cng pha)
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36
H
HC2H5
CH3
Br2 Br H
CH3
Br HC2H5
H Br
CH3
H Br
C2H5
erythro
http://hhud.tvu.edu.vn
d. nh hng ca nhm th lin kt vi ni i
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37
Nhm th y in t tng mt in t caC=C tng kh nng phn ng A
E
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 licho AEhttp://hhud.tvu.edu.vn
Kh nng AE:
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38
O2N H
HH
HOOC H
HH
Cl H
HH
H3C H
HH
H3C CH3
HH
H3C CH3
CH3H
H3C CH3
CH3H3C
< < < < < >
>
> > >
http://hhud.tvu.edu.vn
IV. Phn ng th i in tvo nhn thm (SE)
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43
+ X+
acid + H+
X
Xc tc: cc acid v c: H2 SO4
, H3
PO4
, HF
hay Lewis acid: FeCl3
, AlCl3
, ZnCl2
V d: C6 H6
+ (CH3
)3
C-Br /AlBr3 C6H5-C(CH3)3 +
HBrhttp://hhud.tvu.edu.vn
C ch phn ng: 2 giai on, lng phn t Giai on 1: to phc ( benzonium cation)
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44
p
(
)
+ X -Y
xt
nhanh X -Y phc
chamHX HXHX+ +
+
HX
+
Trong phc : X khng lin kt trc tip vi C no cPhc : X c lin kt trc tip vi 1 C ca benzene
phc
http://hhud.tvu.edu.vn
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45
Giai on 2: tch proton
HX
+nhanh
X
+ HY
http://hhud.tvu.edu.vn
+++ Nhm th y in t (+C, +H, +I) SE tngVd:
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46
* 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 gimV d:-N+N, -NO2
, -CN, -CHO, -COR, -COCl, -COOH,
-CO-NH2 (-I, -C)Cation: -N+R3
(-I mnh)
* halogen (-I > +C)http://hhud.tvu.edu.vn
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1
Ha Hc Hu CTS Phan Thanh Sn NamB mn K Thut Hu CKhoa
K
Thut Ha H c
Trng i Hc Bch Khoa TP. HCMin thoi: 8647256 ext. 5681Email:[email protected]
http://hhud.tvu.edu.vn
Chng 4: AlkaneI. Gii thiu chung
mailto:[email protected]:[email protected]:[email protected]:[email protected]:[email protected]:[email protected] -
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2
g
Alkane hydrocarbon no mch h, nguyn tcarbon lai ha sp3 Cng
thc tng
qut: C
n H
2n+2
Gc ha tr 109o5, lin kt C-H: 1.09, C-C: 1.53 ng phn: cu to, cu dng (quay)
methane
http://hhud.tvu.edu.vn
II. Danh php IUPAC
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3
p p
II.1. Alkane khng phn nhnh:
4 alkane u: gi theo tn thng thngmethane, 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)http://hhud.tvu.edu.vn
II. 2. Alkane phn nhnh
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4
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, nhmcui cng phi vit lin vi tn mch chnh Nu c nhiu nhnh tng ng: dng tip ung di-, tri-, tetra- ch s lng nhm tng ng
http://hhud.tvu.edu.vn
Nu c nhiu nhm th khc nhau: sp xp theoth t alphabetical. Lu : b qua cc tip u
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5
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, nhngvn dng so snh gia chng vi nhau. V d: dimethyl hoc methyl s i sau ethyl haydiethyl
isopropyl i trc methyltert-butyl i trc isobutylsec-butyl i trc tert-butylhttp://hhud.tvu.edu.vn
V d (H vit tt):C C
C
C
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6
C C C C C C
C
C
C
4-Ethyl-2,2-dimethylhexane
C C C C C C C C
C
CC
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)nonanehttp://hhud.tvu.edu.vn
II.3. Tn gc alkyl c ly 1 H t alkane, gi theo tn alkane nhng
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7
c ly 1 H t alkane, gi theo tn alkane nhngi ane yl CH3
-: methyl
CH3 -CH2
-: ethyl CH3
-CH2
-CH2
-: n-propyl
CH3CHCH3 : isopropyl
CH3CH2CHCH3 : sec-butyl
(CH3 )2 CHCH
2 -: isobutyl
