第13章醇、酚和醚 13-1 (CH3CH2CH2ONa ([CH3CH2CH2O]2Mg G)CHCH2CH2ONa (4)Mg(OCH2CH2CH3)I +CH4 (5)CH3CH2CH2ONa CH3C=CH (6)CHCH2CH2OH2HSO ()CH-SO,CH2CHCH(磺酸酯) 0 (s)CH3CH2CH2OCH3 ()CH3CH2CH2OCCH3 (1o)CH3CH2CH2CI (CH;CH2CH2Br (12)CH;CH2CH2I (3)CH:CH2CH2CI (CHCH.CH.Br (i)CHaCHaCHaCI (CH;CH-CHOCHsCH2CH2 (CH3CH=CH2 (is)CH3CH2COOH (19)CH3CH2COOH (20)CH3CH2CHO (21)CH3CH2CHO (22)CH3CH2CH2OC2Hs (23)2CH3CH2CH2I (24)CH3CH2CH2OH+CH3l 13-2 0 CCH3 0CH,②-ONa)CH,@OcCHs)CHoH(Fies重捕) 0 CH(CH3)2 (4)CH3>OCCH3 (s)CHOH CH(CH3)2 (6)CH⊙OCH,CH,CH,()CH②OCH()CH<OCH CH2CH=CH2 (9)CH②O<⊙No2(1OCH-OCH,CH-CH2(II)CHOH Br SO3H (12)[(CH3-OFe (13)CH3-OH (14)CHOH Br NO2 C(CH3)3 CHO (15)cH,-0H(16)cH,三0H (17)CH3OH C(CH3)3
1 13 13-1 (1) CH3CH2CH2ONa (2) [CH3CH2CH2O ]2Mg (3) (4) + CH4 CH3CH2CH2ONa Mg(OCH2CH2CH3)I (5) CH3CH2CH2ONa + CH3C CH (6) CH3CH2CH2OH2HSO4 (7) CH3 SO3CH2CH2CH3 () + - (8 ) CH3CH2CH2OCH3 O 9CH3CH2CH2OCCH3 (10 ) CH3CH2CH2Cl (11 ) CH3CH2CH2Br (12 ) CH3CH2CH2 I (13 ) CH3CH2CH2Cl (14 ) CH3CH2CH2Br (15 ) CH3CH2CH2Cl (16 ) CH3CH2CH2OCH3CH2CH2 (17 ) CH3CH=CH2 (18 ) CH3CH2COOH (19 ) CH3CH2COOH (20) CH3CH2CHO (21) CH3CH2CHO (22) CH3CH2CH2OC2H5 (23) 2CH3CH2CH2 I (24 ) CH3CH2CH2OH + CH3 I 13-2 (1) CH3 ONa (2 ) CH3 O O O CCH3 (3 ) H O CH3 CCH3 (Fries) 4CH3 O CH3 O C CH3 CH(CH3 )2 (5) OH CH(CH3 )2 (6) CH3 OCH2CH2CH3 (7 ) CH3 OCH3 CH3 OCH3 (8 ) CH3 (9) O NO2 (10) CH3 O CH3 CH2CH=CH2 CH2CH=CH2 (11) OH (12 ) CH3 Br Br OH CH3 SO3H [(CH3 O Fe] OH 3- ) 6 (13 ) (14 ) (15) CH3 OH CH3 C(CH3)3 O NO2 (16) H (17) CH3 OH CHO C(CH3 )3
COOH (18)CH->-O(Koble Schmidt反应)(19)CH,-☐OH 13-3 -C-CC O ucas试剂 慢O CH西黄) 室温 c-eocc 慢 立即混浊 (2)CH2OH + CH3CH2OH (1)HIO4 12/Na0 黄色△0壁 OHOH (2)AgNO3 CH2CH2 CI OH A 白↓ LAgNI:NO cJ 紫色 H◆ C D H2 12/NaOH CHI3 Na 色
