CHUYN C CH PHN NG HA H NG HC HU C

CC LOI PHN NG TRONG HA H NG HC HU C C CH PHN NG CH

___________PHN 1: CC LO LOI PHN NG TRONG HA HC H C HU C___________ I. VN TC PHN NG 1. Vn tc phn ng: Xt phn ng: A + B C+D ng ng thi Vn tc phn ng c tnh bng s bin thin nng cht phn ng theo th gian d [ A ] v= = k [A] dt k: hng s tc phn ng. 2. Bc ca phn ng: Vi phn ng n gin v = k [A] phn ng bc 1 v = k[A].[B] phn ng bc 2 phn ng bc (n + m) c v = k[A]n.[B]m 3. Nng lng ca phn ng: A B + Qcalo/mol Energy

II. CC LOI PHN NG TRONG HA H NG HC HU C C nhiu phng php phn loi ph ng nh: n 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 ng 1. Theo phng hng phn ng ng a. Phn ng th: (Substitution) - L phn ng trong mt nguy t hay mt nhm nguyn t trong phn t c thay th bng n nguyn t nguyn t hay nhm nguyn t khc. - Tng qut: RX + Y RY + A ; Trong : X l nhm b th ; Y l nhm th Y th

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CHUYN C CH PHN NG HA H NG HC HU C - Mt s phn ng th thng dng: halogen ha, nitro ha, sulfonic ha, alkyl ha, aryl ha, acyl ha. ng: Di y l mt s phn ng th Phn ng th i nhn SN R X + Y R Y + X ; Trong Y l tc nhn i nhn V d: CH 3Cl + OH CH 3OH + Cl Phn ng th gc t do SR R X + Y R Y + X ; Trong : Y l gc t do. V d: SO 2 Cl 2 + C6 H 5 C 6 H 5 Cl + SO 2 Cl Phn ng th i in t SE R X + E + R E + X + ; Trong : E+ l tc nhn i in t. V d: Ar H + + NO 2 Ar NO 2 + H +

b. Phn ng cng hp: (Addition) n - L phn ng trong hai phn t (hoc ion) kt hp vi nhau thnh mt phn t (ion) mi. n t - Thng xy ra cc hp cht c ni i, ni ba. Phn ng xy ra c s thay trng thi lai ha ca ng i nguyn t C.
xt CH3 C CH + H 2 O CH3 CO CH 3

CH 2 = CH 2 + HBr CH3 CH 2 Br
Di y l mt s loi phn ng cng hp: i Phn ng cng hp i in t AE n CH 3 CH 2 CH = CH 2 + H 2 O CH 3 CH 2 CHOH CH 3 Phn ng cng hp i nhn AN CH3 CH = O + HCN CH3 CH ( CN ) OH Phn ng cng hp gc AR

Cl
+ Cl
c. Phn ng tch loi (Elimination) n - Phn ng lm 2 nguyn t hay nhm nguy t tch ra khi mt phn t. nguyn - Phn ng lm thay i trng thi lai ha ca nguy t C. i nguyn CH3 CH 2 OH CH 2 = CH 2 + H 2O

Br CH 2 CH 2 Br + Zn CH 2 = CH 2 + ZnBr2
d. Phn ng chuyn v: - Trong phn ng c s chuyn ch mt hay nhm nguy t gi l s chuyn v. n nguyn - Phn ng c s chuyn v trong phn t gi l phn ng chuyn v. n l

R R C CH2 X R -X
-

R R C CH2 R
chuyn v

R C CH2 R R

2. Theo s phn ct lin kt a. S ct t d ly: A | B A + + B hoc A | B A + B+

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CHUYN C CH PHN NG HA H NG HC HU C Trong : A + , B+ : carbocation, A , B : carbanion Carbocation v carbanion tham gia cc ph ng th, tch loi v cng hp: c ch in t phn ch b. S ct t ng ly:

A B A + B phn Trong : A , B l cc gc t do, tham gia ph ng theo c ch gc. 3. Theo tc nhn phn ng - Tc nhn i in t: mang in tch + n + + + + H , Cl , NO 2 , R , acid Lewis
Tc nhn i nhn: mang in tch hay c cp e t do n OH , Cl , NH 2 , R OH, base Lewis Tc nhn gc t do: cha in t c thn Br , R

PHN ________________________ ________________________PH II: C CH PHN NG_______________ I. PHN NG TH: (SUBSTITUTION) : 1. Phn ng th i nhn SN a. C ch lng phn t SN2 - Tc phn ng ph thuc nng ca 2 cht phn ng. ng - Phn ng xy ra mt giai on. t phn on Trng thi chuyn tip gia cht ph ng v tc nhn i nhn Y , y l giai o quyt nh tc phn ng. V d: CH 3Cl + HO CH 3OH + Cl
Phng trnh tc phn ng: v = k [CH 3OH] [HO ] Sn phm c s nghch o cu hnh. u
H HO- + H H H Cl H

