第10章烯烃、炔烃、共轭二烯烃和脂环烃 10-1 CH3 HBeCHCl H -C<O· CH3 OH Br Br ®机过单QG码 ~Br w,○CH 69C<0· OH (顺式产物) OH OH -CH3 2)H02,0H OH eoaa9Co CH3 2)NaBH4 0 3)Zn.H.O→CH,CCH6CH0 03 Br y器，○aH,+cH,cBr Br DHs0,了oH CHz 10-2 一丁炔 CI (CH2=CCH:CHs CHs CCH.CHs ，0S8auG4 C.C.CHC (s)CH2=CHCH2CH3 (CH;CH2CH2CH3 ()CH2=CHCH2CH3 (AgG=CCH2CH3 (s)CHCH2C=CCH2CH3 (10)CH:CCH2CH3 (CHCH2COOH CO2 1
1 10 101 Br2 /CCl4 CH3 CH3 Br Br CH3 Br H Br CH3 Br + HBr/CHCl3 CH3 OH Br Br2 /H2O OH CH3 Br + CH3 Br HBr /✂✁☎✄✂✆☎✝✂✞ CH3 OH H2 /Pd CH3 ✟☎✠KMnO4 OH CH3 OH ( ✡☞☛✍✌✏✎✒✑✍✓✔✌✖✕ 1 ) 2 ) H2O2 ,OH CH3 OH 1 )Hg(OAc)2 ,H2O 2 ) NaBH4 CH3 1 ) O3 2 ) Zn,H2O O CH3C(CH2 )6CHO Br2 / ✗✙✘ Br 1 )H2SO4 2 ) H2O CH3 OH CH3 Br + + CH3 OH OH + OH CH3 + CH2Br 10-2 1✚✜✛✣✢ ✤ 1 ✥ CH2=CCH2CH3 Cl (2 ) CH3CCH2CH3 Cl Cl (3) CH=CHCH2CH3 Br Br (4 ) CHBr2CBr2CH2CH3 (5 ) CH2=CHCH2CH3 (6 ) CH3CH2CH2CH3 (7 )CH2=CHCH2CH3 (9 ) AgC CCH2CH3 (10) CH3CCH2CH3 O (8 ) CH3CH2C CCH2CH3 (11 ) CH3CH2COOH + CO2
2-丁炔 (CH3CH=CHCICH3 (2)CH;CH2CCI2CH3 (3)CH;CBr=CBrCH3 OCH,CB,CB,CH6C。 CH3 C-CH CHSCH-CHCHS H H -C<CH0不反应g不 H/ (10 CH3CCH2CH3 ()2 CHCOOH 10-3 () (3)CF3CH2CH2Br CH3 (4)BrCHCH3 (CH3OCHCH2CH3 (6 HOCCH2CH(CH2)COOH G)HECH.CH,OHC 00 COOH ①c C6Hs CoHs (10)CH;CH2C=CAg CH;CH2C=CH 0 (n)CH3CH2CH2C=CNa CH3CH2CH2C=CCH2CH2CHs CH3(CH2)2C(CH2)CH3 OH OH (12)[(CH3)2CHCH]2BCH=CHCH2CH3 .CH3CH2CH=CH2,CH3CH2CHCH2
2 Cl 2 1 CH3CH=CH CH3 (2) CH3CH2CCl2CH3 (3) CH3CBr=CBrCH3 (4) CH3CBr2CBr2CH3 (5 ) C=C CH3 CH3 H H (6) CH3CH2CH2CH3 C=C CH3 H (7 ) CH3 H (8 ) 9 O 10 CH3CCH2CH3 (11 ) 2 CH3COOH 10-3 (1 ) CH3 Br Cl CH3 Br (2) (3 ) CF3CH2CH2Br (4 ) BrCHCH3 Cl (5 ) CH3OCHCH2CH3 Br CH3 O (6) HOCCH2CH(CH2)2COOH O O (7 ) HCCH2CH + OHC O (8 ) O + C6H5COOH (9) O C6H5 + O C6H5 + COOH Cl (10 ) CH3CH2C CAg CH3CH2C CH (11 ) CH3CH2CH2C CNa CH3CH2CH2C CCH2CH2CH3 O CH3(CH2)2C(CH2)3CH3 (12) [(CH3 )2CHCH]2BCH=CHCH2CH3 CH3 ,CH3CH2CH=CH2 , , OH O CH3CH2CHCH2 H
