(4) (CH3CH(CH3)CO)2O (5) (CH3)2CHCOBr (6) (CH3)2CHCOOC2H5 (7) (CH3)2CHCONH2 7、
CH3CH2CH2CHO白色结晶H3O+△CH3CH2CH2CHOCH3CH2COCH2CH3NaHSO3 (饱和溶液)×CH3CH2CH2COOH×2,4-二硝基苯肼CH3CH2CH2CH2OH×HO+黄色3△CH3CH2COCH2CH3×溶于水+NaOH/H2O油水分离水层HCH3CH2CH2COOH×不溶于水油层
8、(1)H3COCOCH3H3CCOOCH(2)CH3CH=CHCOOH3H2CCO(3)O(4)HCH2CH22CCHCO(5)CO2 +H2OH3CCHCH2OCH3
9、(1)A: H3O+ B:PCl3、PCl5(或SOCl2) C:NH3 D:P2O5,△ E:NH3 ,△ F:NaOBr + NaOH G:H2/Pd-BaSO4 (2)①CCOOH2H5MgBr②HO+3,PBr3;
C2H5
(3)2NH3 ,H2NCONHCONH2 (4)OH CN;OHOCOCOOH; COO
10、
(1)CHLiAlH43CH2COOHCH3CH2CHPBr2OH3CH3CH2CH2BrNaCNH3O+△CH3CH2CH2COOH
(2)CHCHCl2HO-CHKMnO3CH22COOH2CH(OH)COOH4PCH2+CH3CH2COOHH△CH2+(3)过氧化物CH2BrNaCNH3OCH2COOHHBr△
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(4)CH3COCH2CH2CBr(CH3)2Mg干醚CO2H3O+HOCH2CH2OH干HClCH2CH2OOH3CCCH2CH2CBr(CH3)2CH3COCH2CH2C(CH3)2COOH
(3)CH2COOHCH2COOH
11、(1)CH2CH2COCH2CH2COCOOHO(2)COOC2H5COOC2H5O(5)COCH3(6)H3CBrOCHCOHCC2H5CH3(4)COOH CN(7)CH3CH2COCH3CH2CH2COO(8)CH2COOC2H5CH2COOC2H5(9)CH3NH2(10)
12、
(1) HCOOCH3 > CH3COOCH3 > CH3COOC2H5 > CH3COOCH(CH3)2 > CH3COOC(CH3)3 (2)O2NCO2CH3∨ClHCNCuCl2△CO2CH3∨CH3OH , H2OH2SO4CO2CH3∨CH3OCH2=CHCOOCH3+CO2CH3
13、(1)HC≡CHCH2=CHCN
NaCN(2)CH3CH(OH)CH3HBrH3O△CH3CH(CH3)COOHH3O+CH3CH(Br)CH3Mg干醚NaCNH3O△+CO2CH3CH(CH3)COOH
(3)C6H5CH3Cl2光C6H5CH2COOHH3O+C6H5CH2ClMg干醚+CO2C6H5CH2COOH
(4)CH3CH2CH2COOHHOBrCl2PNaCNH3O△CH3CH2CH(COOH)2H3O△+
(5)CH2=CH2HOCH2CH2BrNaCNOHCH2CH2COOH
H3O+(6)CH3OCHOHCNCH3OCH(OH)CNO2NCH(OH)COOH
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(7)CH2=CH2C2H5OHHH2O+HBrCH3CH2BrNaCNH3O△+CH3CH2COOHBr2PCH3CH(Br)COOHH2OHClCH3CH(Br)COOC2H5Zn干醚CH3CH(ZnBr)COOC2H5CH3CH2CHO
CH3CH(OH)CH(CH3)COOHPCl5
H2Pd/BaSO4CH3CH2COOHCH3CH2COClCH3CH2CHO
OCH3(8)BrZnCH2COOC2H5OCH3H2OHClCH3COCH3[O]Zn干醚CH3CCH2COOC2H5OZnBrBr2PCH3CCH2COOC2H5OHC2H5OHH+CH3CH2OHCH3COOHBrCH2COOH△BrCH2COOC2H5BrZnCH2COOC2H5
H2O(9)OBrZnCHCOOCH225OZnBrH2OCH2COOC2H5HClOHCH2COOH
14、从氯到两个羧基的距离不同,诱导效应也不同来解释。
15、(1)CH3CO2 负离子的负电荷平均分配在两个碳原子上,而CH3CH2O 负离子的负电荷定域在一个氧原子上,所以较不稳定,与质子作用的倾向较大。
(2)CH3CH2CH2CO2 > ClCH2CH2CO2(由于Cl的诱导作用而较稳定)
—
—
—
—
(3)ClCH2CH2CO2 > CH3CH(Cl)CO2 (Cl 靠近—CO2 中心而较稳定)
—
—
—
