有机化学_第二版_王彦广_课后答案.pdf

2010- 3- 16 2- 6 (1) CH3(CH2)4CHCH2CHCH2CH3 CH3 CH3CCH H3C CH3 CH3 (2) 3- 3- 6-3- 5- (1,1,2-) (3) HC CCHCH2CH3 CH2CH CCH2CH2CH3 CH3 (4) 7- 6- 3-6- 3- 5- 1- 2- 7 (1)(2) CH2CHCH2CH2CH CH2CH3CH CHCHCH CH3 -,- CH C CH3CH2CH C N -,- CH2CH CH OCH C CH2CH CH2 - 78 CH C OCH3CH2CH OCH3 p- p-,- CH3C O OHCH3C O NH2 p-,- p-,- 2 2) ) C CH H 3 3 1- 2 2 C CH HC C - C 2- 8P31 (1) (2) D H (E)- 3- 2- 5- (E)- 1- - 3,3- 2- (CH3)2CH C C CH2CH3 F(3) CH3CH2 (Z)- 2- 3- 4- - 3- CC CH2CH3 CH3CH2CH CH3 CH2 CC CH2CH2CH3 CH2CH(CH3)2H (4) 4E, 7Z- 2,8- 7- 4- 4,7- CC I FBr Cl CC MeEt i- PrPr- n (5) (6) (E)- 1- - 2- - 2- - 1-Z- 2,3- 4- 3- CH3CH C C H CH2Cl CH3 CH3 C Cl C CH2CH3 CH3 (7) (8) CH3 Z- 2,4- 1- - 2-Z- 3- 2- - 2- HC C CH2 C C CH2C(CH3)3 CH3 (9) CH3CH2 Z- 5,7,7- 4- 4- 1- 2- 10 . H Cl CH3 H Cl CH3 CH3 H Br H F Cl (1)(2) : HH Cl Cl H3C CH3 HCH3 F H Cl Br : (8) Z Z - - 3-3- CHCH3 3 Cl 8) 3- - 2-2- CHCH3 3) )3 3 3 4- - 1-1- Cl H CH3 H CH3Cl H H3C Br H ClF : H H3CCl H CH3Cl H H3CBr H ClF CH3 H Cl H CH3 C2H5 H Br CH3 Br CH3 H (3)(4) : C2H5 CH3 H H H3C Cl H H Br Br H3C CH3 : H H3CCl CH3 C2H5H Br HCH3 CH3 HBr : CH3 ClH CH3 C2H5H Br HCH3 CH3 HBr 2- 11 HH H3CH Br H3C HBr FH F H (1)(2) : H H H Br CH3 H3C H Br F H F H : ClCl 3 H H H C 2H5 5 ClH CH H3 3 H H Br H H H CH3H3C H BrF H FH : H BrH H CH3H3C H BrF H FH CH3 CH3 H H F H3C H3C H Cl CH3 H Cl (3)(4) : CH3 H3C Cl H Cl H CH3 CH3 H H H3C F : H H3C Cl CH3 ClH CH3 HCH3 CH3 FH : H H3CCl H CH3Cl CH3 H3CH CH3 FH Br (1)(2) - 3,5-10,10- 7-4.3.2- 3- (3) (4) 2- 7-4.58-2.5- 5- CHCH3 3 C CH H3 3 C H Cl H H 3C C CH H3 H H (5)(6) 3,7,7-4.1.07-3.5 2- 13 Me (1) (2)(3) CH2CH3 Bu- t CH3CH3 C(CH3)3 Me CH3 CH2CH3 H3C CH(CH3)2 Me Bu- t Me CH3 CH3 CH3 (4) (5)(6) Me Me Bu- tCH3 Bu- t Me Me CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH(CH3)2 CH3 CH3CH3(7)(8) (9) H3C CH3 CH3 CH(CH3)2H3C CH3 CH3 CH3CH3 CH3 CH3 CH3 CH(CH3)2 CH(CH3)2 (10)(11) (12) CH3 CH3 H3C CH(CH3)2 CH3 CH3 CH(CH3)2 3 3 C CH H3 3 CH3 CHCH CH( (CHCH3 3) )2 CHCH P45 1. (1)- 1- 4-(2) (2E,4Z)- 2,4- Me t-Bu (3) 3,3-(4) CCCH3CH2CH=CHCH3 (5)(6) CH3CH2CH CH3 CH3 CH2C CH3 CH3 CH3 HC CH3 CH3 CHC CH3 CH3 CH3 H3C CH3CH2 CHC CH3 CH2CH3 CH3 H3C H3C (7) 2,6-3.4- 5- ;(8) 8-4.4.2- 2- . CH3 H3C H3C 2. 