(CH3)3C-: tert-butylhttp://hhud.tvu.edu.vn
III. Cc phng php iu ch alkaneIII.1. Khcc dn xut ca halogen, alcohol,carbonyl:
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8
carbonyl:a. Kh bng HI 80%, 180
oC:
CH3I + HIP o
CH4 + I2
CH3-CH2-OH + HIP o
CH3-CH3 + I2 + H2O
b. Kh bng Zn/HClR C R'
O
Zn(Hg)/HClR-CH2-R'
(Kh
Clemmensen)
http://hhud.tvu.edu.vn
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III.4. Phn ng Wurtz
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10
CH3 CH2
Br + Na CH3CH2CH2CH3 + NaBr
Ch
c
hiu qu
khi
iu ch
alkane
i xng:
CH3
CH2
Br + CH3
Br CH3CH2CH3 + CH3CH3 +CH3CH2CH2CH3
khng c tnh chn lc t s dng
Ch hiu qu cho R-Br & R-IHiu sut: bc 1 (60%) > bc 2 (40%) > bc 3 (10%)http://hhud.tvu.edu.vn
III.5.in phn mui ca carboxylic acid
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11
CH3
COONa CH3COO. CH3. CH3-CH3
III.6. Nhit phn mun natri ca carboxylic acidCH3
COONa + NaOH CH4 + Na2CO3
IV. Tnh cht vt l (t c) Alkane khng phn cc ch tan trong dung mikhng phn cc
to si
ca
alkane
nhnh
< thng
http://hhud.tvu.edu.vn
V. Tnh cht ha hc
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12
Alkane tr khng c phn ng cng, c trngl phn ng th HV.1. Phn ng th H bng halogen
Ch
xy ra
nhit
cao
hoc
khi
c
nh
sng
R-H R-X HX+ X2to
h
+
http://hhud.tvu.edu.vn
a. C ch phn ng (gc t do SR )
Khi mo:to
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13
X-X 2Xt
h
Truyn mch:RX
R-H + X R + HX
R + X2 + X
Phn
ng
c
th
tip tc
to sn phm
di-, tri-,
tetra-
V d chlor ha CH4 c th thu c CH3
Cl,CH2
Cl2
, CHCl3
, CCl4
CH4
+ Cl2 CH3Cl + HCl H = -25Kcal/molhttp://hhud.tvu.edu.vn
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14
X X
R R
R X
R-R
R-X
X-X+
+
+
Ngt mch:
http://hhud.tvu.edu.vn
Giai on to CH3. kh hn giai on to CH3
Clgiai on to CH3
. (hay R. ni chung) s quyt nh
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15
tc phn ng chung
http://hhud.tvu.edu.vn
b. So snh kh nng thay th HH bc 1 & bc 2:
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16
CH3-CH2-CH3 CH3-CH2-CH2-Cl + CH3-CHCl-CH3+ Cl2
25 oC
h 45% 55%
Vn tc tng i khi thay th H bc 1: 45 / 6 = 7.5Thay th H bc 2: 55 / 2 =27.5
t l vn tc tng i H bc 1/ H bc 2 = 7.5/27.5 ~
http://hhud.tvu.edu.vn
H bc 1 & bc 3:
CH3 CH3CH325 oC
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17
H3C C CH3H
H3C CH CH2Cl H3C C CH3Cl+ Cl2
h+
64% 36%
Vn tc tng i khi thay th H bc 1: 64 / 9 ~7Thay th H bc 2: 36 / 1 ~ 36t l vn tc tng i H bc 1/ H bc 3 = 7/36 ~ 1/5T l vn tc tngi bc 1/bc 2/bc 3 = 1/4/5
nhit thng, kh nng thay th H C bc 3cao nht
Lu : 600oC: t l ny l 1/1/1http://hhud.tvu.edu.vn
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18
c. Kh nng phn ng ca dy halogenF2
> Cl2
> Br2
> I2
F ha: mnh lit, t lin kt t dngI ha: rt kh xy r a (H = + 13 Kcal/mol), ch
xy
ra khi loi HI trong qu trnhhttp://hhud.tvu.edu.vn
d. Tnh chn lc ca phn ng Phn ng Br ha c tc chm hn Cl ha
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nhng c chn lc caoT l vn tc tng i 127oC ca Br ha: bc1/bc 2/bc 3 = 1/82/1000
H3C C CH3
CH3
H
H3C CH
CH2Cl
CH3H3C C CH3
CH3
Cl
+ Cl2
25 oC
h
+
64% 36%
H3C C CH3
CH3
H
H3C C
H
CH2Br
CH3H3C C CH3
CH3
Br
+ Br2
127 oC
h
+
1% 99%
CH3-CH
2-CH
3 CH3-CH2-CH2-Br + CH3-CHBr-CH3+ Br
2
127 oC
h 3% 97%http://hhud.tvu.edu.vn
V.2. Phn ng nitro ha alkane
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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%)
http://hhud.tvu.edu.vn
V.3. Phn ng ng phn ha
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Chuyn cc alkane mch thng thnh alkane mchnhnh di tc dng ca xc tc nhit cao Xc tc thng dng: acid Lewis nh AlCl3
