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Cc loi phn ng trong ha hu cv khi nim v c ch phn ng
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Cc loi phn ng trong trong ha hu c
C nhiu phng php phn loi phn ng nh:
- Theo s phn ct lin kt- Theo hng phn ng
- Theo giai on quyt nh tc phn ng
- Theo bn cht tc nhn phn ng
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*Theo phng hng phn ng:
1. Phn ng th: (Substitution)
L phn ng trong mt nguyn t hay mt nhmnguyn t trong phn t c thay th bngnguyn t hay nhm nguyn t khc.
Tng qut: R-X + Y R-Y + A
X: nhm b th
Y: nhm th
Mt s phn ng th thng dng: halogen ha,nitro ha, sulfonic ha, alkyl ha, aryl ha, acyl
ha.
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a. Phn ng th i nhn SN:
R-X + Y- R-Y + X- Y-: tc nhn i nhn
V d: CH3Cl + OH- CH3OH + Cl
-
b. Phn ng th gc t do SR:
R-X + Y. R-Y + X. Y.: gc t do.
V d
: SO2Cl2 +
.
C6H5
C6H5Cl +
.
SO2Cl
c. Phn ng th i in t SE:
R-X + E+ R-E + X+ E+: tc nhn i in t.V d: Ar-H + +NO2 Ar-NO2 + H
+
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2. Phn ng cng hp: (Addition)
L phn ng trong hai phn t (hoc ion) kt hp vinhau thnh mt phn t (ion) mi.
Thng xy ra cc hp cht c ni i, ni ba. Phn ngxy r a c s thay i trng thi lai ha ca nguyn t C.
CH3-CCH + H2O CH3-CO-CH3CH2=CH2 + HBr CH3-CH2Br
Cc loi phn ng cng hp:
a. Phn ng cng hp i in tAE:CH3-CH2-CH=CH2 + H2O CH3-CH2-CHOH-CH3
b. Phn ng cng hp i nhnAN:
CH3-CH=O + HCN CH3-CH(CN)-OHc. Phn ng cng hp gcAR:
+ C l. C l
.
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3. Phn ng tch loi (Elimination)
Phn ng lm 2 nguyn t hay nhm nguyn t tch ra
khi mt phn t.Phn ng lm thay i trng thi lai ha ca nguyn t C.
CH3-CH2-OH CH2=CH2 + H2O
Br-CH2-CH2-Br + Zn CH2=CH2 + ZnBr2.
4. Phn ng chuyn v:
Trong phn ng c s chuyn ch mt hay nhm nguynt gi l s chuyn v.
Phn ng c s chuyn v trong phn t gi l phn ng
chuyn v.
C
R
R
R
C H 2 X C
R
R
R
C H 2- X
-
c h u y e n v CR
R
C H 2 R
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*Theo bn cht tc nhn phn ng:
S ct t lin kt v cc tiu phn ca phn ng:Ty theo bn cht lin kt c th b ct t theo kiu d ly
hoc ng ly.a. S ct t d ly:
A|B A+ + B- hoc A|B A- + B+
A+
, B+
: carbocation, A-
, B-
: carbanionCarbocation v carbanion tham gia cc phn ng th, tchloi v cng hp: c ch in t
b. S ct t ng ly:AB A. + B.
A., B. cc gc t do, tham gia phn ng theo c ch gc.
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Phn ng th: (Substitution)a. Phn ng th i nhn S
N: Theo 2 c ch:
- Lng phn t SN2- n phn t SN1
- C ch SN2:Tc phn ng ph thuc nng ca 2 cht phn ng.Phn ng xy r a mt giai on.Trng thi chuyn tip gia cht phn ng v tc nhn i nhn
Y--y l giai on quyt nh tc phn ng.V d: CH3Cl + HO
- CH3OH + Cl-
Phng trnh tc phn ng: = k [CH3OH][HO-]
Sn phm c s nghch o cu hnh.H
C l
H
H
H O-
H
H
H
C lH O- -
+
H
H O
H
H
C l-+
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C ch SN2
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C ch SN1:
Phng trnh tc phn ng ph thuc nng ca chtphn ng.
