第2章重要有機化學(xué)反應(yīng)

1、第二章第二章 重要有機反應(yīng)重要有機反應(yīng) 2CH3COCH3 Mg,C6H6H3O + (CH3)2C C(CH3)2 OH OH Mg,C6H6 CH3C O CH3 _ - CH3C O CH3 _ - CH3C=O CH3 2 CH3C O CH3 _ - CH3C O CH3 _ -Mg2+ H3O + (CH3)2C C(CH 3)2 OH OH CH3 C C CH 3 CH3CH3 OH OH _ H3O CH3 C C CH 3 CH3 CH3 _ O + CH3 C C CH3 CH3CH3 OH OH _ H3O + CH3 C C CH3 CH3CH3 OH OH2 _ +

2、 CH3 C C CH 3 CH3CH3 OH _ + H2O CH3 C C CH3 CH3 CH3 OH _ + CH3 C C CH3 CH3 CH3 OH _ + -H + CH3 C C CH 3 CH3 CH3 _ O RCH2COOH + Br2 Br P RCHCOOH Br RCHCOOH OH NH3 CN _ _ RCHCOOH RCHCOOH RCHCOOH OH NH2 CN Kolbe-Schmidt反應(yīng)用來制備水楊酸反應(yīng)用來制備水楊酸(酚酸酚酸) ONa H3O + CO2 heat OH COONa COOH OH O heat O COONa COONa OH

3、 - O=C=O H 2 CH3CO2Et 1.EtONa.EtOH 2.H3+O CH3-C-CH2-C-O-Et OO . 酯分子中酯分子中 -H有微弱酸性，在醇鈉作用下，生有微弱酸性，在醇鈉作用下，生 成碳負(fù)離子（烯醇鹽），并作為親核試劑進(jìn)攻另成碳負(fù)離子（烯醇鹽），并作為親核試劑進(jìn)攻另 一分子的酯羰基一分子的酯羰基 ，生成縮合產(chǎn)物。，生成縮合產(chǎn)物。 EtONa CH3-C-O-Et O CH2-C-O-Et - O . CH2=C-O-Et O - . CH3-C-O-Et O +CH2-C-O-Et - O . CH3-C-OEt O - CH2-CO2Et . -EtO- HAc H

4、2O CH3-C-CH2-CO2Et O . EtONa CH3-C-CH2-CO2Et O -Na + CH3-C-CH-CO2Et O . CH3-C=CH-CO2Et ONa . Me2CH-CO2Et EtONa EtOH Me2C-CO2Et - .Me2CH-C-OEt O Me2CH-C-OEt O- Me2C-CO2Et. Me2CH-C-C-CO 2Et O Me Me . C-OEt O + CH3-C-OEt O 1.EtONa.EtOH 2.H3+O C-CH2-C-OEt OO . CH3-C-OEt + H-C-OEt OO 1.EtONa.EtOH 2.H3+O

5、C-CH2-C-OEt OO H . O C-OEt CO2Et 2. H3+O 1. EtONa , EtOH CO2Et O . CO2Et C-OEt O . EtONa C-OEt O CO2Et -. C O OEt CO2Et - . O CO2Et . EtONa O CO2Et - . H3+O O CO2Et . =O + CH3-C- O 1. EtONa , EtOH 2. H3+O CH2-C- O - O C- C-OEt O - . + OH- CH3-C-CH2-C-CH3 OO CH3-C-CH3 O CH3-C-OEt O . -CHO +(CH3CO)2O

6、heat NaAc -CH=CH-COOH. Br RCHCOOEt OH Zn O CH3C HH2O CH3CH-CHCOOEt R CH3CO2Et +(Me2CH)2NLi + - CH2=CH-OEt - OLi + + (Me2CH)2NH OH . + LiO - CH2=CH-OEt O CH3C H CH3 I O CH3CH CH3CH2CO2Et CH2CO2Et Li H2O CH2CO2EtCH3CH OH CH2CO2Et 1. . =O + CH2-CO2Et O BrZn _C-H(R) C-ORC N NO2 O _O _ _ CH2=CHCH2=CHCH2=

