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CH3AH3CCOOHBH3CCOOHCCOOHDH3CCH3COOHCH3
(6)烯醇化反应：A.CH3COCH2COOC2H5 B.CH3COCH2COCH3 C.CH3COCH(C2H5)COOC2H5 D.CH3COC2H5 E.CH3COOC2H5
解: (1) B>A>C>D (2) A>C>B>D (3) B>D>A>C (4) B>D>>C>A (5) C>A>B>D (6) B>A>C>E>D 11．完成下列反应 (1)CH3CH2CH2CH=CH2(2)O2NKMnO4??SOCl2?CH3COONa?C2H5OH浓H2SO4?CH2COOHO2NCHCOOHCl(3)HOOCCH2CHCH2COOHCH3OHH2,Pt?300℃?CH3OH?SOCl2?(4)HNO3
?300℃?①CH3CH2MgBr?②H3O
(5)C6H5CHCHCOOHKMnO4△
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(6)H3C(7)CH3COONaCOOH+O2NHNO3H2SO4
CH2Br(8)油酸KMnO4?
PCl5
(10)KMnO4(CH3)2CHCH2CH2OH△??NH3?P2O5?(11)(12)水杨酸Br,FeKMnO4△?
?Ba(OH)2△?
H3O300℃NH3高温(13)CH2=CH2Br2Br2?2NaCN????LiAlH4??H+
(14)丁二酸(15)(16)
CHCOONaHBr?NaOHCHO+(CH3CO)2O3?H2O,Br2CH2COOHP?NaOH?NaCN ?H3O+?精品
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OOo(17)?NaOH,H2O?H+==?(18)CH3CH=CH2H+H2OHBr???PCl3
??(CH3)2CHMgBr?NH3?NaOBrNaOH(CH3)2CHCOOH(19)CH3?H3CNO2?
COOHO2NPCl5(20)?LiAlH[OC(CH3)3]3???CH2COOHCH2(21)H2CCOH2CCOC2H5OH?C2H5ONa(CH3)2CHBr?C2H5ONaC2H5Br?稀NaOH,H2O?(22)CHO+??OH△?OCCHCCH3H
CH3COCH2COOC2H5C2H5ONa,C2H5OH?(23)O???NaHDMFCOOHC2H5(CH3)2CHCOCl??(24) 2CH3COOC2H5H+?(1)C2H5ONa(2) H+?NaOH,H2O??解:
(1)CH3CH2CH2COOHCH3CH2CH2COClCH3CH2CH2COOOCCH3
(2)Cl2 , POO2NCHCOOC2H5Cl
ClOCCH2CHCH2COOCH3CH3(3)H3COOHOOCCH2CHCH2COOCH3CH3
HOOCCH2CH2CH2CH2COOHOHOCH2CH3
(4)OH(6)(5)COOHH3CO2NCOOH
CH2OOCCH3
(7)O2N(8)
CH3(CH2)7COOH + HOOC(CH2)7COOH精品
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(10)(CH3)2CHCH2COOH(CH3)2CHCH2CONH2(CH3)2CHCH2COCl(CH3)2CHCH2CN
(11)COOHCOOHOHBrCOOHO
(12)Br(13)CH2BrCH2Br
NCCH2CH2CNHOOCCH2CH2COOHooo(14)HOCH2CH2CH2CH2OHOHOOCCH2CH2CONH2
(15)(16)CH=CHCOOHCHBrCOOHCHBrCH2COOHCHBrCOONaCHOHCH2COOH
CHCNCOONaCH(COOH)2(17)(18)CH3CO3HNaOOCCH2CH2CH2CH2CH2OHHOOCCH2CH2CH2CH2CH2OH
Mg , Et2OCO2(CH3)2CClCOOHCH3CHBrCH3(CH3)2CClNH2(CH3)2CClCONH2
COClO2NCHO(19)(20)混酸KMnO4/H+O2NCH2Br
ROORHBrNaCNH+/H2O
H3CCOOC2H5CHCHCOCH3H3C(21)CH3COCH2COOC2H5H3CCHH3CCCOOHH3CCHH3CC2H5CCOOC2H5COCH3C2H5H3CCHCHH3CCCCOCH3H+/H2O(22)COCH3C2H5C6H5HC=HCCH3COCH3H3CCOCH3COOC2H5
(23)HCNCNC2H5Na/C2H5Br
