习题 14.1写出苯甲醛与下列试剂反应的主要产物。 (1)HCN.HO (2)C,HsMgBr,干醚，然后HO (3)n-CHoli,然后H:O (4)CH=CNa,液NH,然后H,O (5)BrCH,COOC.H5,Z,苯，然后H,0(6)PhP=CHCH,CH (7)CH2N2 (8)CHOH,干燥HCI (9)饱和NaHSO3溶液 (10)NH2OH (11)苯腓 (12)2,4.三硝基苯册 (13)氨基脲 (14)苯胺 (15)Tollens试剂 (16)Fehling试剂 (17)KMnO:H2SO4 (18)CH;CO,H (19)LiAIH4,然后HO (20)NaBH. (2)浓NaOH (22)CH,O,浓NaOH (23)CH CHO,稀NaOH (24)(CHCCO)O,CHCOOK (25)HNO3,HS04,10C (26)Al[OCH (CHs)2.(CH3)2CHOH 14.2写出苯乙酮与下列试剂反应的主要产物。 (1)HCN,HO (2)CoHsMgBr,然后H,O (3)CH,C=CNa,然后H,O (4)BrCH-COOC2Hs,Z,然后HO (5)Ph P=CH (6)HOCH-CH,OH,干娱HC (7)HSCH-CHSH,H+ (8)饱和NaHSO溶液 (9)H2N-NH2 (10)CHsNHNH2 (1l)Tollens试剂 (12)CF,C0,H (13)NaBH (14)Na.CH.OH (15)MgHg,无水苯，然后HO (16)Zn-Hg.HCI (17)NH,NH2,KOH,三甘醇 (18)Br,CHCOOH (19)I2,NaOH (20)稀0H (21)HNO3,H2SO4,10C 14.3写出2丁烯醛与下列试剂反应的主要产物。 (1)HBr (2)H2,Ni (3)LiA1H4,乙醚，然后HO (4)NaBH4,C,HsOH,然后H,O (5)i,液氨，然后HO (7)HCN (9)KMnO,H2SO (10)稀NaOH (11)1,3.丁二烯 (12)C,HOH,干躁HC1 14.4写出对苯醌与下列试剂反应的主要产物， (1)2Br (3)CHMgI,干醚，然后HO (4)H-NOH (6)CH.NH (7)CH,0 (8)HCN (9)e,H,0 14.5利用简单的化学方法鉴别下列客组化合物。 (1)A.戊醛 B.2-戊酮 C.3-戊酮 D.环户周 (2)A.2-己酮 B.3-己酮 C.己二醛 D.5-己酮醛
14.1 ✂✁☎✄✝✆✟✞✡✠☞☛✍✌✏✎✡✑✓✒✏✔✖✕✘✗✚✙✚✛✚✜✣✢ ✤ 1 ✥ HCN ✦ HO - ✤ 2 ✥ C2H5MgBr ✦✘✧✚★✖✦✘✩✍✪ H3O + ✤ 3 ✥ n-C4H9Li ✦✫✩✍✪ H3O + ✤ 4 ✥ CH3✬CNa ✦✘✭ NH3 ✦✫✩✚✪ H3O + ✤ 5 ✥ BrCH2COOC2H5 ✦ Zn ✦ ✄ ✦✘✩✚✪ H3O + ✤ 6 ✥ PhP=CHCH2CH3 ✤ 7 ✥ CH2N2 ✤ 8 ✥ C2H5OH ✦✘✧☞✮ HCl ✤ 9 ✥✰✯✍✱ NaHSO3 ✲✭ ✤ 10 ✥ NH2OH ✤ 11 ✥ ✄☞✳ ✤ 12 ✥ 2 ✦ 4-✴☞✵✍✶✄✚✳ ✤ 13 ✥✰✷✍✶✚✸ ✤ 14 ✥ ✄✚✹ ✤ 15 ✥ Tollens ✎✓✑ ✤ 16 ✥ Fehling ✎✓✑ ✤ 17 ✥ KMnO4 ✦ H2SO4 ✤ 18 ✥ CH3CO3H ✤ 19 ✥ LiAlH4 ✦✘✩✍✪ H3O + ✤ 20 ✥ NaBH4 ✤ 21 ✥✰✺ NaOH ✤ 22 ✥ CH2O ✦✘✺ NaOH ✤ 23 ✥ CH3CHO ✦☎✻ NaOH ✤ 24 ✥ ✤ CH3CCO ✥ 2O ✦ CH3COOK ✤ 25 ✥ HNO3 ✦ H2SO4 ✦ 10✼ ✤ 26 ✥ Al[OCH ✤ CH3 ✥ 2]3 ✦ ✤ CH3 ✥ 2CHOH 14.2 ✂✁☎✄✂✽✘✾✡✠☞☛✍✌✏✎✡✑✓✒✏✔✖✕✘✗✚✙✚✛✚✜✣✢ ✤ 1 ✥ HCN ✦ HO - ✤ 2 ✥ C6H5MgBr ✦✫✩✚✪ H3O + ✤ 3 ✥ CH3C✬CNa ✦✫✩✚✪ H3O + ✤ 4 ✥ BrCH2COOC2H5 ✦ Zn ✦✘✩✚✪ H3O + ✤ 5 ✥ Ph3P=CH2 ✤ 6 ✥ HOCH2CH2OH ✦☎✧✚✮ HCl ✤ 7 ✥ HSCH2CH2SH ✦ H+ ✤ 8 ✥✰✯✍✱ NaHSO3 ✲✭ ✤ 9 ✥ H2N ✿NH2 ✤ 10 ✥ C6H5NHNH2 ✤ 11 ✥ Tollens ✎✓✑ ✤ 12 ✥ CF3CO3H ✤ 13 ✥ NaBH4 ✤ 14 ✥ Na ✦ C2H5OH ✤ 15 ✥ Mg-Hg ✦☎❀✡❁✄ ✦✘✩✍✪ H3O + ✤ 16 ✥ Zn-Hg ✦ HCl ✤ 17 ✥ NH2NH2 ✦ KOH ✦☎❂✍❃✡❄ ✤ 18 ✥ Br2 ✦ CH3COOH ✤ 19 ✥ I2 ✦ NaOH ✤ 20 ✥✰✻ OH - ✤ 21 ✥ HNO3 ✦ H2SO4 ✦ 10✼ 14.3 ✂✁ 2-❅✏❆✞✡✠☞☛✍✌✏✎✓✑✓✒❇✔❈✕☎✗✍✙☞✛✍✜❈✢ ✤ 1 ✥ HBr ✤ 2 ✥ H2 ✦ Ni ✤ 3 ✥ LiAlH4 ✦ ✽★✂✦✫✩✚✪ H3O + ✤ 4 ✥ NaBH4 ✦ C2H5OH ✦✫✩✚✪ H2O ✤ 5 ✥ Li ✦✫✭✚✷✖✦✘✩✚✪ H3O + ✤ 6 ✥ Br2 ✦ CCl4 ✤ 7 ✥ HCN ✤ 8 ✥✰✯✚✱ NaHSO3 ✲✭ ✤ 9 ✥ KMnO4 ✦ H2SO4 ✤ 10 ✥✰✻ NaOH ✤ 11 ✥ 1 ✦ 3-❅✍✴✏❆ ✤ 12 ✥ C2H5OH ✦☎✧✍❉ HCl 14.4 ✂✁❋❊✡✄✚●✡✠☞☛✍✌✏✎✡✑✓✒✏✔✖✕✘✗✚✙✚✛✚✜✣✢ ✤ 1 ✥ 2Br2 ✤ 2 ✥ ✤ 3 ✥ CH3MgI ✦✘✧✍★✖✦✘✩✍✪ H3O + ✤ 4 ✥ H2NOH ✤ 5 ✥ HCl ✤ 6 ✥ C6H5NH2 ✤ 7 ✥ CH3OH ✤ 8 ✥ HCN ✤ 9 ✥ Fe ✦ H2O 14.5 ❍✚■✡❏✚❑ ✕✘▲✍▼✚◆✚❖✚P✍◗✍☛✚✌✍❘✍❙✚▲✚❚✚✜❈✢ ✤ 1 ✥ A. ❯ ✞ B. 2-❯ ✾ C. 3-❯ ✾ D. ❱✣❲✾ ✤ 2 ✥ A. 2-❲✾ B. 3-❲✾ C. ❲✘✴✞ D. 5-❲✾✍✞