2 (18 ) CH3 OH COOH (Koble - Schmidt19 CH3 OH 13-3 C C C C C OH OH C C C C C C C C OH C C C C OH C Lucas✂✁ × I2 /NaOH CHI3 × (1) (2 ) CH3OH CH3CH2OH CH2CH2 OH OH CH2CH2 Cl OH × × × ✄✆☎✞✝✠✟☛✡✠☞✠✌ × × ✍✏✎✟✑☞✓✒✔✝✓✕ (1) HIO4 (2)AgNO3 (3 ) [Ag(NH3 )2 ]NO3 ✖ Br2 /H2O ✗✂✘ A B C ✙✂✚ 4 FeCl3 Na H2 KMnO4 /H+ A B C D (5) FeCl3 ✛✂✜ Na A H2 B C D I2 /NaOH CHI3
X 分层 (6) X AgNO醇AgB Na 浓s0 0 溶解不分层 紫色 13-4 环己烷 上层 上层 (①环己醇s0层环己醇 NaOH 分液 分液 苯酚 上层 ⊙CH,OH + (2) O0 爱 0w-©0H ©c HS0, (3) 令OCH,NOH分液、 相 球盐0，可oC H 水相Goe@ 13-5 (I)SN2历程 CH3CHCHCHOH ZnCkCH.CH.CH.CHCl H CH2CH2CH3 CL CH-C-CHCHaCHCHCI+ H ZnCl2(OH)ZnCl2 H2O 3
3 FeCl3 ✢✂✣ Na H2 AgNO3 /✤ AgBr ✥H2SO4 ✦✧ ★✂✩ ✪ 6 ✫ ✬✦✭✧ A B C D E 13-4 ✮ 1 ✯ NaOH ✰✲✱ ONa CO2 /H2O ✳✴ H2SO4 H2O ✰✲✱ CH2OH ✵ 2 ✶ OH NO2 OH O2N ✷✲✸✂✹✲✸✂✺ OH NO2 NaOH ✻✲✼ ONa O2N CO2 OH O2N Cl OCH3 CH3 OH NaOH✽✲✾ CH3 ONa CO2 ,H2O CH3 OH H2SO4 ✿✂❀ H2O (3) OCH3 13-5 (1) SN2 CH3CH2CH2CH2OH CH3CH2CH2CH2 + ZnCl2 ZnCl2 δ δ O H CH3CH2CH2CH2 ZnCl2 ZnCl ZnC 2 l2 Cl δ δ - [Cl CH2 O H ] Cl + (OH) - + H2O CH2CH2CH3
()SNl反应 (CH).COH+r(CH,cdlH(CH,在、三(CHgC-C F(CH,c6H+ZnC、三(CH).C8克Cg→1CHl,t+ZnC,Ol 日 cr (CH)C-CI ZnckHao ) (CH)CCHCHH CH3)CCHOH2(CH)CCH-CH OH 甲#迁毯(CH)CCH(CH)→(CH)CCH(CH力 OH 扩环 Br CH3 HO CH3 (5)(CHC-C(CH)Ag OHBr OH CH3 H CH.CC(CH) OH m (频事麻重) 「r8
4 (2 ) SN1 (CH3)3COH + H + (CH3)3COH (CH3 ) 2 3C (CH3 )3C Cl -H2O (CH3)3COH (CH3 )3CO H (CH3)3C (CH3 )3C Cl H2O + ZnCl2 ZnCl2 + ZnCl2(OH) Cl - H + ZnCl2 δ δ or: + H + (CH3 )3CCHCH3 OH (3 ) (CH3)3CCH CH3 OH2 H2O - (CH3)2CCH CH3 CH3 ❁ ❂❃❄ (CH3 )2CCH(CH3 )2 Cl - (CH3 )2CCH(CH3 )2 Cl (4 ) C(CH3 )2 OH + H + C(CH3 )2 OH2 C(CH3 )2 - H2O ❅❆❇❈ CH3 CH3 CH3 CH3 Br (5) (CH3 )2C C(CH3)2 OH Br Ag + -AgBr CH3 C C(CH3)2 OH CH3 ❉❋❊✲●■❍ CH3 C C CH3 CH3 CH3 HO H + CH3CC(CH3 )3 O (6) OH C CH3 CH3 OH OH C CH3 CH3 OH C CH3 CH3 H + -H2O OH C CH3 CH3 O C CH3 CH3 - H (❏▲❑◆▼P❖❘◗❚❙ C CH3 OH CH3 CH3 CH3 HO CH3 CH3 HO CH3 CH3 O H + -
