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1、?Structures?sp2-hybridized?threesigma-bondRadicalCarbocationCarbanion中心碳原子768價(jià)電子數(shù)?radical----oneelectroninporbital?carbocation----avacantporbitaloneelectronemptyp-orbitalRadicalCCarbocationC+1自由基的生成1)熱解法(CH3)3C-O-O-C(CH3)3→2(CH3)3C-O?2100~110oC2(CH(CH3)3C-O-O-C(CH3)33)3CH-O80~100oC(CH3)2C
2、-N=N-C(CH3)22(CH3)2C+N2CNCNCN450oCPb(CH3)4Pb+4CH32)光解法Cl-Cl→2Cl?OO=hvCH3+CH3C=OCH3-C-CH3320nmCH3-C-CH3激發(fā)態(tài)CH3+COhvR-N=N-R2R+N2RC-O-O-CRhv2RC-O2R+2CO===2OOO33)氧化還原法Fe2++HOFe3++OH-+OH22Cr2++ROOHCr3++OH-+OR-2+(ArCOO)+Cu+ArCOO+ArCOO+Cu2Ti2++2HOTi4++2OH-+2OH22+ArNN+Cu+2+Ar+N2+CuCo3++PhCHOCo2++H
3、++PhCH2OPhCHO+Fe3++2+PhC+H+Fe3+2++Co+Ar-CH3→Ar-CH2?+Co+H三自由基的加成反應(yīng)R+CCRCC（一）鹵素對(duì)烯烴的加成Xhv22XCC+XCCXXCC+XX2CC+XX4Clhv2Cl2Cl2C=CCl2+ClCl2C-CCl3Cl2C-CCl3+Cl2Cl3C-CCl3+ClClCl2Cl3CCCl2Cl3CCCCCl3ClClClhv2Cl2ClClClClClCl2H+ClHClHClClClBrhv2Br2BrBrBr+BrBrBrBr5CHCH2CH2Cl3+Cl+ClCHCHCH333ClClCl2H+ClHCl
4、H（二）溴化氫對(duì)烯烴的加成ROOR2RORO+HBrBr+ROHRCHCH2Br（仲基自由基較穩(wěn)定）RCH=CH2+BrRCHCH2BrRCHCH2Br+HBrBr+RCH2CH2BrhvCH2=CH-CH2Br+HBrBrCH2CH2CH2Br過氧化苯甲酰CH2=CH(CH2)3COOEt+HBrBr(CH2)5COOEt6H3CBrCCH3CBrBrHCH3BrCCHBrHCH3(Z)BrH3CBrCCHCH3H3CHBrBrHCCBr+H3CCCCH3HHBrCH3(R,R)(S,S)H3CCHH3CHCH33BrCH3CCCCHBrH3CCCHBrHBrH(E)B
5、rBrBr(R,S)（內(nèi)消旋體）（三）鹵代烴與烯烴的加成ROOR2RORO+CCl4ROCl+CCl3CH3(CH2)5CH=CH2+CCl3CH3(CH2)5CH-CH2CCl3CH(CH)C-CHCClCCl4CH3(CH2)5CHCH2CCl3+CCl332523ClROOR2RORO+CHCl3ROH+CCl3RCH=CH2+CCl3RCH-CH2CCl3RCH-CH2CCl3+CHCl3RCH2CH2CCl3+CCl37CF3+RCH=CH2RCHCH2CF3RCHCH2CF3+CF3IRCHCH2CF3ICF3I+CF2=CF2ICF2CF2CF3（四）醇和醚
6、對(duì)烯烴的加成'RCH-CH2CHR'RCHOH+RCH=CH2OHRCH-CH2CHR'+RCH2OHOH.RCHCH2CH2R'+RCHOHOH8（五）硫醇對(duì)烯烴的加成ROOR2RORO+RSH'ROH+RS'RS'+RCH=CH''2RSCH'2CHR''RSCH'2CHR''+RSH'RSCH'2CH2R''+RS'（六）醛對(duì)烯烴的加成ROOR2ROOORO+RC-H'RC'+ROHOORC'+RCH=CH''2R-CCH'2-CHR''OOOOR-CCH'2-CHR''+RC-H'R-CCH'2CH2R''+RC'9（七）羧酸和酯對(duì)烯烴的加成引發(fā)劑RR+RCH'2
7、COOHRCHCOOH'RCHCOOH'+RCH=CH''2RCHCH'2-CHR''COOHRCHCH'2CHR'RCHCH'2CH2R''+RCH2COOH+RCHCOOH'COOHCOOH引發(fā)劑RRB+rCH2COOEtRBr+CH2COOEtCH2COOEt+CH2=CH(CH2)5CH3CH3(CH2)5CHCH2CH2COOCH3(CH2)5CHCH2CH2COOEt+BrCH2COOEtCH3(CH2)5CHCH2CH2COOEtBr10四自由基的消除反應(yīng)AB+CABCA+BC?-斷裂RCOR+CO(CH3)3C