7、CH CH2=CH . CH3-C-CH2-C-OEt OO EtONa . OO CH3-C-CH-C-OEt -CH2=CH-C=O H CH3-C-CH-CO2Et O CH2-CH2-CHO . CH3-C-CH2-CH2-CH2CHO O H3+O . 51 CH2(CO2Et)2 EtONa . CH(CO2Et)2 - CH3-CH=CH-C=O OEt CH3-CH-CH2-CO2Et CH(CO2Et)2 . H3+O CHCH3- CH2COOH CH2COOH . 1 5 Beckmann重排重排 例例 Birch 還原還原 H2O2 (CH3CO3H)+ O _N _

8、(CH3)2 _N(CH3)2 CC Ph CH3 CH3 H 115 _O + N CH3CH3 H HC (CH3)2 CPh Ph C (CH3)2 CH H CH3 N + _ 115 HCC Ph CH3 HH PhC (CH3)2 CH H CH3 N + O _ 115 H CC Ph CH3 H H O (CH3)2 H N + _ + (CH3)3N_CH2-CH2-HOH - (CH3)4NCl Ag2O (CH3)4NOH + H2O -+ CH3OH(CH3)3 N + + (CH3)3N_CH3 OH - H2O+ CH2CH2+(CH3)3N + CH3CH2CH2

9、CH _CH 3 N(CH3)3OH _ + CH3CH2CHCH _CH 3CH3CH2CH2CHCH2 98%2% _CH3 CH2R _ CHR2 _ H + N(CH3)3 H H OH _ H2O+(CH3)3N Ph CH2 CH2 N CH2 CH3 OH + CH3 _ _ CH3 - 4%96% + CH2CH2 CHPh _ CH2 CH32I N H N + CH3CH3 I _ N + CH3CH3 _H OH _ Ag2O ICH3Ag2O + (CH3)3N _ _ + CH3CH2 N C CH 3 OH _ CH3CH3 CH3CH3 CH3 _C CH2 CH

10、3 +CH2CH2 93% Ph H CH3 Ph H + N(CH3)3OH _ Ph Ph H H CH3 + N(CH3)3 OH _ R S RS Ph H H CH3 CH3 O _ +N(CH3)2 Ph CH3 H CH3 H O _ N(CH3)2 + S S SS Ph CC CH3 H Ph Ph CC CH3 H CH3 R-C-NH2 O OH - R-C-NH O -Br-Br R-C-NHBr O . OH - R-C-N-Br O - . _Br - R-C-N O O=C=N-R. OH - R-N=C-O - OH R-N-C-O O . - H - R-NH

11、-C-O O R-NH2+ CO2(CO3 - 2 ). Hofmann 重排（降解）重排（降解） CN O . CH2 H CH3 DD CH3 H CH2N NaOH Br2 +- R-C-Cl O R-C-N- O N N NaN3 N2 - R-C-N O R-N=C=O R-NH2 H2O CO2 - R-C-OHHN3 O + H2SO4 R-C-N3 O R-N=C=OR-NH2 -N2H2O RCOOHNaN3+ H2SO4 H2O RNH2CO2N2+ Lossen 反應(yīng)反應(yīng) CH2-C-CH2C6H5 Cl EtONa O C6H5CH2CH2-CO2Et EtONa CH

12、2 CHC6H5 Cl - O C CH2-C-CH2C6H5 Cl O O C CH2 CHC6H5 EtONa - CH2 CHC6H5 C O OEt C6H5CH2CH2-CO2Et RCOOAg + Br2 heat R-C-O-Br O +AgBr O R-C-O-BrO O CR . +Br . . RC O O _ CO2 R . . Br RBr RCOOAg + Br2 heat RBr + CO2 + AgBr H2O heat RBr + CO2 + +R COOHHgOBr2+ + HgBr2 H2O heat O R-C-O-BrO O CR . +Br . . R