Phn ng xy ra 2 giai on
Giai on to carbocation R+ l giai on chm quyt nh tc
phn ng.V d: HO- + (CH3)3C-Br (CH3)3C-OH + Br
-
Phng trnh tc phn ng = k [(CH3)3-Br]
Giai on chm: (CH3)3C-Br (CH3)3C+ + Br-
Giai on nhanh: (CH3)3C+ + HO- (CH3)3-OH
Phn ng theo c ch SN1 c s racemic ha.
C H 3
C+
H 3 CC H 3
H O-
H O-
H 3 C
O H
H 3 C
H 3 C
C H 3
H O
C H 3
C H 3
C a r b o c a t i o n
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C ch SN1:
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Yu t nh hng :
* Trong R-X, nu X gn trc tip vo C bc nht RCH2-X
th phn ng xy ra ch yu theo SN2
.
* Trong R-X, nu X gn trc tip vo C bc b a R3C-X thphn ng xy ra ch yu theo SN1.
* Trong R-X, nu X g
n tr
c ti
p vo C b
c hai R2CH-Xth phn ng xy ra theo SN1 hay SN2 ty thuc vo cu
trc hoc dung mi.
* Dung mi nh hng n c ch phn ng.
- DM phn cc u tin theo SN1.
- DM khng/t phn cc u tin theo SN2.
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Phn ng ester ha
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b. Phn ng th i in t SE:
- Ch yu xy ra cc hydrocarbon thm v d vng thm.- Tc nhn i in t Y+ l nhng tc nhn c orbital trngnh cc ion dng (+NO2, Br
+) hoc nhng hp cht corbital cha cht y (SO3, CO2).
Phn ng th i in t xy ra nhiu giai on:- Giai on tng tc gia E+ v Ar-H to phc .
- Giai on chuyn t phc sang phc .- Giai on to sn phm cui cng.
E+
+
H
E+
H
E
H
EE
+ H+
P h h
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Phn ng Brom ha
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Quy tc Hollemann:
Nhn thm mang nhm th lai I
- I ,+ C
XX lanhng nhom thetang hoat D o hieu ng electr on
CH3, C2H5 ,C3H7 + I , sieu l ien hp
NH2, NR2 , NHCOR ,_O -, OH , OCH3 ,OR , OCOR - I ,+ C
F , Cl , Br , I
OCH3
Br
+ HBr
+ HBrOCH3
Br2FeBr3
( 96%)
4%
para
o-Bromoanisol ( )
+OCH3
Br
OHNO2
+
o-Nitrophenol
paraH2SO4HNO3
OH + H2O
+ H2O
OH
NO2
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Nhn thm mang nhm th lai II
- I ,- C+ - I ,- CNO2 ,SO3H , COOH CN , CHO , COOR , COR
COCl , CONH2 , CN , CCl3, CF3 , NH3 , NHR2+
Do hieu ng electronX la nhng nhom the giam hoatX
CHO
NO2
+ H2O
CHO
HNO3H2SO4
m-Nitrobenzaldehid
+
+
acid m-Bromobenzoic
Br2
COOH
+ HBr
COOH
Br
;
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c. Phn ng th gc t do SR:
Phn ng th theo gc t do l phn ng dy chuyn c 3 giaion.
- Giai on khi mo.- Giai on pht trin mch v to sn phm.- Giai on tt mch v kt thc phn ng.
V d: Phn ng clo ha alkan:- Khi mo: Cl-Cl Cl. + Cl.
- Pht trin mch: R-H + Cl.
R.
+ HClR. + Cl-Cl Cl. + R-Cl
- Tt mch v kt thc phn ng:
R.
+ R.
R-RCl.+ Cl. Cl-ClGiai on quyt nh tc phn ng l giai on pht trin mch.Gc t do c cu trc phng, sn phm c s racemic ha.
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Phn ng clo ha metan
.
CH4
+ Cl. CH
3+ HCl
hCl2 2Cl
.
CH3+ Cl2 CH3Cl + Cl
.
.
H = +270kcal
H = -1kcal
H = -23kcal
CH4+ Cl2 CH3Cl + HCl
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Phn ng cng hp: (Addition)
a. Phn ng cng hp i in tAE:Hp cht c lin kt i, ba + E-Y
Qua cc giai on:- Giai on to tc nhn i in t E+ (t E-Y)- Tng tc ca E+ vi cht phn ng to carbocation
R+
- Tng tc gia carbocation R+ v Y- to sn phm.* Giai on chm quyt nh tc phn ng l giai on
E+ tng tc vi cht phn ng.Dung mi v cu to phn t E-Y nh hng n quytnh s hnh thnh tc nhn i in t E+.
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C ch phn ng A E
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V d: Phn ng cng HBr vo propylen:
CH3-CH=CH2 + HBrH-Br H+ + Br-
C H 3 - C H = C H 2 + H+
C H 3 - C H+
- C H 3
C H 3 - C H 2 - C H 2+
C HC H
2
H
H3
C
+
c h a m
n h a n h
h o a
C H 3 - C H+
- C H 3 + B r-
C H 3 - C H B r - C H 3
C H 3 - C H 2 - C H 2+
+ B r-
C H 3 - C H 2 - C H 2 B r
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b. Phn ng cng hp i nhn AN:
- thng xy ra gia tc nhn i nhn Y- vi cc hpcht c ni i C=O, C=N
Cc giai on ca phn ng:- Tc nhn Y- tn cng vo trung tm mang in tchdng trn C ca nhm carbonyl (C=O +C-O-) tothnh ion mang in tch m trn O.
R-CH=O + Y-
R-CHY-O-
- Ion m s kt hp vi ion dng (H+) to sn phmcui cng.
R-CHY-O- + H+ R-CHY-OH
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C ch cng hp i nhn AN:
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in tch dng trn nguyn t C cng ln th kh nngphn ng cng cao.
O
CR C l
O
CR O C
O
R
O
CR O H
O
CR O R '
O
CR O-> > > >
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c. Phn ng cng gc t do A R:
CH3CH=CH2 + HBr CH3CH2_CH2Br
peroxyd
C ch phn ng (Qui tc Kharasch)
R-O-O-R 2R-O . H = +35 kcalBr
. + CH3CH=CH2R-O
.+ HBr ROH + Br
. H = -23 kcal
CH3CH_CH2Br H = -5 kcal
.
CH3CH_CH2Br.
+ HBr CH3CH2_CH2Br + Br
.H = -11 kcal
Ph t h l i
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. Phn ng tch loi:Theo 2 c ch:
- Lng phn t E2- n phn t E1a. Tch loi E2:
Cc giai on:- Tng tc ca mt base mnh vi cht phn ng to
trng thi chuyn tip- S tch loi xy r a v to sn phm c lin kt i.
V d: Phn ng tch loi HBr t etylbromid.
H C C XY-
X-
H C C XY - H Y C C+ + +
T r a n g t h a c h u y e n t i e p
B r-+
H H
H B r
H 3 C H
C 2 H 5 O-
+
H H
H B r
H 3 C H
C 2 H 5 O
H 3 C H
HH
+ C 2 H 5 O H
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b. Tch loi E1:
Cc giai on:
- Cht phn ng to carbocation R+ l giai on chm
- Tch H+ v to ni i l giai on nhanh.
V d: Tch HBr ca 2-bromo-2,3-dimetylbutan.
H C C X H C C X -+
H C C C C + H+
c h a m
n h a n h
H CC H 3
C H 3
C B rC H 3
C H 3
- B r- H C
C H 3
C H 3
CC H 3
C H 3H
+C
H 3 C
H 3 C
CC H 3
C H 3
C a r b o c a t i o n
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