(13)CH3CHCH2C=CH(1 molHCI) 亲电加成双键较三键活泼 (14)CH2=CHCH2CH=CH2 (16)CH2=CHCH2C=CH2 OCH,CH,亲核加成三键较双键活泼 (1)CH3CH2CH2OSO3H,CH3CH2CH2Br,BrCH2CH2CH2Br,CH3CH2CH3 (18)CH3CHCH2CH3 CH2CH2CH2CH3(二级自由基稳定些) Br Br CH3 (19)CH3CH2CCH3 10-4 (4)>(2)>(1)>(3)(比较碳正离子形成难易) 10-5 (5)>(1)>(4)>(3)>(2 10-6 (1)A>B(2)AC>B(4)A>B(⑤)A<B(稳定性大燃烧热小) 10-7 环丙烷 褪色 ()丙烷 Br2JCCY× KMnQ4 丙烯 褪色 褪色 × 褪色 ) Br2/CCl4 NH HO □ 褪色 褪色 CH≡C(CH2)2CH3 白 CH3(CH2)4CH3 Cu2Cl2 ()CH3(CH2)C=CH CH:(CH2)CH-=CH2 NHHO砖红 Br2/CCl4 褪色
3 CH3CHCH2C CH Cl ( (13 ) 1 molHCl) (14 ) CH2=CHCH2CH=CH2 (16 ) CH2=CHCH2C=CH2 OCH2CH3 (17 ) CH3CH2CH2OSO3H , CH3CH2CH2Br , BrCH2CH2CH2Br , CH3CH2CH3 (18 ) CH3CHCH2CH3 Br CH2CH2CH2CH3 Br ( 19 CH3 CH3CH2CCH3 Cl (20 ) CH3 Br 10 4 10-5 ! "# "$# "%# "# "$# &'()*+,- . (1 ) Br2 /CCl4 × KMnO4 × ✦ 2 ✧ CH C(CH2)2CH3 AgNO3 NH3H2O × × × ★ Br2/ ✩✫✪ × × ✩✫✪ ✩✬✪ CC KMnO4 l4 (3 ) CH3(CH2)4CH3 CH3 (CH2 )3C CH CH3 (CH2 )3CH=CH2 Cu2Cl2 NH3H2O × × × Br2 / CCl4
2-戊炔 0 AgNO3 (4)-戊块 NH;H2O,白O ,3一戊二烯 ×△固体 )0固体 0 Q-CH△×(S反式不反应) 10-8 (1) CH3 CN 〔 ) ()COOCH -COOCH CH3 (s5)S反式的必须转化成 (6)不能 S顺式的才能反应得 CoHs (CH (7) (8 (CH3)3 10-9 HD/Pd or Ni不可以 D/LindlarCa可以 CH,C≡CCH3 )BD. JCHC0oi不可以 )B2D6 CH CH3 CH;COOD DC=C D
4 4 2 1 13 AgNO3 NH3H2O × × × O O O (5) CH2 O O O × S 10 8 ✭ 1 ✮ CH3 COOCH3 COOCH3 CH3 (2) CN CN CH3 CH3 (3) COOCH3 (4 ) O O (5 ) O O O (6 S ) - S - 7 C6H5 o C6H5 (8 ) C C CH33C CH33C O O O 10-9 CH3C CCH3 HD/Pd or Ni D2 /LindlarCat. 1 ✯ B2D6 2 ) CH3COOH 1 ) B2D6 2 ) CH3COOD CH3 D C CH3 C D
10-10 (D(CH)CHCH2·H*→(CH..CCHCHs (CH3).CCHCH- 0H2 CH.CHCH,CHCCH (CHCHCH CH3 CHs CH-CCH CH (2)CH;C=CH2-H>- CH CH3 CH3 CH3CH3 CH →CH3 C CH=-CCH3(住) CH3CH3 CH3 →CH3CCH2C=CH2 CHaCHa 前者比后者稳定。 0X+r→ 尖义进，大产物 (4)孤立的双键比三键更易发生亲电加成。 (⑤)共轭的双键、三键与HC1亲电加成时，三键加HC生成的产物为一个共轭体 系，更加稳定。 10-11 (①)乙炔中，碳原子为SP杂化，电负性大，失去H后的碳负离子，炔基负离 子最稳定，所以酸性强。 乙烯中，碳原子为SP杂化，电负性中，酸性中。 乙烯中，碳原子为SP杂化，电负性小，酸性弱。 (②)炔烃亲电加成的活性中间体是乙烯型正离子，相对不如烯烃亲电加成的活 性中间体烷基正离子稳定，因此炔烃加卤素比烯烃困难，速率也慢。 (3)因为C上H失去后形成下列相应的自由基或C负离子因共振而稳定