CH3H CH3 ()CHCO-CH3+f→CHgC CH3 CH3 a CH3 CH3 CH3 CH3 (8)CH 9H+H、cH, CH2 Ssl CHr G CHa OH CH3 aH,o1CH-CHOH H,产物 CH3OH ()(CH3)C CH2 CHoCHS OCH CH,o (CHC CH OH OCH3 CHO - OCHo 13-6 (1)(CH3)2CCH(CH3)2 (2) OH CHaB. CH3 CH3 3) H C- ④②-C0OHCr0.毗啶 C2Hs CI ℃H5 CH3 C2Hs (5)CH>C CH-CHs (⑥)CrO/吡啶(Sarretti试剂) OH OCH3
5 (7) CH3 C O CH3 CH3 CH3 + H + CH3 C O CH3 CH3 H CH3 CH3OH + CH3 C CH3 CH3 Br - SN1 CH3 C CH3 CH3 Br (8) CH3 O CH3 C CH2 + H + CH3 O CH3 C CH2 H SN1 CH3 C CH2 OH CH3 CH3OH CH3 C CH2 CH3 CH3OH OH -H + 9 O (CH3 )2C CH2 + CH3O - SN2 (CH3)2C CH2 O OCH3 HOCH3 (CH3)2C CH2 OH OCH3 - CH3OO (10) CH2 CH CH2Cl CH3OCH2 CH CH2 O O Cl ❯✲❱❳❲ SN2 _ Cl - CH2 CH CH2 OCH O 3 δ δ 14 14 14 CH3 13-6 (1) (CH3 )2 (CH3 ) CCH 2 Br (2 ) CH2CH2Br OH CH2 O CH2 (3) CH3 C C2H5 Cl Cl H CH3 C C2H5 H (4) COOH CrO3 , , (5) O C C CH3 C CH CH3 C2H5 OH OCH3 (6) CrO3/ ❨❳❩❭❬ Sarrett❪❳❫ ❴ C2H5 CH3 CH3 H
gm2wNo80了微地 0 Ca.C cag猫aw08 OH NHCH3 (CH)C-C)CHCH,C ona (14)CHCH3 HO:SCHCH3 HO-CHCHs CHa CH CH NaOCHCHs CHCH-CHCHOCHCHs CH3 HOCHCH3 HO-CHCH3 CH2=CHCH CH CH2-CHCH CH3 Br Br CH3 (15)HSO/165 ONa OCH:CH:OH (16) ICH3 ()HOCH2(CH2)2CH2CI HO(CH2)4CN OH CH3 (18)CHs CHCOH 了0 Br Br ()OHO.CH.OH OH OCH3 (20)HNO3/H2SO4 NO. ⊙No2 NO2 NO2 13-7 由大到小 (I)ABDC (2)BCA (3)BACD (4)ABCD (5)CBAD (6)ABDC (7)CABD (8)DCAB (9)ACBD 010 BDAC 6
6 CH3 OH ❵ 7 ❛ CH3 CH3 O C (CH3CHO)3Al (8) O O (9) O CH2 CH2 OC2H5 CH3 CH3 OH OH (10) C6H5C CH2 O C6H5CH CH2 NHCH3 (11 ) O (14) CHCH3 CH3 CHCH3 CH3 HO3S CHCH3 CH3 HO CHCH3 CH3 NaO CHCH3 CH3 CH3CH=CHCH2O CHCH3 CH3 CH3 HO CH2=CHCH CHCH3 CH3 HO CH2 CHCH Br Br 15 H2SO4 /165 C ONa OCH2CH2OH Br CH3 CH3 (18) OH Br CH3 O CH3 OH O OCH2CH2OH (19 ) OH OH CH3 ( NO2 20 ) HNO3 /H2SO4 NO2 NO2 NO2 O 13-7 ABDC BCA BACD ABCD CBAD ABDC CABD DCAB ACBD BDAC (CH3)2 H OH CH3 (12 ) (CH3 )2 (CH3 )2 (CH3 ) C 2 C CH3 C2H5 CHCH3 C=C (13 ) ONa Br C2H5 CH3 CH3 (16 ) C OH H + I (17 ) HOCH2 (CH2 )2CH2Cl HO(CH2 )4CN