, xctc acid trn c s zeolite
V d:
CH3-CH2-CH2-CH3AlCl3
H3C C CH3
CH3
Hto
http://hhud.tvu.edu.vn
C ch:
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CH3-CH-CH2-CH3
H
AlCl3
HAlCl3 H3C C CH3
CH3
H
CH3-C-CH2-CH3
H
C C+C
C
H
H
H H
H
H
HHH
to +
+ AlCl3
-HAlCl3
Xu
hng: to
carbocation
bn hn chuyn v
http://hhud.tvu.edu.vn
V.4. Phn ng cracking
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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)
http://hhud.tvu.edu.vn
V.5. Phn ng oxy ha alkane
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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), carboxylicacid (RCOOH)
Phn ng quan trng:2Cn
H2n+2
+ (3n + 1)O2 2nCO2 + (2n+2) H2O
ta nhit mnh, -341 kcal/mol alkane c dnglm nhin liuhttp://hhud.tvu.edu.vn
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1
Ha Hc Hu CTS Phan Thanh Sn NamB mn K Thut Hu CKhoa
K
Thut Ha H c
Trng i Hc Bch Khoa TP. HCMin thoi: 8647256 ext. 5681Email:[email protected]
http://hhud.tvu.edu.vn
Chng 5: ALKENE
mailto:[email protected]:[email protected]:[email protected]:[email protected]:[email protected]:[email protected] -
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I. Gii thiu chung Alkene: hydrocarbon mch h, cha 1 lin kt iC=C (Cn
H2n
, n2)
Trong C=C: 1 & 1, hnh thnh do lin kt caorbital sp2
http://hhud.tvu.edu.vn
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3
Lin kt vung gc vi mt phng phn tAlkene n gin nht l ethylene CH2
=CH2
121.7o
116.6o
1.33 1.08
http://hhud.tvu.edu.vn
II. H danh php
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4
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 )2 C=CH
2 isobutylene
http://hhud.tvu.edu.vn
II.2. Danh php IUPAC
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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 nganghttp://hhud.tvu.edu.vn
CH3-CH-CH=CH2
CH33-methyl-1-butene
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II.3. Tn gc ca alkeneAlkenylCH2 =CH- 1-ethenyl (vinyl)CH2
=CH-CH2
- 2-propenyl (allyl)CH3
-CH=CH-
1-propenyl
CH3-C-CH=CH-CH3
CH3
H
4-methyl-2-pentene (c
cis
& trans)
http://hhud.tvu.edu.vn
III. Cc phng php iu ch
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III.1. Tch nc t alcohol Phn
ng
c
th pha
lng
(xc
tc
acid H2
SO4
,
H3
PO4
, 100-170oC) hay pha kh (xc tc Al2 O3 ,zeolite, 350-400oC)
to
xtC C
H OH
C C + H2O
http://hhud.tvu.edu.vn
Kh nng tch nc: alcohol bc 3 > bc 2 > bc 1
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CH3CH2CH2CH2-OH
CH3-CH-CH
2-CH
3OH
H2SO4 50-60%
(CH3)3C-OHH2SO4 20%
H2SO4 75%
CH2=C(CH3)2
CH3-CH=CH-CH3
CH3CH=CHCH3
100 oC
80 oC
140 oC
http://hhud.tvu.edu.vn
III.2. Tch HX t dn xut ca halogento
KOH/ th l
C C
H X
C C + H2O + KX
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9
KOH/ethanolH X
Kh nng tch HX: RX bc 3 > bc 2 > bc 1
CH3CH2CHCH3
Cl
CH3CH2CH2CH2Cl
CH3CH2CH=CH2
CH3CH2CH=CH2to
KOH/ethanol
to
KOH/ethanol20%
+
80%
CH3CH=CHCH3
Lu
: tch
R-X bc
1 khng
c
chuyn v R-OH bc 1
CH3CH2CH2CH2-OH
H2SO4 75%
CH3CH=CHCH3140 oChttp://hhud.tvu.edu.vn
III.3. Kh dn xut 2 ln th ca halogenC C
X X
C C + ZnX2Zn
to
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10
X X to
H3C C C CH3
H
Br
H
Br
+ ZnX2Zn
to
CH3CH=CHCH3
III.4. Hydro ha
alkyne
C CR R'
H2,xt
Lindla
r
(Pd)
H
R R'
H
H
R H
R'
Na,NH3
http://hhud.tvu.edu.vn
III.5. Nhit phn ester
C H2 1
-O-COR C H2
+ RCOOH
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11
n 2n+1 n 2n Nhit phn ester ca ru bc 1 < bc 2 < bc 3
Ester bc 1 1 sn phm, bc 2 & bc 3 nhiusn phm