5 10-10 (1 ) (CH3)3CH=CH2 + H + (CH3 )3CCHCH3 (CH3 )3CCHCH3 H2O ✰☞✱✳✲✵✴ (CH3 )3CHCH3 OH2 H + CH3C CHCH3 CH3 CH3 H2O (CH3 )2CCH(CH3 )2 OH - (CH3 )3CHCH3 + OH 2 + H + - (CH3 )2CCH(CH3 )2 OH (2 ) CH3C=CH2 CH3 H+ CH3CCH3 CH3 CH3C=CH2 CH3 CH3 CH3 CH3 C CH2 C CH3 CH3 CH3 C CH=C CH3 CH3 CH3 CH3 CH3 C CH2C=CH2 CH3 CH3 CH3 ( -H + /010&'2 (3 ) + H + ✶✂✷ ✸ (4) 3456782 (5) 9:5; HCl 85?@ABC9:D E>6&'2 10 11 FGH>IA JKLM>N()>OPQ15N>GRN S&'>TUV(W2 FXH>IA JK ✹ LM>N(H>V(H2 FXH>IA JK ✺ LM>N(->V(Y2 GZ5 (H[D\FX]>^_`aXZ5 (H[DbR&'>cdGZefXZg>hijk2 cA %lQOP1mn^o5p qRr%Nc9st&'2
[CH2=CHCHCH-CH2 CH2CH=CHCH=CH-CH2=CHCH=CHCH2] [CH2-CHCHCH=CH2-CH-CH-CHCH-CH2CH2-CHCH-CHCH] 而H2CH-CH2.Cl2-CC (4) +Gc 烯丙基正离子 十能量较前者高 10-12 Br Br OH OH CHCHCH (2)CHCHCH CHaCHCH CHaCH-CHs H,C0h且G0H9分qHe0Hov聚合C0 BrBr Cl (1)HBr (2)HBr/ROOR H2O/H+or 1)Hg(OAc)2,H2O NaBH4 (4)a.BH/TH;b.H20/OHrs)aCl/高温；bC2CC4(6a.Cl/高温b.B5CC ()CH,CH=CH,+hO,+NH,含铸的磷钼酸秘高通CH,=-CHCN+ H2O nCH,-CHCN聚合，产物 10-13 (1)较为合理，该反应的两步易于控制和进行。 (2) HCL→C-CC,/NiCHCICI(卤原子同时被还原) (3)产物为混合物 CH;CH2H2Cl和CHCHCH
6 ✻✻ ✻✻ ✻✻ ✻✻ ✻✻ ✻✻ ✻✻ ✻✻ ✼ ✽ H + 10 12 ✾ ✿ ✿ ❀ ❀❀✿ ✿ ✿ ✿ ❁ ❀ ❀✿ ❂ ❃ ❄ ❅ ❃ ❃ ❆ ❃ ❃ (1) HBr (2 ) HBr/ROOR (3 ) H2O/H + or 1 ) Hg(OAc)2,H2O 2 ) NaBH4 (4) B (5) (6 ) b.Br 2H6 /THF ; b. H2O2 /OH - Cl2/❇❉❈ ; b Cl2 /CCl4 a. Cl2/❇❉❈, 2/CCl4 a. a ; . (7) CH3CH=CH2 + 3/2 O2 + NH3 ❊●❋■❍❑❏●▲●▼✙◆/❖◗P CH2=CHCN + H2O nCH2=CHCN ❘✬❙ ❚✫❯ 10 13 1 Auv,wxo5yz{|}~2 2 ❱❲ ❱ ❲ ❱❲ (3) ?@Au@ CH3CH2H2Cl CH3CHCH3 Cl
10-14 0a=oa6akaa画→aa R (2)CH=CCHa/CHaCH2CHO (分CEC0H,a2、CH,CaCNa rC4biCl,0 CH.CH.CH.CH.CH c=ca6n&ataB选rLOtb (4)CHC=CHiCHC-C CHCH-CHr/ CHCH.CH 2NCCCHC=(CH2)C=CCH Br Br 10-15 CHC CHUCTAr →CH三CCH2CHs CH=CH NaNz CHl=CNa yac,含HOCHC,a,c )由上题CH-CHCH,CH,/CHCH.CHCH OH )由()得CH,C,C=CHaC,CH,C三COa CH CH2Br广 →CHCH,C=CCH,CH /Lindlarf催化型顺式产物 分a=脸a品ra的。 0 OH 日由(g程c风aha,CLCF版式产物