(3)A.苯甲醛B.苯乙醛 C.苯乙酮 D.苯基丙阴 (4)A.甲醛 B.乙醛 C.丙酮 D.正丙醇 (5)A.对阴 B.2,4二戊丽C.苯甲醇 D.苯酚 (6)A.1-溴丁烷B.1-丁醇 C.2-丁醇 D.叔丁醇 E路 E1 G正丁醚 14.6分离下列各组化合物 (1)」醛、3-戊啊和正】棉 (2)苯酚、环己酮和正丁醚 (3)对甲苯酚、对甲基苯甲醛和对羟基苯甲酸 14.7下列化合物哪些能发生碘仿反应？那些能顺利地与饱和的NaSO溶液加成？哪些能 发生银镜反应？哪些能发生羟醛缩合反应？哪些能发生Cannizarro反应？哪些能与 Fehling试剂作用？ (1)CH3CHCH2CH2CH3 (2)CH3CH2CHO (3)CH3CH2CH2OH OH (4)CH;COCH (⑤)C6 HsCH(OH)CH3 (7)CH3COCH2CH2COCH3 (8) =0 (9)CH3CHO (10) -CH2CHO (11) CH2CH2OH (12) -CHO 14.8写出下列反应的机理。 ④CH,COCH,CH+HOCH,CH,OHH,CH。0 +H20 2)HOCHCH-CH,CHO+CH, +H20 00C2H5 (3)C.H CHO+H2N-NH2-H-CoH;CH=N-NH2 +H2O CH 0 (4) C-N-NH2 H2SO+CH CNHPH CHO+HCHO浓NaOH, CH2OH HCOONa CCH:I2.NaOH -COONa +CHI3
✤ 3 ✥ A. ✄✝✆✟✞ B. ✄❳✽✫✞ C. ✄✂✽✘✾ D. ✄✶✡❨✾ ✤ 4 ✥ A. ✆✰✞ B. ✽✘✞ C. ❨✾ D. ❩✍❨☞❄ ✤ 5 ✥ A. ❨✾ B. 2 ✦ 4-✴✚❯✾ C. ✄❬✆ ❄ D. ✄✚❭ ✤ 6 ✥ A. 1-❪✍❅✏❫ B.1-❅☞❄ C. 2-❅✚❄ D. ❴✡❅☞❄ E. ❅✞ F. ❅✾ G. ❩✚❅☞★ 14.6 ❵✡❛☛✍✌✚❘✡❙☞▲✍❚☞✜❈✢ ✤ 1 ✥❋❅✞❳❜ 3-❯ ✾ ✱✡❩✍❅☞❄ ✤ 2 ✥ ✄✚❭✂❜ ❱❈❲✾ ✱✓❩✚❅✏★ ✤ 3 ✥ ❊❝✆✟✄✚❭✂❜✘❊✝✆✶ ✄❬✆✰✞✱❊✍❞✶ ✄❬✆✰❡ 14.7 ☛✍✌✚▲✍❚☞✜❣❢❇❤❥✐✏❦✍❧✏♠✡♥✡✒✏✔❈♦❋♣✍❤❥✐rq❍☞s✠✯✚✱ ✕ NaHSO3 ✲✭✚t✍✉ ♦✫❢✏❤✓✐ ❦❣❧✡✈✓✇✂✒✚✔❝♦☞❢✚❤✂✐✡❦❥❧✍❞❣✞✓①❣❚❣✒✍✔❝♦✏❢✍❤✂✐✍❦❣❧ Cannizarro ✒✚✔❝♦✏❢✍❤✂✐✡✠ Fehling ✎✓✑✍②■ ♦ (1) CH3CHCH2CH2CH3 OH (2) CH3CH2CHO (3) CH3CH2CH2OH (4) CH3COCH3 (5) C6H5CH(OH)CH3 (6) C6H5COCH3 (7) CH3COCH2CH2COCH3 (8) O (9) CH3CHO (10) CH2CHO (11) CH2CH2OH (12) CHO 14.8 ✂✁☎☛✍✌✡✒✏✔✖✕☎③✍④✖✢ (1) CH3COCH2CH3 + HOCH2CH2OH H + C O CH3 O C2H5 + H2O (2) HOCH2CH2CH2CHO + C2H5OH HCl O OC2H5 + H2O (3) C6H5CHO + H2N NH2 C6H5CH N NH2 H + + H2O (4) C N NH2 CH3 Ph CH3CNHPh O H2SO4 (5) CHO + HCHO CH2OH + HCOONa NaOH (6) CCH3 O I2 ,NaOH COONa + CHI3