HO H

Cl H

H HO H H + Cl-

b. C ch n phn t SN1 ng ph - Phng trnh tc phn ng ph thuc nng ca cht phn ng. - Phn ng xy ra 2 giai on on Giai on to carbocation R+ l giai o chm quyt nh tc phn ng. V d: HO + ( CH 3 )3 C Br ( CH 3 )3 C OH + Br Phng trnh tc phn ng = k ( CH 3 )3 Br + Giai on chm: ( CH 3 )3 C Br ( CH 3 )3 C + Br Giai on nhanh: ( CH 3 )3 C + + HO ( CH 3 )3 OH
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CHUYN C CH PHN NG HA H NG HC HU C Phn ng theo c ch S

N1

c s racemic ha.
HO-

CH3 HO CH3 CH3

HO-

CH3 C+ H3C CH3

H3C OH H3C H3C

Carbocation C

Cc yu t nh hng n ph ng n Trong RX, nu X gn trc tip vo C b nht RCH2X th phn ng xy ra ch yu theo SN2 p bc y ch Trong RX, nu X gn trc tip vo C b ba R3CX th phn ng xy ra ch yu theo SN1 p bc Trong RX, nu X gn trc tip vo C b hai R2CHX th phn ng xy ra theo SN1 hay SN2 ty p bc y thuc vo cu trc hoc dung mi. c Dung mi nh hng n c ch ph ng. n - Dung mi phn cc u tin theo SN1 - Dung mi khng/t phn cc u tin theo SN2 V d 1: Phn ng este ha -

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CHUYN C CH PHN NG HA H NG HC HU C V d 2: Phn ng th i nhn trn nhn thm

NaOH, 300o Cl NH3, 200o Cu2O NH2 + NaCl OH + NaCl

Nu trn nhn thm c mang nhm th rt in t nh NO 2 v tr orto hay para th ph ng xy ra d u th phn dng. 2. Phn ng th i in t SE - Ch yu xy ra cc hydrocarbon thm v d vng thm. d + - Tc nhn i in t Y l nhng tc nhn c orbital tr ng trng nh cc ion dng (+NO2, Br+) hoc nhng hp cht c orbital cha cht y (SO3, CO2). y - Phn ng th i in t xy ra nhi giai on: y nhiu Giai on tng tc gia E+ v Ar to phc . ArH Giai on chuyn t phc sang ph . phc Giai on to sn phm cui cng. i
H
+ + E

H E
+

H E

E
+ + H

Ph c

Ph c

Br

Br FeBr3

H Br

Br FeBr3

Br

Quy tc Hollemann: ai - Nhn thm mang nhm th lai I

OCH3 CH OCH3 + Br2 FeBr3 + HBr para ( 96%) Br CH OCH3 Br + HBr o-Bromoanisol( o-Bromoanisol 4% ) OH + HNO3 H2SO4 NO2 OH OH + H2O para NO2 + H2O o-Nitrophenol
Do hi ng electron hiu +I, siu lin h hp I, +C I, I, +C I,

X l nhng nhm th tng hot ng th CH3, C2H5, C3H7 NH2, NR2, NHCOR, O-, OH, OCH3, OR, OCOR F, Br, Cl, I

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CHUYN C CH PHN NG HA H NG HC HU C Nhn thm mang nhm th lai II ai

COOH + Br2 COOH OH + HBr Br B obenzoic acid m-Bromo
X

CHO

CHO + HNO3 H2SO4 + H2O NO2 m-Nitrobenzaldehid m-

X l nhng nhm th gim hot ng th NO2, SO3H, COOH, CN, CHO, COOR, COR COCl, CONH2, CCl3, CF3, +NH3, +NHR2

Do hiu electron ng I, C I, C

3. Phn ng th gc t do SR - Phn ng th theo gc t do l ph ng dy chuyn c 3 giai on. phn Giai on khi mo. o sn Giai on pht trin mch v to s phm. Giai on tt mch v kt thc ph ng. t phn 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

R + Cl RCl II. PHN NG CNG HP (ADDITION) P 1. Phn ng cng hp i in t AE - Hp cht c lin kt i, ba - Qua cc giai on: Giai on to tc nhn i in t E+ (t EY) + Tng tc ca E vi cht phn to carbocation R+ ng + 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 ph ng. c t phn - Dung mi v cu to phn t EY nh hng n quyt nh s hnh thnh tc nhn i in t E+ Y C ch phn ng AE

