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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 + OHCH3-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 + OHCH3-CH2-Br + CH3OCH3-CH2-Br + NH3 CH3-CH2-OH + ClCH3-CH2-O-CH3 + BrCH3-CH2-NH2 + HBr
3
y + R-X
cham
a.C ch:
nhanh
R-y + X-
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 + OHCH3-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)-
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
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
+ OH-
H3C
C CH3
OH
+ Br-
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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
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Gc R bc cng cao:
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)
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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 tr cn bng, tnh i nhn tc !!!
v
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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)
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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
ROto H+ to HOt
o
CH
CH2 +
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-, NH2-
cham
R y
C CH2
nhanh
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 cao (thng l sulfuric acid, acid rn) t
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
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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
kho
H H CH3 CH3
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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:
cham
H HH C H H C C+ HH C H H
nhanh
+ Br-
+ C2H5O-
C2H5OH
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(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 28% 72%
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
C2H5-O-C2H5
CH2=CH2 + H2O
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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
C2H5Oto cao
C C
+ X-Y
X C C Y
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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+
i in t
Giai on 2:
Y-
C C X+
nhanh
Y C C X
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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 !!!
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CCl4
H2C CH2 Br Br
CH3OH
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-CH2-C+H2 CH3-C+H-CH3 (bn hn) +
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 H Br CH3 Br H CH3 H Br Br H C2H5 threoH Br H CH3 CH3 Br H H Br C2H5
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C2H5 H
H CH3
Br2
CH3 Br H Br H C2H5
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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
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
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C O + X -Y
OX C Y
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+ Y
cham
C OY carbanion
i nhn
40
Giai on 2:
-
nhanh
C O
H+
C+ OH
in tch (+) ca carbon c tng cng AN cng thun li R-N+ H3 Tuy nhin, acid qu mnh: R-NH2 + H+ 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 Oo
42
Xc tc: cc acid v c: H2SO4, H3PO4, HF hay Lewis acid: FeCl3, AlCl3, ZnCl2 V d: C6H6 + (CH3)3C-Br /AlBr3 HBr C6H5-C(CH3)3 +
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
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X +
H nhanh
X + HY
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+++ 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)
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