Cac Loai Phan Ung Trong Hoa Huu Co Va Co Che Phan Ung

7/30/2019 Cac Loai Phan Ung Trong Hoa Huu Co Va Co Che Phan Ung

1/31

Cc loi phn ng trong ha hu cv khi nim v c ch phn ng


2/31


3/31

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


4/31

*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.


5/31

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

+


6/31

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

.


7/31

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


8/31

*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.


9/31

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-+


10/31

C ch SN2


11/31

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


12/31

C ch SN1:


13/31

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.


14/31

Phn ng ester ha


15/31

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


16/31

Phn ng Brom ha


17/31

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


18/31

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

;


19/31

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.


20/31

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


21/31

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+.


22/31

C ch phn ng A E


23/31

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


24/31

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


25/31

C ch cng hp i nhn AN:


26/31

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-> > > >


27/31

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


28/31

. 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


29/31


30/31

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


31/31

Cac Loai Phan Ung Trong Hoa Huu Co Va Co Che Phan Ung

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