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CHUYN C CH PHN NG HA H NG HC HU C Cng hp trn ni i lin hp

CH2=CH - CHBr -CH2Br CH2=CH - CH=CH2 CH2Br- CH=CH -CH2Br
Cng 1,4 ng Cng 1,2 ng

CH2 -CH=CH -CH2

2. 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 a i - Cc giai on ca phn ng: Tc nhn Y tn cng vo trung tm mang i tch dng trn C ca nhm carbonyl to thnh ion n in a mang in tch m trn O (C = O C + O )

R CH = O + Y R CHY O Ion m s kt hp vi ion dng (H+) to sn phm cui cng. i + R CHY O + H R CHY OH V d: Phn ng cng HBr vo propylen: ng CH 3 CH = CH 2 + HBr CH 3 CHBr CH 3
H Br H + + Br Quy tc Markonikof H CH3 CH CH3 CH3 CH CH2 + H+ slow CH3 CH CH3 + BrCH3 CH2 CH2 + Bror CH3 CH2 CH2 CH3 CH CH3 Br CH3 CH2 CH2 Br fast H3 C CH C CH2

C ch cng i nhn AN

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CHUYN C CH PHN NG HA H NG HC HU C in tch dng trn nguyn t C cng l th kh nng phn ng cng cao. ln ng Cl CH2 C H > H C H > R C H > R C R
O R C O O O

Cl > R C OR > R C NH2 > R C OH > R C O O O O O O

a Xc tc H+ lm tng s phn cc ca nhm C=O 3. Phn ng cng gc t do AR peroxyd CH 3 CH = CH 2 + HBr CH 3 CH 2 CH 2 Br

C ch phn ng (Qui tc Kharasch) c

ROOR 2RO RO + HBr ROH + Br

H = +35 KCal / mol H = 23 KCal / mol H = 5 KCal / mol

Br + CH 3 CH = CH 2 CH 3 C H CH 2 Br

CH 3 C H CH 2 Br + HBr CH 3 CH 2 CH 2 Br + Br H = 11 KCal / mol

III. PHN NG TCH LOI (ELIMINATION) N 1. Tch loi lng phn t E2 - Cc giai on: Tng tc ca mt base mnh v cht phn ng to trng thi chuyn tip i S tch loi xy ra v to sn phm c lin kt i.
Y- + H C C X YH C C X

HY + C C + X-

Tra g thai chuye tie n a n p

V d: Phn ng tch loi HBr t etylbromid.

H H3C C2H5O+ Br H H3C H Br H H H3C H H

+ C2H5OH + Br-

C2H5O

C ch tch E2

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CHUYN C CH PHN NG HA H NG HC HU C 2. Phn ng tch n phn t E1 - Cc giai on: o Cht phn ng to carbocation R+ l giai on chm + Tch H v to ni i l giai o nhanh. i on
H C C X H C C + Xcha m

H C C

C C +

H+

nhanh

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

H CH3 CH3 C C Br CH3 CH3 H CH C 3 CH3 C C CH C 3 CH3 H3C H+ H3C C C CH3 CH3

- Br

C ch E1

Carbo ocation

Yu t nh hng - Cht phn ng bc cng cao d cho E1 c d - Dung mi cng phn cc th u tin cho E1 c - S cnh tranh gia SN1 v E1 (iu kin kh khn d cho phn ng tch l ng lai) Quy tc zaisev Alken c nhiu nhm th CH3CHCHCH3 -HBr CH3 CH CH CH3

Br

CH3CHCH2CH3

Quy tc Ingold: E2 xy ra khi 2 nhm tch l v tr trans y lai

H X

- HX

Quy tc Barton: E2 xy ra khi 2 nhm tch l cu dng trans y lai X

- HX H
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CHUYN C CH PHN NG HA H NG HC HU C

10

________________________PH PHN

III BI TP P DNG________________________

y Cu 1: Cho bit cc phn ng sau x ra theo c ch g. Vit c ch phn ng. H+ a. CH3MgCl + C2H5COCH3 g. 2C2H5OH b. CH3CH2Cl + KCN h. Pyridin + C2H5I c. CH3Cl + H2NCH3 H+ i. C6H5OH + HCHO OH d. CH3CH2Cl + H2O OH j. C6H5CHO + CH3CHO e. C6H5ONa + CH3I to k. CH3CH2CH(OSO3H)CH3 + H2O OSO f. C6H5OH + CH3OH l. CH3COOC2H5 + OH

Cu 2: Xc nh cc cht cn li trong cc s sau v nu c ch to ra chng i a. Hon thnh s sau: CH3CH2CH3 (A) B C

A D C

b. Hon thnh s sau:

CH3CH=CH2(A)
c. Hon thnh s sau: HC CH (B)

(B B)

(C)

(D)

+(E)

H CH3 (F) CH3 C OH H C2H5 (G)

CH3 CH CH2 CH2 CH CH3 H OH OH

Cu 3: Cho bit sn phm to thnh trong cc ph ng sau, nu c ch phn ng o phn ng

600 C a. CH3CH=CH2 + Cl2 1:1
CCl4 b. CH2=CH2 + Br2 1:1 CCl4 c. H2C=CHCH=CH2 + Br2 1:1
o

t C d. C6H5CH3 + Cl2 1:1,Fe,xt

Cu 4: So snh kh nng phn ng c cc cp cht sau: ng ca 1 a. Theo SN : CH3CH2CH2Cl (1) ; CH2=CH2CH2Cl (2). b. Theo SN2: CH2=CHCl (1) ; CH3CH2Cl (2). c. Theo SN1: p-NO2C6H4CH2Cl (1) ; p p-CH3OC6H4CH2Cl (2) ; CH3CH2CH2Cl (3). Cu 5: Dng mi tn cong ch r c ch chuyn 7-dehydrocholesterol (I) thnh vitamin D3 (II) v cho bit ch cu dng bn ca n. Bit trong cng th di y: R l: -CH(CH3)-(CH2)3-CH(CH3)2 t thc CH(CH
R
R

(I)

(II)

HO

HO

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CHUYN C CH PHN NG HA H NG HC HU C Cu 6: Cho s phn ng:

CH 3C=O C2H5
1.

11

C 6H 5MgBr
2.

H (A) C 3H 7

HBr a c B

H2 O

a. Vit c ch phn ng v cng th cu to cc sn phm. ng thc b. Gi tn cu hnh ca B, C theo danh php R, S. a Cu 7: Hy gii thch s to thnh nhanh chng 2,4,6 3C6H2NH2 (D) khi cho p 2N-C6H4-SO3H (A) o 2,4,6-Br p-H hoc p-H2N-C6H4-COOH (B) tng tc v dung dch nc Br2. vi Cu 8: Hy ch ra c ch phn ng v s phm cui ca phn ng cng Br2 (1:1) v nhng cht sau: ng sn vi a. Acid maleic (1). b. Acid fumaric (2). c. But-2-in (3). HOOC COOH HOOC H

H
(1)

COOH
(2)

H 3C C C CH 3 (3)

Cu 9: Xt phn ng th: RCl + OH ROH + Cl c biu thc tc phn ng l: v = k[RCl] hoc n

v = k[RCl][OH ]

a. Cho mt v d c th v RCl trong m trng hp, gii thch. mi b. S dung mi gii ca tertButyl bromur trong acid acetic xy ra theo c ch nh sau: Butyl y ch + (CH 3 )3 CBr (CH 3 )3 C + Br (1)

(CH 3 )3 C+ + CH 3COO (CH 3 )3 COCOCH 3 (2)

Hy gii thch ti sao, khi tng hm l i lng Natri acetate (CH3COONa) th khng lm t tng tc phn ng. Cu 10: Hp cht 2,2,4-trimethylpentan (A) c sn xut vi quy m ln bng ph trimethylpentan ng phng php tng hp xc tc t C4H8 (X) vi C4H10 (Y). A cng c th c iu ch t X theo hai b c: th nht, khi c xc tc acid v c, X to thnh Z v Q ; th hai, hydro ho Q v Z. a. Vit cc phng trnh phn ng minh ha v tn cc hp cht X, Y, Z, Q theo danh php IUPAC. ng b. Ozon phn Z v Q s to thnh 4 h cht, trong c aceton v formaldehyd trnh by c ch. o hp t, formaldehyd, Cu 11: Gii thch: a. Ti sao phn ng sau khng dng tng hp tert-butyl propyl ether. ng

(CH3)3COCH2CH2CH3 CH3CH2CH2ONa + (CH3)3CBr Natri propoxid tert-butyl bromur butyl tert-butyl propyl ether. b. Sn phm chnh ca phn ng ny l g. ng c. Hy ngh phng php tng h tert-butyl propyl ether tt hn. ng hp Cu 12: X l - halogen ceton v base mnh to thnh cc sn phm chuyn v S chuyn v ny gi i n v. l phn ng Favorski: - clocyclohexanon s chuyn v thnh methylcyclopentancarboxylat khi c mt CH3ONa trong ether. Hy xc nh c ch ca phn ng ny. nh ch O
Cl + CH3ONa H ether COOCH3 + NaCl

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CHUYN C CH PHN NG HA H NG HC HU C
LiAlH 4 H2 Cu 13: Cho cc phn ng sau: But 2 in A (1) ; But 2 in A (2) . Trong Pd/CaCO Pd /CaCO3

