习题 13.1写出正丙醇与下列试剂反应的主要产物。 (1)Na (2)Mg (3)NaH (4)CHMgl (5)CHsC=CNa (6)冷浓HS04 (7)CH -s02a (8)(CH0)SO2 (9)CHCOOH,H' (10)浓HC1+无水ZnCl2 (11)NaBr,H:SO (12)P+L (13)PCl (14)PBrs (15)s0C, (16)浓HS0,加热(温度低)(17)浓H,S0,加热(温度高)(18)K,C,0,稀硫酸 (19)过量KMnO. (20)C02·册啶,CH,C1 (21)Cu,△ (22)(1)的产物+CH,Br (23)(16)产物+过量H用 (24)(8)产物+HI 13.2写出对甲苯酚与下列物质反应的主要产物。 (1)NaOH,H2O (2)CHCOCI (3)CH3C0C1,A1C13,165C (④)(CH3CO)20 (5)CH3 CH2CH2OH,浓H2SO4 (6)CH;CH2CHzBr.NaOH (7)(CH3O)2SO2.NaOH (⑧)CH2N2 ON-〉--(,0CH=cHcH,Br (11)(10)的产物,高温 (12)FeC3,H20 (13)Br2,H20 (14)浓H2S04,△ (I5)稀HNO3 (1O(CH32C=CH2,浓H2S0 (17)CHC,Na0H,H,0,然后H181的产物,C02.150℃(19)H,Ni 13.3用简单的化学方法鉴别下列各组化合物。 (1)A.1-戊醇B.2-戊醇C.戊醇D.2-甲基-2丁醇 (2)A.甲醇B.乙醇C.乙二醇D.2-氯乙醇 (3)A.CH=CCH2CH2OH B.CH2=CHCH2CH2OH C.CH;CH2CH2CH2OH (4)A.苯酚B.环己醇C.环己烷D.甲苯 (⑤)A. —CH2CH2OHB.CH3CH OH C.C2Hs -OH D. -CH2OCH3 (⑥)A.正己烷B.1-溴丁烷C.正丁醇D.正丁醚E.苯酚 134分离下列各组化合物。 (1)环己烷、环己牌和苯酚 (2)苯甲醇、邻硝基苯酚和对硝基苯酚 (3)氧苯、苯甲醚和邻甲苯酚
13.1 ✂✁☎✄✝✆✟✞✡✠✟☛✝☞✍✌✡✎✑✏✍✒✔✓☎✕✗✖✗✘✗✙✛✚ ✜ 1 ✢ Na ✜ 2 ✢ Mg ✜ 3 ✢ NaH ✜ 4 ✢ CH3MgI ✜ 5 ✢ CH3C✣CNa ✜ 6 ✢✥✤✝✦ H2SO4 ✜ 7 ✢ ✜ 8 ✢ ✜ CH3O ✢ 2SO2 ✜ 9 ✢ CH3COOH ✧ H + ✜ 10 ✢✥✦ HCl + ★✡✩ ZnCl2 ✜ 11 ✢ NaBr ✧ H2SO4 ✜ 12 ✢ P + I2 ✜ 13 ✢ PCl5 ✜ 14 ✢ PBr3 ✜ 15 ✢ SOCl2 ✜ 16 ✢✥✦ H2SO4 ✧☎✪✝✫ ✜✭✬✡✮✝✯ ✢ ✜ 17 ✢✥✦ H2SO4 ✧☎✪✝✫ ✜✭✬✡✮✑✰ ✢ ✜ 18 ✢ K2Cr2O7 ✧☎✱✟✲✑✳ ✜ 19 ✢✵✴✟✶ KMnO4 ✜ 20 ✢ CrO3 ✷✹✸✝✺ ✧ CH2Cl2 ✜ 21 ✢ Cu ✧ ✜ 22 ✢ ✜ 1 ✢ ✓✻✘✗✙ + C2H5Br ✜ 23 ✢ ✜ 16 ✢ ✘✝✙ + ✴✗✶ HI ✜ 24 ✢ ✜ 8 ✢ ✘✝✙+HI 13.2 ✂✁✽✼✿✾❁❀✗❂✡✠✗☛✗☞✟✙✝❃❄✏❅✒❆✓✻✕✝✖✟✘✝✙❆✚ (1) NaOH,H2O (2) CH3COCl (3) CH3COCl,AlCl3,165❇ (4) (CH3CO)2O (5) CH3CH2CH2OH, ❈ H2SO4 (6) CH3CH2CH2Br,NaOH (7) (CH3O)2SO2,NaOH (8) CH2N2 (9) O2N Cl,NaOH (10) CH2 CHCH2Br (11)(10)❉✝❊❆❋❍●❏■❏❑ (12) FeCl3,H2O (13) Br2,H2O (14) ❈H2SO4 , (15) ▲ HNO3 (16) (CH3)2C CH2, (17) ❈ H2SO4 CHCl3,NaOH,H2O, ▼❆◆H + (18)(1)❉✝❊❆❋❍● CO2,150❇ (19) H2,Ni 13.3 ❖✑P✟◗ ✓✻❘✡❙✟❚✝❯✗❱✗❲✝☛✝☞✗❳✡❨✟❘✝❩✟✙✛✚ (1) A. 1- B. 2- C. D. 2--2- (2) A. B. C. D. 2- (3) A. CH CCH2CH2OH B. CH2 CHCH2CH2OH C. CH3CH2CH2CH2OH (4) A. B. C. D. (5) CH2CH2OH CH3CH OH C2H5 OH CH2OCH3 A. B. C. D. (6) A. B. 1- C. D. E. 13.4 ❬✡❭☛✝☞✗❳✡❨✟❘✝❩✟✙❆✚ ✜ 1 ✢✥❪✛❫✥❴❆❵✻❪✛❫✞✗❛✝❀✟❂ ✜ 2 ✢ ❀❜✾❁✞ ❵✻❝✝❞✗❡❀✟❂✗❛✝✼❞✗❡❀✟❂ ✜ 3 ✢✽❢❀ ❵ ❀❣✾❁❤✗❛❝ ✾❁❀✗❂ CH3 SO2Cl
135写出下列反应的机理。 (1)CHCH-CH-CHOH+HCI ZnC-CH CH-CH.CH-CI )(CH)COH+HCI ZnC(CH)C-CI (3)(CH3)3CCHCH3 +HC →(CH3)2CCH(CH32 OH ④〈◇-CCH2+HBr →CH OH CH3 Br ⑤(CHC-C(CH Ag(CH,CCCH OH 0 OHOH (6) -C-CH3→CH CH3 (7)(CH3)3COCH3+HBr →(CH3)CBr+CH,OH (8)(CH3)C-CH2+CHOHH(CH)C-CH2OH 0 OCH3 (CHa)C-CH2+CHOH CHONa-(CHC-CH2OCHs o (10) GCH-CH.CI CHO →CH2一CH-CHz-OCH 13.6完成下列反应。 (CH3)3CCHCH3 HBr? OH CH2CH2OH (2) OH CH3 S0C2→? (3) C--H C2HS OH 1s0C2→2 吡 KMnO4.H2O-2 -CH2OH- CHO
13.5 ✂✁✻☛✝☞✡✏✍✒✔✓✻✐✝❥✔✚ . (1) CH3CH2CH2CH2OH + HCl CH3CH2CH2CH2Cl ZnCl2 (2) (CH3 )3COH + HCl (CH3 )3C Cl ZnCl2 (3) (CH3 )3CCHCH3 + HCl OH (CH3 )2CCH(CH3 )2 Cl (4) C(CH3 )2 + HBr OH CH3 CH3 Br (5) (CH3)2C OH C(CH3)2 (CH3 )3CCCH3 O Ag (6) OH C CH3 OH CH3 CH3 C O H + + CH3 CH3 O (7) (CH3 )3COCH3 + HBr (CH3 )3CBr + CH3OH (9) (CH3 )2C CH2 + CH3OH O (CH3 )2C OCH3 (8) (CH3 )2C CH2 + CH3OH CH2OH O (CH3 )2C OH CH2OCH3 CH3ONa (10) CH2 CH CH2Cl O CH2 CH CH2 O OCH3 CH3O 14 - 14 13.6 ❦✝❧☛✝☞✡✏✍✒❆✚ (1) (CH3 )3CCHCH3 OH ? HBr (2) CH2CH2OH OH ? ? HBr NaOH (3) CH2OH ? ? KMnO4 ,H2O CHO C CH3 H C2H5 OH SOCl2 SOCl2 (4)
(5) CHs CFCO,HCHON C-CH CH (6)CH;CH=CHCH2OH- ?→CH,CH=CHCHO 〉-oH→ OH 9cH=c0→0, mcwa-aco4,滑 wa山瓷 ②H,02,H0 (12)CH)CCH= (3)(CH)CHCHN(CH.CHOCH CH, OH CH (14) ◇aa=am,会2, 周陈N0u4,0出,QHcH=cC,△0, ②F as◇’一◇器na 6CH,CH,CHCH,+HImo△,2+? OCH3 (17) (18 > HBr NaOH.CH:CH2OH HOBr?Ca(OH)2? (19) OHHSO PCOH HOCH-CH2OH.H △ (20)C1 ?C1 NO.NaOHH2OCHO)SO2 ② NaOH No
(5) C C C2H5 CH3 CH3 H ? ? CF3CO3H CH3ONa CH3OH (6) CH3CH CHCH2OH CH3CH CHCHO ? (7) OH ? O (8) OH OH ? Ag2O (9) CH2 CH2 ? ? Ag,O2 C2HOH H + (10) C6H5CH CH2 ? C6H5CO3H ? CH3NH2 CH3OH (11) CH3 ? ♠ ♥ B2H6-THF H2O2 ,HO - ? CrO3 H2SO4 (12) (CH3)3CCH CH2 ? ? H + ,H2O Al2O3 (13) (CH3)2CHCH3 OH ? Na (CH3 )2CHOCH2CH3 CH3 ? (14) + CH3CH CH2 ? AlCl3 ? ♦ H2SO4 ? ♠ ♥ ♣✟q NaOH, H + ? NaOH ? ? ? CH3CH CHCH2Br Br2 CCl4 (15) ? SO3H r NaOH s❆t ? NaOH HOCH2CH2Cl (16) CH3CH2CHCH3 + OCH3 HI(1mol) ? + ? (17) O ? HCl ? KCN (18) ? ? HBr NaOH,CH3CH2OH ? HOBr r Ca(OH)2 (19) OH ? H2,Pt ? H2SO4 ? PhCO3H ? HOCH2CH2OH,H + (20) Cl ? Cl NO2 NO2 ? ♠ NaOH,H2O ♥ H + ? (CH3O)2SO2 NaOH