IV. Tnh cht vt l (tc)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)Xc tc, to... lin kt d bthttp://hhud.tvu.edu.vn
V.1. Phn ng cng hp i in t
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V.1.1. C ch: Giai
on 1:
C C + X -Ydung moi
xuc tac C C
X
Yphc
khong ben
nhanh
C+ C
X
cham C Cben hoa
X+
Giai
on chm:
X+ tn
cng
vo
C=C i in t
http://hhud.tvu.edu.vn
Giai on 2:
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13
C CX+
Y- nhanh
C CX
Y
Y-
tn cng vo pha i lp vi X Nhm th y in t (+C, +I, +H) tng mt in tca C=C tng kh nng phn ng AE
http://hhud.tvu.edu.vn
V.1.2. Phn ng cng hp halogen
Ph h CH CH i B i
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Phn ng cng hp ca CH2 =CH2
vi Br2
vi s cmt ca NaCl, NaNO3
, sn phm thu c l 1 hnhp:Br-CH2
-CH2
-Br + Br-CH2
-CH2
-Cl
+
Br-CH2 -CH2
-ONO2
Nu phn
ng
thc hin
trong
dung mi
l
CH3
OH,
sn phm chnh l Br-CH2 -CH2 -OCH3 !!!http://hhud.tvu.edu.vn
H2C CH2 CCl4 H2C CH2+ Br2
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H2C CH2
H2C CH2
H2C CH2
CCl4
H2O
CH3OH
H2C CH2
Br Br
H2C CH2Br OH
H2C CH2
Br OCH3
+ Br2
+ Br2
+ Br2
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V.1.3. Phn ng cng HXa. Quy tc Markonikov (dnh cho C=C khng i
) H+ t b h hi H
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17
xng): H+
s tn cng vo carbon cha nhiu H
CH3-CH=CH2
CH3-C=CH2
CH3
CH3-C-CH3
CH3
Br
CH3-CH-CH3
Br
+ HBr
+ HBr
b. Quy tc Zaitsev-Wagner: H+
s tn cng vo pha to thnh carbocation trung gian bn nhtCH
3-CH=CH-CH2-CH
3
HBr
CH3-CH-CH-CH2-CH3Br
http://hhud.tvu.edu.vn
Q t Kh h khi t id h
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c. Quy tc Kharasch: khi c mt peroxide, phn ng
s i theo hng
ngc vi
Markonikov
&
theo c ch cng hp gc t doCH3
-CH=CH2
+ HBr CH3-CH2-CH2-Br
Cc peroxide:
H2
O2
,
acetyl peroxide CH3
CO-O-O-
CO-CH3
, benzoylperoxide C6
H5
CO-O-O-COC6
H5
http://hhud.tvu.edu.vn
Cch: Theo hng to gc t do bnCH3-C-O-O-C-CH3
CH3
to + CH3-CO-O + CO2
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CH3-CH=CH2
CH3-C-O-O-C-CH3O O
Br
HBr
Br
3
CH3-CH-CH2
Br
CH3-CH2-CH2Br Br
2
+ HBr + CH3COOH
+ CH3-CH-CH2Br
+
CH3-CO-O
CH3-CH-CH2Br
L
u : HI & HCl khng tham gia phn ng cng gc tdo nh HBr!!!http://hhud.tvu.edu.vn
V.1.4. Phn ng cng hp nc Cn xc tc acid: H2SO4, H3PO4 (khng dng HX)H2SO4 CH CH CH
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CH3-CH=CH2 H2SO4 CH3-CH-CH3OH
+ H2O
Tun theo quy tc Markonikov C
ch:
CH3-CH=CH2-H+
CH3-CH-CH3-H2O
H3C C
H
CH3
OH
H
-H+ CH3-CH-CH3
OH
+ H+ ++ H2O
+ H+
Nu dng nhiu H2 SO4
:
CH3
-CH=CH2
+ H2
SO4 (CH3)2CH-OSO3H
(CH3 )2
CH-OSO3
H + H2
O (CH3)2CH-OH + H2SO4http://hhud.tvu.edu.vn
V.1.5. Phn ng cng hp B2 H6 Phn ng quan trng iu ch alcohol bc 1 & 2
t lk i h M k ik
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t alkene, ngc vi sn phm MarkonikovCH3-CH=CH2 CH3-CH2-CH2-OH
1. B2H6
2. H2O2 / NaOH
C ch: B2 H6 BH3
CH3-CH=CH
2
BH3
[CH3-CH2-CH2]3BH2O2
CH3-CH-CH2-B HH
H
H-
CH3-CH2-CH2-OH
[CH3-CH2-CH2-O]3B
CH3-CH
2-CH
2-BH
2
OH-
(Lewis acid)
+
http://hhud.tvu.edu.vn
V.2. Phn ng hydro haV.2.1. C ch:C C + H Ni C C
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22
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
+ H2
H H H H
C C
C C
H H
http://hhud.tvu.edu.vn
V.2.2. Tnh lp thPhn ng cng hp cis (syn) ng phn cis c th thu sn phm meso (1 snphm)
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phm) ng phn trans sn phm l hn hp racemic (1i i quang)
C
C
H COOH
COOHH
D2
C
C
H COOH
HHOOC
D2
Ni
Ni
H C D
COOH
CH D
COOH
H C DCOOH
CD H
COOH
D C HCOOH
CH D
COOH
mesomaleic acid
rac-fumaric acid http://hhud.tvu.edu.vn
V.3. Phn ng oxy haV.3.1. Tc nhn oxy ha peracid
