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Tieu Luan
Tieu Luan
+
RMgX
1)
RCH2CH2OH
2) H3O+
1) HCHO
2) H 3O
RCH2OH
1) R ' CHO
2) H 3O
RCH(OH)R
R(R)C(OH)R
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
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+
tb
R' X
O-
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)
CO + HCl
AlCl 3
HCO-N(R)2
POCl 3 hoac COCl 2
HO
* Hc sinh cn lu :
CHCl 3
NaOH
CHO
CHO
(Phn ng Gatterman)
R
CHO
(Phn ng Vilsmeier)
HO
OHC
C2H5ONa
- C2H5OH
+-
Na CH
RBr
HC
1) C2H5ONa
2) RBr
R2
1) C2H5ONa
R(R')
2) R'Br
RCOCl
RCO HC
X
Y
C
X
Y
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
chnh cacbanion
Y
RCO HC
+ CH
RCO
X
+ H 2C
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
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
- BH
X
CH
C O
C HC
O
BH
-B
X
C HC
OH
X
- 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
3COONakhan
CH CH
C6H5 CH=O + (CH3CO)2O
C6H5 CH= CH COOH
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
- BH
X
CH
H2C CH CH O H2 C
CH CH O
BH
CH X
-B
H2C CH2 CH O
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:
CH3COOC2H5 + CH3COOC2H5 C2 H5ONa CH3COCH2COOC2H5 + C2H5OH
C ch phn ng:
O
CH3
H
CH2
OC2H5
O O
CH3
C2H5O
-C2H5OH
CH2 C
C
OC2H5
OC2H5
OC2H5
- C2H5O
CH2COOC2H5
CH3
CH2
COOC2H5
CCl
3
O
Br2 , NaOH ,t o
CO2
RNH2
CH3COOH + CH3COCH3
CH3
CH3CH=O + CH3COCH3
C + C
O
O
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
CH R2
ien
* Hc sinh cn lu :
ienophin
R
+
X
R
R
+
X
R
+
X
C C CH
HO
[O ] xeton
4
(Qu trnh oxi ha ancol bc I thnh anehit cn khng ch cn thn khng chuyn thnh
axit).
+ vic-iol HIO4 cacbonyl.
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
[O ] 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
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
C C
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
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:
5
C OH
...
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
C O
C O
...
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
Ph-CH 2-OCOCl
NH
N CO R
N OCO-CH2-Ph
Ph3-CCl
OH
...
H 2/Pd
...
N C-Ph3
...
NH
CH 3COOH khan
B. MT S BI LUYN TP:
Bi 1: Cho s chuyn ha:
OH
(H3C)2C=CH2
H2SO4
H3C
H2 / Ni
(p sut)
CrO3
1) CH3MgBr
2) H2O
OH
H+, t0
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:
Bi 6: Vit cc phng trnh phn ng( dng cu to) to thnh A, B, C, D, M, N theo s sau:
0
a) BrCH2CH2CH2CH=O
A
CH3OH,HCl khan B
dd NaOH, t