12

A, B l 2 ng phn lp th. Khi ch ha ring bit A v B bng acid mnh th chng u chu s chuyn nh ha sau: ng phn ha v tr, ng phn ha khng gian. ng a. Xc nh A, B v cc sn ph chuyn hoa nu trn. m b. Vit c ch cho qu trnh chuy ha trn. chuyn Cu 14: Khi un nng 2methylcyclohexan methylcyclohexan1,3dion vi but3en2on trong dung d on dch kim ngi ta thu c mt hp cht hu c (sn ph n phm chnh) c cng thc C11H14O2. Hy vi cng thc cu to ca vit sn phm ny v gii thch qu trnh t ra n. i to Cu 15: C mt phn ng chuyn ha theo phng tr n trnh sau: H3C CH3 H3C CH H3C CH3 CH3 CH3 + H CH3 C OH H CH3 + CH3 C H + . . . + CH3 CH3

CH3

CH3

a. Gii thch c ch. b. Nu thay cht ban u l pxylen th sn phm no to thnh. xylen Cu 16: Vit c ch ca cc phn ng sau y: ng Base a. C6 H 5COCl + CH 3CH 2 OH C 6 H 5COOCH 2 CH 3
acid b. CH 3CONH 2 + H 2 O CH 3COOH + NH + 4

Cu 17: Sildenafil (mt loi thuc tng l c lc) c tng hp theo s : O O NH2NH2 HNO3, H2SO4 OEt A 1. Me2SO4, dd NaOH B o 2. NaOH, H2O 50 C, 2 h O

SOCl2, DMF, toluen, 55 C, 6 h dd NH3, 20 C, 2 h

o

H2 (50 psi), 5% Pd/C EtOAc, 50 C, 4 h

0

OEt

O OH
ClSO3H, SOCl2 to phng, 18 h

CH3-N

NH , H2O
o

(N

N)2CO NH N

10 C, 2 h

hi l- u, 2 h, - N

O OEt HN
N NH

CH3 N N Pr

E, EtOAc
to phng, 70 h

L O2 S N

N CH3

1. Hy hon chnh dy phn ng trn, bi rng: ng bit o Qu trnh chuyn qua G c to thnh acid sunfonic trung gian ri mi chuyn thnh sunfonyl clorur. o gian, n , o N,N -carbonyldiimidazol (CDI) l m loi tc nhn dng hot ha acid ca azol mt carboxylic cho phn ng th nucleophin ca nhm carbonyl. bonyl. 2. Vit c ch phn ng chuyn [I] thnh K.
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CHUYN C CH PHN NG HA H NG HC HU C Cu 18: Khi x l acidsalixylic vi dung d i dch nc brom d th acid d dng t thnh tribromphenol. to Vit c ch. C th ch i phn ng c acid m- v p-hydroxybenzoic khng? ng ca Cu 19: Trnh by c ch phn ng t ng tng hp quinolin bng phng php Skaraup. i ch quinolin t hng iu anilin, glyceryl, nitrobenzen trong mi tr eryl, trng acid sunfuric m c xc tc st (II) sunfat t Cu 20: Ephedrine (G) l mt ho cht dng lm thuc cha bnh v h h c chit t cy ma t p
hong. Ephedrine c tng hp nh sau: C6H6 CO , HCl / D CH 3CH 22 E H 2 / F p NO , OH Ni AlCl 3 CH G 3Br a. Vit cng thc cu to ca D, E, F v G trong s trn. b. Vit c ch phn ng ca cc giai o to thnh D v E. a on ________________________PH PHN Cu 1:
2

13

IV HNG DN GII________________________

AN a. CH3MgCl + C2H5COCH3 (CH3)2C(C2H5)OMgCl

SN b. CH3CH2Cl + KCN CH3CH2CN + Cl SN c. CH3Cl + H2NCH3 CH3HNCH3 + HCl SN d. CH3CH2Cl + H2O CH3CH2OH + HCl SN e. C6H5ONa + CH3I + NaI
2 2 2

SE f. C6H5OH + CH3OH CH3C6H4OH (o-, p-) + H2O

SN g. 2C2H5OH C2H5OC2H5 + H2O SN h. Pyridin + C2H5I [pyridin [pyridin(N+) C2H5]I
2 2

SE i. C6H5OH + HCHO (o-, p-) CH2OHC6H4OH AN j. C6H5CHO + CH3CHO C6H5CH=CHCHO + H2O

SN k. CH3CH2CH(OSO3H)CH3 + H2O CH3CH2CH(OH)CH3 + SN l. CH3COOC2H5 + OH CH3COO + C2H5OH Cu 2:
2 1

CH3CH2CH3 (A)