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C CR-C-O-O-H
O
C C
OH2O C C
OH
OH
C C
O
++ RCOOH
(H+, OH-)
Cng
hp
trans, to
-diol
Phn ng khng gy ct mch C=Chttp://hhud.tvu.edu.vn
V.3.2. Oxy ha bng ddch KMnO4 long (pH 7, 0
oC )
Cng hp cis to diol
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Cng hp cis, to diol
Phn ng khng ct mch C=C
C C + MnO4- 0oC
pH 7
C C
O O
MnO O
-
OH-
H+
H2OC C
OH OH
+ MnO3-
http://hhud.tvu.edu.vn
V.3.3. Oxy ha bng ddch KMnO4 m c, to
cao
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Phn ng gy ct mch C=C Sn phm l carboxylic acid
CH3
-CH=CH-CH3
+ KMnO4
/ to 2 CH3COOH
(CH3
)2
CH=CH-CH3
+ K2
Cr2
O7
/H2
SO4
/to
(CH3
)2
C=O + CH3
COOH
http://hhud.tvu.edu.vn
V.3.4. Oxy ha bng ozone Phn ng gy ct mch C=C
Sn phm l carbonyl (khc KMnO )
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Sn phm l carbonyl (khc KMnO4 )
C CO3
C C
O O
O
C
O O
CO
C O
H
2O(H+) C O
C O
molozonide ozonide
Zn/CH3
COOH + H2O
H2/Pt + H2O
+ H2O2
CH3-C=CH-CH2-CH3
CH3
CH2-C-CH3
O
CH3-CH2-CHO1. O32. H2O
+ + H2O2
L
u : H2 O2 d dng oxy ha carbonyl thnh carboxylic acid sn phm cui l acid!!!http://hhud.tvu.edu.vn
V.4. Phn ng polymer ha Phn ng to polymer di tc dng ca nh
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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 H2
SO4
, AlCl3
,BF3
)
hay anion (xc
tc
LiNH2
)
ClCl
CH2-CH-
Cl
CH2-CH--
Cl
nCH2=CHperoxide
polyvinyl chloride
--CH2-CH-
H2C C
CH3
CH3
H+
H3C C
CH3
CH3
CH2 C
CH3
CH3
CH2 C
CH3
CH3
http://hhud.tvu.edu.vn
H H H C
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Ha Hc Hu CTS Phan Thanh Sn NamB mn K Thut Hu CKhoa
K
Thut Ha Hc
Trng i Hc Bch Khoa TP. HCMin thoi: 8647256 ext. 5681Email:[email protected]
http://hhud.tvu.edu.vn
Chng 6: ALKADIENEI Phn loi
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I. Phn loi
I.1. Hai ni i ng lin nhau (allene)CH2
=C=CH2
propadieneCH3
-CH2
=C=CH2
1,2-butadiene
http://hhud.tvu.edu.vn
I.2. Hai ni i lin hpC cu to c bit c tnh cht ha hc quant h t h ht
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C cu to c bit c tnh cht ha hc quantrng ch trng cc hp cht nyCH2 =CH-CH=CH
2
1,3-butadieneCH2
=C(CH3
)-CH=CH2
2-methyl-1,3-butadiene(isoprene)
http://hhud.tvu.edu.vn
I.3. Hai ni i xa nhauTnh cht ging nh alkene
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Tnh cht ging nh alkeneCH2
=CH-CH2
-CH=CH2
1,4-pentadiene
http://hhud.tvu.edu.vn
II. Cc phng php iu chII.1. Tch nc t1,3-butadiol
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i t acetylene
HC CH HgSO4
H2SO4CH3-CHO+ H2O
H3C CO
H
Al2O3
H2C CO
HH
CH2=CH-CH=CH2
OH- H3C C CH2 C
H
OOH
H
H3C C CH2 CH2OH
OH
H
+ H2/Ni
350o
C
+ 2H2O
http://hhud.tvu.edu.vn
II.2. T ethanol2 CH3-CH2-OH CH2=CH-CH=CH2
ZnO/Al2O
3
4 0 00 oC
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450-500 oC
II.3. T 1,4-butadiol
HC CH
HO-CH2-CH2 CH2-CH-OHAl2O3
HO-CH2-C C-CH2-OH
CH2=CH-CH=CH2
+ HCHOH2/Ni
350oC
http://hhud.tvu.edu.vn
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III.1. Phn ng cng halogenThu c 2 sn phm cng 1,2 & 1,4CH2=CH-CH-CH2
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CH2=CH-CH=CH2
C C C C
Br
Br
Br
CH2-CH=CH-CH2
Br
+ Br-Br
C
ch:
CH2=CH-CH=CH2 CH2=CH-CH-CH2
CH2=CH-CH-CH2
Br-
Br Br
Br
Br
CH2-CH=CH-CH2
CH2-CH=CH-CH2
Br-
Br
Br+ Br-Br
+ +
http://hhud.tvu.edu.vn
III.2. Phn ng cng HXTy theo nhit m thu c hn hp sn phmkhc nhau
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Ty theo nhit m thu c hn hp sn phmkhc nhauCH2=CH-CH=CH2
CH2=CH-CH-CH2
Br H
CH2-CH=CH-CH2
Br H
CH2=CH-CH-CH2
Br
Br
H
CH2-CH=CH-CH2
H
+ HBr
-80oC 40
oC
80%