13.7排列顺序. (1)与金属钠反应的速率:A.甲醇B.乙醇C.叔丁醇D.仲丁醇 (2)与Lucas试剂反应的速率:A.正丁醇B.叔丁醇C.仲丁广醇 (3)与HBr水溶液反应的活性: A. -CH2OH B.CH3O- -CH2OH C.CH- -CH2OH D.O2N- CH2OH (4)脱水反应活性: A.CH2=CHCHCH B.CH;CH2CHCHs OH OH C.Cl3CCH2CH2CH2OH D. (5)酸催化脱水反应活性 CHCH OH C.CHgO- -CHCH3 D.O2N CHCH OH OH (6)酸性: (7)酸性: A.02N OH B.OH C.n.CO,D.OH (8)碱性: A.(CH3)3CO B.CH3O C.CH2=CH D.CH;CH2 (9)亲核性: A.(CH3)3CO B.HO C.CH;CH2CH2CH2O D.PhO
13.7 ✉ ☞✟✈✝✇❆✚ ✜ 1 ✢ ✠✗①✗②✗③✑✏✍✒✔✓✽④✡⑤✂⑥ A. ✾✥✞ B. ⑦✞ C. ⑧✝⑨✞ D. ⑩✡⑨✞ ✜ 2 ✢ ✠ Lucas ✌✑✎✡✏✍✒❆✓✵④✑⑤✔⑥ A. ✄ ⑨✞ B. ⑧✝⑨✞ C. ⑩✑⑨✞ ✜ 3 ✢ ✠ HBr ✩✝❶✗❷✏❅✒✔✓❹❸✗❺✂⑥ A. B. C. D. CH2OH CH3O CH2OH Cl CH2OH O2N CH2OH ✜ 4 ✢✵❻✝✩✏✍✒✡❸✗❺✂⑥ CH2 CHCHCH3 OH CH3CH2CHCH3 OH Cl3CCH2CH2CH2OH OH A. B. C. D. ✜ 5 ✢✵✳✗❼❘ ❻✗✩✏❅✒✑❸✟❺✂⑥ CHCH3 OH CHCH3 OH CH3 CHCH3 OH CHCH3 O2N OH CH3O A. C. D. B. ✜ 6 ✢✵✳❺✂⑥ OH NO2 OH O2N A. B. C. CH3 OH D. OH ✜ 7 ✢✵✳❺✂⑥ A.O2N OH B. OH C. H2CO3 D. OH ✜ 8 ✢✥❽❺✂⑥ (CH3 )3CO - CH3O - CH2 CH - CH3CH2 - A. B. C. D. ✜ 9 ✢✵❾✝❿❺✔⑥ (CH3 )3CO - HO - CH3CH2CH2CH2O - PhO - A. B. C. D
(10)亲核性: 0 B.CH3O- C.O2N- o D.CH 13.8以C2~C4的烯烃、苯、甲苯、萘为原料,合成下列化合物(无机试剂任选) (1)CH3CH2CH2CHO (2)CH;COCH2CH (3)(CH3)2CHCOOH (4 =0 (5)C- -OCH2CH3 (6)CH3O- Br (7)(CH3CH2CH2CH2)2O (⑧)二甘醇二乙醚 OCH2CH=CH2 (10)Br -CH20 NO (11) (12)15-冠-5 OHH 13.9化合物A(CH20)可以发生碘仿反应,A与浓HSO共热则声称化合物B(CHo), B的臭氧解产物为C和D,C为醛,D为酮。试推测化合物A、B、C、D的构造式, 并写出相关反应式。 13.10中性化合物A(CH6O2),与Na反应放出H,与PBr反应生成化合物B(CHB) A用KMnO,氧化生成C(CH1O2).A与浓HSO一起共热生成D(CH2),D可以 使Br-CCL溶液褪色。D在低温下与硫酸作用再水解,生成A的同分异构体E,E与浓 H,SO4共热也生成D,但E不能被KMnO,氧化.D臭氧解产物为2,5-己二酮和乙二醛. 试写出A一E的构造式及相关反应式。 13.11化合物A(CH,O),不与Na发生反应,但能与浓Ⅲ溶液反应生成B和C.B能溶 于NaOH溶液,并且B与FeCL3水溶液作用生成有颜色的物质。C能与AgNO,溶液作 用,生成Ag沉淀。试写出A、B、C的构造式及相关反应式。 13.12化合物A(C,HO),不溶于水,与B-CCL溶液、金属Na都不反应,在稀盐酸溶液 中反应的化合物B(CHO2),B与等物质量的高碘酸反应得甲醛和化合物C(CH,O), C可发生碘仿反应。试写出A、B、C的构造式及相关反应式。 13.13化合物A(CH0),不与金属钠反应,其核磁共振氢谱数据为:64.1(1H),七重