)CH,CH,CHO稀OH, CH2CH2CHO 0 (CH.CCH.CH-CH,CI KOH CHC 14.9完成下列反应。 Br ()CH,CH,CH=CH2？→CH,CH,CHCH,KMnO,? NaoH? (2)CH;C=CH HeSO4、?C2H,MgBr?HO,HBr→， H2S04 c-c △ s0g,?日，40 干醚 4cm=0ma公aao9,-, ②H0* OH 会器，0 awdca0aH8ooi2qe,g?gaag,4g, Br 干HC1干醚 (9)2CH;COCH; ②H20 (CCOOH CH Mgg、 OH NOHC CHCHCHCOC (1)CHCOCH-CH-COCHNaOH?HBr? △
(7) CH2CH2CHO CH2CH2CHO OH - CHO (8) CH3CCH2CH2CH2Cl O KOH CH3C O 14.9 ⑤✍✉☛✍✌✡✒✏✔❈✢ (1) CH3CH2CH CH2 ? CH3CH2CHCH3 OH ? KMnO4 H2SO4 ? ? Br2 NaOH Br2 CH3COOH (2) CH3C CH ? HgSO4 H2SO4 C2H5MgBr ? ? H3O + ? HBr (3) CH2 CH2 ? PdCl2 -CuCl2 O2 ? ⑥ OH - ? H2 ,Ni ? SOCl2 M ⑦ g ⑧✖⑨ ? O ? H3O + (4) CH3CH CH2 ? PdCl2-CuCl2 ? ⑩ ❶ CH3C CNa H3O + ? Lindlar❷❳❸✂❹ H2 (5) OH ? Ni H2 ? K2Cr2O7 H2SO4 ? HOCH2CH2OH ⑧ HCl ? Ni H2 (6) CHO + CH3CHO ? ⑥ NaOH ? 2CH3SH ? Ni H2 ? H + ❺ H2O (7) CH3 O ? NH2OH ? PCl5 (8) (CH3)2CHCHO ? Br CH3COOH ? 2CH3OH ⑧ HCl M ⑦ g ⑧✖⑨ ? (CH3 )2CHCHO ? H3O + (9) 2CH3COCH3 ? ⑩ ❶ Mg-Hg H2O ? H + (CH3)3CCOOH + CHBr3 ? (10) OH ? NaOH,C2H5Br ? CH3CH2CH2COCl AlCl3 ? Zn-Hg HCl (11) CH3COCH2CH2COCH3 ? ⑥ NaOH ? HBr
1molBr2.CH;COH.H2O (12) -CH3 2moBr0H→ (13)CH,COCH,CH,CHO Imol HCN (14) △ △ (15) 9,,2, C2HMg,4O,P0、?B,T匹 干醚 H20 ②H202,HO 16CH,CH,CH,0HC0眦壁？3CH9? OH OH (17) 0,0导 H2SO4 干醚 (18) CHICOOH NoH C03 LHC、7KC94?HC? 14.10排列顺序。 (1)亲核加成反应： A.CH3CHO B.CF3CHO C.CH3COCH3 D.CH3COC2Hs (2)与HCN加成反应活性： A.CICH2CHO B.FCH2CHO C.CH3CH2CHO D.CH2=CHCHO (3)与HCN加成反应活性： A.C6HsCHO B.CH3- -CHO C.CH3O- CHO D.O2N CHO