7 10 14 ❳ ❨ ❩❬❭❪ ❫ ❴❛❵❝❜❡❞❝❢ ❣❨ ❩❴❤ ❨ ❨ ✐ ❥ ❦❛❧♥♠♣♦rqts✈✉✇❧②① ♠♣❧✒①❡❧②③❡①✇♠ ❥ ✐ - ④ ④ ⑤✈⑥t⑤❡⑦♣⑧ ④ ⑨❛⑩❡❶✇⑦♣⑧②❶✇⑦♣⑧②❶✇⑦✈❷ ❸ ④ ❸❸❸❸④ ④ ❸ ④ ❸❸④ H2 Lindlar Cat HBr/ ❹ ❹ ❺ ❻❼ ❽❾❿➀ ❺❺ ➁❛❻❛❼❝❾❝➂❛➃❡➃❝➂ ❺❺❺ ➄✈➅✇➆ ❹ ❹ ❺❹ ❹ ➁❽❾❡➇➉➈➋➊✈➌✈➍➎➅❝❼ 2 cat. 10-15 ➏ ➐ ➐ ➑ ➐ ➐➑ ➒✈➓✇➔✇→♣➣❝↔❡↕❝➙ ➛➝➜ ➐➐➑ →❛➞♥➟♣➠ ➔❝➡♣➢ ➞✒↕ ➟♣➞②↕❡➞➔ ↕✇➟❛➤ ➐ HOCH2CH2CH2CH3 H2 LindlarCat. NaNH2 HBr ➥ ➥ ➥➦ ➧➨➩ ➫➧ ➭ ➦ ➥➦ ➯ ➲ ➯ ➳ ➵➸ ➺➵➻➼ ➯ ➳ ➯ ➳ ➯ ➳ ➳ ➯ ➻♣➽➺❡➾➉➚➶➪✈➹✈➘ ➸❝➴➷☎➬➝➮ ➱✳✃❒❐ ✃❒❐ ❮✇❰❝ÏÐ❮❒Ñ➶ÏÓÒ➎Ô✇Õ✇ÖÓ❮✈Ñ ✃❒❐ ✃×✃❒❐×Ø×✃❒❐➱ Õ❡Ù ÏÐÚÒtÕÏÓÛ Õ❝Ï♥Ü ÛÖ Ý ✃❒❐ßÞà✃×✃❒❐áØ➉✃❒❐➱ ÛÏÓÒãâ❛Ù Ý Ý ✃❒❐áÞ➶✃➉✃➉❐✫✃❒❐➱ ä②å➎æ ç è é è é ê✈ëÓì é é í➝î✂ï➉ð❛ñ ì❡ò H +
10-16 (CHCH-CH C/CCH,CH-CH 飞·a8c=4a=om0 g由0将00生 NNac三出了 CH2C=CH M些ORC-O,消 0《·风，40《·m学 COOH 日《·06→a@,产物)飞·0→产物 10-17 CHa CH3-C=C-CH-CH3 10-18 CH A☐ CHz 10-19 (CH3)2C=CHCH2CH2CCH=CH2 CH2 10-20 CH;C=CCHCH3CH;CH2CH2C=CCHs CH3 各步反应略。 10-21 A.CHECCH,CHCH B.CHC=CCH:CH C
8 1016 ó✇ôãõ CH3CH=CH2 Cl2 öø÷ ClCH2CH=CH2 + CH2Cl NaC CH CH2Cl CH2C CH H2O /HgSO4 ù✙ú û 2 ü✫ý û 1 ü☎þ NaC CH CH2Cl H2 /Ni CH2Cl CH2C CH H2 /Lindlar CH2C H CH2 B2H6/H2O2/H2O ÿ✁ ✂☎✄✝✆ ✞ ✟✡✠ ☛✌☞✝✍✏✎✒✑ ✓✕✔✕✖ ✞ ✟✡✗✙✘ ✚ ✛✢✜ ✎✒✑ ✣✥✤✧✦ ★ ✩✫✪✡✪✫✩✡✬✙✭ ✮✰✯✧✮✲✱✴✳✶✵✸✷✹✮ ✺✼✻ ✽✿✾✡❀ ★ ✩✫✪✫✪✡✬ ✺✼✻ 10-17 ❁ ❂ ❁ ❁ ❁ 10-18 A . CH3 CH3 B. CH3 CH3 C. O O CH3CCH2CH2CCH3 D. OH OH CH3 CH3 10-19 (CH3 )2C=CHCH2CH2CCH=CH2 CH2 10-20 CH3C CCHCH3 CH3 CH3CH2CH2C CCH3 10-21 A. CH CCH2CH2CH3 B. CH3C CCH2CH3 C.
10-22 H CHC=CCHS CH CH3 CHs D.Hc-c 一H CH3 C=C CH CH CH 10-23 A.CC-C B CHCI-CCGI CC 10-24 AAB:△个
9 10-22 A. CH3 C=C CHC CCH3 H H CH3 B. CH3CH2CH2CHCH2CH2CH3 CH3 C. H CH3 C=C H CH3 H CH3 C=C CH H D. H CH3 C=C H H CH3 CH3 C=C CH H 10-23 A. CH3CH=CC CH C2H5 B. CH3CH=CCH=CH2 C2H5 C. O CH3 C C O O C2H5 10-24 A: B: