第三章反应历程

1、 CH4Cl2CH3ClCH3CH3+ hv Ph Ph Br2 MeOH Ph Ph Ph PhOMe Br Br Br + RCONH2NaOBrRNH2+ RCONH2NaOBr RNH2 + C O NR H Br C O NR R-N=C=O H2O NaOH + CO2 Cl+O H3C H3C CH3 CH3 O LiTMP THF, Heat N- CH3 CH3 H3C H3C Li+ LiTMP 2,2,6,6-四甲基氢化吡啶 C H3C C6H13 H Br (R) (S) + OH- C CH3 H C6H13 HO KMnO4 Br2 + H OH H OH + Br

2、 H H Br C O ORR + H 218OC O 18OH RROH+ CH2CH2NH2 * NaNO2 HCl CH2CH2OH * CH2CH2OH * + 50% 50% CC + H2O -H+ 1:1 CH4CD4 Cl2 hv CH3Cl CD3Cl + + + E + 慢 E H + 快 E + H -dA dt =kA -dA dt =kAB C + (CH3)3C-Br(CH3)3C + Br RXR+X R OHR H2O+ H R OH2 (CH3)3C-H(CH3)3C + SbF5-FSO3H .SbF5-FSO3 H2 C H CH2H3C + HBr H

3、CCH3H3C+Br H CCH3H3C Br O OH H+ H NO2 NO2+ O2NH R NH2 + NaNO2 R N NR+N2 CH3CH2 FCH2CH2 CH3CHCOOC2H5 (CH3)2CH CH3CH2 CH3 CN (CH3)3C (CH3)2CH CH3CH2 CH3 H3COC CH3 CH3 R2N RO Ar RCH=CH2 R H Br H2O Br Me Me Me Cl Et Me Cl Me Me But Me Cl Pri Pri Pri Cl k 1.00 2.062.43 6.94 Me Me Me Cl k 1.00 Me Cl Me Cl

4、 0.1 0.0 R3 R2 R1 : R1 R2 R3 : R3 R2 R1 : SP3杂化 SP2杂化SP3杂化 RH B: R+ HB Ph -CH2 P+ Ph Ph Ph CH2P Ph Ph O:O(C6H5)3COOC(C6H5)3 “六苯乙烷” 2(C6H5)3C. 2(C6H5)3C.+ O Na CONa C HCH 单线态碳烯三线态碳烯 ; +COAr2C Ar2C OC Cl3CH NaOH Cl2CClCl2C:+ Cl C2H5C O CN2 H C2H5 C O C: H N2 O O + O O H HOH Ph Ph OH O H HOH Ph2C=NNH2,

5、 PhI(OAc)2, CH2Cl2, -10 C 6H5 C 6H5 C 6H5C HO :C HC 6H5 + O H CH3 C H CH3 CH2I2,Zn Cu H CH3 CH2 H CH3 CCC H3CCH3 HH + :CH2( ) H H H3C CH3 HCH3 HH3C + :CH2( ) H H3C H CH3 + 23% 77% H H H3C CH3 H H3C H CH3 + 23% 77% H3CCH3 HH + :CH2( ) H H H3C CH3 HCH3 HH3C + :CH2( ) H H3C H CH3 % 77 H H CH3 CH3 % 23

6、CH3CH 3 HH . . CH3 H C CH3 H CH2 C C CH2 H CH3 C H CH3 . . C CH2 H CH3 C H CH3. . . . CH3 H C CH3 H CH2 C :CH2 ( ) H CH3 CC H + CH3 CH3 + H CC CH3 H ):CH2( H3CCH3 HH + :CH2( ) H H H3C CH3 HCH3 HH3C + :CH2( ) H H H3CCH3 C H2 H H3C H CH3 H H3C HCH3 C H2 . . CH3ONa, (2) (1) H2NNHTs O CH3 CH3 C CH.(CH3)

7、2CCH C CH3 CHCH3 50%9% + R C O OH R C O CHN2 -N2 R C O CH R C O CHN2 Ag2O H2O RCH C O RCH2C O OH H2O RCH2COOH (1) SOCl2 (2) CH2N2 CH: . . NN sp sp 单线态氮宾三线态氮宾 . . . . . + + E tOC O N3 2 54nm E tO C O NN2 P hN3P h NN2. . ArSO2O-+BH+RN B RN H OSO2Ar. . . RC O NOC NR OCNHR C O2 H2O OH . . . . +RNH2 N N

8、H2 N N . . . . P b (C H 3C OO )4 CH2CH2CH2CH3 NO2 2(EtO)3P CH2CH2CH2CH3 N3 H2C N CH2 CH H CH3 2(EtO)3PO NCH3 H RC O NR 3C HRCNHCR3 O . . + H3C CH H2CCH2 CHN HH 插入 H3C CH H2CCH2 HC NH H 50% H2O H3C CH H2CCH2 HC O H N H H3C 20% 插入 EtOC O NEtOC O N3EtOC O N MeEt MeEt MeEt N EtO2C MeEt N CO2Et Me N Et CO2Et MeEt N CO2Et 单线态三线态 + PhN3 ArN PhN ArN3 OMe PhNNAr PhNNPh ArNNAr Ar = Cl NH2 - NH2 Cl NH2 Cl + Cl CH3CH3 NH2 CH3 NH2 CH3 NH2 - + I NaNH2 O + O H H H H SP2 F- F Li F Li F Br 慢 快 NH2 CO2H HNO2 N2 + CO2- CO2N2+ N N N NH2 Pb(OAc)4