✜ 10 ✢✵❾✝❿❺✔⑥ O - O - CH3O O - O CH3 - O2N A. B. C. D. 13.8 ➀ C2➁C4 ✓✵➂✡➃❵ ❀ ❵ ✾✥❀❵❹➄✑➅✗➆❅➇✔✧ ❩ ❧ ☛✝☞✝❘✗❩✗✙ ✜ ★ ✐✗✌✡✎✗➈✗➉ ✢ ✚ (1) CH3CH2CH2CHO (2) CH3COCH2CH3 (3) (CH3 )2CHCOOH (4) O (5) Cl C OCH2CH3 l (6) CH3O CH2CH3 Br (7) (CH3CH2CH2CH2 )2O (8) ➊❆➋✿➌❜➊➎➍❄➏ (9) OCH2CH CH2 (10) Br CH2O NO2 NO2 (11) OH H H OH (12) 15-➐-5 13.9 ❘✝❩✟✙ A ✜ C5H12O ✢➒➑✛➀✻➓✝➔✍→✝➣✏❅✒ ✧ A ✠✦ H2SO4 ↔✫✡↕✝➙✍➛❘✝❩✟✙ B ✜ C5H10 ✢➜✧ B ✓✽➝✝➞✗➟✝✘✗✙➅ C ❛ D ✧ C ➅✍➠❏✧ D ➅❅➡ ✚✥✌✡➢✝➤✝❘✝❩✟✙ A ❵ B ❵ C ❵ D ✓✻➥✗➦✡➧ ✧ ➨✂✁✻➩✡➫✝✏✍✒✝➧❆✚ 13.10 ➭ ❺✗❘✝❩✟✙ A ✜ C8H16O2 ✢➜✧ ✠ Na ✏❅✒✝➯✔✁ H2 ✧ ✠ PBr3 ✏❅✒➔✍❧❘✗❩✗✙ B ✜ C8H14Br2 ✢➜✧ A ❖ KMnO4 ➞✡❘➔✟❧ C ✜ C8H12O2 ✢ ✚ A ✠✦ H2SO4 ➲✟➳✡↔✫✑➔✍❧ D ✜ C8H12 ✢✭✧ D ➑❆➀ ➵ Br2-CCl4 ❶✗❷✗➸✗➺ ✚ D ➻ ✯✗✬☛✡✠✲✑✳✗➼✗❖✝➽✝✩➟ ✧➾➔✍❧ A ✓✝➚❬✗➪➥✗➶ E ✧ E ✠✦ H2SO4 ↔✫✝➹✡➔✍❧ D ✧➴➘ E ➷✑➬➱➮ KMnO4 ➞✝❘✔✚ D ➝✗➞✝➟✝✘✗✙➅ 2 ✧ 5-❫☎✃✗➡❛ ⑦➱✃✗➠ ✚ ✌❄❏✁✿❐➁❅❒ ✓✻➥✗➦✝➧✗❮✝➩✡➫✡✏❅✒✡➧✔✚ 13.11 ❘✗❩✗✙ A ✜ C7H8O ✢❰✧➱➷✠ Na ➓✝➔✏❅✒ ✧✻➘❄➬✠✦ HI ❶✝❷✏❅✒➔✍❧ B ❛ C ✚ B ➬❅❶ Ï NaOH ❶✗❷✂✧ ➨✗Ð B ✠ FeCl3 ✩✝❶✝❷✝➼✟❖❄➔✍❧✗Ñ✗Ò✝➺ ✓✻✙✗❃✛✚ C ➬ ✠ AgNO3 ❶✟❷✗➼ ❖✔✧❅➔✍❧ AgI Ó✡Ô ✚✵✌✑❏✁ A ❵ B ❵ C ✓✻➥✗➦✝➧✗❮✝➩✝➫✡✏✍✒✝➧❆✚ 13.12 ❘✝❩✟✙ A ✜ C5H10O ✢❰✧➒➷✗❶Ï✩❏✧ ✠ Br2-CCl4 ❶✝❷✂❵ ①✝② Na Õ✝➷✏✍✒ ✧Ö➻✝✱✡×✗✳✝❶✗❷ ➭ ✏✍✒✔✓☎❘✗❩✟✙ B ✜ C5H12O2 ✢➜✧ B ✠✗Ø✟✙✝❃✶ ✓✰→✝✳✏✍✒✝Ù❜✾➠ ❛✝❘✝❩✟✙ C ✜ C4H8O ✢➜✧ C ➑✝➓✡➔❅→✡➣✏✍✒❆✚✵✌✑❏✁ A ❵ B ❵ C ✓✻➥✗➦✝➧✗❮✝➩✝➫✡✏✍✒✝➧❆✚ 13.13 ❘✝❩✝✙ A ✜ C4H10 ✢➜✧➱➷✠✗①✡②✗③❄✏✍✒ ✧☎Ú✡❿✗Û↔✝Ü✝Ý✡Þ✡ß✗à➅ ⑥➎á 4.1 ✜ 1H ✢➜✧❹â✡ã