1 CH3CH CH3 2 CH3CH2CHCH3 3 C CH3 CH3 H3C 4 CH3CHCH2 CH3 5 CH3CH2CH2CH2CH2CH2 6 C CH3 CH3 CH2H3C 7 CH2=CHCH2 81- CH3CH=CH 9 CH2=CH 10HC C 112- HC CCH2 121-. CH3C C H H 4.4.24.2 C CH2 5 5 C C CH H3 3 CHCH CHCHC 6.,.pp41- 42 H H H H H H H H H H H H 1 2 3 4 5 6 180pm CH2 CH2 H H H HH H H H 1 23 4 5 6 H H H H H H H H H H H H 1 2 34 5 6 H H H H H H H HCH2 CH2 1 2 3 4 5 6 C- 1C- 4 180pm240m C- 2C- 3C- 5C- 6 7. 1,3-1,4-?.p27,p28 1,3-p - p-,- p -p-, - p CC CC H H H H H H 1,3- 1,3-1,4- - ? 1 3- 11.5 g50 mL10 cm 20+9315 cm2 50 mL150 mL10 cm D t = lx c 1+ 2.79 o 2+ 1.395 o 3- 2 (1) (3)(2) CH2H2C CH2H2C Cl Cl COOH HOH OHH COOH 1i;23i C2 3- 3R/S (1) (2)ClCH2 Cl CH3 CH(CH3)2CH2=CH H Br CH2CH3 SR 3- 4L- (- )-(+)-DL L 3- 5FishcherR/S 11,2,3,4-22,3,4- OH OH H OH OH H OH OH H HOH HO R S S R Br Br Br CH3 H H C2H5 HH H H CH3 Br Br C2H5 BrH Br Br CH3 H H C2H5 BrH H Br CH3 Br H C2H5 Br 2R, 3R, 4S2S, 3S, 4R2R, 3R, 4R2R, 3S, 4R OH OH OH OH OH H H OH H HHO HO S SR R Br H Br CH3 Br H C2H5 HBr H H CH3 Br Br C2H5 HBr Br H CH3 H Br C2H5 HH Br H CH3 H Br C2H5 Br 2R, 3S, 4S2S, 3S, 4S2S, 3R, 4S2S, 3R, 4R 8 CHCH2 2= =CHCH H H BrBr CHCH2 2CHCH R +)- 2 3- 6FischerR/S 2 3 CH3 HOH COOH HCl BrH CH3 HCl CH2Cl H3C H HO CH3 H OH (1) CO2H CH3 H OH Cl H R S R CH2Cl CH3 H Br Cl H R R CH3 CH3 H OH HO H R 3- 7Fischer 1(2 ,3 )-2-3-2(2 ,3 )-2-3- CH3 CH3 BrH ClH R S CO2H CO2H HHO HCl S R H3C Cl CH3 HO2C OH Cl CO2H Br 3meso-2,3-(4) (12 )-2-. CH3 CH3 BrH BrH R S H3C Br CH3 Br HO Cl Cl OH 3- 8 / O O O O OH MeO OMe OMe R R O O O O OH MeO OMe OMe R R HO ) HO2C C OHOH CO (12 2 )-2- HO ClCl 3 3- 9 (1) (2) Br Cl OH OH Br Cl Br Cl Br Cl Br Cl R S R S R S S R OH OH OH OH OH OH OH OH R R S R S R S S 3- 10 C H3C C CH3 O O Cl H3CH2CH2 Cl CH3 (1) (2) CH3 CH3 O Cl NO2 O2N CO2H (3) (4) 1/ (1)(2)HOCH2CHOHCHOHCH2OHCH3CH(NH2)CHFCH3 3- 5 (1)1 R CH3 CH3 H NH2 F H R S CH3 CH3 F H H H2N S R CH3 CH3 F NH2 H H S S CH3 CH3 H H F H2N R CH3 H C 4 (4) (3) CH3CHBrCHBrCHBrC2H5 CH3OCH3 3- 5 (2), 4 CH3OCH3 CH3OCH3 RS RS CH3OCH3 CH3OCH3 S RSR (5)(6)ClCH3 CH3CHBrCHO ClCH3 ClCH3 RS CHO CH3 OHH CHO CH3 HHO 2. (1) CH3 BrH CH3 Br H CH3 HBr H CH3 Br (2) CH3 HOH CH3 OHH OH HCH3 CH3 OHH (3) Cl Cl Cl Cl 3. (1) Cl H Cl H (2) NH N H HN H N O O O (4)(3) Cl H3C Cl Br Cl Br 