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. 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
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)
R CHO
HO
(Phn ng Vilsmeier)
HO OHC
* 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 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
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
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
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
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
OH
PBr3
COOC2H5
(COOC2H5)2
C2H5ONa
E F G
KCN
H+
C2H5OH H
+
(D)
OCH3
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
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
h)
OH NH2
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
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
(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
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)
+ CH3 C CH3
CH3
C CH3
CH3 CH3 CH3 CH2 C CH C CH3 -H+ CH3 CH2 CH3 CH2 C C C CH3
CH3 CH3 CH3 CH2 C C C CH3 ozon ph n CH3 CH C CH2 O C CH2 CH3 CH2 C C O
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
CH3 CH2
CH3
C CH3
CH2 C CH3
C
CH2
CH3
CH3
CH2 C
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+
Bi 4:
10
CH = CH2 CH = CH2 H
+
CH CH3
CH3 C CH2 HC
+
Bi 5:
H3C
H3C
+
-
+ H2B
H2O2/OH - H3BO3
CH3 H
CH3 H B 3
Bi 6: a)
Br-(CH2)3-CH=O
NaOH
HO-(CH2)3-CH=O
t0 O
(A)
H OH
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
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
Br
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
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
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
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
H 2SO 4,t
CH3
OH O
+
Bi 14:
NH2 CH3
C 2H 5ONa
CH3 N
CH3 CH CH3 CH OH CH
t0 COOH -CO2
COOH
CH CH CH2 OH
CH3 CH3
CH3 CH CH2 COOH H+ CH3 C O
CH2 C O
COOH -H2O
H+ ,t0
CH CH (A2) CH
COOH
CH2 COOH
CH
CH
COOH
[O]
COOH + HOOC
COOH
CH2
CH2 C O (A1)
LiAlH4
15
CH3 CH3 C O
CH2
+ 2 CH
CH2 C OH
Cl
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.
ONa Cl
4.
Cl
NaOH -H2O CH2COONa Cl
CH3COOH
Cl2, P -HCl
CH2COOH Cl
16
OCH2COONa Cl H+
OCH2COOH Cl
Cl
Cl
Cl Cl 5. Cl Cl (X) Cl H+ Cl Cl
S to ioxin:
Cl OCH2COONa
Cl
Cl Cl
Cl + ONa
NaO Cl
Cl Cl
Cl Cl
O O
Cl + 2NaCl Cl
17
18