第14章醛、酮和醌 14-1 OH OH CN 日）⊙CHCH,6)CHCH-n OH OH O⊙d+C=CCH,)⊙CHCH,cooH8©CH-CHCH,cH OH aGa。ga000u0N C-NOIEA0E。0 (CH-NH-NHENH2 (CH-N ()-COONHAg (1)No Reaction (-COOH ()COOH (1)-CH.OH (20-CH:OH (21)-COOH CH2OH )O-CH,OH+HCOOH()《◎CH=CHCH0 NO2 a)⊙CH=CHCOOH(s)《○CH0(6)○CH,OH+CH3COCH 14-2 OH OH OH 0OCcN日@cH6)OCc=ccH, CH3 OH (4)CHCOOH (s)C-CH2 (No Reaction CH3 CH3 ()图No Reaction(9◎C=NNH, CH3
1 14 14-1 C2H5 OH (1) CH OH CN (2) CH OH ( CHC4H9-n 3 ) CH CH3 OH OH (4 ) C C (5 ) CHCH2COOH (6 ) CH=CHCH2CH3 C C2H5 H OH (7 ) O CCH3 (8 ) CH O OC2H5 (9 ) SO3Na CH=NOH (11 ) CH=NH NH NO2 (10 ) (12) CH=NH NH NO2 COONH4 O (13) CH=NH NHCNH2 (14) CH=N (15) + Ag (16 ) No Reaction (17) COOH (18 ) COOH (19 ) CH2OH CH=CHCHO (20 ) CH2OH (21 ) COOH CH2OH (22 ) CH2OH + HCOOH (23 ) (24 ) CH=CHCOOH (25 ) CHO CH2OH NO2 (26 ) + CH3COCH3 14-2 C CH3 OH (1 ) CN (2 ) C CH3 OH C6H5 C CH3 OH C CCH3 (3 ) No Reaction CH3 C C=CH2 CH3 OH (4 ) CH2COOH (5) (6 ) C No Reaction C NNH2 CH3 CH3 (7) S S (8) (9)
(10)C-NNHCalts (11)No Reaction (2CH CH3 -o -a OH OH CHsCH3 。-CH,(克莱门森还原)()-CH,(黄鸣龙还原) CHBr (COOH.CH O-am0Ow⊙8a OH 14-3 (1)CH:CHCH2CHO (2)CH3CH2CH2CH2OH Br (3)CHCH=CHCHO (CH3CH=CHCH2OH CH3(CH2)2CH2OH (s)CH3CH2CH2CHO (CH3CHCHCHO Br Br (CHCH-CHCH OH CH3CHCH2CHO CN CN 日CH,CH-CHCHSO,Na OH CH3CHCH2CHO SO3Na (9)CH3COOH CO2 (CHCH-CHCH-CHCH-CHCHO ()CHO (Diels-Alder) CCH3 9C2H5 CHCH-CHCH OC.Hs
2 CH3 CH3 O C=NNHC6H5 (10) (11) No Reaction (12) O C CH3CH3 CH3 OH OH OH CH C C (13 ) (14 ) CH3 OH CH (15 ) C2H5 (16 ) ✂✁ C2H5 Br O CCH2 C NO2 CH3 18 COOH O (19 ) + CHI3 (20) (21 ) C CH2 C OH CH3 O 14-3 Br (1) CH3CHCH2CHO (2) CH3CH2CH2CH2OH (3 ) CH3CH=CHCHO (4 ) CH3CH=CHCH2OH + CH3 (CH2 )2CH2OH OH (5 ) CH3CH2CH2CHO (6 ) CH3CHCHCHO Br Br CN (7 ) CH3CH=CHCH + CH3CHCH2CHO CN (8 ) CH3CH=CHCH SO3Na OH (9 ) CH3COOH + CO2 CH3CHCH2CHO SO3Na CHO CH3 (10) CH3CH=CHCH=CHCH=CHCHO (11) (Diels-Alder) OC2H5 (12 ) CH3CH=CHCH OC2H5
14-4 0 OH (2) G3) 6 OH N-OH (1molH2N-OH) (2mol H2N-OH) 0 N-OH H OH O () -OCH3 OH OH OH 8)HO○-OH(g)HO○-OH CN 14-5 A) Ag 0 BIANH-NONon×as CHI3 D 「结晶 A ×NaOH/2 CHI3 (2) B[AgNH2INO3×J Ag NaOH/L× Ag CHI3 A Ag Fehlingi试 6) B [Ag(NH )JNO3Ag c NaHSO× D 结晶 (4) 砖红) NaOH/2 BFehlingi试剂、砖红广 CHI3 ×Ao,CH d/