13-8 (CHCH-CHCHCH.CHOHCHCHCHO OH CaHCH-CH C CHCH,CCH (3)CH:CH-CH2 HBr CHCHBrMCO CH CHCOOH CH3 CH3 4⊙→0u→om&Go,0:O0 6⊙→⊙a→⊙HC→产物 分0H→0C,s压产物 分)由)2c,HC,cH,oH0产物 ⊙cH=c4→c94o+9HH:7→94c0aH8出 0 ,BC4产物 00→0S0H一→002产物 I0)O-CH,→Br-OCH,→BrO-CH,C →Br-OCH,OH→Br-CH2ONa O→OQ+0N-Qa①cHo产物 NO2 mO-oH→○-0H→Ccc0Q产物
7 13-8 C2H5 C2H5 OH C2H5 (1) CH=CH2 B2H6 /THF H2O2 /OH- CH2CH2 CrO3 -❜✲❝ CH2CHO C2H5 C2H5 (2 ) CH=CH2 H2O/H + CHCH3 OH C2H5CCH3 O -H2 Cu CH3 CH3 (3) CH3CH=CH2 HBr CH3CHBr H2O/H + CH3CHCOOH Mg/ CO2 (2) (1) (4) OH OH O K2Cr2O7 /H2SO4 (5) Cl OH Cl2/Fe OH 6 OCH3 CH2=CH2 AlCl3 Br2 /Fe 71 2C2H5CH2CH2OH H2SO4 - H2O C2H5 OH OH ❞❢❡ (8) CH2=CH2 CH2 CH2 O HOH CH2 CH2 OH OH CH2 CH2 O CH2 CH2 O CH2 CH2 Na Br SO3H OH (9 ) Br NaOH/H2O CH2CH=CH2 CH3 CH3 Cl B CH2 r Cl (10) Br Br CH2OH Br CH2ONa Cl NO2 O2N Br CH2ONa ❣❤ OH OH (11) O CH3CO3H
wc-cH→0。一→8肚6腊 o CH O-CH:CH O-CH.H OH -c-0a8沿→g-G0-a-g 13-9 A.(CH3)CHCHCHs B.(CH3)2 C-CHCH3 C.(CH3)2C=O D.O=CHCH3 OH 13-10 A. CH ,Ho入cH 13-11 A©OCHB.GOHC.CHI 13-12 CH3 CH3 0 B.CH2 G CH:-CH C.C.H.CCHs OH OH 13-13 A.CH-o CH.CHo
8 OH OH (12 ) CH2=CH2 O CH2 CH2 O CH2 CH2 CH2 CH2 2 OH OH OH OH Cl Cl CH2 CH2 O CH2 CH2 O CH2 CH2 CH2 CH2 O CH2 CH2 CH2 CH2 O CH2 CH2 KOH THF 13-9 (CH3 )2 (CH3 ) (CH3)2 2 C O D. O=CHCH3 C OH A. CHCHCH3 B. CHCH3 C. 13-10 CH3 CH3 OH Br OH A. B. CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 Br C. O O D. E. CH3 HO CH3 HO 13-11 CH3 CH3 O OH A. B. C. I 13-12 CH3 C2H5 OH OH A. CH2 C CH2 CH3 CH3 B. CH2 C CH2 CH3 C. CCH3 O O 13-13 CH CH3 CH3 CH3 A. O