3 H H H H CHCH 3 CH CHCH3 3 H H 5 (5) (6) FCl FCl C CC CH3 OC2H5 H3C C2H5O 4A (C5H8)AB (C5H10) AB A B 5C6H12H2C6H14 6I N H C6H5 OH C6H5 OH I N H C6H5 OH C6H5 OH N H C6H5 OH C6H5 OH N H C6H5 OH C6H5 OH N H C6H5 OH C6H5 OH 74-2- N N H C OHOH I OHOH C6H5C 1 1 1 2 3 4 5 (6) () 7 8 CH3CH2CH2CCH+ 1/2B2H6 H2O2 OH-,H2O CH3CH2CH2CH2CHO 9 10 11 12 CH3 C CH3 CH2 + HBrH3C Br CH3 CH3 CH3CHC CH3 CH3 HClO CH3CH Cl C OH CH3 CH3 + CH3CH C CH3 CH2CH3 + Br2 CCl4 CH3CH Br Br CH3 CH2CH3 CH3C CH+ HI(1mol)CH3C CH2 I (CH3)2CCHCH2CH2C CCH3+HBr( 1mol) (CH3)2CCH2CH2CH2CCH3 Br CH3CH2CH2CCH + H2O HgSO4 H2SO4 CH3CH2CH2CCH3 O CH3C CCH CHCH3+ Br2 C Br CH3 Br C Br C H Br Br CHCH3 Br CH3CH2CCCH3+H2 Pd- BaSO4 H CH3CH2CH3 H CH3CH2C CCH3 Na NH3 H CH3CH2 CH3 H CH3 1)B2H6 2)H2O2,OH CH3 OH H2O2,OH CH2 CH3 CH3 CH2 + B2H6 H2O CH3 CH3 OH OH ( ( HB Br r( + BrBr2 2 ) CH+ + 2 H H2 2O O 2 13 14 15 16 17 18 3.1- 6KMnO4/OH- HC CCH2CH2CH3 KMnO4 / OH CH3CH2CH2CO2H+HCO2H CO2 +H2O 7ICl HC CCH2CH2CH3 ICl (excess) HC CCH2CH2CH3 I I Cl Cl 5.DielsAlder (1) CH3C CHCH2CH3 CH3 1)O3 2)Zn- H2O CH3CCH3 O + CH3CH2CHO + 1)O3 2)Zn- H2O CH3CH2CCH CH3CH2COOHHCOOH +1/2O2 Ag O + 1)O3 2)Zn- H2O OHC CHO 2CHO- CHO CH3 + HI CH3CH2CHCH3 I CH3 + Br2 H3C CH3 BrCH2 H C CH3 C(CH3)2 Br O4 / OHOH CH2CHCHCH3 3 CO2CH3 + CO2CH3 LiAlH4 CH2OH SOCl2 CH2Cl (2) CN + CN (3) CHO + CHO Ph3P=CH2 CH=CH2 (4) CHO + CHO (5) + CO2CH3 CO2CH3 CO2CH3 CO2CH3 (6) + O O O O O O 8. 2-2- ? (1) CH2 HO O 4 CH3 H3C +Br2 CCl4 H3C H CH3 H Br Br meso- (2) CH3 CH3 +Br2 CCl4 H CH3 CH3 H Br Br (3) CH3 H3C PhCO3H CH3 H H3C H O (4) CH3 H3C HOCl H3C H CH3 H Cl OH (5) CH3 H3C KMnO4/ OH, cool H CH3 CH3 H OH OH 9.C10H161molKMnO4 C10H16O2 1 mol H2 / Raney Ni KMnO4 / OH O O AB C H H O OH H, c cool 5 A. 10.C4H6 CH3CH2CO2HHO2CCH2CH2CO2HHO2CCO2H CH3CH2C CH CHCHH2CCH2 A B C KMnO4 / H CH3CH2CO2H HO2CCH2CH2CO2H HO2CCO2H 1 1. . CHCH=CH2 CH2 H3C C CH3 CH2CH2CH3 CH3CH2 . . . CH3(1)(2)(3)(4) (5) 32541 2C5H12 (1); C CH2Cl CH3CH3 CH3 (2); CH3CH2CHClCH2CH3 CH3CHClCH2CH2CH3CH2ClCH2CH2CH2CH3 (3); H C CH2CH2ClCH3 CH3 H C CH2CH2ClCH3 CH3 Cl C CH2CH3CH3 CH3 H C CH2CH3CH3 CH2Cl (4). C CHCl2 CH3CH3 CH3 C CH2Cl CH2ClCH3 CH3 3. (CH3)2CHCH2CH3 (1) Br2 hv (CH3)2CBrCH2CH3 (2) CH3 CH3 Br2 hv CH2Cl CH3 (3) CHCH=CH Cl2 CH3 CH3CClCH=CH CH3 CH3 CH3 (4) NBS(1 mol) ROOR CH3 Br (5) CH3 500 Br2 CH3 Br r2 hvhv ( 2 (6) CH2 CH3 HBr ROOR CH2Br CH3 (7) BrCCl3CH2=C (PhCO2)2 CH2CH3 CH2CH3 CH2=C CHClCH3 CH2CH3 +HCCl3 (8) CCl4 (PhCO2)2 Cl +HCCl3 4 12.3 2.3/12 1/6 2.3 2 5 (1) (2) (3) (4) Cl2 2Cl Cl CH3CH3+CH2CH3+ HCl CH2CH3+ Cl2ClCH2CH3 + Cl 2ClCl2 CH2CH32CH3CH2CH2CH3 CH2CH3 Cl+ ClCH2CH3 (i) (ii) (iii) (iv) (v) (vi) hv or 1i2 (ii)(iii)3(i)4 i(iv) 6. () 7 CH Cl2 3 CH3CHCH3+ + CCl4 + 2 (i) (ii) (iii) (iv) (v) (vi) hv (CH3)3COOC(CH3)3(CH3)3CO 2 (CH3)3CO CH3 (CH3)3COHCH3CCH3 CH3 + CH3CCH3 CH3 CCl3CH3CClCH3 CH3 CCl3CH3CHCH3 + CH3 + HCCl3CH3CCH3 CH3 CH3CCH3 CH3 (CH3)3CC(CH3)32 CCl3 CCl3CCl3 CH3CCH3 CH3 CCl3+CH3CCH3 CH3 CCl3 (vii) 8- H Cl2 Cl 9- H- H 10.CH CH3CH2CH2CH2CH3 H (1) CH3CH2CH2CH CH CH2(2) - H- H CH H 2CH CH2CHCH 2. (2)(1)CHCH2CHCH3CH3CH CH3CH3 CH3 CH2 CH2CH3 HH 2,5-3-(3-) ( )-1-2- (4) (3) CH3 CHO OH COOH CH3 NO2 4-3- 5-2- (6) (5) CH3 CH3 ClSO3H 1,5- 8- (8)(7) NO2 Cl NO2NO2 1,8- 2-4 - SO3H CHONO2 (9) (10) NH2 OH CH3 3-5- 3-4- 3. (1)+CH2Cl2 AlCl3 () ( (6)6) S SO O3 3H H 8- 8- 1,8- (2)+ Br2CH2CH3 Fe CHCH3 Br CH2CH3 Br CH2CH3 Br + +CH3CH2CH2OH BF3 HF (3) O CH2CH2CH2CCl O AlCl3 Zn- Hg HCl (4) CH2CH2CHCH3 OH BF3 HF (5) C2H5H3C KMnO4 H, (6) (CH3)C=CH2 HF, BF3 (CH3)3C C2H5Br AlCl3 (CH3)3CC2H5 (CH3)3CCO2H K2Cr2O7/ H2SO4 + NO2ClNO2 Cl NO2 Cl2/ Fe HNO3 / H2SO4 (8) CHCH3 3 BF OO BF3 3 HFHF C C2 2H H5 (9) O2 / V2O5 400500 oC O O O (10) H2/ Ni (11) Na / NH3(l) CH3CH2OH KMnO4 H CO2H CO2H (12) HO2C + O O O AlCl3Zn- Hg HCl HO2C O SOCl2 ClOC AlCl3 O Zn- Hg HCl 9. (1) CH3CH2CH2Cl AlCl3 CH2CH2CH3 Cl2 CH2CHCH3 Cl CH3CH2CH2Cl AlCl3 CH(CH3)2 (2) CH3CH2Cl AlCl3 HNO3 H2SO4 NO2NO2 CH2CH3 NO2 CH2CO2H KMnO4 (3) CH3COCl AlCl3 HNO3 H2SO4 OCH3OCH3OCH3 O2NO2NCOCH3 O O 2C C CH H2C (4) CH3COCl AlCl3 Br2 Fe BrBr CH3OC HNO3 H2SO4 Zn- Hg HCl Br CH3CH2 Br CH3CH2 O2N (5) Cl2 Fe Cl CH3 Cl2 CH2Cl AlCl3 Cl CH2Cl CH2Cl AlCl3 2 HNO3 H2SO4 NO2NO2 NO2 (6) HNO3 H2SO4 NO2 NO2O2N (7) AlCl3 ClCH=CH2 + CH=CH2 (8)CH3COCl AlCl3 CH3OC + 2 COCH3 CH2 2ClCl NO2 2 HNOHNO3 3 H2 2SOSO4 4 C 11Huckel (1) (2) (3) CH=CH2 266 (4)(5) (6) 8p4 (7)(8) (9) 26 (10) 14 14 123 1. AlCl3 (1) (CH3)2CHCl CH(CH3)2 AlCl3 CH3CCl O CH(CH3)2 CCH3 O 1.Br2,NaOH 2.HCl,H2O CH(CH3)2 COOH 2 ( (9)9) 6 3 AlCl3 CH3CCl O CCH3 O 1.Br2,NaOH 2.HCl,H2O (2) HNO3,H2SO4 CCH3 O NO2 COH O NO2 CH3Cl AlCl3 CH3 HNO3,H2SO4 CH3CH3 + NO2 NO2 KMnO4 COOHCOOH + NO2 NO2 Fe Cl2 (3) CH3 H2SO4 CH3 SO3H ClCl H2O CH3 SO3H CH3 ClCl Fe Br2 Zn- Hg HCl CCH3 O CH2CH3 CH2CH3 Br (4) 2. Zn- Hg HCl AlCl3 CH3CH2CH2CCl CCH2CH2CH3O O CH2CH2CH2CH3 (1) AlCl3 CH3CH2CH2CH2Cl (2) CHCH2CH3 CH3 Cl2 Fe Cl H2SO4 Cl SO3H Cl SO3H HNO3 H2SO4 NO2 Cl NO2 H2O (3) 3 SOSO Fe Cl2 2 Cl 3H Hg HClHCl KMnO4 (4) COOH COOH Fe Br2 HNO3,H2SO4 (5) CH3 H2SO4 CH3 SO3H BrBr H2O CH3 SO3H CH3 BrBr CH3 BrBr NO2 HNO3,H2SO4 H2SO4 160oC SO3HSO3H NO2 (6) (7) CH3 hv,Br2 CH2Br 1.Mg,Et2O 2.CH3CHO CH2CHCH3 OH EtOH,EtOK CH CHCH3 AlCl3CH3CCl 2.Br2,NaOH 3.HCl,H2O CH3 (8) O 1. CH3 COOH 1.PCl3 AlCl32. CH3 , C O CH3CH3 HNO3,H2SO4 CH3 hv,Br2 AlCl3 , H2 CNO2 (9) CH3 NO2 CH2Br NO2 HNO3,H2SO4 H2 CNO2NO2 hv,Br2 1.Mg,Et2O 2.CH3Br (10) Na- Hg,CH3CH2OH Br Br CH3 CH3 g,EtEt2 2EtEt O O 2.C CH H3 3C CHOHO CHCH NO CHCH2 2C CH HCH OHOH CH3 C 11- 1NaOH CH3CH2CH2CH2CH2Br NaOH,H2O CH3CH2CH2CH2CH2OH 2Mg/ CH3CH2CH2CH2CH2Br Mg,Et2O CH3CH2CH2CH2CH2MgBr 3AgNO3- CH3CH2CH2CH2CH2Br AgNO3,ROH CH3CH2CH2CH2CH2ONO2 +AgBr 4CH3CCNa CH3CH2CH2CH2CH2BrCH3CH2CH2CH2CH2C CH3C CNa CCH3 5NaCN CH3CH2CH2CH2CH2Br NaCN CH3CH2CH2CH2CH2CN+ NaBr 6 C2H5ONa/C2H5OH CH3CH2CH2CH2CH2Br C2H5ONa/ C2H5OH CH3(CH2)4OC2H5 7NaI 8KOH- CH3CH2CH2CH2CH2Br KOH/ROH CH3CH2CH2CH CH2 2 (1) CH3CH=CH2 NBS NaCN CH2CH=CH2 Br CH2CH=CH2 CN (5) OH PCl3NaCN Cl CN CH3CH2CH2CH2CH2Br NaI CH3CH2CH2CH2CH2I CH3CH=C(CH3)2 (2) HBr R- O- O- R NaI CH3CHCH(CH3)2 Br CH3CHCH(CH3)2 I (4) + Br2(1mol) 500oC KOH/ Br (3) + Cl2 KOH ClCl 5O ON Na a/ / C C2H N N Br K K CH2CHCH CH3CHCH2 2CHCH H5O OH H CH O OH aI (6) CH3CH- CH2CHCH3 CH3Cl NH3 CH3CH- CH2CHCH3 CH3NH2 (9) CH3CCH NaNH2 CH3I NH3 CH3CCNa CH3CCCH3 (10) C CH C CAg COOH Ag(NH3)2+HNO3 (11) CH3CH2CCH + CH3CH2MgI 1) CH3COCH3 2)H3O+ CH3CH2C CMgI +CH3CH3 CH3CH2C CC(CH3)2 OH (12) BrMe Mg Et2O MgBrMe C6H5Br Pd(PPh3)4,Et3N Me (13)(CH3CH=CH)2CuLi +CH3CH2CH2BrCH3CH=CHCH2CH2CH3 3 1AgNO3/C2H5OH a. 1-b. 2-c. 2- 2- c b a 1NaI- a.3-b. 2-c. 1-d. 2- a c d b 2KOH- a.CH3CH2- C- Cl CH3 CH3 b.CH3CH2- CH- Cl CH3 c. CH3CH2CH2CH2Cl a b c 3NaCN a. CH3CH2CH2Clb. CH3CH2CH2Brc. CH3CH2CH2I c b a (7) CH3CH2CH- CHCH2CH3 