20%
20%
80%
40oC
http://hhud.tvu.edu.vn
III.3. Phn ng Diels-AlderPhn ng cng hp & ng vng ca1,3butadiene
hay dn xut ca n vi cc hydrocarbon khng no
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hay dn xut ca n vi cc hydrocarbon khng nokhc (i diene)
C
C C H
HC
H
H
H
H
C
CH
CH3CH
H
O
+to
CH3
O
http://hhud.tvu.edu.vn
Cc hp cht i diene phi mang nhm th htin t, ethylene phn ng rt chmCH2=CH-CHO acrolein
CH2=CH-CN acrylonitrile
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CH2
CH CN acrylonitrile(CN2
)C=C(CN)2
tetracyan ethylene
C6 H5 -CH=CH-COOH cinnamic acidO
O
O
maleic anhydrideO
O
benzoquinone
http://hhud.tvu.edu.vn
III.4. Phn ng trng hp
CH CH CH CH CH CH CH CH
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n CH2=CH-CH=CH2--CH2-CH=CH-CH2--
n
Trng
hp
isoprene cha
94% cis
~ cao
su
thin nhin
n CH2=C-CH=CH2
CH3
CH3
--CH2-C=CH-CH2--n
http://hhud.tvu.edu.vn
Ha H c Hu C
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1
Ha Hc Hu CTS Phan Thanh Sn NamB mn K Thut Hu CKhoa
K
Thut Ha H c
Trng i Hc Bch Khoa TP. HCMin thoi: 8647256 ext. 5681Email:[email protected]
http://hhud.tvu.edu.vn
Chng 7: ALKYNEI Gii thiu chung
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I. Gii thiu chungHp cht hydrocarbon khng no, mch h, chalin kt b a C CCng
thc
chung: Cn
H2n-2
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31.2 1.06
180
o
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II. Danh phpII 1 Tn thng thng
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II.1. Tn thng thng Alkyne n gin nht l HCCH acetylene
Cc
alkyne
n gin khc c
xem
l
dn xut
ca acetyleneHCC-CH2
-CH3
ethylacetylene
CH3
-CC-CH(CH3
)2
isopropylmethylacetylene
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II. 2. Tn IUPAC Cch gi tn ging nh alkene, ch i ene thnh yne Mch chnh phi cha CC
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Mch chnh phi cha C C Nhng hp cht cha nhiu hn 1 ni badiyne, 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-ynehttp://hhud.tvu.edu.vn
III. Cc phng php iu chIII.1. Thy phn calcium carbide CaC2
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y p
CaC2
CaC2
HC CH
CaO + 3C 2000o
C + CO
+ 2H2O + Ca(OH)2
III.2. Oxy ha
methane
6CH4 HC CH+ O21500 oC + 2CO + 10H22
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III.3.i t dn xut dihalogenH2C CH2
Br BrHC CH
KOH/EtOH
to
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CH3-CH2-CHCl2
Br Br
CH3-CH2-C-CH3
Cl
ClNaNH
2
CH3-C
CH
CH3-CH
C CH3
CH
t
KOH/EtOH
to
KOH/EtO
H
to
to CH3-CH2-Chttp://hhud.tvu.edu.vn
III.4. Alkyl ha dn xut natri hay c magnesiumca acetyleneHCCNa + R-X HCC-R + NaX
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HCC-MgX + R-X HCC-R + MgX2
iu ch
dn xut ca
acetylene
HCCH + NaNH2 HCCNa + NH3
HCCH + CH3
MgX HCC-MgX + CH4
IV. Tnh
cht vt l (t c)
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V. Tnh cht ha hcV.1. Phn ng th H u mch
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Hu mch th hin tnh acid
HCC-H + NaNH2 HCCNa + NH3HCC-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-HH+ d tch ra Alkene & alkane khng c tnh cht nyhttp://hhud.tvu.edu.vn
V.2. Phn ng cng hydrogenC CR R' + H
2
Ni hay PtR-CH
2
-CH2
-R'
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C CR R' + H2
Pd/C
R-CH2-CH2-R'
Pd/CaCO
3
Pd/BaSO4
C C
R
H H
R'
C CR R' + Na/NH3 C C
R
H R'
Hhttp://hhud.tvu.edu.vn
V.3. Phn ng cng halogen
BrBr
Br
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H3C C CH H3C C CH
Br
Br2 H3C C CHBr2
Br
+ Br-Br
Sn phm trans trong ln cng th nhtLu : nu ni i & ni ba khng lin hp, X2
