第一節(jié)醛和酮

1、 COR C H Ar C H H C HOOO醛：R C R Ar C R Ar C ArOOO酮：/00OO 對 苯 醌00OO 萘醌1,4-HHC Osp2雜化HHC O+-脂肪醛酮：芳香醛酮：CH3CH2CH2CHO CH3CH=CHCHO CHOCCH3O0OHCHO CH3CHO CH3CH2CHO CH3CH2COCH3 CH3COCH3甲醛 乙醛 丙醛 甲乙酮 二甲酮 CH3CH2CH2CHOC H3C H2C H2C O C H3C H3C H = C H C H O2-2-丁烯醛丁烯醛2-2-戊酮戊酮丁醛丁醛C H2C H OC O C H3苯乙酮苯乙酮 (1-苯基苯基-1

2、-乙酮乙酮)C H = C H C H OC H OOCH3CCH2CH3OC O C H3CH3CH2CHCHOCH3CH CHCHOCH3CH3CHCH2CHOCH3CH2CH2CH2CHOClBrCH2CH2CH2CH2CHO-甲基丁醛-甲基丁醛-氯丁醛-溴戊醛-溴戊醛（）-丁烯醛 一、羰基的親核加成反應(yīng)一、羰基的親核加成反應(yīng) 二、還原反應(yīng)二、還原反應(yīng) 三、氧化反應(yīng)三、氧化反應(yīng) 四、歧化反應(yīng)四、歧化反應(yīng) 五、五、 -H的酸性的酸性C C HHO -活潑活潑H的反應(yīng)的反應(yīng) （1）烯醇化）烯醇化 （2） -鹵代（鹵仿反應(yīng)）鹵代（鹵仿反應(yīng)） （3）醇醛縮合反應(yīng)）醇醛縮合反應(yīng)醛的氧化醛的氧化羰基

3、親核加成羰基親核加成及氫化還原及氫化還原（1）碳碳雙鍵的親電加成）碳碳雙鍵的親電加成 （2）碳氧雙鍵的親核加成）碳氧雙鍵的親核加成 （3） , -不飽和醛酮的共軛加成不飽和醛酮的共軛加成 （4）還原）還原C=CC=OC H3C C H3ON aCN , H2SO4C H3C C H3O HC NCNOHC H CNC=O+反應(yīng)機(jī)理：H C N O HC N+H2O+C = OC NC NOCH2OC NO HC慢慢快快C H OC H OC H OO2NC H3O K 1420 210 3238K 104CH3CHO CH3COCH2CH3 ( CH3 )3COC( CH3 )31SO32適用

4、范圍：醛、脂肪族甲基酮、適用范圍：醛、脂肪族甲基酮、8 8碳以下的環(huán)酮碳以下的環(huán)酮C = O+ N aH SO3CO HSO3N aC H3C = OHC H3C = OC H3C H3C = OC H3C H2產(chǎn)率（產(chǎn)率（1h,%1h,%）C H3C H2C H2C = OC H3(C H3)2C HC = OC H3C H3C = O(C H3)3C128936 56236SO3N aO HCRHRC = OH+ N aC l + SO2 + H2O+ N a2SO3 + N aH C O3HC = ORHRCO HSO3N aH C lN a2C O3O HCC = ORO H , H+

5、O R+RO H , HO RCO R+ H2O C = OC = OH+H+RO HO RCO HH+HO RCO HO HCO R+HO RCO HH+H2OO RC+RO HO RCO RH+H+O RCO R C H3C H2C H OC H3O H , H+C H3C H2C HO C H3O C H3C H3C C H3H O C H2C H2O H , H+C H3 C C H3OOO C H3C = C H ( C H2 )2C H C H2C H OC H3C H3C H3O H , H+C H3C = C H ( C H2 )2C H C H2C H ( O C H3 )2

6、C H3C H3KM nO4H O O C ( C H2 )2C H C H2C H ( O C H3)2C H3H C l , H2OH O O C ( C H2 )2C H C H2C H OC H3HOOC ( CH2 )2CHCH2CHOCH3CH3C=CH ( CH2 )2CHCH2CHOCH3CH3從C = OHHHC = ORRC = OR1. RM gX2. H2ORC H2O HRC H R2. H2O1. RM gXO H1. RM gX2. H2OR3C O HORMgXCOMgXRCOHR+H2OC H3C H2C H C H3O H(1) C H3C H O + C

7、H3C H2M gX (2) C H3C H2C H O + C H3M gIC H3O HC H3C H2 C C H2C H2C H3C H3M gI + C H3C H2C O C H2C H2C H3C H3C H2M gBr + C H3C O C H2C H2C H3C H3C H2C H2M gBr + C H3C O C H2C H3 C H3C O C H2C H2Br O H O HH+ C H3C C H2C H2Br O OM g, Et2OO O C H3C C H2C H2M gBr 1. C H3C H O2. H2O , H+O HC H3C O C H2C H

8、2C H C H3思考題：思考題：HOCH2CH2CH2CH2CHOClCH2CH2CHO 從制備例例2 2：制備從 CH3COCH2CH2Br CH3COCH2CH2CHCH3OHCH3CH=O + NH3CH3CH-NHHOH-H2OCH3CH=O + RNH2CH3CH=O + R2NHCH3CH=NHCH3CH-NRCH2CH-NR2HOOHH-H2OCH3CH=NRH-H2OCH2=CH-NR2親核加成親核加成親核加成親核加成親核加成親核加成+ H2N O HC = OH2OC = N O H 羥胺羥胺 肟肟C = N N H2H2OC = O+ H2N N H2 肼肼 腙腙+ H2