13、C O O _ CO2 R . . Br + RBr R COOHHgO Br2+ + Hg (RCOO)2Hg (RCOO)2Hg+ R-C-O-Br O Br2 COOH EtOOC2 科爾伯反應(yīng)科爾伯反應(yīng)(Kolbe) COOH2CH3CH3CH3 . C O O _ CO2 . 2CH3CO2 _ . C O OCH3 -e CH3CH3 CH3 CH3. . CH3+ CH3 EtOOC (CH2)4COOEt. + NH3CO H2Ni NH2CH_NH2C + NCOR_NH2C _R H2Ni HC _NHR R2NH +CO H2Ni H _ N _ R R C Edvhwe

14、iler-Clarke 反應(yīng)反應(yīng) 例例 Mannich 反應(yīng)反應(yīng) CH3-C-O-CH2CH2CH3 O 500 C 0 CH3-C-OH + CH3-CH=CH2 O . C6H5 _CH2 O-C-CH3 CH _ O _C 6H5 H H C6H5 C6H5 H O C=O CH3 H H C6H5 C6H5 NH2NHNR2 O H2O + + N H N TsOH _SO3H CH3_TsOH = H + OH + O H N N H + HON + H2O_H2O H N + H _ + N NN + - H NNN O HH TsOH H N O N Br-CH2CO2Et I

15、CH3OH _ CH3 CH3_C O_ Cl CH2CH CN _ H2O CH3 N + H2O O CH3 N + CH2CH2CN H2O O CH2CH2CN N + C O_ CH3 H2O O C O_ CH3 O CH2CO2Et O CH3 TsOH H N N CH3 + 85%15% CH3 N O CH2CH2CN _ + O _ CH2CNCH2_ O _ CO2Et CO2Et H+ - CH3_ + N O O CH2 -_N O O - + N O OH CH2= - + 例例 R-C-O-H O + CH2-N N + - + R-C-O O - CH3-N

16、N + RCOOCH3N2+ HX RSO3H ArOH CH2N2 CH3-C-CH=C-CH3 OHO H+ CH3X RSO3CH3 ArOCH3 CH3-C-CH=C-CH3 OOCH3 + N2 R-C-R O - CH2-N N + + R C R CH2 N N + O- R-C-CH2-R O R C CH 2 N R O- N + + N 2 R R CC O H2 =O +CH2-N N +- O - + CH2-N N =O + N2 CH2N2CH2 C=C CC CH2 C=C R H R H C CH2 C R R HH CH2I2Cu(Zn) Et2O C=C R

17、 RH H + CHCl3 Me3COK Me3COH Cl2 C C C R R H H + CHCl3HB +B - CCl3 - CCl3 - +CCl2Cl - C H CH3 C6H5 H C O C2H5MgBr R H CH3 C6H5 H C O C2H5MgBr C2H5MgBr H CH3 C6H5 H C2H5 MgBr C O H H CH3 C6H5 H C2H5 C O H3O + C H CH3HC O C2H5MgBr HO S H HCH3 H C O O C2H5MgBr HCH3 H C2H5 C O HO MgBr HCH3 H C2H5 C O HO

18、H H3O + -NH2 NaNO2/HCl 0 0C -N2Cl +- N2Cl +- H2O -OH -I -Cl -Br -CN -H KI r.t. CuCl CuBr CuCN H3PO2 50% NH2 HBF4 0 0C NaNO2 N2BF4 - + F /H2O Cu NaNO2 NO2 Br-Br Br HNO3 H2SO4 NO2 Fe HCl NH2 Br2 H2O Br-Br Br NH2 NaNO2 HCl 00C H3PO2 TM +-N2Cl +- -OH NaOH pH 7-9 -N=N-OH + -N2Cl +- -NMe2 NaAc/H2O PH 5-7 -N=N-NMe2 + HCHO + HCl-CH2Cl ZnCl2 Reimer-Tieman