2011 -chuyên đề tổng hợp hưu cơ

8/6/2019 2011 -Chuyn tng hp hu c

1/19

TT LUYN THI & BI DNG KIN THC NGY MI 18A/88INH VN T - TP. HI DNG

HOAHOC.ORG NG XUN QUNH09798.17.8.85 09367.17.8.85 - netthubuon Website: www.hoahoc.org - [email protected]

CHUYN : TNG HP HU C

Trng THPT chuyn H Ni -Amsteram

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

+ 23

1)

2)

CO

H O RCOOH

+ 1) O RCH2CH2OH

RMgX + 31)

2)

HCHO

H O

RCH2OH+

3

1) '

2)

R CHO

H O RCH(OH)R

+3

1) ' ''

2)

R COR

H O R(R)C(OH)R

+3

1) ' hoac ' ''

2)

R COOH R COOR

H O RCOR (R)2C(OH)R

*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

2. Phng php anky ha ion axetilua:

R C CH 2 3/longNaNH NH R C C

Na+ 'R X R C C R3. Cc phng php ankyl v axyl ha hp cht thm:

a) Cc phn ng ankyl ha:

R

+ anken/ xt: HCl/AlCl3 hoc axit protonic (HF > H2SO4 > H3PO4)

+ ancol/ xt: axit protonic hoc Al2O3.

b) Cc phn ng axyl ha:

R

2)H3O+

O

RL

tb N

R-

O-

RL

tb N

R

+ dn xut halogen/ xt: axit Lewis (AlCl3 > FeCl3 > BF3 > ZnCl2)

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


2/19

TI LIU LUYN THI & BI DNG KIN THC NM 2011


Mt s phn ng formyl ha(thng dng gn nhmCHO vo phenol, ete thm hoc nhn thm

giu electron)

-

CO + HCl

AlCl3R R CHO

(Phn ng Gatterman Koch)

-

HCN + HCl/ AlCl3

H2OR R CHO

(Phn ng Gatterman)

-

HCO-N(R)2

POCl3 hoac COCl2R R CHO

(Phn ng Vilsmeier)

-

CHCl3

NaOHOH OH

OHC (Phn ng Reimer Tiemann)

*Hc sinh cn lu:

+ 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 dngX CH2 YhocX 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.

H2CY

X C2H5ONa

- C2H5OH

-CH

Y

X

Na+ RBr

R HCY

X 1) C2H5ONa

2) RBrR2 C

Y

X

1) C2H5ONa

2) R'BrR(R') C

Y

X

RCOClRCO HC

Y

X

*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 +Inh hn s c a vo trc

+ Sn phm ca phn ng axyl ha cng c nguyn t Hlinh ng, c th d dng b tch H+ bi

chnh cacbanion

-CH

Y

X

c phn ng cnh tranh:

-CH

Y

XRCO HC

Y

X+ RCO

-C

Y

X+ H2C

Y

X


3/19



ngn phn ng ph ni trn, ngi ta dng baz mnh (mnh hn cacbanion) vi lng d.

b) Cht phn ng c dngR CH2 XhocR2 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 Hkm linh ng hn so vi trng hp c 2 nhm X, Y ht elect ron.

5. Cc phng php ngng t:

a) Phn ng andol croton ha ca anehit v xeton:

C C

H

H

O

C C

H

H

O

+ C C C C

H

H

OH H

H

O

C C C C

H

H H

O

H+

hoac OH-

H+

hoac OH-

*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 Hlinh 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:

H2CY

X-CH

Y

XB

-

- BH

C O

C HC

O- Y

X BH

- B- C HC

OHY

X

C CY

X

- H2O

*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 axitto thnh axit , khng no (phn ng ngng

t Perkin) cng c c ch tng t nh trn.

C6H5 CH=O + (CH3CO)2O 33

OOOOH

khanCH C Na

CH CC6H5 CH= CH COOH

c) Phn ng cng Micheal - cng cc hp cht c nhm metylen hoc metyn linh ng vo hp cht

cacbonyl-,-khng no:

H2CY

X -CH

Y

XB

-

- BH

H2C CH CH O H2C-CH CH O

CH

Y

X

BH

- B-

H2C CH2 CH O

CH

Y

X

*Hc sinh cn lu:

+ Xc tc baz c th l C2H5ONa (nhit phng); piperidin (nhit caohn).

