第十二章醛酮 1.写出下列合成的中间产物或试剂 CH2C、 Zn-Hg SOCl2 Ha CH(CH3)2 CH(CH3)2 AlC H3C 2 COOH Zn-Hg 9 2SO4_Zn-H 2.如何完成下列转变? (1) CH3CH2 CH2 CH=0-CH3, CH2CH3 CH2OH (2)CH2CH2CH2COCH3——-(CH3)2C=CCH2CH3 CH3 (3) CH3(CH,)CHO CH3(CH2)4CHO (4)HC≡ccH2CH2CH2OH—CH3CCH2CH2C(CH2)4CH3 3.推测下列化合物的结构: (1)C4HO,含有羰基,δ:1.0(t,3H),1.5(m,2H),2.4(t,2H),9.9(s,1H)pm (2)C6H10O2,mnax:1700,1380cm,δH:2.2(s,6H),2.7(s,4H)ppm (3)CHCO,cmax:1695,1600,1500,830cm3,δH:1.2(t,3H),3.0(q,2H),7.7(q,4)ppmn 4.用化学方法鉴别下列各组化合物 ( CHO, CHs COCH3, C6Hs COCH2 CH3 (2)C6H5 CH(OH)CH3, C6Hs CH2OH, CH3 COCH2 CH3, C6HSOH 5.先完成反应,再写出反应机理 ()cH:0co+rcHo-浓u (2)2 CH, CH, CHO (3) HCN
第十二章 醛酮 1. 写出下列合成的中间产物或试剂. CH3 (1) CH2C CH2C O O O AlCl3 ? Zn-Hg HCl ? SOCl2 H3C CCl O AlCl3 ? ? CH(CH3 )2 ? H3C CH(CH3 )2 (2) ? COOH O Zn-Hg HCl ? H2SO4 ? Zn-Hg HCl ? Pd ? 2. 如何完成下列转变? (1) CH3CH2CH2CH=O CH3CH2CHCHCH2CH2CH3 CH2OH OH (2) CH3CH2CH2COCH3 (CH3 )2C=CCH2CH3 CH3 (3) CH3 (CH2 )2CHO CH3 (CH2 )4CHO (4) HC CCH2CH2CH2OH CH3CCH2CH2C(CH2 )4CH3 O O 3. 推测下列化合物的结构: (1)C4H8O,含有羰基,:1.0(t,3H),1.5(m,2H),2.4(t,2H),9.9(s,1H)ppm. (2)C6H10O2,max:1700,1380 cm-1 , :2.2(s,6H),2.7(s,4H)ppm. (3)C9H9ClO, max:1695,1600,1500,830cm-1 , :1.2(t,3H),3.0(q,2H),7.7(q,4H)ppm. 4. 用化学方法鉴别下列各组化合物. (!) C6H5CHO, C6H5COCH3, C6H5COCH2CH3. (2) C6H5CH(OH)CH3, C6H5CH2OH, CH3COCH2CH3, C6H5OH. 5. 先完成反应,再写出反应机理. (1) CH3O CHO + HCHO 浓OH - (2) 2 CH3CH2CHO 稀OH - (3) O + HCN
6.将下列化合物按羰基活性次序排列 (1)(CH3)3CCOC(CH3)3 CH3 COCHO CH3COCH2CH3 CH3CHO (2) CH3 CH_COCH3 CH3COCCl3 7.化合物A(CsH1O2),对碱稳定在酸溶液中A水解为B(C2H6O2)和C(C2H6O2),B可以与 苯肼生成衍生物,能起碘仿反应,但不能与 Tollens试剂生成银镜C可以氧化生成D(C2H2O4) D与CaCl2水溶液生成不溶于水的E(C2OCa),求A,B,C,D,E的结构式并写出反应式 答案(1-7 (I)CH3 CH2CO CH,CO COCH2 CH2CO2H Zn-Hg CH2CH2 CH2CO2H O、CH(CH3)2 SOCk AlCI CH3)CHMgBr H3C H3C CH(CH3) Hac CH(CH3)2 H CHoCO CHcoO COOH Zn-I AlCl3 △ OH (1)2CH3CH, CH2 CH-=Q OH(d) OCHCHCHCH,CHCH OH CH3 CH3 NaBH4- CHa CH, CHCHCH2CH2CH3 (2) △ 1)B,H6, THF 2)H3O -H2O 2)H,O2, OH O 1)CH3 Mgl OH CHo NaBH CH2OH PBr CH2B 2)H3O
6. 将下列化合物按羰基活性次序排列: (1) (CH3 )3CCOC(CH3 )3 CH3COCHO CH3COCH2CH3 CH3CHO (2) CH3CH2COCH3 CH3COCCl3 (3) O O 7. 化合物 A (C5H10O2),对碱稳定.在酸溶液中 A 水解为 B (C2H6O2)和 C (C2H6O2), B 可以与 苯肼生成衍生物,能起碘仿反应,但不能与 Tollens 试剂生成银镜. C 可以氧化生成 D (C2H2O4), D 与 CaCl2 水溶液生成不溶于水的 E (C2O4Ca), 求 A, B, C, D, E 的结构式并写出反应式. 答案(1-7): 1. CH3 (1) CH2CO CH2CO O AlCl3 Zn-Hg HCl SOCl2 AlCl H3C 3 H3C CH(CH3 )2 CH2CH2CH2CO2H H3C COCH2CH2CO2H H3C H3C COCl H3C O CH(CH3 ) HO 2 (CH3 )2CHMgBr H3C CH(CH3 )2 Pd (2) COOH O Zn-Hg HCl H2SO4 Zn-Hg HCl Pd CH2CO CH2CO O AlCl3 CO2H O 2. (1) 2CH3CH2CH2CH=O CH3CH2CHCHCH2CH2CH3 CH2OH OH OH - (d) OCHCHCHCH2CH2CH3 OH CH3CH3 NaBH4 (2) O 1) CH3MgI 2)H3O + H2O 1) B2H6 , THF 2) H2O2 , OH - OH [O] O 1) CH3MgI 2) H3O + H2O (3) CHO NaBH4 CH2OH PBr3 CH2Br Mg CH2MgBr 1) O 2) H3O + [O] CHO
