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

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

*Theo phng hng phn ng:

1. Phn ng th: (Substitution) L phn ng trong mt nguyn t hay mt nhm nguyn t trong phn t c thay th bng nguyn 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.

a. Phn ng th i nhn SN: R-X + Y- R-Y + XY-: tc nhn i nhn V d: CH3Cl + OH- CH3OH + Clb. 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+

2. Phn ng cng hp: (Addition) L phn ng trong hai phn t (hoc ion) kt hp vi nhau thnh mt phn t (ion) mi. Thng xy ra cc hp cht c ni i, ni ba. Phn ng xy ra c s thay i trng thi lai ha ca nguyn t C. CH3-CCH + H2O CH3-CO-CH3 CH2=CH2 + HBr CH3-CH2Br Cc loi phn ng cng hp: a. Phn ng cng hp i in t AE: CH3-CH2-CH=CH2 + H2O CH3-CH2-CHOH-CH3 b. Phn ng cng hp i nhn AN: CH3-CH=O + HCN CH3-CH(CN)-OH c. Phn ng cng hp gc AR:
+ Cl

Cl

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 nguyn t gi l s chuyn v. Phn ng c s chuyn v trong phn t gi l phn ng chuyn v.
R R C CH2 R
X
R R C CH2 R
c h u y e n v
R C CH2 R
R

-X

*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-: carbanion Carbocation v carbanion tham gia cc phn ng th, tch loi 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.

Phn ng th: (Substitution)

a. Phn ng th i nhn SN: 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 ra 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 + ClPhng trnh tc phn ng: = k [CH3OH][HO-] Sn phm c s nghch o cu hnh.
H

HO- +
H H

Cl

HO
H

Cl
H

HO

+
H H

C l-

C ch SN2

C ch SN1: Phng trnh tc phn ng ph thuc nng ca cht phn 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 + BrPhng trnh tc phn ng = k [(CH3)3-Br] Giai on chm: (CH3)3C-Br (CH3)3C+ + BrGiai on nhanh: (CH3)3C+ + HO- (CH3)3-OH Phn ng theo c ch SN1 c s racemic ha.
CH3 HO CH3 CH3 H 3C HOCH3 C+ CH3 H 3C H 3C HOH 3C OH

C a r b o c a tio n

C ch SN1:

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 ba R3C-X th phn ng xy ra ch yu theo SN1. * Trong R-X, nu X gn trc tip vo C bc hai R2CH-X th 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.

Phn ng ester ha

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 trng nh cc ion dng (+NO2, Br+) hoc nhng hp cht c orbital 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.
H E
+

H E

H E

E + H+

P h c

P h c

Phn ng Brom ha

Quy tc Hollemann:
Nhn thm mang nhm th lai I

X la nhng nhom the tang hoat

CH3, C2H5 ,C3H7 NH2, NR2 , NHCOR , _O -, OH , OCH3 ,OR , OCOR F , Cl , Br , I

Do hieu ng electron
+ I , sieu lien hp - I ,+ C - I ,+ C

OCH3 OCH3 + Br2 FeBr3 + HBr para ( 96%) Br OCH3 Br + HBr o-Bromoanisol ( 4% ) OH + HNO3 H2SO4

OH + H2 O NO2 OH para NO2 + H2 O

o-Nitrophenol

Nhn thm mang nhm th lai II

X la nhng nhom the giam hoat

NO2 ,SO3H , COOH CN , CHO , COOR , COR + + COCl , CONH2 , CN , CCl3, CF3 , NH3 , NHR2

Do hieu n g electron
- I ,- C - I ,- C

COOH + Br2

COOH + HBr Br acid m-Bromobenzoic

CHO

+ HNO3

H2SO4

CHO + H2O NO2 m-Nitrobenzaldehid

c. Phn ng th gc t do SR: Phn ng th theo gc t do l phn ng dy chuyn c 3 giai on. - 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. + HCl R. + Cl-Cl Cl. + R-Cl - Tt mch v kt thc phn ng: R. + R. R-R Cl.+ Cl. Cl-Cl Giai 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.

Phn ng clo ha metan

CH3 + Cl2 CH4 + Cl2

Cl2 . CH4 + Cl

CH3 + HCl CH3Cl + Cl .

2Cl

H = +270kcal H = -1kcal H = -23kcal

CH3Cl + HCl

Phn ng cng hp: (Addition)

a. Phn ng cng hp i in t AE: 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 quyt nh s hnh thnh tc nhn i in t E+.

C ch phn ng A E

V d: Phn ng cng HBr vo propylen: CH3-CH=CH2 + HBr H-Br H+ + Br-

C H 3-C H = C H 2 + H +
c h a m C H 3-C H + -C H 3 + B rC H 3-C H 2-C H 2 + B r
+ -

C H 3-C H +-C H 3 C H 3-C H 2-C H 2

C H 3-C H B r-C H 3 C H 3-C H 2-C H 2B r
+

H
h o a c +

H 3C
nhanh

CH

CH2

b. Phn ng cng hp i nhn AN: - thng xy ra gia tc nhn i nhn Y- vi cc hp cht c ni i C=O, C=N Cc giai on ca phn ng: - Tc nhn Y- tn cng vo trung tm mang in tch dng trn C ca nhm carbonyl (C=O +C-O-) to thnh 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 phm cui cng. R-CHY-O- + H+ R-CHY-OH

C ch cng hp i nhn AN:

in tch dng trn nguyn t C cng ln th kh nng phn ng cng cao.

O
R

O C O H > R

O C O
R' > R

O C O-

Cl > R

C O C R > R

c. Phn ng cng gc t do A R:
peroxyd CH CH _CH Br 2 3 2

CH3CH=CH2 + HBr

C ch phn ng (Qui tc Kharasch)

R-O-O-R R-O . + HBr . Br + CH3CH=CH2 ._ CH3CH CH2Br + HBr

. ROH + Br CH3CH_CH2Br . CH3CH2_CH2Br + Br

2R-O .

H = +35 kcal H = -23 kcal H = -5 kcal H = -11 kcal

. Phn ng tch loi: Theo 2 c ch: - Lng phn t E2 - n phn t E1 a. 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 ra v to sn phm c lin kt i.
Y- +

H C C

H C C

HY +

C C

+ X-

T r a n g t h a i c h u y e n t ie p

V d: Phn ng tch loi HBr t etylbromid.

H
Br
H
Br
H

H H

H 3C C 2H 5O
-

H 3C

H 3C

+ C 2H 5O H + B r-

C 2H 5O

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.
H C C X H C C + Xc h a m nhanh

H C C

C C +

H+

V d: Tch HBr ca 2-bromo-2,3-dimetylbutan.

H CH3 CH3 C C Br CH3 CH3 - B rH CH3 CH3 C C CH3 CH3 H 3C H+ H 3C C C CH3 CH3

C a rb o c a tio n