+ 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 Claisenngng t este vi cc hp cht c nhm metylen linh ng:


4/19


5/19



+ Nu dng Na2Cr2O7 (khng c H+) s to thnh xeton m khng b ct mch

CH2 R C R

O

Na2Cr2O7

250oC, p

+ 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 R2OH

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 ienophin

*Hc sinh cn lu:

+ 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 X

R

R

+

X

R X

R

+X

R

X

R+

R

X

X


6/19



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

OH

c) Cc phn ng oxi ha ankyl, ankenyl hoc dn xut ca benzen

d) Cc phn ng oxi ha ancol:

+ Ancol bc I [ ]O anehit

+ Ancol bc II [ ]O xeton

(Qu trnh oxi ha ancol bc I thnh anehit cn khng ch cn thn khng chuyn thnh axit).

+ vic-iol 4HIOcacbonyl.

e) Cc phn ng oxi ha anehit, xeton:

+ Anhit [ ]O axit cacboxylic

Tc nhn oxi ha: O2/xt, [Ag(NH3)2]+, KMnO4/H

+, K2Cr2O7/H+

+ Xeton [ ]Ob ct mch thnh axit cacboxylic v xeton

Tc nhn oxi ha: KMnO4/H+, HNO3

2. Cc phn ng kh:

a) Phngphp hidro ha xc tc:

Tc nhn kh:

+ H2/ Ni, Pt, Pd:

C C C C C C

RCOCl RCH=O

RCH=O RCH2OH

R-CO-R

R-CH(OH)-RR-COO-R RCH2OH + ROH

RX RH

RNO2 RNH2

R-CN R-CH2NH2

R-CO-NHR RCH2NHR

+ H2/ Pd/ BaSO4, BaCO3 (xc tc Lindlar): kh la chn lin kt ba v lin kt i

C C C C + H2/ [(C6H5)3P]3RhCl: kh la chn lin kt i C=C ch cha 1 hoc 2 nhm th.

Tc nhn oxi ha: CuO, K2Cr2O7/H+, CrO3/H

+


7/19



*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

RX RH

RNO2 RNH2

R-C

N

R-CH2NH2R-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:

+ Na/NH3 lng: C C C C (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 R ... C OHHI

b) Chuyn thnh nhm este (nhm este tng i bn trong mi trng axit):

C OH C OCO R ... C OHNaOH

c) Chuyn thnh nhm axetal hoc xetal (bo v cc iol):

C

C

OH

OH+ O C

R

R

CR

RC

C

O

O

... H+ C

C

OH

OH

Khng kh c bng NaBH4


8/19



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:

NH

RCOCl hoac (RCO)2O

N CO ROH

-

NHPh-CH2-OCOCl

N OCO-CH2-PhH2/Pd

Ph3-CClN C-Ph3

CH3COOHkhan

...

...

...

B. MT S BI LUYN TP:

Bi 1: Cho s chuyn ha:

OH

1) CH3MgBrA D

H2SO4

H2 / Ni

(p sut) H2O

CrO3

OHH3C

C E(H3C)2C= CH2

B2) H2O

H+, t0 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 H2SO460%, 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 H2SO4ta thu c hp cht:

Hy gii thch qu trnh hnh thnh sn phm trn.


9/19



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, Ntheo s sau:

a) BrCH2CH2CH2CH=O0dd NaOH, t

A 3CH OH,HCl khan

B

b) BrCH2 CH2CH2COOH0

1) ,2)ddNaOH tddHCl C0

,H t

D

c) HOCH2(CHOH)4CH=O2 2

Br ,H O M

0,H t N

Bi 7:Cho s chuyn ha:

OH

OCH3

A B C

H

OCH3

COOC2H5

(D)

E

F

G

(COOC2H5)2

HCOOC2H5

(C2H5O)2CO

C2H5OHKCNPBr3 H+

H+

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:

a)CH2 CH2 NH CH3

b)

CH CH

OH NHCH3

CH3

c)NH COC2H5

O

CH3

d)