(4)HC=CCH, CH,CH OH HgsO4, H2s04, CH3,,OH CH3 CCH CH2CH,OH CH..CHO OH O lO D)CHa(CH)4CH-MgBr,CH3 CCH2 CH2 CH(CH2)4CH 2)H3O CH3 CHC(CH2)4CH3 (1) CH3 CH2CH2 CHO (2)CH,CCH,CH,CCH CCH2 CH C6HSCHO 显紫红色 Schiff (1)C6HsCOCH3 I++ Naoh 试剂 C6Hs COCH2 CH3 C6HSCH(OHCH 黄 I+ NaOH (2)6HSCH2OH Br2+H,O 2△ CH3COCH2CH3 C6HSOH 白 (1)CH3O CHO+HCHO CH3O CH2OH HCOOH 机理 OH CH3O 长9+H-x OH C-O.+ HCOOH CH3O CH,OH+ HCOO
(4) H C C C H 2 C H 2 C H 2 O H C H3C C H2C H2C(C H2)4 C H3 O OHgSO4, H2SO4 C H3C C H2C H2C H2O H O O H O H C H3C C H2C H2C H2O H O O [O] C H3C C H2C H2C H O O O 1) CH3(CH2)4CH2MgBr 2) H3O+ CH3CCH2CH2CH(CH2)4C H3 O O OH [O] H+ 3.(1) CH3CH2CH2CHO (2) CH3CCH2CH2CCH3 O O Cl CCH2CH3 O (3) 4. C6H5C O C H3 C6H5CHO C6H5COCH2C H3 (1) Schiff 试剂 显 紫 红 色 I2 + NaO H 黄 色 C6H5C H(O H)C H3 C6H5CH2OH CH3COCH2CH3 C6H5OH (2) Br2+ H2O 白 色 Na H2 H2 I2 + NaO H 黄 色 5. (1) CH3O CHO + HCHO 浓OH- CH3O CH2OH + HCOOH 机理 HC O H + HO- H2COH O- CH3O CH O + CH O- OH H CH3O H2 C O- + HCOOH CH3O CH2OH + HCOO-
2 CH3 CH2CHO CHCHCHCHO 机理HO 快 H2O+ CH3 IHC-=--H=8-9;1 CH3 慢 CHyCH2CH HC-A CH3, CHCHCH=O C CH3 CH3 CH_CHCHCH=O:+ H2O CH3CH,CHCHCHO CHa (3) 机理HCN+OH、块 -cN H,O + 快 XCn +OH (1)CH3 COCHO >CH3 CHO CH3 COCH2CH3 >(CH3)3CCOC(CH3)3 (2)CH3COCCl3 CH3 CH2COCH3 7.A的u.s.=1,从已知条件估计是缩酮,而且是二元醇的缩甲基酮;A应是C3的甲基酮与 C2的二元醇缩合所得的缩酮 H3C HO O COoH CaCh COO (CH3h2C H HO COOH COO A, CsH1oO, B, C3H6O C, C2H6O2 D, C?HO4 B, CH3 COCH3: CHS NHNH2(-) I,, NaoH (+
(2) 2 CH3CH2CHO 稀OH - CH3CH2CHCHCHO CH3 OH 机理 HO - + H CH CH3 C H O 快 H2O + [ HC CH3 C H O HC CH3 C H O ] CH3CH2CH O HC CH3 C H + O 慢 CH3CH2CHCHCH CH3 O - O CH3CH2CHCHCH CH3 O- O + H2O CH3CH2CHCHCHO CH3 OH 快 (3) O + HCN OH CN 机理 HCN + OH - CN - + H2O NC - + O O - CN O - CN + H OH OH CN + OH - 快 慢 快 6. (1) (CH3 )3CCOC(CH3 ) CH3COCHO CH3CHO CH3COCH2CH3 3 (2) CH3COCC CH3CH2COCH3 l3 (3) O O > > > > > 7. A 的 u.s.=1,从已知条件估计是缩酮,而且是二元醇的缩甲基酮;A 应是 C3 的甲基酮与 C2 的二元醇缩合所得的缩酮: (CH3 )2C O O H3O + C O H3C H3C + HO HO [O] COOH COOH CaCl2 COO COO Ca A,C5H10O2 B,C3H6O C,C2H6O2 D,C2H2O4 E B, CH3COCH3 : C6H5NHNH2 ( ) I2 , NaOH ( + ) Tollens ( )