(4)FCH2CO2 > F2CHCO2 (含有两个氟原子) (5)CH3CH2CH2CO2 > HC≡CCH 2CO2
—
—
——
(HC≡C—吸电子诱导效应)
16、10×1000×(183.5/1000)=1835克,需KOH 1.835千克 17、反应式略
(A)的结构式为:HOOCCH2CH(C2H5)CH2COOH (B)的结构式为:HOOCCH2CH(C2H5) COOH
18、(A)的结构式为:CH3COOCH=CH2 (B)的结构式为:CH2=CHCOOCH3
O19、(A)H3COOCH2COOH(B)CHCOOCH25CH3(C)CHCOOHCH3CH2COOC2H5(D)CH2COOC2H5CHCOOC2H5CH3
20、(1)HCOOCH2CH2CH3 (2)CH3CH2COOCH3 (3)CH3COOCH2CH3
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第十四章 β— 二羰基化合物
1、(1)2,2 -二甲基丙二酸 (2)2-乙基-3-丁酮酸乙酯 (3)2-氧代环己烷甲酸甲酯 (4)甲酰氯基乙酸 (5)3-丁酮酸(乙酰乙酸)
2、(1)环戊酮 (2)CH3COCH2CH2CH2COOH (3)CH3CH2CH2COOH 3、(1)加FeCl3/H2O CH3COCH(CH3)COOC2H5 有颜色反应. (2)加FeCl3/H2O CH3COCH2COOH有颜色反应. 4、(1)互变异构 (2)共振异构 (3)互变异构 5、
O(1)CH3CH2CCHCOOC2H5CH3COCH(CH3)COOC2H5+C2H5OH(2)+C2H5OH
(3)H3CCHCOOC2H5COCOOC2H5+C2H5OH(5)OCHO+C2H5OH
(4)H2CCH2CH2COCH2CHCOOC2H5+C2H5OH
6、(1)CHOCHO;CHO
(2) C2H5ONa , CH3CH(Br)COOC2H5 , CH3COCH2CH(CH3)COOC2H5 (3) HOCH2CH2OH / 干HCl , CH3COCH2C(OH)(C6H5)2 (4)NaCH(COOC2H5)2,(C2H5OCO)2CCH2OC6H5CH2OCH3CH2CH2COCH3HOOCCHCH2CH2COCH3CH2,HOOCCHCH2CH2CH(OH)CH3CH2,NaOCH3
7、C6H5CH2COCH2C6H5C6H5CHCOCH2C6H5-CH2=CHCOCH3C6H5CH2CH2CHCOCCH2CH3OC6H5C6H5NaOCH3C6H5CH2CH2CH-CCCHOC6H5OCH3CH2CH2-OCC6H5CHCCHCH3OC6H5CH3OHCH2CH2OHCHCCH3CCHOC6H5- H2O△CH2CH2C6H5CHCCH3CHCOC6H5- 24 -
8、丙二酸酯合成: CH3CH2OH[O]Cl2PNaBrH2SO4① NaCN②H3O+2C3H5OHH+CH2(COOC2H5)2
NaBrH2SO4(1)CH3CH2OHCH3CH2BrCH3OHCH3BrC2H5CH(COOC2H5)2CH2(COOC2H5)2①C2H5ONa②CH3BrC2H5ONa+NaHC(COOC2H5)2C2H5BrHH2OH△NaBrH2SO4+- CO2△CH3CH2CH(CH3)COOHO2AgMg干醚
+(2)CH3CH2OHCH3CH2OHCH2=CH2H2COCH2H3OCH3CH2BrCH3CH2MgBr
CH3CH2CH2CH2OHCH2(COOC2H5)2NaBrH2SO4CH3CH2CH2CH2BrCH3CH2CH2CH2BrHH2O+C2H5ONa- CO2△+CH3CH2CH2CH2CH2COOH
(3)CH3CH2OHLiAlH4NaBrH2SO4CH3CH2BrH△+NaCNHCH3CH2CNH2OCH3CH2COOHCH3CH(Br)CH2BrCH3CH2CH2OH- H2OCH2=CHCH3Br22CH2(COOC2H5)2H+2C2H5ONa2NaCH(COOC2H5)2CH3CH(Br)CH2Br- CO2△CH2CH2COOHH3C+H2OCHCH2COOH
1,2-二溴乙烷合成酮 (3). (4)CH3CH2OHH△- H2OCH2=CH2Br2CH2BrCH2BrCH2BrCH2Br2CH2(COOC2H5)2CH2CH(COOC2H5)2CH2CH(COOC2H5)2C2H5OCO2C2H5ONa2NaCH(COOC2H5)2CH2BrCH2Br2C2H5ONaCOOC2H5COOC2H5H+- CO2△
C2H5OCOH2OHOOCCOOH
(5) 1,2-二溴乙烷合成同 (4).
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