Cl

SO2NH2NH2

e)NHC4H9 COO CH2CH2N(CH3)2

f)

CH CH2 NH2OH

OH

OH

g)

CH2 CH2 NH2OH

OH h)

CH CH CH3OH

OH

OH NH2

Bi 11: T benzen v cc cht 3 C, tng hp:

a) CH3 CH3 b)O

O

O c)OH C(CH3)2 OH

Bi 12: T CH3CH2CH2CH2OH v cc cht v c, tng hp

CH3 CH3

CONH2

O

C2H5ONa


10/19



Bi 13:

T

H3CO

H3CO

OH

CH3

CH3

COOH

v cc cht v c, iu ch

H3CO

H3CO

OCH3

CH3

Bi 14: T H2N-CH3 v CH2=CH-COOC2H5, tng hpN OCH3

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.

(A5 bn hn)A5, A6H3PO4

A4HClA1

A3LiAlH4A1

(hp 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 OCH2COOH

Cl

Cl

OCH2COOH

Cl

Cl

Cl

(A) (B) (C) (D)

1. Gi tn A, B, C.2. A c iu ch t naphtalen v axit cloaxetic c mt cht xc tc 180 - 2150C. 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 :

X NaOHmetanol

ClCH2COOHH+

1.2.

D

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:

O

O

Cl

Cl

Cl

Cl

Gii thch s to thnh ioxin.


11/19



C. BI GII:

Bi 1:

a)

(A)

CH3

OH

CH3H3C

(B)

CH3

OH

CH3H3C

(C)

CH3

O

CH3H3C

(D)

CH3CH3

H3C

CH3

(E)

CH3

O

CH3H3C

CH3

O

b)

H+

C+

OH

OH

H

+ - H+

OH

Bi 2:

+

CH3

CH3CCH3H

CH3

CH2CCH3(1)

CH3

CH3CCH2

CH3

CH3

CCH3+

CH3

CH3CCH3

CH3

CH2CCH3 (2)

CH3 C

CH3

CH3

CH2 C CH3

CH3

CH3 C CH C CH3

CH3

CH3

CH3(A) (> 80%)

(< 20%)(B)CH3

CH3

CH3

CH2CH2 CCCH3

Zaixep

- H

(A)CH3

CH3

CH3

CH3CCHCCH3H2/Ni CH3 C

CH3

CH3

CH2 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 :

-

+


12/19


13/19



CH3 C CH CH3

CH3

H+

CH3

CH3CCH3 CH2 CH2CH2 C CH3

CH3

H+-

CH2CH3 C CH3

CH3 CH3

CH3CCH2 CH2+ CH3 CH2 C CH2 C CH2 CH3

CH3CH3

CH3

CH3 CH2 C CH C CH2 CH3

CH3CH3

CH3CH3

CH3 CH3

CH3CH2CCH2CCH2CH3 H+

Khi :

CH3

CH3

CH3CH2CCHO

CH3

OCCH2CH3

CH3

CH3 CH2 C CH C CH2 CH3

CH3CH3

CH3

+v HCHO

ozonphn

CH3CCH2 CH2

Bi 4:

CH = CH2H

+ CH+

CH3

CH = CH2

CCH2

CH3

CH+

Bi 5:

H3C

+

CH2

CH2

CH2

CH2

H3Ct0,p

CH3

H2B

H

CH3

H

BH2

CH3

H

3

B

H2O

2/OH

- H3BO3

CH3

H

OH

Hiu sut 75%

+

-

-

+


14/19



Bi 6:

a)

Br-(CH2)3-CH=ONaOH

HO-(CH2)3-CH=O

O

t0

OH

HCH3OH

HCl khanO OCH3

H

(A) (B)

b)

Br-(CH2)3-COOHNaOH

HO-(CH2)3-COONa

O (D)(C)

ddHClHO-(CH2)3-COOH

H+

O

c)

HOBr

O (N)H+

OCH2

OH

CH

OH 4

CH =O CH2

OH

CH

OH 4

COOH

(M)

HO-CH2

-CH

OH

Bi 7:

a)

(A)Br

OMe

B r

O Me

B r

O Me(B)CN

OMe

(C)COOH

OMe

(E)

OMe

C2H5O2C C

C

O

O

OC2H5

(F)

OMe

C2H5O2C C

O

H

(G)

OMe

C2H5O2C C

O

OC2H5

b) Gii thch s hnh thnh ca:

E:

COOC2H5H

OCH3

C2H5ONa

CH-

COOC2H5

OCH3

C

C

OH5C2O

OH5C2O

H5C2OOC

OCH3

C

COOC2H5

O-

OC2H5

H5C2OOC

OCH3

COOC2H5

O

- C2H5O-

Tng t, gii thch c s hnh thnh F v G.