9、N N HC = OH2OC = N N HN O2N O2N O2N O2 2,4- 2,4-二硝基苯肼二硝基苯肼 2,4-2,4-二硝基苯腙二硝基苯腙+ H2N N H C N H2C = OH2OC = N N H C N H2OO 氨基脲氨基脲 縮氨脲縮氨脲C = N RH2OC = O+ H2N R 伯胺伯胺 西佛西佛堿（取代基堿（取代基為為芳基）芳基）+ H N H GC = OC N GO HHH2OC = N G用途：鑒別醛和酮用途：鑒別醛和酮 應(yīng)用：應(yīng)用：b 保護(hù)羰基保護(hù)羰基C=N-ZC=OC=O+ H2N-Z重結(jié)晶重結(jié)晶稀酸稀酸C=OBA+ H2NRC=NRAB稀酸稀酸參與

10、反應(yīng)參與反應(yīng)C=OBA CH3 C CH2 HOCH3 C CH2O H酸或堿酸或堿CH3CCH3OC2H5OCCH2COC2H5OOOCH3CCH2COC2H5OOCH3CCH2CCH3OOCH3CCH2CCF3OOC H3C H O C lC H2C H OC l2C H3C O C H3 BrC H2C O C H3Br2 H + CH2=C CH3HHOCH2 C CH3OHHOCH3CCH3+ HCH3CCH3O快慢OCH2 C CH3BrHBr CH2 C CH3OHBr + HOCH2=C CH3Br Br +快快 C H3C H O , C H3C O , C H3C H2O

11、H , C H3C HO HCOOHCCH3O1 X2, -OH2 H+(CH3)2C=CHCCH3OKOClH2OH+(CH3)2C=CHCOOH + CHCl3CH3COClAlCl3, 200oC反應(yīng)機(jī)理：反應(yīng)機(jī)理：CH3CHO + HCHCHO CH3CHCH2CHOOHOH-稀CH3CH CHCHO-H2O例例1:1:2 C H3C H2C H O C H3C H2C H C H C H OO HC H3O H 例例2:2:例例3:3:O HC H3C H O + C H3C H2C H OOH+ CH3CHOOHC HHOCH2CH2CHO例例4:4:H O C H2C H2C H

12、 = OC H2= C H C H = O例例5 5：C H = C H C H OO H+ C H3C H OC H O C H3C H3C = O+H C H2C C H3OO H( C H3 )2C C H2C C H3O HOO( C H3 )2C = C H C C H3C CH3O+ HCHO + (CH3)2CHCHOH+C CH2CH2N(CH3)2.HCl + H2OO脫水脫水 + 水解水解C HO+ CH3COOC2H5NaOC2H550CHCHCOOC2H5 醇醛縮合反應(yīng)概括起來看，就是醛的羰基氧原子與另一反應(yīng)醇醛縮合反應(yīng)概括起來看，就是醛的羰基氧原子與另一反應(yīng)物的物的2

13、個個-H脫水的反應(yīng)。脫水的反應(yīng)。 RCHO + 2Cu2+ + NaOH + H2O RCOONa + Cu2O + 4H+ HCHO + Cu2+ + NaOH + H2O HCOONa + Cu + 4H+斐林試劑可以用來區(qū)分脂肪醛和芳香醛斐林試劑可以用來區(qū)分脂肪醛和芳香醛 OH O O C ( C H2 )4 C O O HH N O3Pt ( or Pd, Ni )0.3 MPa , 25oCRCR + H2 RCHROHORCHO + H2 RCH2OHPt ( or Pd, Ni )0.3 MPa , 25oCC H3C H = C H C H O C H3C H = C H C

14、H2O H1. LiA IH42. H2O( C H3 )3C C H2C C H3O1. N aBH42. H2O( C H3 )3C C H2C C H3O H保留了碳碳雙鍵保留了碳碳雙鍵（適用于對堿穩(wěn)定的化合物）（適用于對堿穩(wěn)定的化合物） CH2CH2CH3CCH2CH3ONHNH2 2-NH-NH2, 2, NaOH NaOH (HOCH(HOCH2 2CHCH2 2) )2 2O O bp bp 245 245o oC C 82%82%C = ON H2N H2C = N N H2KO HC H2 + N2 肼肼 腙腙 克萊門森法克萊門森法（適用于對酸穩(wěn)定的化合物）（適用于對酸穩(wěn)定的

15、化合物） CCH3OCH2CH3Zn-Hg, HClZn-Hg, HClZn-Hg, HClZn-Hg, HCl回流回流回流回流CHOCH3OHOCH3CH3OHO80%80%65%65%2 HCHO + NaOH HCOONa + CH3OHCH O2N aO HCO O N a + CH2O H 3 H C H O + C H3C H O O HH O C H2C H2O HC H2O HC H OCH C H OO HCC H2O H + H C O OC H2O HC H2O HH O C H2 ， -不飽和醛酮： ， -不飽和醛酮： CH2 CHCH2CHO CH2 CHCHO CH3CH CHCHO 丙烯醛丙烯醛 巴豆醛巴豆醛 3-丁烯醛丁烯醛 CH2 CH CH O CCCOHHHH丙烯醛分子的共軛體系丙烯醛分子的共軛體系CH2 CH C CH3 + HCN CH2CH C CH3OOH-OHCNCH2CH2CCH