(24)CH3COCH2COC2H5CH3COCHCOONaCOCH(CH3)2-CH3COCHCOC2H5Na+CH3COCHCOOHCOCH(CH3)2CH3COCHCOC2H5COCH(CH3)2CH3COCH2COCH(CH3)2
13. 由指定原料合成下列化合物
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(1)乙炔─→丙烯酸甲酯
(2)异丙醇─→α-甲基丙烯酸甲酯 (3)丁酸─→乙基丙二酸 (4)乙烯─→β-羟基丙酸
(5)对甲氧基苯甲醛─→α-羟基对甲氧基苯乙酸 (6)丁酸─→丙酸 解:
(1)H+/H2OHCCHHClCH2=CHClH2SO4 , CH3OHNaCNCH2=CHCNNaNH2 , NH3H+/H2OCH2=CHCOOHH2SO4CH2=CHCOOCH3
Br2(2)CH3CHOHCH3H3CCCHROORHBrCH3CH=CH2CH3CHBrCH2BrCH3CH=CHCNNaCNCH3CH=CHBrH2SO4 , CH3OHNaCNH+/H2OCH3CH=CHCOOHCH3CH=CHCOOCH3(3)CH3CH2CH2COOHCH3CH2CHCNCOOHP , Cl2CH3CH2CHClCOOHHOOCCHCOOHCH2CH3NaCNH+/H2O
(4)CH2=CH2H+/H2OCl2 , H2OCH2ClCH2OHHOCH2CH2CN
H/H2O+HOCH2CH2COOHCHOHCN(5)H3COH3COCHOHCNH3COCHOHCOOH(6)CH3CH2CH2COOHCH3CH2CH=CH2LiAlH4KMnO4 , H+CH3CH2CH2CH2OHCH3CH2COOHH2SO414.由乙酰乙酸乙酯作为原料之一合成下列化合物。
(1)2-庚酮 (2)苯甲酰丙酮 (3)2，7-辛二酮 (4)3-乙基-2-戊酮 (5)甲基环丁基甲酮 (6)γ-戊酮酸 解:
(1)CH3COCH2COOC2H5酮式分解C2H5ONaC4H9ClCH3COCHCOOC2H5C4H9
CH3COCHCOOC2H5CH3COCH2C4H9C2H5ONaC6H5COCl(2)CH3COCH2COOC2H5酮式分解CH3COCH2COC6H5C2H5ONaClCH2CH2CH2COCH3COC6H5
(3)CH3COCH2COOC2H5CH3COCHCOOC2H5酮式分解CH2CH2CH2COCH3CH3CO(CH2)4COCH3精品
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(4)CH3COCH2COOC2H5C2H5ONaC2H5ClC2H5ONaC2H5ClCH3COCHCOOC2H5C2H5酮式分解C2H5CH3COCCOOC2H5C2H5CH3COCH(C2H5)2
(5)CH3COCH2COOC2H5C2H5ONa酮式分解C2H5ONaBrCH2CH2CH2BrCH3COCHCOOC2H5CH2CH2CH2BrCOCH3C2H5ONaCH3COCH2Cl酮式分解
(6)CH3COCH2COOC2H5CH3COCH2CH2COOH15.由丙二酸二乙酯为原料之一合成下列化合物
(1)正已酸 (2)环丙烷甲酸 (3)1,4-环已烷二甲酸 (4)庚二酸 (5)2-乙基-3-丙基丁二酸 解:
(1)CH2(COOC2H5)2NaOHH2OC2H5ONaCH3CH2CH2CH2Cl-CO2CH3CH2CH2CH2CH(COOC2H5)2CH3CH2CH2CH2CH2COOHCH3CH2CH2CH2CH(COOH)2C2H5ONa(2)CH2(COOC2H5)2NaOH-CO2H2OBrCH2CH2BrCH(COOC2H5)2
COOHC2H5ONaBrCH2CH2Br(3)CH2(COOC2H5)2C2H5ONaNaOHH2O
(C2H5COO)2CHCH2CH2CH(COOC2H5)2BrCH2CH2Br-CO2(C2H5OOC)2COOHBr(CH2)5Br(COOC2H5)2HOOCC2H5ONa
(4)CH2(COOC2H5)2NaOHH2O-CO2(C2H5COO)2CH(CH2)5CH(COOC2H5)2HOOCCH(CH2)5CHCOOHC2H5ONaCH3CH2CHBrCHBrCH2CH2CH3(5)CH2(COOC2H5)2CH2CH2CH3(C2H5COO)2CCH(COOC2H5)2CH2CH3NaOHH2O-CO2CH2CH2CH3HOOCCHCHCOOHCH2CH3
16.某化合物A的分子式为C7H12O4，已知其为羧酸，依次与下列试剂作用：(1)SOCl2;(2)C2H5OH;(3)催化加氢(高温)；(4)与浓硫作用；(5)与高锰酸钾氧化后，得到一种二元羧酸B。将B单独加热，则生成丁酸。试推测A的结构，并写出各步化学反应式。
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第六章 有机化学课后习题答案
