《有机化学》课程教学资源（作业习题）第十二章 醛酮

第十二章醛酮 1.下列各组化合物分别用同一试剂处理,哪些有反应,哪些无反应。 (1)饱和 NaSO3溶液:C6 HscOch,C6H5CHO,CHCH2CHO,CHCH2COCH (2)HCN: C6Hs CHO, CH3 CH2 COCH3 ChS COCH (3)12+NaOH: CH3CH2OH, OH, CH3 CHO, CH3 CH2 COCH3, CHs COCH; (C2H5 )2CO, CH3 CH2 CHO (4)浓NaOH (CH3)3C-CHO. CH: CH2 CHO CH3COCH3 (5)Tollen iF]: C6Hs CHO, C6HsCOCH3, CH3 CH2 COCH3, CH3 CH2 CH2CHO 鉴别 (1)C6Hs CHO, C6Hs COCH3, C6Hs COCH2CH3 (2)HCHO, CH3 CHO, CH3 COCH3 (3)CH3 COCH2 CH2CH3, (C2H5 )2CO CH3CH CH CHCH (4)CH3(CH2)3CHO OH, (C2H5)2CO 3排序 (1)按羰基活性 a (CH3 )3 CCOC(CH3)3, CH3 COCHO, CH3 COCH2 CH3, CH3 CHO b CH3 CH2 COCH3 CH3 COCCI3 (2)按酸性 a CH3NO2, CH3 CHO, CH3 CN, CH3 COCH3 b CH2(NO2)2, CH3 COCH2COCH3, CH3 CH2 COCH2COCH2CH3 C6HsCOCH2 COCH3. C6HsCOCH2COCF3 烯醇式含量

第十二章 醛 酮 1. 下列各组化合物分别用同一试剂处理，哪些有反应，哪些无反应。 (1)饱和 NaHSO3 溶液: C6H5COCH3, C6H5CHO, CH3CH2CHO, CH3CH2COCH3, O (2) HCN: C6H5CHO, CH3CH2COCH3, O , C6H5COCH3 (3) I2+NaOH: CH3CH2OH, CH3CH2CHCH3 OH , CH3CHO, CH3CH2COCH3, C6H5COCH3, (C2H5)2CO, CH3CH2CHO, O , O (4) 浓 NaOH: H3C CHO , (CH3 )3C CHO, CH3CH2CHO, CH3COCH3 (5) Tollen 试剂：C6H5CHO, C6H5COCH3, CH3CH2COCH3, CH3CH2CH2CHO 2. 鉴别。 (1) C6H5CHO, C6H5COCH3, C6H5COCH2CH3 (2) HCHO, CH3CHO, CH3COCH3 (3) CH3COCH2CH2CH3, (C2H5)2CO, O (4) CH3(CH2)3CHO, CH3CH2CH2CHCH3 OH , (C2H5)2CO 3.排序。 （1）按羰基活性 a. (CH3)3CCOC(CH3)3, CH3COCHO, CH3COCH2CH3, CH3CHO b.CH3CH2COCH3, CH3COCCl3 c. O , O (2) 按酸性 a. CH3NO2, CH3CHO, CH3CN, CH3COCH3 b. CH2(NO2)2, CH3COCH2COCH3, CH3CH2COCH2COCH2CH3, C6H5COCH2COCH3, C6H5COCH2COCF3 c. 烯醇式含量

CH3 COCH2CO0C2Hs, CH3 COCH2 CH3, CH3 COCH2COCH3, CH(COCH3 )3 (CH3 CO)2 CHCOOC2Hs 4.从指定原料合成 CHO CHO →,CH3CCH2OH 5.下列各化合物都可由分子内羟醛缩合反应得到,写出其前体 6.比较下列各组化合物的水合物的稳定性。 (1)CH3 CCH2 CH2Br, CH3 CCH2Br (2)CH3COCOCOCH3, CH3 COCOCH3, CH3 COCH2CH3 CHO Hsco CHO 7.写出下列反应的产物。 HC≡CNa、(NH4(,-33℃ (2)H3O DEt,O CKH COCH; HC=CMgBr (2H3O

CH3COCH2COOC2H5, CH3COCH2CH3, CH3COCH2COCH3, CH(COCH3)3, (CH3CO)2CHCOOC2H5 4. 从指定原料合成。 (1) CHO O Br (2) CHO OH OH (3) CHO CH3C(CH2OH)3 (4) Br CHO 5．下列各化合物都可由分子内羟醛缩合反应得到，写出其前体。 (1) O (2) O (3) O 6．比较下列各组化合物的水合物的稳定性。 (1) CH3CCH2CH2Br O ， CH3CCH2Br O (2) CH3COCOCOCH3, CH3COCOCH3, CH3COCH2CH3 (3) O2N CHO , H3CO CHO (4) O , O 7. 写出下列反应的产物。 (1) O + HC C Na (1)NH3 (l), -33 oC (2)H3O + (2) (2)H3O + C6H5COCH3 + HC CMgBr (1) Et2O