15/19



Bi 8:

a) CH2 = CH CH3 20450Cl

C CH2 = CH CH2Cl

0,Na t CH2 = CH CH2 CH2 CH = CH2

HBr

CH3 CH(Br) CH2 CH2 CH(Br) CH3 eteMg

CH3 CH(MgBr) CH2 CH2 CH(MgBr) CH3

2

3

1)2) H

CO

O HOOC CH(CH3) CH2 CH2 CH(CH3) COOH

b) CH2 = CH CH32

0450

Cl

C

CH2 = CH CH2Cl

0,Na t

CH2 = CH CH2 CH2 CH = CH22

1:1

Br

CH2Br CH(Br) CH2 CH2 CH = CH2 2

/H Pd CH2Br CH(Br) CH2 CH2 CH2 CH3

2

1) / tan2)

KOH e ol

KNH HC C CH2 CH2 CH2 CH3 3

CH MgClClMgC C CH2 CH2 CH2 CH3

2

3

1)2) H

CO

O

HOOC - C C CH2 CH2 CH2 CH3

Bi 9:

OH Br MgBr COOH COOH

ClCOOH

OH

COOH

O

HBr Mg/ ete khan 1) CO2

2) H3O+

Cl2/ P

to

NaOH, to

CuO, to

Bi 10:

a)

C2H5 CH CH2 CH2CH2BrCH2=CH2

H+

Pd, to

HBr, peoxit

CH2CH2NHCH3CH3NH2

b)

CHO CH C2H5

OH

CH = CH - CH3CO, HCl 1) C2H5MgBr KOH/etanol

AlCl3 2) H3O+

HOCl

CH CH

OH

CH3

Cl

CH3NH2CH CH

OH

CH3

NHCH3

c)

NO2HNO3 Fe, HCl

C2H5Cl

H2SO4d

to

NaNO2+HCl

NH2 NHCOCH3CH3COCl

HNO3

H2SO4

NHCOCH3O2N

Fe, HClNHCOCH3NH2 NHCOCH3OH NHCOCH3OC2H5

d)

NO2HNO3 Cl2

NaHCO3

H2SO4d

NH3

NO2

Cl

NH2

Cl

Fe, HClNH3

+HO3S

Cl

PCl5

AlCl3

H2SO4d HSO4-

NH3+

ClO2S

Cl

HSO4-

NH3+

H2NO2S

Cl

HSO4-

NH2H2NO2S

Cl


16/19



e)

CH3HNO3CH3Cl

H2SO4d

C4H9Cl

NO2H3CFe, HCl

PCl5

AlCl3

KMnO4, to

NHC4H9HOOC

NO2HOOC

NH2HOOC NHC4H9ClOC

(CH3)2 - N - H +O

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

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

H9C4HN COO-CH2-CH2-N(CH3)2

f)

OHCl2

NaNO2 + HCl

AlCl3

HNO3

2) H+

Fe, HCl

to

1) NaOH,to,p

CO + HCl

Cl OH

NH2

OH

NO2

OH

OH

OH

OH

CHOAlCl3

OH

OH

CH

OH

CNHCN H2/ Pd

OH

OH

CH

OH

CH2 NH2

g)

KOH/ etanol H2/ PdOH

OH

CH

OH

CH2 NH2 OH

OH

CH CH NH2 OH

OH

CH2 CH2 NH2

h)

OH

OH

CHOOH

-

Fe, HCl

OH

OH

CH

OH

CH CH3

NO2

CH3CH2NO2 OH

OH

CH C CH3

NO2

H2O/H+

OH

OH

CHOH

CH CH3NH2

Bi 11:

a)

