王积涛著《有机化学》第二版课后习题答案.pdf

2011-7-24?1 ? ? 2011-7-24?2 ? ?CHCl3 1? ? ? ? ?H2S S H H H Cl Cl Cl C N H CH3 H ? ? ?CH3NH2 ? 2011-7-24?3 ? ?BH3B H H H ? ? ?C2H6 ?(BH3)?. BH3?B?sp2? ? ? ?. C H H Cl Cl H H H H H H ?: ?C C? C H?. ? ? ?CH2Cl2 ? 2011-7-24?4 2. ?,? ?,?p?. ? ? H HH H ?,?, ?,?. 3. ?CH3CH2CH3?,? ?. H HHH H HH H ? 2011-7-24?5 4?2?1?1? ?H2CO? ? H H C O 5?CH3CH = CH2?sp3? ?sp2? CH3 - CH = CH2 sp3 sp2 sp2 ? 2011-7-24?6 6? ?-? ?-? ?-?-? ?-? 7? ?sp? CH3C CH CH3C CH sp3 spsp ? ?2?sp?1800?sp ? CH2 = CH - CH = CH2 ? 2011-7-24?7 8?CO2? ?HCO3-?H2CO3,? ? O = C = O ? ? ? C HO O O- C HO O OH ? 2011-7-24?8 ? C -O O O- C HO O OH -2H+ ? ?H+? ? ? ? 2011-7-24?9 9?+/?-?: ? H3C _ Br? H3C _ NH2 ? H3C _ Li? NH2_H ? H3C _ OH(6)H3C _ MgBr ?+ ?- ?+?+ ?+ ?+ ?+ ?- ?- ?- ?- ?- 10?H2N-?HO-?NH3 ?H2O? ?H2O? ? ?H+? ? 2011-7-24?10 11.HCOOH?pKa= 3.7 ?pKa= 0.3 ? ? ? ? ? OH NO2 NO2 O2N ? ? 2011-7-24?11 12?NH3?pKa?36?CH3COCH3?pKa?20? ? ? 13?1?1?pKa? ?HCN? O = CH3 _ C _CH3 CH3 _ C _CH2-Na+ = O ? ? Na+? -NH2 + NH3+ (1) HCN + CH3COONaNa+ -CN + CH3COOH pKa: 9.2pKa: 4.72 (2) CH3CH2OH + Na+ -CNCH3CH2O-Na+ + HCN pKa: 16 pKa: 9.2 ? ? 2011-7-24?1 ? ? 2011-7-24?2 1? ? ? ? 1?CH3CH2CH2CH2CH2CH2CH3 ? heptane 2? 2-? 2-methylhexane 3? 3-? 3-methylhexane 4? 2,3-? 2,3-dimethylpentane ? CH3CHCH2CH2CH2CH3 CH3 ? CH3CH2CHCH2CH2CH3 CH3 CH3CHCHCH2CH3 ? H3C ? CH3 ? 2011-7-24?3 2,4-? 2,4-dimethylpentane 2,2-? 2,2-dimethylpentane 5? 6? 7? 3,3-? 3,3-dimethylpentane CH3CHCH2CHCH3 ? CH3 ? CH3 CH3CCH2CH2CH3 ? ? CH3 CH3 CH3CH2CCH2CH3 ? CH3 ? CH3 ? 2011-7-24?4 8? 9? 3-? 3-ethylpentane 2,2,3-? 2,2,3-trimethylbutane CH3CH2CHCH2CH3 ? CH3 ? CH2 ? CH3 ? CH3 ? CH3 CH3CCH CH3 ? 2011-7-24?5 2? 1? 2? 2-? 2-methylpentane 3,3-?-4-? 3-ethyl-4,4-diethylhexane ? CH3 CH3CHCH2CH2CH3 ? CH3 ? ? CH3 CH3CH2CH-C-CH2CH3 CH3CH2 ? 2011-7-24?6 3) 2,3,6-?-6-? 2,3,6-trimethyl-6-ethyloctane 4? 3,5,5,6-? 3,5,5,6-tetramethylnonace ? CH3 ? CH3 ? H3CCH2CH3 CH3-CH-CH-CH2CH2-C-CH2CH3 ? ? CH3 ? H3C ? CH3 CH3 ? CH3CH2CH2-CH-C-CH2-CHCH2CH3 ? 2011-7-24?7 3? ? ? ? ? ? 3,3-? ? ? ? ? ? 2-? ? ? ? ? ? 2-? ? 4? ? ? ? 1) ?2? 3?2?2-? ? 2011-7-24?8 1)? 15.8%42.1% 42.1% CH3CH2CH2CH2CH2CH3 CH2CH2CH2CH2CH2CH3 ? Cl CH3CHCH2CH2CH2CH3 ? Cl CH3CH2CHCH2CH2CH3 ? Cl 1H?2?H=1?4 616 84 = 32 6 38 100%=15.8% 38 100%=84.2% 32 84.2% / 2=42.1% ? 2011-7-24?9 2? 20% 17% 26.5% 26.5% 10% ? CH3CHCH2CH2CH3 CH3 ? CH2CHCH2CH2CH3 ? CH3 Cl ? CH3CCH2CH2CH3 CH3 Cl ? ? CH3CHCHCH2CH3 CH3 Cl ? ? CH3CHCH2CHCH3 CH3 Cl ? ? CH3CHCH2CH2CH2 CH3 Cl ? ? 2011-7-24?10 45% 40%15% 5? 1) Et- CH3CH2-2) i-Pr- ? CH3CCH2CH3 CH3 CH3 ? 3) 2,2-? ? CH2CCH2CH3 CH3 CH3 ? Cl ? ? CH3-C-CHCH3 CH3 H3C ? Cl ? ? CH3-C-CH2CH2 CH3 H3C ? Cl ? CH3 CH3 CH- ? 2011-7-24?11 3) i-Bu-4) S-Bu- 5) ? 6) ? 7? CH3-CH-CH2- CH3 ?CH3-CH2-CH-CH3 ? CH3 CH3-CH-CH2-CH2- ? CH3 CH3-C-CH2- ? CH3 ? CH3-C-CH2-CH3 ? CH3 ? ? 2011-7-24?12 6? 2)? 3)? + CH3-CH3+ HClCH3-CH22Cl ? + Cl2 Cl CH3-CH3CH3-CH2+ Cl CH3-CH2-CH2-CH3 ? ClCH3-CH3CH3-CH2Cl + CH3-CH3+ CH2-CH3 ClCl + Cl2 ? hv 1)? 2ClCl2 ? 2011-7-24?13 ? ? ? ? ? ? ? ? ? ? ? 2011-7-24?14 7? 1? ? ? ? H H H F Cl Cl H H H F Cl Cl H H H F Cl Cl Cl Cl F H HH Cl Cl F H H H Cl Cl F HH H ? ? 2011-7-24?15 2? ? ? ? ? Cl Cl Cl Cl F F F F H H H H Cl Cl Cl Cl F H F F F H H H ? 2011-7-24?16 8? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? 130? 2(CH3)3CO (CH3)3CO-OC(CH3)3 ? 2011-7-24?17 2) ? 1) ? ? 130? 2(CH3)3CO ?(CH3)3CO-OC(CH3)3 50% (CH3)3C-OH + H CH3 ? CH3-CH-CH3 ? CH3 ? + CH3-C-CH3(CH3)3CO ? +CCl4 CH3 CH-CH-CH3 _ CH3 CH3-C-CH3 _ Cl +?CCl3 CH3 CH3-C-CH3 H + CH3 CH3-C-CH3+ _ CCl3 ? CHCl3 ? 2011-7-24?18 3) ? CH3 ? ? CH3-C-CH3 CH3 ? CH3-C-CH3 + CCl3 CCl3 CH3 ? CH3-C-CH3 ? H3C CH3 ? +CH3-C-C-CH3 ? ? CH3 CH3 ? CH3-C-CH3 H3C +Cl3CCCl3CCl3CCl3 ? 2011-7-24?1 ? ? 2011-7-24?2 1? (1) ? (2) (Z)-3-?- 4- ?-3-? (3) (Z)-3-chloro-4-methyl-3-hexene C = C CH3CH2 CH3 CH(CH3)2 CH2CH2CH3 C = C CH3 Cl CH2CH3 CH3CH2 CH3 CH3-C=CH2 ? 2011-7-24?3 (4) 2,4,4-trimethyl-2-pentene (5) trans-3,4-dimethyl-3-hexene C = C CH3 CH3 CH2CH3 CH3CH2 CH3CH3 CH3 CH3-C=CH-C-CH3 ? 2011-7-24?4 2? (Z)-2-?-3-?-3-? (Z)-3-ethyl-2-methyl-3-heptene ?-1-?-2-?-2-? cis-1-chloro-2-methyl-2-butene (E)-1-?-2-?-2-? (E)-1-chloro-2-methyl-2-butene (1) CH3CH2 CH2CH2CH3 H C=C (CH3)2CH (2) CH3CH3 H CH2Cl C=C ? 2011-7-24?5 3,3-?-1-? 3,3-dimethyl-1-butene ? -3-? cis-3-heptene (3) (CH3)3CCH=CH2 (4) CH3CH2 HH CH2CH2CH3 C=C ? 2011-7-24?6 3? ? ? ? (1) H2,Ni ?2-? (2) Cl2 1?2-?-2-? CH3CH-CH3 CH3CH3 H2,Ni CH3-C=CH2 _ _ CH3 CH3-C-CH2 CH3 ClCl Cl2 CH3-C=CH2 ? 2011-7-24?7 (3) Br2 1?2-?-2-? (4) I2 CH3 CH3-C=CH2 _ I2 ? CH3 CH3-C-CH2 Br2 CH3-C=CH2 BrBr CH3 ? 2011-7-24?8 (5) HBr 2-?-2-? ? ? ? (6) HBr(?) 1-?-2-? ? ? ? CH3C-CH3 CH3 HBr CH3-C=CH2 Br CH3 CH3CH-CH2 CH3 HBr CH3-C=CH2 BrCH3 ? 2011-7-24?9 (7) HI 2-?-2-? ? ? ? (8) HI(?) CH3C-CH3 CH3 HI CH3-C=CH2 I CH3 ? CH3 HI CH3-C=CH2 ? 2011-7-24?10 (9) H2SO4 ? (10) H2O,H+ ? CH3 CH3-C-CH3 OSO3H H2SO4 CH3-C=CH2 CH3 CH3-C-CH3 OH CH3 H2O CH3 CH3-C=CH2 CH3-C-CH3 OH CH3 H2O H+ ? ? 2011-7-24?11 (11) Br2,H2O 1-?-2-?-2-? (12) Br2+NaI(?) 1,2-?-2-?1-? ?-2-?-2-? 1-?-2-?-2-? CH3 CH3-C-CH2 Br2, H2O CH3-C=CH2 CH3 HO Br CH3 CH3-C-CH2 CH3 Br Br2 H2O/NaI CH3-C-CH2 CH3 CH3-C-CH2 CH3 I Br BrHO CH3-C=CH2+ + Br ? 2011-7-24?12 (13) O3;?Zn,H2O ? (14) RCO3H 2-?-1,2-? CH3 (1)O3 Zn,H2O CH3-C=O + H-C-H CH3 O = CH3-C=CH2 CH3CH-CH2 CH3 RCO3H CH3-C=CH2 O ? 2011-7-24?13 2-?-1,2-? (15)?KMnO4 (16)?KMnO4 ? KMnO4 ? CH3-C=O +CO2CH3-C=CH2 CH3 CH3 KMnO4 ? OH- CH3 CH3-C-CH2 CH3 OHHO CH3-C=CH2 ? 2011-7-24?14 ? ? ? ? ? ? ? ? CH3CH = CH2 + Br2 CH3CH_CH2 Br Br ? ? ? ? CH3CH_CH2 Br Br CH3CH_CH2 Br CH3CH _ CH2 BrBr 4?Br2? E?2 E?1 ? ? ? ? ? ? ? ? ? ? 2011-7-24?15 E?2 E?1 ? ? ? ? ? ? ? ? ? ? 2011-7-24?16 5? 3,3,3?HCl?F3CH2CH2Cl ? ? ? ?C+? CF3CH=CH2 + H+ F_ C_ CHCH3 (1) (2) F F ? ? ? ? ? ? ? ? F_ C_ CH2CH2 F F ? ? ? ? ? ? ? ? (1) (2) CF3-?C+? ? ? ? ? ? ? ? ? ? 2011-7-24?17 6?A C7H14?KMnO4? ? ? ? ? ?A? ? ? ? C=C CH3 CH3 CH3 CH2CH3 A: ?H+? ? ? ? CF3_ CH = CH2 + H+ ? CF3_CH_CH2+ +Cl- CF3_CH_CH2 HHCl ?CF3-? ? ? ?H+? ? 2011-7-24?18 7?(A) (B) (C)?(A) ? ? ? ?CH3CHO? CH3CH2CH2CH2CHO? ? ? ? (B)?(C) ? CH3CHO?, ? (A) ?B) ? (C) ? CH3CCH3 O = = CH3CH2CCH3 O CH3CH2CCH2CH3 = O ( A ) CH3CH=CHCH2CH2CH2CH3 ( B ) C=C CH3 CH3 CH3 CH2CH3 CH3CH=C CH2CH3 CH2CH3 ( C ) ? 2011-7-24?19 8? ? ? ?1? ? ? ?2?2-? ? ? ?3?1?2-? ? ? ?4?CH2= CH-COOH ?5?2-? ? 2 -? ? ? ?1?2-? ? ? ?CH2= CH-COOH ?2-? ? 2011-7-24?20 9? ?1-?2-?-1-? CHCl3?1,1,1-?3-?-1,1,1? ? ? ? (1) ? (2) ? ? R-O-O-R2 R-O 2R-O+ CHCl3 R-OH + CCl3 ? 2011-7-24?21 ?2?30?1?20? ? ? ?2? CCl3 CH3 CH3(CH2)4CH=CH2+CH3(CH2)4-C-CH2-CCl3 CH3 ? ? ? ? 20? 30? ? CH3(CH2)5CH-CH2-CCl3 + CHCl3 CH3(CH2)5CH2-CH2-CCl3 + CCl3 CCl3 CH3 CH3(CH2)4CH-CH2CCl3 +CH3(CH2)4-C-CH2-CCl3 CH3 CHCl3+ CH3(CH2)5CH=CH2 + CCl3CH3(CH2)5CH-CH2-CHCl3 ? 2011-7-24?22 10? BrCH2CHBrCH2Cl? ? ? ? ? ? ? ? CH2-CH=CH2 + Br2 Cl CH2CHCH2 Cl BrBr CCl4 CH3-CH=CH2 + Cl2 500? Cl CH2-CH=CH2 ? 2011-7-24?23 11? ? ? ? ? ?1? CH3-CH3 + Cl2 Cl CH3-CH2 CH2=CH2 hvKOH C2H5OH ( 2 ) ? hv CH3-CHCH3 + CH3CH2CH2 Cl Cl CH3CH2CH3 + Cl2 CH3CH2OH KOH CH3-CH=CH2 + HCl ? 2011-7-24?24 (3) ?1?2-? Br2 BrBr CH3CH=CH2 CH3-CH-CH2 (4) ?1-? ? CH3CH=CH2 CH3CH2-CH2 Br + HBr ?2? ? ? ?2? ? 2011-7-24?25 (5) ?2-?1-? (6) ?1-?1-?-2-? Cl2 H2O CH3CH2-CH2 I CH3CH=CH2 KOH C2H5OH OH CH3CH-CH3 Cl Br CH3CH-CH3CH3CH=CH2 KOH C2H5OH ? HBr CH3CH2-CH2 Br (7) ? ?2? ? H2SO4 OH ? H2O CH3-CH-CH3 CH3CH=CH2 ? 2011-7-24?26 (8) ?2-? ? ? ?9? CH3 OH CH3-C-CH2CH2CH3 H2SO4 CH3 OH CH3-C-CH2CH2CH3 ? CH3 CH3-C=CHCH2CH3 H2 Ni CH3-CHCH2CH2CH3 CH3 H2SO4 ? CH3CH2CH2CH2-OH HI CH3CH2-CH-CH3 I CH3CH2CH=CH2 ? 2011-7-24?27 ?10?3-?-2?2-? 2?2-? ? ? ? ? Cl CH3 H3C CH3-C-CH-CH3 R-OH KOH CH3 CH3 CH3-C-CH=CH2 H2 Pt CH3 CH3 CH3-C-CH2CH3 ? 2011-7-24?28 12? ? ? ? ? CH3C = CH2 CH3 _ H+ CH3C - CH2CHCH3 _ _ _ CH3 CH3CH3 +CH3CH CH3 CH3 _ CH3C = CH2 CH3 _ H+ _ _ CH3 CH3 CH3C+ CH2= C CH2 CH3 _ CH3C - CH2CCH3 _ _ CH3 CH3CH3 CH3 _ CH3CCH3 _ H CH3C - CH2CHCH3 _ _ _ CH3 CH3CH3 CH3 _ + CH3CCH3 + + ? 1 ? ? 2 1? ? ? ? ? ? ? CH3CH=CHCH2CH2CH=CH2 (2) CH3CH=CHCH2C?CH (3) CH3CH=CHC(CH3)=CHCH3 (4) (CH3)2C=CHC?CCH3 ? 3 ?1? ?-1?6-?-1?6-? ?2? C=C CH2C? CH CH3 H H ?-4-?-1-? C=C H HCH3 CH2C? CH ?-4-?-1-? C=C CH2CH2CH=CH2 CH3 H H C=C H HCH3 CH2CH2CH=CH2 ? 4 ?3? C=C CH3 H H C=C H CH3CH3 C=C CH3 H H C=C HCH3 CH3 C=C CH3 H H C=C H CH3 CH3 C=C CH3 H H C=C H CH3 CH3 (2E,4Z) ?,? -3-?-2,4-? -3-?-2,4-? ?,? (2Z,4E) -3-?-2,4-? ?,? (2E,4E) -3-?-2,4-? ?,? (2Z,4Z) ? 5 ?4? 2-?-2-?-4-? 2?1? ? ? ? C=C C?C-CH3 CH3 H CH3 C=CHCH2CH=CH2 + Br2(1mol) CH3 CH3 CH3 CH3-C-CHCH2CH=CH2 BrBr (1) ? 6 (2) (3) CH3CH=CHCH=CH2+Br2(1mol) BrBr CH3CH-CH=CH-CH2 (4)CH3CH=CHCH=CHCH=CH2 Br2?1mol?CH3CHCH = CHCH = CHCH2 BrBr CH3CH=CHCH2C? CH + Br2(1mol) ? BrBr CH3CH-CHCH2CCH ? 7 3? (1)3,5-? (2) ?CH3-CC-CH2CH2CH3 CH3 Br2?1mol? Br CH2C=CH-CH2 CH3 CH2=C-CH=CH2 (5) Br CH3 ?CH C-CHCH2-CHCH2CH3 CH3 methylpropylacetylene ? 8 (4)1?5-?-3-?(3) 2-?-1-?-3-? ? C-CH=CH2CH2=CH-C CH3 ? CH3 CHCH3 C-C=CH-CHCH2CH3 CH3-C (5) 4,7-?-6-?-4-?-2-? (6)?2?,4?-3-t-butyl-2,4-hexadiene ? CH3 CH2=C-CC-CH3 HC-CH2CH3 C=C CH3 C(CH3)3 H C=C H H CH3 ? 9 4?1-? ?1?1molH2?Ni? ?2?2molH2?Ni H2(2mol) Ni CH3CH2CH2CH3 (3) 1molBr2 Br2(1mol) H2, 1mol CH3CH2CH = CH2? CH3CH2CCH ?CH3CH2CCH ?CH3CH2C CH C=C CH3CH2 Br Br H ? 10 (4) 2molBr2 Br2(2mol) (5)1mol HCl CH3CH2CH=CH2 Cl ?6?2mol HCl HCl(2mol) CH3CH2C-CH3 Cl Cl HCl(1mol) ?CH3CH2CCH ?CH3CH2CCH ?CH3CH2CCH CH3CH2C_CH BrBr BrBr ? 11 ?7?H2O?Hg2+?H+ Hg2+,H+ H2O ?8?Ag?NH3?2+OH- +Ag(NH3)2+OH- ?9? NaNH2 NaNH2 ?10?9?+C2H5Br ?CH3CH2CC-C2H5+NaBr ?CH3CH2CCH ?CH3CH2CCH ?CH3CH2CCH CH3CH2C-CH3 O = ?CH3CH2C CNa ?CH3CH2C CNa+ C2H5Br ?CH3CH2CCAg ? 12 ?11?O3? (1)O3 (2) H2O ?12?KMnO4? KMnO4 ? CH3CH2COOH+CO2 CH3CH2COOH+CO2 ?CH3CH2CCH 5?1,3-?1-?4? ? ? ? ?1?1molH2?Ni? CH2=CH-CH=CH2 H2(1mol) Ni CH3-CH = CH - CH3 ?CH3CH2CCH ? 13 ?2?2molH2?Ni? CH2=C H-CH=CH 2 H2(2mol) Ni CH3-CH2-CH2-CH 3 ( 3 ) 1molBr2 CH2=CH-CH=CH2 Br2(1mol) Br CH2-CH-CH=CH2+CH2-CH=CH-CH2 BrBrBrBr 15?55% 45% 60?10% 90% (4) 2molBr2 Br2(2mol) CH2-CH-CH-CH2 Br CH2=CH-CH=CH2 BrBrBr ? 14 (5) 1mol HCl CH2=CH-CH=CH2 HCl(1mol) H CH2-CH-CH=CH2+CH2-CH=CH-CH2 ClHCl ?20?75-80% 20-25% ?20?25% 75% (6) 2mol HCl CH2=CH-CH=CH2 HCl(2mol) CH2-CH=CH-CH2 Cl H H Cl CH2-CH-CH-CH2 Cl H ? 15 (11) O3,? ?12?KMnO4? ? ?(8)?(9)?(10)? ? O3 ? Zn,H2O HCHO + H-C-C-H + HCHOCH2=CH-CH=CH2 O = O = KMnO4 + CO2 ? HO-C-C-OH KMnO4 CO2 + H2O CH2=CH-CH=CH2 O = O