b) BrCH2 CH2CH2COOH
1) ddNaOH ,t 0
2) ddHCl
c) HOCH2(CHOH)4CH=O
Bi 7: Cho s chuyn ha:
H ,t 0
Br2 ,H 2 O
H ,t 0
OH
D
N
COOC2H5
(COOC2H5)2
PBr3
KCN
H+
C2H5OH
C2H5ONa
H+
HCOOC 2H5
(D)
OCH3
OCH3
(C2H5O)2CO
E
F
G
CH
a)
CH CH3
C2 H5 O
OH NHCH3
b)
NH
C CH3
c)
Cl
C4H9 NH
SO 2NH2
H2N
d)
COO CH2CH2N(CH3)2
e)
HO
CH
HO
CH2 NH2
HO
f)
g)
Bi 11: T benzen v cc cht 3 C, tng hp:
h)
HO
CH3
OH NH2
OH
HO
CH
CH
HO
O
H3C
HO
CH3
OH
C(CH3)2
a)
b)
c)
Bi 12: T CH3CH2CH2CH2OH v cc cht v c, tng hp
O
O
H3C
CH3
CONH2
Bi 13:
H3CO
T H3CO
OH
H3C
H3C
H3CO
COOH
v cc cht v c, iu ch
H3C N
CH3
CH3
H3CO
A1
LiAlH4
A1 HCl
A3
H3PO4
OCH2COOH
OCH2COOH
OCH2COOH
Cl
Cl
Cl
(A)
(B)
Cl
Cl
(C)
(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
metanol
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
Cl
Cl
(B)
OH
(C)
(D)
O
OH
(E)
CH3
CH3
O
O
H3C
CH3
CH3
H3C
CH3
CH3
H3C
CH3
CH3
H3C
CH3
CH3
H3C
CH3
CH3
b)
H
OH
+
OH
-H
OH
Bi 2:
CH3
C
CH3
CH2 + H
CH3
CH3
(1)
CH3
CH3 + CH3
+
CH3
CH2
CH3
Zaixep
CH3
CH
CH3
CH3
CH3
CH
CH3
H2/Ni
CH3
CH2
CH3
CH2
CH3
(B) (<20%)
CH CH3
CH3
CH3
CH3
(A)
CH2 C
CH3
CH3
CH3 (2)
CH3
CH3
CH3 (A) (>80%)
-H
CH3
CH3
CH3
CH3
CH3
CH2
CH3
CH3
C
CH3
CH2
CH3
CH3
CH3
CH3
Isooctan(C)
2,2,4 - trimetylpentan
(Qui c c chs 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
CH2
CH3 + CH3
CH3
CH3
CH3
CH3
CH
CH2
CH3
CH3
CH3
(C)
CH3
H3C
CH CH3
CH3
+ CH3 C
CH3
CH3
CH
H+
CH3
CH3
CH3
CH3
CH2 CH3
CH3
CH
CH3
CH3
CH2
CH
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH2
CH
CH3
CH2
CH3
CH3
CH3
CH2
CH
CH2
CH3
CH3
CH3
CH2
CH3
C
CH3
CH2
CH3
ozon ph
n
CH2
CH2
CH3 CH3
CH3
CH
CH3
CH2
CH
O C
CH3 v HCHO
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
CH2 CH3
CH3
H+
CH3 CH2 C
CH3
CH
CH3
CH2 CH3
CH3
CH3
CH3
CH2
CH3
CH3
Khi :
CH3 CH2 C
CH2
CH3
CH3
CH2 C
CH2 C
CH3
CH3
CH3
CH3
CH
CH3
CH3
CH2 CH3
CH3CH2CCHO
CH3 CH2 C
CH3
O+
CH3
v HCHO
CH3
Bi 4:
10
CH = CH2
CH = CH2
CH3
C
CH2
CH CH3
HC
Bi 5:
CH2
H3C
+ H2B
t0,p
H3C
CH2
CH2
CH2
CH3
CH3
CH3
BH2
CH3
H2O2/OH
- H3BO3
OH
Bi 6:
a)
Br-(CH2)3-CH=O
NaOH
HO-(CH2)3-CH=O
t0
H
OH
CH3OH
HCl khan
(A)
(B)
b)
Br-(CH2)3-COOH
NaOH
HO-(CH2)3-COONa
ddHCl
OCH3
H+
HO-(CH2)3-COOH
O
O
(C)
(D)
c)
CH2
OH
CH
OH 4
CH =O
HOBr
CH2
CH
OH
OH 4
COOH
+
(M)
HO-CH2-CH
OH
(N)
Bi 7:
a)
11
(A)
B r
OMe
Br
OMe
(B)
(C)
Br
(E)
CN
COOH
O
C2H5O2C
C
C
OC2H5
O
OMe
OMe
OMe
OMe
(F)
(G)
O
C2H5O2C
O
C2H5O2C
OC2H5
OMe
OMe
COOC2H5
COOC2H5
HC
H5C2OOC
H 5 C 2O C O
H 5 C 2O C O
C 2H5ONa
OCH3
E: OCH3
t, gii thch c s hnh thnh F v G.
Bi 8:
450Cl02C CH2 = CH CH2Cl
a) CH2 = CH CH3
ete
CH3 CH(Br) CH2 CH2 CH(Br) CH3
Mg
1) CO2
2) H 3O
C O
COOC2H5
- C 2H 5O
COOC2H5
OCH3
OCH3
Na ,t 0
H5C2OOC
Tng
HBr
2
450Cl02C CH2 = CH CH2Cl Na ,t 0 CH2 = CH CH2 CH2 CH = CH2
Br
b) CH2 = CH CH3
1:1
CH2Br CH(Br) CH2 CH2 CH = CH2
CH2Br CH(Br) CH2 CH2 CH2 CH3
H 2 / Pd
1) KOH / e tan ol
CH
3 MgCl
1) CO2
2) H 3O
Br
HBr
MgBr
1) CO 2
2) H3O
NaOH, t
COOH
OH
CuO, t
COOH
COOH
Cl 2/ P
o
t
Cl
COOH
O
Bi 10:
a)
12
CH 2=CH 2
+
H
Pd, t
C2 H5
CH 3NH 2
CH CH2
HBr, peoxit
CH2CH2Br
CH2CH2NHCH3
b)
CO, HCl
CHO
AlCl3
CH 3NH 2
CH CH CH3
HO
OH
CH C2H5
1) C 2H5MgBr
+
2) H 3O
KOH/etanol
HOCl
CH = CH - CH3
CH CH CH3
Cl
HO
NHCH3
c)
HNO 3
H 2SO 4d
Fe, HCl
Fe, HCl
NO2
NHCOCH3
H2N
HNO 3
H 2SO 4 d
NH2
NaNO 2+HCl
NHCOCH3
NO 2
Fe, HCl
Cl
PCl5
NH3HSO4
ClO 2S
C 2H 5Cl
NHCOCH3
HO
to
Cl2
AlCl3
NO 2
CH3COCl
NH2
HNO 3
C 2H 5 O
H 2SO 4d
NHCOCH3
Cl
+
NH3 HSO 4
H2NO 2S
Cl
d)
+
NH3 HSO4
HO 3S
Cl
NH3
NHCOCH3
O2N
H 2SO 4
NaHCO 3
NH2
H2NO 2S
Cl
Cl
e)
(CH3)2 - N - H +
CH 3Cl
CH3
AlCl3
NH2
HOOC
(CH3) 2-N-CH2-CH2-OH
HNO 3
H 2SO 4d
C 4H 9Cl
NO2
H3 C
NHC4H9
HOOC
KMnO4, t
PCl5
Fe, HCl
NO2
HOOC
NHC4H9
ClOC
COO-CH2-CH2-N(CH3) 2
H9C4HN
f)
o
1) NaOH,t ,p
+
2) H
Cl2
Cl
AlCl 3
OH
HNO 3
OH
Fe, HCl
NH2
NO 2
NaNO 2 + HCl
o
t
OH
CO + HCl
AlCl3
OH
HO
HO
HO
HO
CHO
HCN
HO
HO
OH
CH CN
H 2/ Pd
HO
CH CH2 NH2
HO
g)
13
HO
KOH/ etanol
CH CH2 NH2
HO
HO
HO
CH CH
NH2
H 2 / Pd
HO
HO
HO
h)
HO
CH 3CH 2NO 2
OH
CHO
HO
HO
CH
HO
HO
CH
CH CH3
OH
NH2
HO
NO 2
HO
Fe, HCl
H 2O/H
C CH3
CH
HO
HO
CH CH3
NO 2
Bi 11:
a)
CH2=CH-CH 2Cl
CH2-CH=CH2
AlCl3
HBr/ peoxit
1) (CH 3)2CO
CH2-CH2-CH2-MgBr
2) H 3O
CH2-CH2-CH2-Br