+ Br2 SR

CH3CHBrCH3 H
SN2

KOH/ethanol E2

CH3CH=CH2

H2/Ni

CH3CH2CH3 CH3CH=CH2
SN2 E1
AE

CH3CHOHC 3 CH
AN

CH3CH2CH2(A)

CH3CHCH3(B) H Br

CH3CHCH3(C) OH

CH3CCH3 O

C2H5MgCl

CH3 C2H5 F) OMgCl

CH3CHO AE

(D)

AN

CH3 C

H3 O+ SN2

CH3 CH C 3 C OH C2H5(G)

HC

CH

CH3 CH C H OH H

CH CH3 OH

H2/Ni AE

CH3 CH CH2 CH2 CH CH3 H OH H OH

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CHUYN C CH PHN NG HA H NG HC HU C

14

Cu 3:
600 C a. CH3CH=CH2 + Cl2 Cl CH 2 CH = CH 2 + HCl SR
CCl4 b. CH2=CH2 + Br2 Br 2CH2Br CH AE CCl4 c. H2C=CHCH=CH2 + Br2 (1) + (2) ; AE
o

(1) ClCH2CH(Cl)CH=CH2 ; (2) ClCH2CH=CHCH2Cl

t C,1:1,Fe,xt d. C6H5CH3 + Cl2 p CH3C6 H 4 Cl + HCl SE
o

Cu 4: a. (2) > (1) b. (2) > (1) c. (2) > (3) > (1) Cu 5:
2.
R H H2C R

as
HO HO O

to
R

HO HO O

C d ng b S u -trans n: n

Cu 6: a a. C ch AN. Cng thc ca B v C

CH3 C2H5

C O H C3H7

CH3 C6H5MgBr H2O HO C2H5 C6H5 H C3H7 HBr Br C2H5

CH3 C6H5 H C3H7

b. B: (2R)(3S)2phenyl3ethylhexan ethylhexan2ol, C: (2R)(3S)2phenyl2brom brom3ethylhexan

i dng ion lng cc: Cu 7: Trong nc (A), (B) tn ti d - p-H2N-C6H4-SO3H (A) pp +H3N-C6H4-SO3 (A) p-H2N-C6H4-COOH (B) p-+H3N-C6H4-COO (B) Mt nhm SO3 trong A hoc COO trong B l do: Br2 Br+ + Br c - Sau tc nhn electrophil (Br+) s tn cng vo nguyn t carbon ca nhn th thm th nhm SO3 trong A hoc COO trong B. - Sau xy ra qu trnh tch H+ to thnh nhm NH2. Nhm NH2 vi hiu ng C s nh nh hng nhm th tip theo vo v tr ortho- theo s sau: o v
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CHUYN C CH PHN NG HA H NG HC HU C

15

SO3 + Br+ Br NH3 COO + Br+ NH3 NH2 - H+ Br + 2Br+ B Br NH2 Br Br

NH3

Cu 8: C ch cng Brom vo ni i C=C x ra theo c ch cng hp electrophil AE, gm 2 bc: i xy p

Y C C + Y X C C Y C C

Y C C

Y C C

Trng hp a, b xy ra theo c ch AE nu trn. a. Phn ng to thnh hn hp raxemic g p gm 2 acid: acid (2R)(3R)2,3dibrombutan dibrombutandioic v acid (2S)(3S)2,3dibrombutandioic dioic b. C 4 cch tn cng u cho 1 s phm duy nht l acid (2R)(3S)2,3dibrombutan u sn dibrombutandioic c. Cng tng t c ch AE nhng s phm l: (E)2,3dibrombut2en. sn Cu 9: a. Ta c: ng th i halogenur - v = k[RCl] phn ng th n phn t SN1, trng hp thun li l halogen bc III nh (CH3)3CCl. - v = k[RCl][OH] phn ng th lng phn t SN2, trng hp thun l l halogenur bc I nh ng th i CH3CH2CH2Cl on c b. Phn ng theo SN1 , m giai o (1) l giai on chm quyt nh tc phn ng v biu thc tc phn ng khng ph thu [CH3COO ] nn tng nng CH3COONa khng lm thay thuc i tc phn ng. Cu 10: a. Sn phm phn ng
CH3 H 3C C CH2 + H CH3 C CH3 CH3 H t p
o,

CH3 C CH3 CH3

H 3C

C H

C H (A) )

2-Metylpropen (X)

CH3 2-Metylpropan (Y)

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CHUYN C CH PHN NG HA H NG HC HU C