Br CH3 KOH CH3CH2CH=CCH2CH3 CH3 (8) CH3 BrKOH- CH3 O Me CHCH3 3CHCH2CH 2 2H H5 5OH OH 4 a. CH3CH=CHCH2CH2Clb. CH2=CHCH2CH2Clc. CH3CH2CH=CHCl d. CH3CH2CH=CHCH2Cl a d b c 5SN2 a.b.c.Br Br Br b a c 6SN1 Br Br Br a. b. c. c b a 8HBr a bcCH3C CH3 Br CH2CH3CH3CH CH3 CH CH3 Br CH3CH CH3 CH2CH2Br a b c (9)E1 CHCH3 Cl CHCH3O2N CHCH3H3CO Cl Cl a b c c a b 8. (1) CH2=CH- CH2CH(CH3)2 CH3C- O- CH2CH2CH3 CH3CH2CHCH2CH3CH3CH- CHCH3 () CH3 CH3 (2) (3) OH (4) Br Br 1 H2C CHCH3 HBr CH3CHBrCH3 H2C CHCH3 Br2 CH2BrCH=CH2 hv Mg/ Et2O (CH3)2CHMgBr CH2=CHCH2CH(CH3)2 CHCHCHCH Cl 3 CHCH CH CHCH CHCH3 Cl c c CHCH- - CHCH2CH 2 H2C CHCH3 HOCH2CH2CH3 B2H6 H2O2, OH H2C CHCH3 CH3CHOHCH3 H2O / H2SO4 KMnO4 CH3COCH3 1. CH3MgBr 2. H2O, H CH3CCH3 CH3 OH HBr CH3CCH3 CH3 Br AgNO3 HOCH2CH2CH3 (CH3)3COCH2CH2CH3 (3) HC CCH3 B2H6 H2O2, OH CH3CH2CHO CH2=CH2 HBr CH3CH2Br Mg/ Et2O CH3CH2MgBr CH3CH2CHCH2CH3 OH 1. 2. H2O, H (4) HC CH 1. NaNH2 2. CH3Br HC CH3 1. NaNH2 2. CH3Br CH3C CCH3 Na/ NH3( liquid ) CH3 CH3 Br2/ CCl4 CH3CHCHCH3 Br Br ( 11.AC6H10Br2- CCl4B BKOH-C CDiels- AlderC OHC- CHOOHCCH(CH3)CHOABC CH3 1. O3 2. Zn, H2O OHCCHO +OHCCH(CH3)CHO C CHO Mg gBrBr CHCH3CHCH 2 2. H H CH3 1. N Na aNHNH 2 2. CH CHCCHC CH3 C O O O O H3C O O + CH3 C CH3 A Br2- CCl4 CH3 Br Br KOH- C2H5OH B 12 (1) CH3CH CH NaNH2 NH3(l) (2) CH3CH2CH2Br CH3CHCNa CH3CH CCH2CH2CH3 CH CH NaNH2 NH3(l) CH CNa O OH COCH3 (3) OH C CH H2SO4,HgSO CH CH NaNH2 NH3(l) (4) O CC H H5C2 C2H5 H CH3CH2Br CH CCH2CH3 NaNH2 NH3(l) NaC CCH2CH3 CH2CH2Br CH3CH2C CCH2CH3 1.Na,NH3 2.NH3,H2O HCH2CH3 CH3CH2H C6H5CO3H CHCNa CH CH NaNH2 NH3(l) CH CNa CH3CH2CH2CH2Br CH CCH2CH2CH2CH3 O OCHCH3 C CH HC C O CHCH3CH CCHCH2 2CHCH H H CHCH3CHCH2 Na 9 1 (1) CH2CH CH2OH PCC, CH2Cl2 CH2CH CHO HCO3H CH3OH, CH3ONa (2) OOH OCH3 CH2OH SOCl2Mg O 1) 2) H3O (3) CH2ClCH2MgCl CH2CH2CH2OH (4)CH3CH CH2 O +CH3OH H CH3CH CH2 OH OCH3 CH CH2 O + CH3OH CH3ONa (5)CHCH2 OH OCH3 (6)CH3SH NaOH CH3SCH3 CH3SNa CH3I (7)C2H5SC2H5 KMnO4 C2H5SC2H5 O O (8) SCH2CH3 CH3CH2I SCH2CH3 CH2CH3 I 2. (CH3)3CCHCH3 OH H3PO4(85%) (CH3)3CCH CH2 (CH3)2CHC CH2 CH3 (CH3)2C C(CH3)2 + + (1) H CHCH3 3OHOH CH3 3C CH H O OH O O OH CHCH3 3O ONaNa aOHOH H H5 5 K KMMnO (CH3)3CCHCH3 OH H+ (CH3)3CCHCH3 OH2 H2O (CH3)3CCHCH3 (a) (CH3)3CCHCH2 