CH2
CH3
C OH
3 CH3
Mg/ ete
H 2SO 4
b)
CH 3Cl
Cl2, as
CH3
AlCl3
CH2Cl
Mg/ ete
CH2MgCl
1) O
2) H 3O
CH2-CH2-CH2-OH
COCl2
Cl 2
CHCl-CH2-CH2-OH
NaOH
CH(OH)-CH2-CH2-OH
O
O
O
c)
o
1) NaOH,t ,p
Cl
+
2) H
Cl2
AlCl3
H3C C CH3
OH
OH
CH3
H3C C CH3
HO
CH3
OH
OH
CH3
+
C
CH3
HO
OH
CH3
C
CH3
HO
+
H
- H 2O
OH
Bi 12:
OH
NH 3, t
CuO, t
Br 2, H 2O
CHO
COOH
Ag2O
CONH2
CONH2
Bi 13:
14
CH3
CH3
OH
CH3
CH3
CH3
LiAlH 4
CH3
CH3
H 2SO 4,t
CH3
CH3
COOH
CH3
OH
Bi 14:
O
NH2
O
OC2H5
CH3
CH3
OC2H5
CH3
C 2H 5ONa
CH3 N
+ o
H ,t
CH3 N
COOC2H5
CH
CHO +CH2
COOH
COOH
CH3
CH3
CH
CH3
CH
CH
t0
COOH -CO2
OH
CH
CH3
CH CH2
COOH
OH (A)
CH
CH
CH3
H+,t0
COOH
CH CH
(A2)
CH3
CH3
COOH
-H2O
CH2
OH
CH
CH3
CH
CH3
CH3
OH
CH
COOH
CH2 COOH
CH3
CH3
CH
CH
CH
COOH
[O]
CH3
CH3
CH
COOH + HOOC
COOH
CH3
CH3
CH3
C
CH
CH2 COOH
H+
CH3
CH3
CH2
CH3
CH3
COOH
CH
CH3
COOH
CH
CH3
Piriin
C
O
CH2
CH2
C
LiAlH4
O
CH2
C
O (A1)
CH3
C
CH3
OH
CH2
CH2 CH2
(A3)
OH
15
CH3
CH3
CH3
CH2
CH2
H+ CH3
(HCl)
O
+ 2
CH
CH2
C
Cl
OH
O -
CH3
O
C
CH2
CH2 C
CH3
Cl
CH
OH
(A4)
CH3
C
CH3
C
CH3
OH
CH2
CH2 CH2
(A3)
H3PO4
OH
CH3
CH3
(A 6)
H2C
CH2
CH2
CH3
2.
CH2COOH
t0, xt
SE
+ HCl
OH
OSO3H
H2O
ClCH2COOH
-H2SO4
Kim, SN2
-HCl
H2SO4
3.
+ H2O
(A 5)
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]
+ ClCH2COOH
OH
OCH2COONa
OCH2COOH
H+
-Na+
OH
OH
4.
ONa
Cl
Cl2/CCl4
-HCl
Cl
NaOH
-H2O
Cl
CH3COOH
Cl2, P
-HCl
CH2COOH
Cl
Cl
NaOH
-H2O
CH2COONa
Cl
16
ONa
OCH2COONa
Cl
Cl
+ CH2COONa
Cl
H+
-NaCl
Cl
Cl
OCH2COOH
Cl
Cl
Cl
Cl
Cl
5.
OCH2COONa
ONa
ClCH2COOH
NaOH
SN2Ar Cl
Cl
Cl
Cl (X)
Cl
SN2
Cl
Cl
Cl
OCH2COOH
H+
Cl
Cl
S to ioxin:
Cl
Cl
NaO
Cl
Cl
Cl
Cl
Cl
+
Cl
ONa
Cl
+ 2NaCl
Cl
17
18