CHSC=CMgBr ()EO-15C (2)H3O 8.写出下列反应的产物。 (1)c6H3C≡cH+CH3OH(过量)BsO4 (2)C2H5 CH-NCH3 NaHSO C6HsCH-A OCH3 HOCH2 CH2OH HOCH, CHCH, CH,CCH, CH, CHCH2OH (4) CH (5) CF3CH=O+CH; CH(OCH,h -H HCI (6)HOCH2 CH2CH2=O+ CH3OH Ooo C6HSCCCC6H6 CH3O 9.下列化合物中哪些在碱性溶液中会发生外消旋化? (1)(R)-2-甲基丁醛 (2)(S)-3-甲基2-庚酮 (3)(S)-3-甲基环己酮 (4)(R)-1,2,3-三苯基-1-丙酮 10.下面化合物中哪些可以起卤仿反应。 CH3 CH2 CHO CH3 CH(OH)CH2 CH2 CH3 CH3 CH2 CH2OH CH3 CH2COCH3 C6H5 COCH3 CH3 COCH, CH2 COCH sHsCHOHCH3 CHs CH2 CHOH 1l.下列化合物可以从什么原料合成? CH3COCH, CHCH, CH3 CH CHCH, COCHCH CH3 CH3CH, COCHCHCH2CH3 (CH3)CHCHCCHO (6) OH CH3

(3) (2)H3O + (1) Et2O, -15 oC H2C CH2 O + C2H5C CMgBr 8．写出下列反应的产物。 (1) C6H5C CH + CH3OH (过 量 ) H2SO4 (2) C2H5CH NCH3 + NaHSO3 (3) C6H5CH C H OCH3 + HOCH2CH2OH H3O + (4) HOCH2CHCH2CH2CCH2CH2CHCH2OH CH3 O CH3 (5) CF3CH O + CH3CH(OCH3 )2 H + (6) HOCH2CH2CH2CH O + CH3OH HCl (7) H + C6H5CCCC6H6 CH3OH OOO + 9．下列化合物中哪些在碱性溶液中会发生外消旋化？ (1) (R)-2-甲基丁醛 (2) (S)-3-甲基-2-庚酮 (3) (S)-3-甲基环己酮 (4) (R)-1,2,3-三苯基-1-丙酮 10．下面化合物中哪些可以起卤仿反应。 CH3CH2CHO CH3CH(OH)CH2CH2CH3 CH3CH2CH2OH CH3CH2COCH3 C6H5COCH3 CH3COCH2CH2COCH3 C6H5CHOHCH3 C6H5CH2CH2OH 11. 下列化合物可以从什么原料合成？ (1) O (2) CH3COCH2CHCH2CH3 OH (3) CH3CHCH2COCH2CH3 OH (4) O C(CH3 )3 (5) CH3CH2COCHCHCH2CH3 CH3 OH (6) (CH3 )2CHCHCCHO OH CH3 CH3

12.写出下列合成的中间产物或试剂。 Zn-h CH(CH3)2 COOH HSO Zn-He CH,CCH,(CH3hC (3) (H3C)3C (H3C)3C 13. Match the name from each list to the proper IR spectrum. Identify the diagnostic bands in each spectrum. (A-D)( Spectrometric Identification of Organic Compounds, Fifth Edition) Allyl phenyl ether Benzaldehyde o-Cresol

12. 写出下列合成的中间产物或试剂。 (1) CH3 AlCl3 H2C H2C C C O O O ? Zn-Hg HCl ? SOCl2 H3C CCl O AlCl3 ? ? CH(CH3 )2 ? H3C CH(CH3 )2 (2) ? COOH O Zn-Hg HCl ? Zn-Hg HCl ? H2SO4 ? Pd, ? (3) CH3CCH3 O ? (CH3 )2C CHCCH3 O ? O ? ? COOH COOH (H3C)3C ? (H3C)3C O 13．Match the name from each list to the proper IR spectrum. Identify the diagnostic bands in each spectrum. (A-D) ( Spectrometric Identification of Organic Compounds, Fifth Edition). Allyl phenyl ether Benzaldehyde o-Cresol m-Toluic acid Δ

A ⊥L⊥⊥⊥⊥ ⊥1L1⊥ aH,A识HA FREGUENCY tcm Wavelength .NEAT WAVENUMBERS NICOLET 20SX FT-R

A B C D