scng
vo
ni
i!!!
CH2
=CH-CH2
-CCH + Br2 BrCH2-CHBr-CH2-CCH
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V.4. Phn ng cng HX
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C C C HH
H
H
H-BrC C CH2H
H
H Br
H-BrC C C H3H
H
H Br
Br
Tun theo quy tc Markonikov
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V.6. Phn ng cng hp alkylborane
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C CCH
H
HC
H
HCH3 C CH3C CH2 CH3
H BR2CH3COOH
BHR2
C CH3C CH2 CH3
H OH
CH2 CH3C CH2 CH3
O
C CH
H3C C2H5
H
H2O2/OH-
To
alken: cng
cis
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V.7. Phn ng cng hp cht carbonyl Cng
hp
i
nhn
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C C HH C O
H
HC CH CH2-OH HCHO C CHO-H2C CH2-OH
C C HH C O
R
R
C CHO-C C-OH
R
R
R
R+ 2
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V.8. Phn ng cng hp i nhnR-OH, R-SH, R-COOH, H-CN, amine monomer quan trngHC CH
RO-
150 oCROCH CH- ROH ROCH CH2 + RO-
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C CHC6H5CO
R2NH
C C
C6H5CO
H H
NR2
C6H5C CHC2H5ONa
C C
C6H5
H H
OC2H5
CH2 CH C CHROH
CH2 CH CH CHOR
RO-
150 oChttp://hhud.tvu.edu.vn
V.9. Phn ng oxy haOxy ha alkyne bng KMnO4 hay ozone to
carboxylic acidR-CC-R + KMnO4 hay ozone RCOOH +
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4 y
RCOOH
R-CC-H + KMnO4 hay ozone RCOOH +CO2
V. 10. Phn
ng
trng
hp
C C HHCuCl
CH2-CH=C CH2
Cl
CH2=CH-C CHHCl
CH2=CH-C
Cl
CH22to
chloroprene
n
cao su neoprene
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Ha Hc Hu C
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Ha Hc Hu CTS Phan Thanh Sn NamB mn K Thut Hu CKhoa
K
Thut Ha Hc
Trng i Hc Bch Khoa TP. HCMin thoi: 8647256 ext. 5681Email:[email protected]
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Chng 6: HYDROCARBON THM
I Cu to ca benzene
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I. Cu to ca benzene Kkul a ra cng thc cu to ca benzenenm 1865
6C, 6H vng 6 cnh c 3 ni i nhng khng
th l cyclotriene
C
CC
C
CC
H
H
H
H
H
H
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Kkul chng minh rng v tr 3 Lin kt i khngc nh m c th thay i
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Phn
ng
th
2 ln Br ch
cho
1 sn phm
+ Br2
Br
Br
Br
Br
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Cu to thc t: h in t phn b u cho 6C(khng phi ca ring 3 cp C=C)
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6C nm trong cng 1 mt phng, trng thilai ha
sp2
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120 o120 o
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120
o
1.09
1.39
121.7o
116.6o
1.33 1.08
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II. Tnh thm
Hydrocarbon thm
(arene) nhng hp cht vng
lin hp c cu to phng, c cu to in tgingb kh h h d h h
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benzene, kh cho phn ng cng, d cho phn ngth
Br2
CCl4
Br2
CCl4
Br
H
H
Br KMnO4 L
H2
O
OH
OH
H
HKMnO4 L
H2O
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Arene thng l vng phng 5, 6, 7 cnh, c hin t lin hp, s t tun theo quy tc Hkel4n + 2, n = 0,1,2,3,4V d h h h d
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V d cc hp cht arene thng dng
n=1 n=2 n=3
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Mt s trng hp c bit
(-)
cyclopentadienyl
6 in t (i
t
ca
anion
tham
gia
h
lin
hp) n=1 c tnh thm
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(+)
cycloheptatrienyl
6 in t (C+ tham
gia
orbital trng p vo h lin hp) c tnhthm
(+)
4 in t khng c tnh thm
(+)
2 in t c tnh thm
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(.)