. (12) CH3 O ? ? 1molBr2 ,CH3COH,H2O 2molBr2 ,OH - (13) CH3COCH2CH2CHO ? 1mol HCN ? H3O + (14) O ? C6H5CO3H ? NaOH ? H3O + (15) O O O ? AlCl3 ? Zn-Hg HCl ? H2SO4 ? + C2H5MgI ? H3O + ? P2O5 -H2O ? B2H6 -THF H2O2 ,HO - (16) CH3CH2CH2OH CrO3 ? 3CH2O OH - (17) OH ? K2Cr2O7 H2SO4 ? CH3MgI ? H2O H + (18) ? CrO3 CH3COOH Br2 ? ? NaOH ? HCl ? KClO HCl 4 14.10 ❻ ✌☞q✍❼❈✢ ✤ 1 ✥❾❽✍❿✚t✍✉✒✏✔✖➀ A. CH3CHO B. CF3CHO C. CH3COCH3 D. CH3COC2H5 ✤ 2 ✥ ✠ HCN t✍✉✒✏✔✡➁☞➂✖➀ A. ClCH2CHO B. FCH2CHO C. CH3CH2CHO D. CH2 CHCHO ✤ 3 ✥ ✠ HCN t✍✉✒✏✔✡➁☞➂✖➀ A. C6H5CHO B. CH3 CHO C. CH3O CHO D. O2N CHO
(4)与饱和的NaHSO,溶液反应活性 A.CICH2CHO B.CICH2COCH3 C.PhCHO D.PhCOCH3 (5)酸性： A.CHCHO B.CH;COCH3 C.CH3COCH2COCH3 D.PhCOCH2COCH (6)烯醇式含量： A.CH3COCH2CH3 B.CH3COCH2COCH3 C.CH3COCH2COOC2Hs D.CH3COCHCOCH3 COCH: (7)烯醇式含量 8)稳定性： 14.11以C2~C4的烯烃、苯、甲苯为原料合成下列化合物（无机试剂任选）
✤ 4 ✥ ✠✯✚✱ ✕ NaHSO3 ✲✭ ✒✏✔✡➁✚➂✂➀ A. ClCH2CHO B. ClCH2COCH3 C. PhCHO D. PhCOCH3 ✤ 5 ✥ ❡✍➂ ➀ A. CH3CHO B. CH3COCH3 C. CH3COCH2COCH3 D. PhCOCH2COCH3 ✤ 6 ✥✟❆✓❄✚➃✚➄✚➅ ➀ A. CH3COCH2CH3 B. CH3COCH2COCH3 C. CH3COCH2COOC2H5 D. CH3COCHCOCH3 COCH3 ✤ 7 ✥✟❆✓❄✚➃✚➄✚➅ ➀ O O O O O O O O A. B. C. D. ✤ 8 ✥❾➆✡➇➂✖➀ A. OH B. O C. O D. O 14.11 ➈ C2➉C4 ✕❆✡➊❜✘✄✂❜❳✆✟✄❥➋☞➌✏➍✍❚✉ ☛✍✌✚▲✍❚✚✜ ✤ ❀ ③✚✎✡✑✚➎✚➏ ✥ ✢