CH2-CH=CH2Mg/ ete

1) (CH3

)2

CO H2SO4

2) H3O+

CH2=CH-CH2Cl

AlCl3

HBr/ peoxitCH2-CH2-CH2-Br

CH2-CH2-CH2-MgBr CH2 C OH

CH3

CH3

3


17/19



b)

CH3Mg/ ete

Cl2 NaOH

2) H3O+

CH3Cl

AlCl3

COCl2

CH2-CH2-CH2-OH

Cl2, as CH2Cl CH2MgClO1)

CHCl-CH2-CH2-OH CH(OH)-CH2-CH2-OH

O

O

O c)

OHCl2

AlCl3 2) H+

1) NaOH,to,p

Cl

H3C C CH3

O

H+

H3C C+

CH3

OH

OH CH3

CH3

OH OHH

+

- H2O

CH3

C+

CH3

OH

OH CH3

C

CH3

OHOH

Bi 12:

OH OCuO, t

0H

+

CHO COOH

CONH2 CONH2

O

NH3, t0

Ag2O

Br2, H2O

Bi 13:

CH3

CH3

OH

CH3

CH3

O

COOH

O

OH

+H

+CH3

CH3

O

O

LiAlH4

CH3

CH3

O

OH

CH3

CH3

OH2SO4,t

o

Bi 14:

CH3

NH2

O

OC2H5

CH3 NH CH2 CH2 COOC2H5

O

OC2H5

CH3 N CH2 CH2 COOC2H5

CH2 CH2 COOC2H5

C2H5ONa

NCH3 O

COOC2H5

H+

, to

NCH3 O

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


18/19



Bi 15:

(A)OH

PiriinCH3

CH

CH3

CH CHCOOH

COOH

+

COOH

COOHCH2CHO

CH3

CH

CH3

OH

CH3

CH

CH3

CH CH COOHCOOH

COOHCH2CH

CH3

CH

CH3

OH

-CO2t0

H+,t0

OH

CH3

CH

CH3

CH CH2 COOH-H2O

COOHCHCH

CH3

CH

CH3

CH3

C

CH3

CH CH2 COOH

(A2)

+ COOHHOOCCOOH

CH3

CH

CH3[O]

CH3

CH

CH3

CH CH COOH

CH3

C

CH3

CH CH2 COOH

(A1)

H+ C

O C

CH2

CH2

O

CH3

CH3

C

O C

CH2

CH2

O

CH3

CH3

(A3) OHOH

CH2CH2CH2

CH3

C

CH3LiAlH4

O

(HCl)

C

O C

CH2

CH2

O

CH3

CH3

(A4)Cl OH

CCH2CH2CH3

C

CH3H+ CH3

CH3

OH

C

O C

CH2

CH2

Cl

CH3

C

CH3

CH2 CH2 CH2

OH OH(A3)

H3PO4 OH

CH2CH2CH

CH3

C

CH3

(A6)

+ H2O

CH2

CH2H2C

CO

CH3

CH3(A5)

H2O+

+

-


19/19


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]

ClCH2

COOHt0, xt

SE+

CH2COOH

+ HCl2.

ClCH2COOH

3.H2SO4

-H2SO4

OSO3H

H2O

OH

Kim, SN2

-HClOCH2COONa OCH2COOH

H+

-Na+

OH

Cl2/CCl4

-HCl

OH

Cl

Cl

ONa

Cl

Cl

-H2O

NaOH4.

CH3COOHCl2, P

-HClCH2COOH

Cl

NaOH

-H2O

Cl

CH2COONa

-NaCl

ONaCl

ClCl

CH2COONa+

OCH2COONaCl

Cl

H+OCH2COOH

Cl

Cl

Cl

OCH2COOH

Cl

Cl

Cl

OCH2COONa

Cl

ClSN2

ClCH2COOH

Cl

ONa

Cl

ClSN2Ar

NaOH5.

(X)

Cl

Cl

Cl

Cl

H+

S to ioxin:

Cl

ONaCl

Cl

Cl

NaO Cl

Cl

+

O

O

Cl

Cl

Cl

Cl

+ 2NaCl

2011 -chuyên đề tổng hợp hưu cơ

Documents