H H+ (CH3)3CCHCH2 H+ (2)CH2OH + H+ H2O CH2OH CH2OH2 CH2 (a) H+ CH2 H (b) H+ CH2 CH3 H H H+ CH2(C) H C CH3 CH3 H3CCH2OH HBr C CH3 Br H3CCH2CH3 (3) CHCH2 2OHOH + 2 H+ (4) OH - H2O (5) OH OH H2SO4 O H+ H2O H+ OH OH O OH2OH OH HO HO (6) CH3 CHCH3 OH H+ H+ H2O H+ CH3 CHCH3 OH CH3 CHCH3 OH2 CH3 CHCH3 H 4 (1) (CH3)3COH (CH3)3CCH2CH2OH (CH3)3COH (CH3)3CCH2CH2OH KBr (CH3)3CBr Mg Et2O (CH3)3CMgBr O (CH3)3CCH2CH2OMgBr H2O (2) CH3COCH3 H3C H C CH3 OCH2CH2CH3 CH3COCH3 H3C H C CH3 OCH2CH2CH3 Al(OCHMe2)3 Me2CHOH CH3CHCH3 OH Na CH3CHCH3 ONa CH3CH2CH2Br (3) OH OCH3 CH3 CH(OH)CH3 H H3 3C CHCH3 3 OHOH Na H C CHCH3 O OCHCH CHCH3 C (4) O CH2CH3 OH Al(OCHMe2)3 Me2CHOH O CH2CH3 OH (1) LDA (2)CH2CH2Br O CH2CH3 CHCH OH (5) (6) O OCH3 NaOCH3 OH OCH3 K2Cr2O7/H2SO4 O OCH3 (7) O Br2 hv Br CH3CH2OH CH3CH2ONa O PhCO3H OH O O (8) OH H2SO4 1. O3 2. Zn, H2O O O O OCHCH3 3 3 2Cr2 2 Cr O7/ / (9)OH H O CH3 OH H2SO4PhCO3H O (1) CH3MgCl (2) H2O / H OH CH3 CH2=CH2(10) 7. OC2H5 (1) NO2 NO2 O2N OH H2SO4 100 oC OHHO3S SO3H HNO3 OHO2N NO2 NO2 CH3CH2Br NaOH OCH2CH3O2N NO2 NO2 (2) Br2, FeBr3 Br Mg / Et2O MgBr Cl2/ hv Cl NaOH / EtOHH2O / H OH K2Cr2O7 / H2SO4 O MgBr OH H2O / H OHOH SOSO3 3H H H HNONONO3 O O2N (7)OH Br Br OH H2SO4 OHHO3SOHHO3S Br Br Br2 OH Br Br H2SO4 / H2O 9.ABIR 1H NMR 1AC3H8OIR 36003200 cm- 1 1H NMR 1.1d, 6H 2.2s, 1 H4.0m, 1 H H3C CH H3C OH 2.2, s 1.1, d 1.1, d 4.0, m 36003200 cm- 1 2BC9H12OIR301016101510825 cm- 1 1H NMR 7.82 Hd J = 8.0 Hz7.32 HdJ = 8.0 Hz3.82 Hq2.23 Hs1.13Ht OCH2CH3H3C 2.2, s1.1, t3.8, q 7.3, d 7.8, d 11.C10H14O C10H12Br2O 1H NMR 1.39 Hs4.91 Hs7.44 Hm C10H14O C(CH3)3HO Br Br C(CH3)3HO Br2/ H2O 4.9, s 1.3, s 7.4, m C10H14O 3010301016101610 Hz3.83.8 O OCHCH 3.83.8 3 3, d 13 1LiAlH4 O CH3CH2 LiAlH4 OH CH3CH2 2H2, Ni O CH3CH2 H2, Ni OH CH3CH2 3C6H5NHNH2 O CH3CH2 C6H5NHNH2 CH3CH2 NNHC6H5 4(a) C6H5MgBr, (b) H+, H2O O CH3CH2 1. C6H5MgBr OH CH3CH2 C6H5 2. H , H2O 5NaCN, H2SO4 O CH3CH2 NaCN OH CH3CH2 H2SO4 CN 6HCl O CH3CH2 CH3CH2OH OCH2CH3 CH3CH2 HCl OCH2CH3 7Zn(Hg), HCl O CH3CH2 Zn- Hg CH3CH2 HCl C C6 6H H5 5MM NNHC gBr CHCH3 3CHCH . H , H2 2O O O 2. 1 CH3 CH3 O CH3 OH CH3 O 1. B2H6 2. H2O2, OH CrO3 N HC CNa 1. 