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CHUYN : TNG HP HU C A. MT S VN L THUYT: I. Cc phng php lm tng mch Cacbon: 1.

. Cc phng php ankyl ha bng hp cht c magie (RMgX): R' X + R-R 1) CO2 + RCOOH 2) H O +
3

+ RMgX + + + +

1)

RCH2CH2OH
2) H3O
+


1) HCHO 2) H 3O +
3

RCH2OH RCH(OH)R R(R)C(OH)R

1) R ' CHO 2) H O +


1) R ' COR '' 2) H 3O +

1)R ' COOH hoac R ' COOR '' RCOR (R)2C(OH)R 2)H 3O +

* Hc sinh cn lu : + Hp cht c magie RMgX rt d phn ng vi cc hp cht c hidro linh ng (H2O, NH3, ancol, amin) bo qun v tin hnh phn ng trong ete khan. + Lp th ca phn ng cng RMgX vo hp cht cacbonyl: quy tc Crammer L L R RR R N tb O 2. Phng php anky ha ion axetilua: NaNH 2 / NH 3long R C CH R C C Na+ 3. Cc phng php ankyl v axyl ha hp cht thm: a) Cc phn ng ankyl ha:
R

tb

O-

R' X R C C R

+ dn xut halogen/ xt: axit Lewis (AlCl3 > FeCl3 > BF3 > ZnCl2) + anken/ xt: HCl/AlCl3 hoc axit protonic (HF > H2SO4 > H3PO4) + ancol/ xt: axit protonic hoc Al2O3. b) Cc phn ng axyl ha:
R

+ dn xut ca axit cacboxylic (RCOX > (RCO)2O > RCOOR)/ xt: AlCl3

Mt s phn ng formyl ha (thng dng gn nhm CHO vo phenol, ete thm hoc nhn thm giu electron)
R
CO + HCl AlCl3 HCN + HCl/ AlCl3 H2 O HCO-N(R)2 POCl3 hoac COCl2
CHCl3 NaOH

CHO

(Phn ng Gatterman Koch)


R CHO

(Phn ng Gatterman)
R CHO

HO

(Phn ng Vilsmeier)
HO OHC

* Hc sinh cn lu :

(Phn ng Reimer Tiemann)

+ C ch ca cc phn ng ankyl v axyl ha nhn thm l c ch SE2(Ar); trong ch c ch to tc nhn electronfin. + Cc phn ng ankyl ha thng to thnh hn hp mono v poliankyl mun thu c sn phm mono cn ly d cht phn ng. + Hng chnh ca phn ng khi th vo cc dn xut ca benzen. 4. Cc phng php ankyl v axyl ha cc hp cht c nhm metylen hoc nhm metyn linh ng: a) Cht phn ng c dng X CH2 Y hoc X CH(R) Y; vi X, Y l COR, -COOR, -CN, -NO2 Do X, Y l cc nhm ht electron mnh nguyn t H rt linh ng dng baz tch H+, to thnh cacbanion.
X H2C Y
C2H5ONa - C 2H5OH

Na CH

+-

X Y

RBr

HC

X Y

1) C 2H5ONa 2) RBr 1) C 2H5ONa 2) R'Br

R2

X Y C X Y

R(R')

RCOCl

RCO HC

X Y

* Hc sinh cn lu : + Khi th 2 nhm ankyl R v R khc nhau, nhm ankyl c kch thc nh hn hoc c hiu ng +I nh hn s c a vo trc + Sn phm ca phn ng axyl ha cng c nguyn t H linh ng, c th d dng b tch H+ bi
-

X CH Y
RCO HC X + CH
-

chnh cacbanion

X RCO

Y Y Y Y c phn ng cnh tranh: ngn phn ng ph ni trn, ngi ta dng baz mnh (mnh hn cacbanion) vi lng d. b) Cht phn ng c dng R CH2 X hoc R2 CH X; vi X l COR, - COOR, - CN, - NO2 Cc phn ng c tin hnh tng t, nhng phi s dng xc tc l baz rt mnh (NaNH2; C2H5ONa) do nguyn t H km linh ng hn so vi trng hp c 2 nhm X, Y ht electron. 5. Cc phng php ngng t: a) Phn ng andol croton ha ca anehit v xeton: H C C H O + H C C H O
+ H hoac OH

X + H 2C

H H C C C C H OH H O

+ H hoac OH

H H C C C C H O

* Hc sinh cn lu : + C ch ca giai on cng andol: AN + Giai on croton ha c th xy ra theo c ch E1 hoc E1cb (khi c H linh ng, xt baz mnh) + Khi thc hin phn ng andol croton ha t 2 cu t khc nhau c th to ra hn hp sn phm, trong sn phm chnh l sn phm ngng t gia: - cu t cacbonyl c tnh electrophin cao hn - cu t metylen c H linh ng hn. b) Phn ng ngng t ca anehit, xeton vi cc hp cht c nhm metylen hoc metyn linh ng:
X H 2C Y
B
-

X CH Y

C O C HC O
-

X Y

BH -B
-

- BH

C HC OH

- H 2O

* Hc sinh cn lu : + Xc tc dng trong cc phn ng ny thng l cc baz hu c yu, c th ngn chn c phn ng t ngng t vi nhau ca cc anehit, xeton. + Phn ng ngng t anehit thm vi anhidrit axit to thnh axit , khng no (phn ng ngng t Perkin) cng c c ch tng t nh trn.
2

CH 3COONakhan C6H5 CH= CH COOH C6H5 CH=O + (CH3CO)2O CH 3COOH c) Phn ng cng Micheal - cng cc hp cht c nhm metylen hoc metyn linh ng vo hp cht cacbonyl-,-khng no:

X H2 C Y

X CH Y

H2C CH CH O H2 C

CH CH O

BH -B
-

H2C CH2 CH O CH X Y

- BH

CH X Y

* Hc sinh cn lu : + Xc tc baz c th l C2H5ONa (nhit phng); piperidin (nhit cao hn). + C th thay th hp cht cacbonyl-,-khng no bng cc hp cht nitro (NO2) hoc nitril (CN)-,khng no. d) Phn ng ngng t Claisen ngng t este vi cc hp cht c nhm metylen linh ng: + Phn ng ngng t gia cc este vi nhau: C2 H 5ONa CH3COOC2H5 + CH3COOC2H5 CH3COCH2COOC2H5 + C2H5OH C ch phn ng:
O CH3 H CH2 C OC2H5 C2H5O -C2H5OH CH2 C O CH3 C O CH2 COOC2H5 OC2H5 C OC2H5

O O CH3 C

- C2H5O CH2COOC2H5

OC2H5

+ Phn ng ngng t este vi hp cht nitril: C2 H 5ONa CH3COOC2H5 + RCH2CN CH3COCH2(R)CN + C2H5OH + Phn ng ngng t este vi anehit hoc xeton: C2 H 5ONa CH3COOC2H5 + CH3COCH3 CH3COCH2COCH3 + C2H5OH II. Cc phng php lm gim mch Cacbon: 1. Phn ng ecacboxyl ha bi nhit: xy ra khi nhm COOH gn vi nhm c kh nng ht electron mnh CaO RH + Na2CO3 2. Phng php vi ti xt: RCOONa + NaOH to
CCl4 RBr + CO2 + AgBr 3. Phn ng Hunzdicker: RCOOAg + Br2 to 4. Phn ng halofom:RCOCH3 + 3X2 + 4NaOH RCOONa + CHX3 + 3NaX + 3H2O Br2 , NaOH ,t RNH2 5. Phn ng thoi phn Hoffman: R CO NH2 CO2
o

6. Cc phn ng oxi ha lm gy mch Cacbon: a) Cc phn ng lm gy lin kt lin kt i C=C: KMnO4 ,t o + CH3COOH + CH3COCH3 CH3CH= C(CH3)2 O O CH3 O3 +H C C HC 3
O CH3

CH3COOH + CH3COCH3 CH3CH=O + CH3COCH3

b) Cc phn ng lm gy lin kt C C vic-iol:


C C OH OH
HIO4 hoac Pb(OOCCH 3)

C + C O O

c) Phn ng oxi ha ankyl, ankenyl hoc dn xut ca benzen:


R
KMnO 4 hoac K 2Cr 2O 7 + H

COOH

* Hc sinh cn lu : + Nu v tr ca mch bn khng cn H th phn ng oxi ha hu nh khng xy ra. + Nu dng Na2Cr2O7 (khng c H+) s to thnh xeton m khng b ct mch
3

CH2 R

Na2Cr2O 7 o 250 C, p

C O

+ Nu v tr ca mch bn ch cn 1 nguyn t H th phn ng s to ra ancol bc 3 (khng ct mch cacbon)


CH R2 C R2 OH

III. Cc phng php to vng: 1. Cc phng php ankyl, axyl ha v ngng t ni phn t: nguyn tc tng t nh cc phn ng ankyl, axyl ha v ngng t nu trn. 2. Phn ng cng Diels Alder:
+

ien * Hc sinh cn lu :

ienophin

+ ien phi cu dng s-cis; dng s-trans (V d: ) khng phn ng. + Cc nhm th v tr cis u mch ien gy cn tr khng gian kh phn ng. + ien c nhm th y electron (khng gy cn tr khng gian) tng kh nng phn ng. + ienophin c nhm th ht electron tng kh nng phn ng. + Cu hnh ca sn phm ging vi cu hnh ca ienophin. + Hng ca phn ng:
R + X R + X R + X R X R X X R

R +

R X

IV. Cc phn ng oxi ha v kh trong tng hp hu c: 1. Cc phn ng oxi ha: a) Cc phn ng oxi ha anken b) Phn ng oxi ha nguyn t H v tr allyl: Tc nhn oxi ha: Pb4+, SeO2
C C CH2 C C CH HO

c) Cc phn ng oxi ha ankyl, ankenyl hoc dn xut ca benzen d) Cc phn ng oxi ha ancol: [O ] + Ancol bc I anehit Tc nhn oxi ha: CuO, K2Cr2O7/H+, CrO3/H+ [O ] + Ancol bc II xeton (Qu trnh oxi ha ancol bc I thnh anehit cn khng ch cn thn khng chuyn thnh axit).
4

HIO4 + vic-iol cacbonyl. e) Cc phn ng oxi ha anehit, xeton: [O ] + Anhit axit cacboxylic Tc nhn oxi ha: O2/xt, [Ag(NH3)2]+, KMnO4/H+, K2Cr2O7/H+ [O ] + Xeton b ct mch thnh axit cacboxylic v xeton Tc nhn oxi ha: KMnO4/H+, HNO3 2. Cc phn ng kh: a) Phng php hidro ha xc tc: Tc nhn kh: + H2/ Ni, Pt, Pd:

C C

C C

C C

RCOCl RCH=O R-CO-R R-COO-R RX RNO2 R-CN R-CO-NHR + H2/ Pd/ BaSO4, BaCO3 (xc tc Lindlar):
C C

RCH=O RCH2OH R-CH(OH)-R RCH2OH + ROH RH RNH2 R-CH2NH2 RCH2NHR kh la chn lin kt ba v lin kt i
C C

+ H2/ [(C6H5)3P]3RhCl: kh la chn lin kt i C=C ch cha 1 hoc 2 nhm th. * Hc sinh cn lu : c th lp th ca cc phn ng ny u l cng syn b) Phng php kh bng hidrua kim loi: Tc nhn kh: thng dng LiAlH4, NaBH4 RCOCl RCH2OH RCH=O RCH2OH R-CO-R R-CH(OH)-R RCOOH RCH2OH R-COO-R RCH2OH + ROH Epoxit 1,2-iol Khng kh c bng NaBH4 RX RH RNO2 RNH2 R-CN R-CH2NH2 R-CO-NHR RCH2NHR * Hc sinh cn lu : phn ng kh xy ra theo c ch cng AN. c) Cc phng php kh bng kim loi ha tan: Tc nhn kh: C C C C + Na/NH3 lng: (lp th: cng trans) + Na/ C2H5OH: RCOOH RCH2OH R-COO-R RCH2OH + ROH + Zn (Hg)/ HCl: R-CO-R R-CH2-R V. Bo v nhm chc: * iu kin ca nhm bo v: + c to ra trong iu kin nh nhng + n nh trong sut qu trnh phn ng cc trung tm phn ng khc. + D ti sinh nhm chc ban u. 1. Bo v nhm ancol: a) Chuyn thnh nhm ete:

C OH

C O

...

HI

C OH

b) Chuyn thnh nhm este (nhm este tng i bn trong mi trng axit): ... NaOH C OCO R C OH C OH c) Chuyn thnh nhm axetal hoc xetal (bo v cc iol):
C OH C OH R + O C R C O C O C R R
+

...

C OH C OH

2. Bo v nhm cacbonyl: To thnh axetal hoc xetal tng t nh bo v cc iol; thng s dng etilen glycol. 3. Bo v nhm cacboxyl: Chuyn thnh nhm este; thng to thnh tert-butyl este (d loi bng H+) hoc benzyl este (d loi bng hidro phn) 4. Bo v nhm amino:
RCOCl hoac (RCO) 2O

N CO R N OCO-CH2-Ph N C-Ph3

... ... ...

OH

NH

Ph-CH 2-OCOCl

H 2/Pd

NH

Ph3-CCl

CH 3COOH khan

B. MT S BI LUYN TP: Bi 1: Cho s chuyn ha:


OH
(H3C)2C=CH2 H2SO4

H3C

OH
H+ , t0 H2O

H2 / Ni (p sut)

CrO3

1) CH3MgBr 2) H2O

1) O3 2) H2O/Zn

a) Hy vit cu to cc cht t A n E b) Hy vit c ch phn ng t phenol to thnh A. Bi 2: Khi cho isobutilen vo dung dch H2SO4 60%, un nng ti 800C thu c mt hn hp gi tt l i - isobutilen gm hai cht ng phn ca nhau A v B. Hiro ho hn hp ny c hp cht C (quen gi l isooctan). C l cht c dng nh gi cht lng nhin liu lng. C cng c th c iu ch bng phn ng trc tip ca isobutilen vi isobutan khi c mt axit v c lm xc tc. Hy gi tn C theo IUPAC v vit cc phng trnh phn ng gii thch s to thnh A, B, C. Bi 3: Tin hnh phn ng ime ho trimetyletilen c H+ xc tc thu c hn hp sn phm l cc ng phn c cng thc phn t C10H20. Cho bit cc sn phm to thnh da vo c ch phn ng. Khi ozon ho hn hp thu c sau phn ng ime ho trn , ngoi cc anehit v xeton ca sn phm d kin cn thu c mt lng ng k butan -2-on, gii thch c ch hnh thnh butan-2-on trong cc phn ng trn. Bi 4: un nng Stiren vi axit H2SO4 ta thu c hp cht:

Hy gii thch qu trnh hnh thnh sn phm trn. Bi 5: T isopren hy vit cc phng trnh phn ng iu ch trans - 2 - metylxiclohexanol. Bi 6: Vit cc phng trnh phn ng( dng cu to) to thnh A, B, C, D, M, N theo s sau:
6

dd NaOH, t a) BrCH2CH2CH2CH=O A

CH3OH,HCl khan
+ 0

b) BrCH2 CH2CH2COOH

1) ddNaOH ,t H ,t C D 2) ddHCl
+ 0

Br2 ,H 2 O H ,t c) HOCH2(CHOH)4CH=O N M Bi 7: Cho s chuyn ha:

OH
PBr3

COOC2H5
(COOC2H5)2
C2H5ONa

E F G

KCN

H+

C2H5OH H
+

(D)
OCH3

HCOOC 2H5 (C2H5O)2CO

OCH3

a) Cho bit cu to ca cc cht t A n G. b) Gii thch s hnh thnh cc cht E, F, G. Bi 8: T propilen v cc cht v c cn thit, vit s phn ng iu ch: a) Axit 2,5-imetyladipic b) Axit hept-2-inoic Bi 9: T xiclopentanol iu ch axit 2-oxoxiclopentancacboxylic. Bi 10: T benzen v cc hp cht 2 C, hy tng hp:
O

CH2 CH2 NH CH3

CH

CH CH3

C2 H5 O

NH

C CH3

a)
Cl H2N SO 2NH2

b)
C4H9 NH

OH NHCH3

c)

COO CH2CH2N(CH3)2

d)
HO CH CH2 NH2 OH

e)
HO HO CH2 CH2 NH2 HO CH HO CH CH3

HO f) g) Bi 11: T benzen v cc cht 3 C, tng hp:

h)

OH NH2

O O a) b) c) Bi 12: T CH3CH2CH2CH2OH v cc cht v c, tng hp


H3C CH3

HO

C(CH3)2

OH

H3C CONH2

CH3

Bi 13:
H3CO OH H3C H3C COOH H3CO O CH3 CH3

T H3CO

v cc cht v c, iu ch
H3C N

H3CO

Bi 14: T H2N-CH3 v CH2=CH-COOC2H5, tng hp Bi 15: Khi cho isobutanal tc dng vi axit malonic c mt piriin thu c hp cht A. un nng A trong mi trng axit thc hin phn ng ecacboxyl ho thu c hai sn phm A1 v A2 l ng phn ca nhau.
A1 LiAlH4 A3 H3PO4 n h n) A5, A6 (A5 b
7

A1 HCl

A4(h p cht no)

Bit rng A2 khi b oxi ho to thnh axit oxalic. A1 l lacton. Xc nh cu to ca A1, ...,A6 v vit cc phng trnh phn ng. Bi 16: C mt s dn xut gc CH3 ca axit axetic biu hin hot tnh tng trng cy trng.
CH2COOH OCH2COOH Cl OCH2COOH OCH2COOH Cl Cl Cl (A) (B) (C) Cl (D)

1. Gi tn A, B, C. 2. A c iu ch t naphtalen v axit cloaxetic c mt cht xc tc 180 - 215 0C. Vit phng trnh phn ng v gi tn c ch ca phn ng. 3. B cng c iu ch t nguyn liu trn qua cht trung gian l 1 - naphtol. Vit s cc phn ng v nu c ch. 4. C cng c iu ch t phenol v axit axetic. Vit s phn ng. 5. Khc vi C, D c iu ch t mt dn xut tetraclobenzen(X) theo s : NaOH 1. ClCH2COOH D X m etanol 2. H+ a) Hon thnh s trn. b) Trong qu trnh sn xut D sinh ra mt lng nh ioxin l cht cc k c c cng thc:
Cl Cl O O Cl Cl

Gii thch s to thnh ioxin. C. BI GII: Bi 1: a) (A)


OH

(B)
OH

(C)
O

(D)
CH3

(E)
CH3 O O

H3C

CH3 CH3

H3C

CH3 CH3

H3C

CH3 CH3

H3C

CH3 CH3

H3C

CH3 CH3

b)
H +

OH H + OH
-H

OH

Bi 2:
CH3 C CH3
CH3 C CH3

CH2 + H

CH3

C CH3

CH3
CH3 CH3 C CH3

(1)

CH3 + CH3
+

CH2

CH2

C CH3

CH3 (2)

CH3

CH3 CH3 CH3 C CH3 CH2 C CH3 CH3 CH3 Zaixep -H CH3 C CH C CH3

CH3 CH3 CH3 (A) (>80%) C CH3 CH2 C CH2

CH3 CH3 C CH3 CH (A) C CH3 CH3

CH3 H2/Ni CH3 C CH3 CH2

CH3 (B) (<20%)

CH CH3 CH3

Isooctan(C) 2,2,4 - trimetylpentan (Qui c c ch s octan l 100) * Isobutilen vi isobutan khi c mt axit v c lm xc tc cng to ra C: C ch ca qu trnh tng t phn ng trn trong giai on (1) v (2), sau : CH3 CH3
CH3 C CH3 CH3 H3C C CH3 sinh ra li l p li (2). C nh vy.
CH3 H+ CH3 C CH3 CH2 CH3

CH2

C CH3

CH3 + CH3

CH CH3

CH3

CH3

C CH3

CH2 (C)

CH CH3 CH3 CH3

+ CH3 C CH3

Bi 3: * Sn phm to thnh khi ime ha trimetyletilen:


CH3 C CH3 CH

CH3 C CH3 CH CH3 CH3 CH2 C CH C CH3

CH3

C CH3

CH2 CH3 + CH3

CH3 CH3 CH3

CH3 CH3 CH3 CH2 C CH C CH3 -H+ CH3 CH2 CH3 CH2 C C C CH3

CH3 CH3 CH3 CH3 C CH C CH2

CH3 CH3 CH3

CH3 CH3 CH3

* Ozon phn hn hp trn thu c:

CH3 CH3 CH3 CH2 C C C CH3 ozon ph n CH3 CH C CH2 O C CH2 CH3 CH2 C C O

CH3 CH3 CH3 C CH C O

CH3 CH3 CH3 CH3 CH3 CH2 C

CH3 CH3 CH3 CH3 v HCHO

CH3 CH3 CH3

CH3 * S to thnh mt lng ng k butanon - 2 l do c s ng phn ha trimetyletilen, to thnh sn phm ph: H+ CH3 C CH CH3 CH3 C CH2 CH3 - + CH2 C CH2 CH3 H CH3 CH3 CH3 CH
3

CH3 C CH3

CH2 CH3 + CH2 C CH3


CH3

CH2 CH3

CH3 CH2
CH3

C CH3

CH2 C CH3
C

CH2

CH3

CH3

CH2 C

CH2 C CH2 CH3 CH3

H+

CH3 CH2 C

CH

CH2 CH3

CH3

CH3

CH3
CH3

Khi :
CH3 CH3 CH2 C CH2 C CH3 CH C CH2 CH3 ozon ph n CH3 CH2 C CH3 O+

CH3CH2CCHO CH3 v HCHO

CH3 CH3 CH2 CH3

Bi 4:

10

CH = CH2 CH = CH2 H
+

CH CH3

CH3 C CH2 HC
+

Bi 5:
H3C

CH2 + CH2 CH2 CH2 t0,p

H3C

+
-

+ H2B
H2O2/OH - H3BO3

CH3 H

CH3 H BH2 CH3 H OH Hi u sut 75%

CH3 H B 3

Bi 6: a)
Br-(CH2)3-CH=O
NaOH

HO-(CH2)3-CH=O

t0 O
(A)

H OH

CH3OH HCl khan

O
(B)

OCH3

b)
Br-(CH2)3-COOH
NaOH

HO-(CH2)3-COONa

ddHCl

H+
HO-(CH2)3-COOH (C)

O O
(D)

c)
CH2 OH CH OH 4 CH =O
HOBr

CH2 OH

CH OH 4

COOH (M)

HO-CH2-CH OH

O O
(N)

Bi 7: a)

11

(A)
Br

B r

B r

O M e

O M e

(B)
CN

(C)
COOH

(E)
O C2H5O2C C C O OC2H5

OMe

OMe

OMe OMe

(F)
O C2H5O2C C H

(G)
O C2H5O2C C OC2H5

OMe

OMe
OC2H5

b) Gii thch s hnh thnh ca:


H COOC2H5
C 2H5ONa

HC

COOC2H5

H 5 C 2O C O H 5 C 2O C O

H5C2OOC

C O COOC2H5

H5C2OOC
- C 2H 5O -

O COOC2H5

OCH3 OCH3 OCH3 E: OCH3 Tng t, gii thch c s hnh thnh F v G. Bi 8: Cl2 HBr Na ,t 0 CH2 = CH CH2Cl a) CH2 = CH CH3 CH2 = CH CH2 CH2 CH = CH2 4500 C Mg CH3 CH(Br) CH2 CH2 CH(Br) CH3 CH3 CH(MgBr) CH2 CH2 CH(MgBr) CH3 ete
1) CO2 HOOC CH(CH3) CH2 CH2 CH(CH3) COOH 2) H 3O +
Cl2 Br2 Na ,t 0 CH2 = CH CH2Cl b) CH2 = CH CH3 CH2 = CH CH2 CH2 CH = CH2 1:1 4500 C H 2 / Pd CH2Br CH(Br) CH2 CH2 CH = CH2 CH2Br CH(Br) CH2 CH2 CH2 CH3 1) KOH / e tan ol CH 3 MgCl HC C CH2 CH2 CH2 CH3 ClMgC C CH2 CH2 CH2 CH3 2) KNH 2

1) CO2 2) H O +
3

HOOC - C C CH2 CH2 CH2 CH3 Bi 9:


OH
HBr

Br

Mg/ ete khan

MgBr

1) CO 2 2) H 3O +

COOH

Cl 2/ P o t

COOH Cl

NaOH, t

COOH OH

CuO, t

COOH O

Bi 10: a)

12

CH 2=CH 2 + H CH 3NH 2

C2 H5

Pd, t

CH CH2

HBr, peoxit

CH2CH2Br

CH2CH2NHCH3
OH CH C2H5

b)
CO, HCl AlCl3

CHO

1) C 2H5MgBr + 2) H 3O

KOH/etanol

CH = CH - CH3

HOCl

CH CH CH3 HO Cl

CH 3NH 2

CH CH CH3 HO NHCH3
CH3COCl HNO 3 H 2SO4

c)
HNO 3 H 2SO 4d Fe, HCl

NO2

Fe, HCl

NH2

NHCOCH3
C 2H 5Cl

O2N

NHCOCH3

H2N
HNO 3 H 2SO 4 d

NHCOCH3

NaNO2+HCl to

HO

NHCOCH3
Fe, HCl

C 2H 5 O
H 2SO 4d

NHCOCH3

d)

NO2

Cl2 AlCl3

NO2 Cl

NH2 Cl

HO3S Cl

+ NH3 HSO4

PCl5

ClO 2S Cl

NH3HSO4

NH3

H2NO2S Cl

NH3 HSO4

NaHCO3

H2NO2S Cl

NH2

e)
(CH3)2 - N - H +
+ +

(CH3) 2-N-CH2-CH2-OH
o

CH 3Cl AlCl3

CH3

HNO 3 H 2SO 4d

H3 C

NO2

KMnO4, t

HOOC

NO2

Fe, HCl

HOOC

NH2

C 4H 9Cl

HOOC

NHC4H9

PCl5

ClOC

NHC4H9

(CH 3)2-N-CH 2-CH 2-OH

H9C4HN
o 1) NaOH,t ,p + 2) H

COO-CH2-CH2-N(CH3) 2

f)
Cl2 AlCl3

Cl

OH

HNO 3

OH NO2

Fe, HCl

OH NH2

NaNO2 + HCl o t

OH OH

CO + HCl AlCl3

HO HO

CHO

HCN

HO HO

CH CN HO

H 2/ Pd

HO HO

CH CH2 NH2 HO

g)

13

HO HO

CH CH2 NH2 HO

KOH/ etanol

HO HO

CH CH

NH2

H 2 / Pd

HO HO

CH2 CH2 NH2

h)
HO HO
Fe, HCl

CHO

CH 3CH 2NO 2 OH

HO HO

CH

C CH3 NO2

H 2O/H

HO HO

CH HO

CH CH3 NO2

HO HO

CH OH

CH CH3 NH2

Bi 11: a)
CH2=CH-CH 2Cl AlCl3

CH2-CH=CH2
1) (CH 3)2CO 2) H 3O +

HBr/ peoxit

CH2-CH2-CH2-Br CH3 C OH 3 CH3


H 2SO 4

Mg/ ete

CH2-CH2-CH2-MgBr

CH2

b)
CH 3Cl AlCl3

CH3

Cl2, as

CH2Cl

Mg/ ete

CH2MgCl

1) O 2) H 3O +

CH2-CH2-CH2-OH
COCl 2

Cl 2

CHCl-CH2-CH2-OH

NaOH

CH(OH)-CH2-CH2-OH

O O O

c)
Cl2 AlCl3 + o 1) NaOH,t ,p Cl + 2) H

OH

H3C C CH3 O

H3C C CH3 OH

OH HO

CH3 OH CH3

+ H - H 2O

HO

CH3 + C CH3
CuO, t 0

OH HO

CH3 C CH3
H +

OH

Bi 12:
OH
NH 3, t 0

O
Ag2O

Br2, H 2O

O CONH2

CHO

COOH

CONH2

Bi 13:

14

CH3

O H
+

CH3 OH

O COOH

CH3

LiAlH4

CH3 CH3 CH3

CH3

CH3

H 2SO 4,t

CH3

OH O
+

CH3 O OC2H5 CH3 NH CH2 CH2 COOC2H5


+

Bi 14:

NH2 CH3

OC2H5 CH3 N CH2 CH2 COOC2H5

CH2 CH2 COOC2H5 CH3 N O COOC2H5


+ o H ,t

C 2H 5ONa

CH3 N

(S dng phn ng cng Micheal v ngng t Claisen) Bi 15:


CH3 CH CH3 CHO +CH2 COOH COOH Piri in CH3 CH CH3 CH CH COOH COOH OH (A)

CH3 CH CH3 CH OH CH

t0 COOH -CO2

COOH

CH3 CH CH3 CH OH CH2 COOH

CH3 CH3 CH CH3


CH3 CH CH3
CH3 C CH3
CH3 CH3 C O CH2 CH3 C CH3 OH CH2

CH CH CH2 OH
CH3 CH3
CH3 CH CH2 COOH H+ CH3 C O
CH2 C O

COOH -H2O

H+ ,t0

CH3 CH3 C CH3


CH

CH CH (A2) CH

COOH

CH2 COOH

CH

CH

COOH

[O]

COOH + HOOC

COOH

CH2

CH2 C O (A1)

LiAlH4

CH2 CH2 (A3) OH

15

CH3 CH3 C O

CH2

CH3 CH2 C H+ CH3 (HCl) O O C

+ 2 CH

CH2 C OH

Cl

CH3 C CH3 Cl CH2 CH2 C (A4)

O OH

CH3 CH3 C CH3 OH CH2 CH2 CH2 (A3) OH C H3PO4 CH3 CH3 H2C C O CH CH2 CH2 + H2O OH CH2 CH2 (A 5) + H2O (A 6)

CH3

Bi 16: 1. A: Axit (1 - naphtyl)axetic. B: Axit (1 - naphtoxi)axetic. C: Axit (2,4 - iclophenoxi)axetic. [2,4 - D] D: Axit (2,4,5 - triclophenoxi)axetic. [2,4,5 - T]

CH2COOH + HCl
OH

2.

+ ClCH2COOH

t0, xt SE
OSO3H

3.

H2SO4 OCH2COONa H+ -Na+ OH OH Cl2/CCl4 -HCl Cl Cl NaOH -H2O

H2O -H2SO4 OCH2COOH

ClCH2COOH Ki m , SN2 -HCl

ONa Cl

4.

Cl
NaOH -H2O CH2COONa Cl

CH3COOH

Cl2, P -HCl

CH2COOH Cl

16

ONa Cl + CH2COONa Cl Cl -NaCl

OCH2COONa Cl H+

OCH2COOH Cl

Cl

Cl

Cl Cl 5. Cl Cl (X) Cl H+ Cl Cl
S to ioxin:

Cl NaOH SN2Ar Cl Cl OCH2COOH ONa ClCH2COOH SN2 Cl

Cl OCH2COONa

Cl

Cl Cl

Cl + ONa

NaO Cl

Cl Cl

Cl Cl

O O

Cl + 2NaCl Cl

17

18

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