3 14-4 OH OH CH3 O O O O Br Br Br Br (1) (2) (3) OH O (4) N OH) OH (1molH2N-OH) N OH N (2mol H2N Cl OH OH (5 ) (6 ) OH OH NH (7) OH OH OCH3 (8 ) (9 ) HO OH CN HO OH 14-5 (1 ) A B C D [Ag(NH3 )2 ]NO3 Ag × × × × × × NaOH/I2 CHI3 NaHSO3 NaOH [Ag(NH3 )2 ]NO3 × × /I2 NaOH/I2 CHI3 CHI3 Ag 2 A B C D × × Ag NaHSO3✄✆☎ × [Ag(NH3 )2 ]NO3 A B C D × × × Ag Ag (3 ) Fehling✝✟✞ Cu2O NaOH/I2 NaOH/I2 CHI × 3 A B C d Fehling✠☛✡ (4) × × × CHI3
A) (5) B CHeC,紫红色 NaOH n:CHI D 紫色 × (6) A AgBry B x Bx BH, c CCHIs C H2 Na E 试剂D混 Fx G x 14-6 丁醛 结晶HCT醛 (①)3一戊酮7 心，沉淀0一皮用 过滤 正丁醇 ×过滤 正丁醇 OH 水相心000H (2) Co NaOH/H 分液 [CH3(CH2)3]2O 4并达o,GHco CH,○oH 油相炮as0,油相 (3)CH3-CHO NaHCOs 分液 HO-COOH 水相c,H0-O-c0oH 14-7 能发生碘仿反应的有：1,4,5,6,7,9。 能顺利与饱和NaHS03反应的有：2,4,7,8,9,10,12。 能发生银镜反应：2,9,10,12
4 × × NaOH /I2 CHI3 (5 ) A B C D CHI3 × × FeCl3 FeCl3 Ag NaOH /I2 CHI3 CHI3 ☞ 6 ✌ A B C D E F G Tollens✍✏✎ × × × × × × C F Na H2 F × AgNO3 /ROH A AgBr Lucass✍✑✎ ✒✔✓ Na H2 × × × × × × C G D B B D G B G 14-6 (1) 3 ✕✗✖ ✘✔✙ NaHSO3 HCl/H2O × × H3O + 3 O OH × × × 2 [CH3 (CH2 )3 ]2O NaOH /H2O ✚✗✛ ONa CO2 OH ✜ H2SO4 H2O [CH3 (CH2 )3 ]2O ✢✤✣ ✥✦✣ CH3 OH (3) CH3 CHO HO COOH NaHCO3 ✧✩★ HCl ✪✩✫NaHSO3 ✬✤✭ Na2SO3 or HCl CH3 CHO HO COOH ✥✦✣ 14-7 1 4 5 6 7,9 NaHSO3 2 4 7 8 9 10 12 2 9 10 12
能发生羟醛缩合反应：2,4,6,7,8,9,10。 能发生Cannizzaro反应：12 能与费林试剂作用：2,9,10。 14-8 CH.cCH.:CCH.CHs- CHCH.CLOH OH OH OH2 二里cHg0ct0HoH÷KaH-OCH.CH.OH C2Hs CH-0CH,CHOH、三CH,C0D产物 OH H H CHD-C2Hs CHO-C2Hs H20、 CHOC2Hs c=No其CH Ph Ph C=NOCH在N 0 OH2 OH
5 2 4 6 7 8 9,10 Cannizzaro 12 2 9,10 14 8 H C2H5 OH OH (1 ) CH3CCH2CH3 O + H + CH3CCH2CH3 HOCH2CH2OH CH3C OCH2CH2OH C2H5 OH CH3C OCH2CH2OH - H + + H + C2H5 OH2 CH3C OCH2CH2OH - H2O H C2H5 O CH3C OCH2CH2OH C2H5 CH3C O - H + (2 ) OH C O H + H + H H + HOC2H5 O C OH + + O C O OH H H C2H5 O C O OH H C2H5 + H H H H O C O OH2 H C2H5 H- + + H C2H5 + H + O C O H H2O H C2H5 O O C CH3 CH3 C H - + + H2O (4) N Ph OH C CH3 N Ph OH2 + N Ph H2O OH - CH3 C + N Ph CH3 C N Ph OH2 H + ✮ ✯ ✰ ✱ CH3CNHPh O Beckmann