2. H2O 2 O OH OH TsOH, C6H6 O O 1. NaNH2 2. MeI O O Me HCl, H2O Me O 3 MeO MeO MeOBr CHO OHOH TsOH, C6H6, MeO MeO MeOBr CH O O 4 CH3CH2CHO + (CH3)2NHNH2CH3CH2CH=NN(CH3)2 5 CCH2CH2CH3 CH2CH2CH2CH3 O CH3CH2CH2COCl AlCl3 Zn- Hg, HCl 6 C6H5CCH3 O C6H5CCH3 OH CN 1. NaCN 2.H2SO4 7 H3C H H CH3 O H3C H H O C CH3 O PhCO3H CHCl3 OHOHOHOH TsO OH,H, C C6 6H6,6, MMeOeO MMeO 3)2N NH HN NH H 3CH CH2 2CHCH2C A AlCl 8 C6H5CCH3 O C6H6, C6H5C=CH2 TsOH OHN+N O 9 CH3CH2CHO 1. CH3(CH2)3MgBr Et2O 2. H Ch3CH2CCH2CH2CH2CH3 OH H Ch3CH2CCH2CH2CH2CH3 O H2CrO4 8 3MeOCO(CH2)4CHO 41 Cr2O3 N CH3CH2CH2CH2CH2Br MgBr Et2O CH3CH2CH2CH2CH2MgBr 1.CH2O 2.H CH3CH2CH2CH2CH2CH2OHCH3CH2CH2CH2CH2CHO (7) O CN Me O Me O 1. NaNH2 / Et2O 2. MeI O Me NaOEt O Me O CH2=CHCOCH3 NaOH O OH Me O CN Me NaCN Michael Michael CrCr O O CHCH 2OH 1014 1 O O + KOH MeOH O O ? 2 O O + NaOMe, MeOH ? O O 3 O O O + NaOMe, MeOH ? O O O 4 O O + NaOMe, MeOH ? OCH3 O OCH3 O 5 CN+ NaOMe, MeOH ? OO O O CN MMe ? OCH3 Na aO OMMe 2. a) CH3CH2CH2CO2HCH3CH2CH2CH2OH LiAlH4 b) CH3CH2CH2CO2HCH3CH2CH2CH2OH LiAlH4PDC CH2Cl2 CH3CH2CH2CHO c)1- CH3CH2CH2CO2HCH3CH2CH2CH2OH LiAlH4SOCl2 CH3CH2CH2CH2Cl d) CH3CH2CH2CO2H SOCl2 CH3CH2CH2COCl e) CH3CH2CH2CO2H SOCl2 CH3CH2CH2COCl PhMgBr Et2O CH3CH2CH2COPh f)N- N- CH3CH2CH2CO2H SOCl2 CH3CH2CH2COCl PhNHCH2CH3 CH3CH2CH2CONPh CH2CH3 g) CH3CH2CH2CO2H(CH3CH2CH2CO)2O Ac2O h) CH3CH2CH2CO2H SOCl2 CH3CH2CH2COCl CH3CH2CH2CH2OH Py CH3CH2CH2CO2CH2CH2CH2CH3 CH CHCH3 3CHCH CH2 2COCOClCl CH2CHCH2 2C CO O 2 CHCH ON NPhPh CHCH2CH 3. 1 CO2H 1. LiAlD4, Et2O 2. H2O ? CD2OH 2 MeO2CCHOMeO2C HO Ph3P=CH2 LiAlH4 3 O OEt 1. NaOEt, EtOH 2. H3O+ 1. KOH, H2O 2. H3O+ O OEt O O OH O O (4) O O OEt 1. MeMgI (1 mol), Et2O 2. H3O+ O O () (5) OPOCl3 CN 85% H3PO4 SOCl2 NaCN H2SO4 OH CN CO2HCOCl (POCl3/) (6) OHHO2CO O H2, Pd / BaSO4 OH O OH H2SO4 4. 12- POOOHOH CNCN O O O Cl3 CO (CH3)3COH CH3CHCO2H CH3 CH3CHCH2OH CH3 CH3CH=CH2 CH3 H2SO4 1. B2H6 2. H2O2, OH H2CrO4 33,3- (CH3)3COH(CH3)3CBr (CH3)3CMgBr (CH3)3CCO2H HBrMg / Et2O 1. CO2 2. H 7 CH3CH2OHCO2H 1. KMnO4 2. H LiAlH4 H2SO4 CO2CH2 93- CO2HCO2Et CO2EtO O EtOH H NaOEt EtOH 1. NaOH(aq.) 2. H , 123- 6- 2- O O O O O CO2Et O CO2Et O CO2Et NaOEt (CH3)2CHBr NaOEt O 1. NaOH(aq.) 2. H , NaOCH3 CH3OH 5.- 4-A B COCO2Et Na aO OEtEt E EtOHtOH t- Bu OH TsCl Py t- Bu OTs A PhCO2Na DMF, t- Bu O2CPh N