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
OH mec-Hm&ca→pnct-1·i 0 pm8 CH-H OH,PHOCHI→Pm&cah·i PHeCI:-cmc 0 PHeCIs OHPh 9 Cg,→PhC+c， OH OH →PhCo0+CH1 H ) CH-CHCHO OH CH2CHCHO CH2CH2CHO H (CH,CCHCH,CH,OH CH,CCHCH.CH,C子内sg8CH 0 CH CCH-CH2 14-9 0oot第去aa8a,GHCl8o。 0
6 H H H C H C O O O - OH OH (5) + H C O - CHPh H C H O O + H Ph - NaOH HCOONa + H2CPh OH O H - - (6 ) PhCCH2 OH slow O PhCCH2 I2 fast O PhCCH2 I + I - - - O PhCCH H I I OH I O PhCCH I - 2 O PhCCHI2 + C C O O OH H - I2 O PhCCI2 I OH - - - O PhCCI2 O PhCCI3 + O PhCCI3 - OH Ph CI3 - Ph - OH + CI3 PhCOO + CHI3 - (7) CH2CHCHO CH2CH2CHO H OH - CH2CHCHO CH2CH2C O H CHO O CHO O H H H2O CHO O (8) CH3CCHCH2CH2Cl H OH - O CH3CCHCH2CH2Cl CH2 CH3CCH CH2 - Cl - O ✲✴✳✦✵ SN2✶✩✷ 14-9 O (1 ) H2O/H3PO4✸ ✹ ✺✼✻ CH3CH2CCH3 , CH3CH2CONa O , CHBr3, CH3CH2CCH2Br O
OMgBr OH Br (2)CH3CCH3 CH3CCH3 CH3CC2Hs C2Hs CH3 CH3 (3)CH3CHO,CH3CH=CHCHO,CH3CH2CH2CH2OH,CH3CH2CH2CH2 CI CH;CH2CH2CH2MgCI CH;CH2CH2CH2CH2CH-OMgCI CH3(CH2)sOH 0 OH CH、C(OH(CH2 (4)CHCCH3 CHCC=CCH3 CC=C. CH H H 0O.C0·CX0mOs+,am (6CH=CHCHO aoa ○CH,CH,CHO 0 ()CH-○NOH NH OCH3 (s)(CH3)2CCHO (CH3)2CCH OCH (CH)CCH OCHs Br Br MgBr OCH OMgBr (CH)CCH-C(CH)CH-OCH (CH3)CHCHC(CH3)CHO OCH3 OH CH3 CH3 O CH3 (9)CH3-C-C-CH3 CH3-C-C-CH3 Br2/NaOH OH OH CH >
7 Br O (2) CH3CCH3 CH3CCH3 OMgBr C2H5 CH3CC2H5 OH CH3 CH3CC2H5 CH3 (3) CH3CHO , CH3CH=CHCHO , CH3CH2CH2CH2OH , CH3CH2CH2CH2 Cl CH3CH2CH2CH2MgCl CH3CH2CH2CH2CH2CH2OMgCl CH3 (CH2 )5OH O (4 ) CH3CCH3 CH3CC CCH3 OH CH3 C=C CH3 C(OH)(CH3 )2 H H S S (5 ) OH , O , , + NiS CH3 CH3 + CH4 (6 ) CH=CHCHO CH=CHCH O O CH2CH2CHO CH2CH2CH O O O (7 ) CH3 NOH NH CH3 (8) (CH3 )2CCHO Br (CH3 )2CCH OCH3 OCH3 Br (CH3 )2CCH OCH3 B OCH3 Mg r OCH OH 3 (CH3 )2CCH OCH3 OMgBr C(CH3 )2CH (CH3 )2CHCHC(CH3 )2CHO C O OH OH (9) CH3 CH3 CH3 CH3 C CH3 C CH3 CH3 CH3 C Br2 /NaOH
(10)-OCHs CHOCH2CH2CHs C.HOCH.CH.CH2CHs 0-Qa2, 8a CH BrCHa OH CH3COCH2CH=CHCOOH CCN (14) CONa OOH 0 (15) CCH2CH2COOH ○CHCH,CH,COoH C2H5OH CHs CaHs OH (16) CH3C(CH2OH)3 HCOOH CH3 OMgI OH (17) ⊙CH OH 9 (18) Br OH a OH 14-10 由大到小： (1)B A C D (2)B A C D (3)D A B C (4④)ABCD (⑤)DCAB (6)D B C A (7)D C B A (8)A D C B
8 (10) OC2H5 C2H5O CCH2CH2CH3 O C2H5O CH2CH2CH2CH3 CH3 Br O (11) CH3 O B CH3 r O (12) CH3 Br Br O OH (13) CH3COCH2CH2CH CN CH3COCH2CH=CHCOOH O O C OH (14) OONa C OH OOH (15) CCH2CH2COOH O CH2CH2CH2COOH O C2H5 OH C2H5 OH C2H5 (16) CH3CH2CHO CH3C(CH2OH)3 + HCOOH CH3 O (17) O CH3 OMgI O OH OH Br O O (18) O O O O Br Br OH OH Cl O O Cl O O Cl Cl 14-10
14-11 OH CCLORG-GUCCAGC-CUCMBOIC OH (2)CH.CCHCH-CHCHCH.CHCH3Br+CH3CH.CHO )CH,CH.CH.CCH8☐←CHCHa,C4ccH8-cH,CH,cH-CC0←2 CH.CH.CHO CH a)CH、 CH3、 CctCnc cgcouCb 66.G.O0·c6 ⊙oH→○0H QHdc4cHoO←-oH←CoH C Gt cieo OH OH 0ca0-Oama2°9：a0-Oa0cm8G° NO2 cH0-CHOCH,0-G←③-oH cm8-6°，O-cH←@ 9
9 (1 ) CH3CH2CH2CCH2CH3 Br CH3 Br CH3 CH3CH2CH2CCH2CH3 OH CH3 (CH2 )2Mg + CH3CC2H5 O CH3 CH3 CH2Br OH (2) CH2 CH2 CH2CHO C O CH2CHCH2CH3 + CH3 CH CH3 3 C CH O O (3) CH3CH2CH O C CH O O CH3CH2CH CH3CH2CH=CCHO 2 CH3CH2CHO CH3 OH CH2 C CH3 C CH3 O (4 ) CH3 CH3 CH3 CH2CH3 C CH3 C CH3 H CH3CHMgBr + CH3CCH2CH3 OH OH OH C2H5 (5) C2H5 OH C2H5 O + C2H5MgBr OH OH O (6 ) HC(CH2 )4CHO O3 OH OH C CH2 CH3 CH3 CH O 3 CH3 CH2=C CH3 C C CH3 Mg/Hg ✽ CH3CCH3 (7) Al2O3 O O CH=CHC CHO (8 ) CH3O NO2 CH3O NO2 + CH3C CH3 OH C O O CH3O CHO CH3O NO2 CH3C HCCl3 /KOH
O◇CHOCH,CH=CH,←CHON,BCH,cH=CH, CHONa&CHOH。◇CH,Br←+BrCH,CH=CH CH3 (10)CHaCOCH3 HC=CH_KOH HC=C-OH CH3CH3 CIKON HOCC OH LM C HOCCOH CH3 CH3 CHs CH Hs0头产物 (）O-CcCH,cH年KoRo"CH-CHaH/OR CCCCLLC-CCCC cmdon aa82-c8,肥X CH3 CHO 0X0i←aHa0·3cHcH0 0C2H5 QC2Hs 0 8HGH,GH,CHeBr·HCCH.CHCH←HOCHS,CH.CH.CH CHs CHz=CHCH2CHs 0C2H5 MgBr」 0C2H5 0C2H5 COCH3
10 CH2OCH2 CH2 + ONa (9) CH=CH2 BrCH2CH=CH2 CH2ONa CH2OH + BrCH2CH=CH2 CH2Br (10 ) CH3COCH3 + HC CH KOH HC C C CH3 CH3 OH CH3COCH3 KOH C C C CH3 CH3 HO C OH CH3 CH3 Lindlar.Cat. C C CH3 CH3 HO C OH CH3 CH3 C H2SO4 ✾ 11 ✿ CH2=CH2 CH2CH3 Cl2 /❀ KOH/ROH CH=CH2 CH2CH2Br HBr/ROOR HC CNa CH2CH2C CH CH2CH2CCH3 O H2O/HgSO4 /H+ HNO3 /H2SO4 CH2CH2CCH3 O NO2 Cl2 /Fe ❁✦❂ CH3 O O CH CH3 CH O O OH OH + (12) CH3 CHO HO HO CHO CH3 + CH3 CHO 2 CH3CHO OH OH HO HO CH3CHO + 3 CH3CHO C2H5 OH O (13 ) CHCH2CH2CH3 OC2H5 C2H5 MgBr OC2H5 + HCCH2CH2CH3 CH2=CHCH2CH3 HOCH2CH2CH2CH3 C2H5 OH C2H5 MgBr OC2H5 Br OC2H5 COCH3 OC2H5 OC2H5 Br COCH3 OC2H5