5 in t khng c tnh thm
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(.) 7 in t khng c tnh thm
(-) 8 in t khng c tnh thm
NH
Pyrrole
O
Furan
S
Thiophene
6 in t (i in tp tham gia h lin hp)c tnh thmhttp://hhud.tvu.edu.vn
III. Danh php
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Hu ht cc arene u c tn thng thng, 1 stn thng thng c chp nhn lm tn IUPAC
Tn IUPAC: benzene c chn lm tn gc, tncc nhm th t trc, nhm th c nh s theo
nguyn
tc tng
ch
s
nh
nht, xp theo
alphabeticalhttp://hhud.tvu.edu.vn
III.1. Dn xut ca benzene
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12http://hhud.tvu.edu.vn
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NO2
Cl Br
NH2
Br Br
OH
Cl Cl
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C
3-bromo-5-chloronitrobenzene
Br
2,4,6-tribromoaniline
Cl
2,4,6-trichlorophenol
Br
Br
Br
1,2,4-tribromobenzene
OH
NO2
Cl
2-chloro-4-nitrophenol
O2NCH3
NO2
2,6-dinitrotoluene
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III.2. Vng a ngng t
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Naphthalene Anthracene
1
2
3
45
6
7
8
9
10
1
2
3
45
6
7
8 9
10
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III.3. Cc arene c d t trong vng
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N
Pyridine
N CH3
2-methylpyridine
NH
Pyrrole
O
Furan
S
Thiophenehttp://hhud.tvu.edu.vn
IV. Cc phng php iu chIV.1. Chng ct mui ca benzoic acid
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COONa
+ NaOHto + Na2CO3
IV.2.i t acetylene
HC CH3 Cu hay phc Ni
to
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IV.3. Alkyl ha benzene
AlCl3R
R Cl + HCl
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IV.4.ng vng & dehydro ha phn on du mC6-C8
CH3(CH2)4CH3Cr2O3 / Al2O3
V. Tnh cht vt l (t c)
3+ R-Cl + HCl
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V. Tnh cht ha hcV.1. Phn ng th i in t
V 1 1 C h h
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V.1.1. C
ch
phn
ng
+ X+ acid + H+
X
Xc
tc:
H
2 SO
4 , H
3 PO
4 , HF
hay Lewis acid: FeCl3 , AlCl3
, ZnCl2
C6H6 + (CH3)3C-Br /AlBr3 C6H5-C(CH3)3 + HBrhttp://hhud.tvu.edu.vn
C ch phn ng: 2 giai on, lng phn t Giai
on 1: to phc
( benzonium
cation)
t
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+ X -Yxt
nhanh
X -Y phc
cham
HX HXHX
+ +
+
HX
+
Trong phc : X khng lin kt trc tip vi C no cPhc
: X c
lin
kt trc tip vi 1 C ca
benzene
phc
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Giai on 2: tch proton
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HX
+nhanh
X
+ HY
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V.1.2. Kh nng phn ng v quy lut tha. Kh nng phn ng: Nhm th y in t (+I, +C, +H) mt
i t t h th t t h i
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in t trong nhn thm tng tc nhn iin t cng d tn cng tc phn ngtng
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)
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Nhm th ht in t (-C, -I) mt in t canhm thm gim khng thun li cho tc nhn iin t gim tc phn ng
Cc