16

Phn ng qua 2 bc: m gia Bc th nht gm tng tc gi hai phn t trong mi trng acid:
CH3 H CH3 2 H3C C CH2 H+ H3C C C CH3 C CH2 2,4,4-trimetyl pent-1-en CH3 C CH3 2,4,4 4-trimetyl pent-2-en

CH3 H CH3 H H3C C CH3 C

Bc th hai hydro ho Q v Z
CH3 H H 3C C C CH3 C CH2 + H2
Ni , t
o

CH3 H CH3 H H3C C CH3 C CH3 C CH3 + H2

CH3 H H 3C C C

CH3 C H CH3

CH3 H

b. C ch phn ng
b (0,75 m).
O R1 C CH3 Z O O R2 C H Q R2HC C CH3 CH3
O3

O O R1 O C CH2
O3

O CH2 O
Zn/H3O
+

R1

C CH2 CH3 H

R1

C CH3

O + O

CH2

CH3 O O C CH3 CH3 H R2 O C H C O

R2

CH3 CH3

Zn/H3O

O + CH3COCH3

Cu 11: a. Phn ng sau khng dng tng hp tert-butyl propyl ether.

CH3CH2CH2ONa + (CH3)3CBr (CH3)3COCH2CH2CH3 Natri propoxid tert-butyl bromur butyl tert-butyl propyl ether. 2 Do phn ng th SN khng th hin vi alkyl halogenur bc ba thc b. Ion Alcolat l mt base mnh, l tc nhn nucleophile nn ph ng tch chi u th nn sn nh, phn ng chim phm chnh ca phn ng ny l s phm tch E2 ng sn
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CHUYN C CH PHN NG HA H NG HC HU C

17

H CH3 CH3CH2CH2ONa + H C C

CH3

E2

CH3 CH2 C + N NaBr + CH3CH2CH2OH

CH3 H Br Phng php tng hp hiu qu l dng phn t phn ng SN2 c nhm alkyl t c tr hn v alcolat cn cn tr nhiu hn: H CH3 CH3 SN2 H C C ONa CH3CH2CH2O C CH3 + NaBr + CH3CH2CH2Br H H CH3 CH3
Cu 12:
O Cl CH O 3 CH3OH O Cl O O CH3O OCH3

OCH3 H 2O OH

OCH3

Cu 13: a. Gii thch cu hnh A, B phn en. - Do phn ng cng LiAlH4 l ph ng cng trans nn A l transBut2en - Do phn ng cng H2 xc tc Pd/CaCO3 l phn ng cng cis nn B l cis ng cisBut2en. b. C ch chuyn ha A B
ng phn ha v tr: CH3 H C H
H C CH3 C CH3 CH3 H C
+

H C CH3 H C CH3 -H
+

C CH3
H

+H +

-H

+ +

CH2 C H CH2 C H CH2 CH3

-H

H CH3 H C
+

+H

+H +

-H

+H+

CH2 CH3

ng phn ha khng gian Hai cation trung gian hnh thnh khi protone ha A v B l ng nht nn c th chuyn ha A t th thnh B v ngc li.

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CHUYN C CH PHN NG HA H NG HC HU C

18

H C CH3 C

+H +

+ +

CH3 H C H C

H - H+ CH3 +H
+

CH3 C H C

CH3

-H

CH3

(B) cation trung gian (A) Cu 14: Khi un nng 2methylcyclohexan methylcyclohexan1,3dion vi but3en2on trong dung d on dch kim ngi ta thu c mt hp cht hu c (sn ph chnh) c cng thc C11H14O2. n phm
O H O CH3 O H 3C O
EtONa EtOH O

CH3 O
CH3

CH2 CH O O C CH3

CH C 2

CH

H2O O

CH3 CH3 O

O CH2 CH3 O H2O O H 3C O OH - H 2O E1 H 3C O O

O
EtONa

Cu 15: C ch phn ng a. Phn ng xy ra qua 4 bc - Bc 1: To carbocation

H2 O (CH3 )3C OH + H + (CH3 )3C O+ H 2 (CH3 )3C+

Bc 2: To isobuten v isobutan o CH3 CH3 H CH3 C CH3 V CH3 H C CH2 + H+

CH3 CH3 CH3 C CH3 +

H CH

CH3 CH3 CH3 C H + CH3

CH3

CH3

CH3 H
Bc 3: To carbocation trung gian o CH3 CH3 C

CH3 CH3 CH3 CH2 C

CH3 CH3

CH3 C CH3 CH3

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CH2

+ CH3

CHUYN C CH PHN NG HA H NG HC HU C
Bc 4: To sn phm CH2 H3C CH3 C C H3C CH3 H

19

H3C H3C CH3 CH3 + H+

CH3

CH3

b. Nu thay bng p-xylen th ph ng theo c ch SE thng thng v s ly ion hydrid t nhm phn methyl l khng th c. S phm l: n CH3 CH3
C CH3 CH3 CH3

Cu 16: a. C ch phn ng:

Cl CH3CH2OH+ Cl C O
Cl CH3 CH2 O C OH
- HCl CH3CH2 O C O

CH3CH2

+ O H

C O

b. C ch:
+

H CH3 C O -H
+

+ OH CH3 C OH
+

NH2 CH3 C OH O+

NH2

NH2

NH2 CH3 C OH OH

NH3+ CH3 C OH OH CH3COOH + NH4+

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CHUYN C CH PHN NG HA H NG HC HU C Cu 17:

O
O O OEt O
NH2NH2

20

EtO

H N

O
1. Me2SO4, dd NaOH

N 2. NaOH, H2O A Pr P H2 N O2N D Pr

HO

CH3 N HNO3, H2SO4 N 50oC, 2 h , Pr H2 N H2 N E

O HO O2 N

CH3 N N C Pr

B CH3 N N

O CH3 N N Pr

SOCl2, DMF, toluen, 55 C, 6 h dd NH3, 20 C, 2 h

o

H2 (50 psi), 5% Pd/C EtOAc, 50 C, 4 h

0

OEt

O OH ClSO3H, SOCl2
to phng, 18 h

OEt

O OH CH3-N NH , H2O
10 C, 2 h
o

O OEt

O OH

G SO2Cl Et OE
(N N)2CO

H O2 S N O OEt N N
N NH

N CH3 O N N

O O

hi l- u, 2 h ,

-N

NH

Me

O2 S N

N CH3

K O2 S N

N CH3

O OEt K E, EtOAc
to phng, 70 h

H2N

O N H

CH3 N N Pr

L O2 S N

N CH3

2. C ch t [I] sang K
OEt O C O N O N N
-H
+

OEt

O(- )

O OEt O N N N N
+ H+ + CO2 + HN

C N
O2 S

O N N

HN
O2 S

N CH3

N CH3

O2 S N

N CH3

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CHUYN C CH PHN NG HA H NG HC HU C Cu 18:

OH COOH

21

OH COOH

O C O H

O CO2 Br Br 2 H
+

OH Br Br

Br2

Br

-H

Br

-H

Br

To thnh cetoacid torng gian, lo hp cht ny d b decacboxyl ha. loi ng phn meta- kh xy ra phn ng v khng t thnh cetoacid ng to ng phn para- c th c v hp ch ny l cetoacid c ni i , p cht
Br

COOH

ng on Cu 19: C ch phn ng qua 4 giai o sau:

Giai on 1: Dehydrat ha glyceryl b bng H2SO4 un nng c aldehyd acrolein c

H 2SO4 Glyceryl CH2=CHCHO + 2H2O to

Giai on 2: Phn ng cng i nhn c anilin vi acrolein thu c: (phenyla min o)propionaldehyd ng ca

O NH2 + H C CH CH2

O H C N H CH2 CH2

Giai on 3: Tc nhn i in t tc d dng vo vng thm bi nhm carbonyl ca aldehyd proton a c

ha (y l giai on ng vng)
O H C N H CH2 CH2
+

OH H C + H N H CH2 CH2 - H+

OH -H - 2O N H N H 1,2-dihydroquinolin

Giai on 4: Oxy ha bi nitrobenzen thu vng thm i c

NO2 3 N H 1,2-dihydroquinolin + H+ NH2 3 N quinolin + + 2 H2O

St (II) sunfat c tc dng lm cho ph ng xy ra t t theo chiu thun ng phn

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CHUYN C CH PHN NG HA H NG HC HU C Cu 20: a. Tng hp ephedrine:

C6H6
CH3Br CO, HCl AlCl3

22

C6H5CHO

CH3CH2NO2, OH-

C6H5CH CHNO2 OH CH3

H2/N Ni

C6H5CH CHNH2 OH CH3

C6H5CH CHNHCH3 OH CH3

b. C ch phn ng:
C ch phn ng to thnh D: phn ng th electrophil vo nhn thm, SE: n

C=O + HCl

Cl

CH O

AlCl3

O C

H AlCl4 CHO

O C H AlCl4

HC + AlCl3 Cl

C ch phn ng to thnh E: phn cng nucleophil vo nhm carbonyl, AN: ng

CH3CH2NO2 CHO + CH3CHNO2
OH
-

CH3CHNO2 + H+ O

O CH CH CH3 NO2 H+

OH CH CH CH3 NO2

- - - - - - - - - - - - - - - - - - - - HT - - - - - - - - - - - - - - - - - -

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