天津大学：《高等有机化学》课程电子教案（PPT课件）第十二章 Molecule Rearrang

Chapter 12 Molecular rearrangements PRODUCER:张文勤 I Classification of Rearrangement Reactions( I Nucleophilic rearrangement ( 1 Wagner-Meerwein rearrangement() 2 Pinacolic Rearrangement ( 3 O-ethandione rearrangement() 4 Beckmann Rearrangement ( 5 Baeyer-Villiger Rearrangement O In Electrophilic rearrangement( I favorskii Rearrangement 2 Stevens Rearrangement 3 Wittig rearrangement 4 Fries Rearrangement IV Radical rearrangement

Chapter 12 Molecular Rearrangements I Classification of Rearrangement Reactions( ) II Nucleophilic Rearrangement ( ) 1 Wagner-Meerwein rearrangement( ) 2 Pinacolic Rearrangement ( ) 3 α-ethandione Rearrangement ( ) 4 Beckmann Rearrangement ( ) 5 Baeyer-Villiger Rearrangement ( ) III Electrophilic Rearrangement( ) 1 favorskii Rearrangement 2 Stevens Rearrangement 3 Wittig Rearrangement 4 Fries Rearrangement IV Radical Rearrangement PRODUCER：张文勤

I Classification of Rearrangement Reactions Molecular rearrangements: it refers those reactions in which the carbon skeleton or the position of functional group changed. H3PO4 CH3 CH2 CH=CH2 CH3CH=CHCH3 H CH3-C-CH20H r* CH3C=CHCH3 CH HO 3 CH3

I Classification of Rearrangement Reactions Molecular Rearrangements:it refers those reactions in which the carbon skeleton or the position of functional group changed. CH3 CH2 CH=CH2 H3 PO4 CH3 CH=CHCH3 CH3 C CH3 CH3 CH2 OH H + H2 O CH3 C=CHCH3 CH3

D-CHNB2 HNO3 CH2OH CHOH < - NH2 CHch CHo CH -C-C-CH, 3 OH OH H2OCH2C—C-C CH 3

CH2 NH2 HNO3 CH2 NH2 CH2 OH CH2 OH H2 O H + CH3 C CH3 OH C CH3 CH3 OH CH3 C CH3 CH3 C O CH3

Usually the rearrangement was classified by the electron property of the moving group, such as Nucleophilic rearrangement, Electrophilic rearrangement, Radical rearrangement. etc Nucleophilic rearrangement CH3CH2CH2CH2OH、H CH3CH2CH2CH2OH2-H2O CH(HHCH2→CHH2H(CHH CH3CH=CHCH3

Usually the rearrangement was classified by the electron property of the moving group, such as Nucleophilic rearrangement, Electrophilic rearrangement, Radical rearrangement, etc. Nucleophilic rearrangement CH3 CH2 CH2 CH2OH H + H2O CH3 CH2 CH2 CH2OH2 CH3 CH2 CHCH2 H CH3 CH2 CH + CH3 H + CH3 CH=CHCH3

Electrophilic rearrangement PhLi Ph-CH2-0-CH3-C6H6Ph-CH-o-CH Lit- CH HO 3 Ph-CH-oLi Ph-CH-OH Radical rearrangement CI-C-CHCH2+ Bro CI-C-CH-CH,Br r B CIC-CH-CHbBr CIC-CH-ChBr C

Electrophilic rearrangement Ph CH2 O CH3 PhLi C6 H6 Ph CH O CH3 Li + Ph CH O - Li + CH3 H2 O Ph CH OH CH3 Radical rearrangement C Cl Cl Cl CH=CH2 Br C Cl Cl Cl CH CH2 Br Cl C Cl CH CH2 Br Cl Br2 Cl C Cl CH CH2 Br BrCl

I Nucleophilic Rearrangement 1 Wagner-Meerwein rearrangement Carbon cation rearrangement H CH -C-CH,OH-Ark CH3-C-CH,OH2 HO CH3-—CH2CH3 CH3-C--CH2 CH3-f-CH2CH3 CH cH 3 CH3C=CHCH3 CH3

II Nucleophilic Rearrangement 1 Wagner-Meerwein rearrangement ( Carbon cation rearrangement ) H + CH3 C CH3 CH3 CH2 OH H2 O CH3 C CH3 CH3 CH2 OH2 CH3 C CH3 CH3 CH2 H + Cl - CH3 C CH3 CH2CH3 CH3C=CHCH3 CH3 CH3 C CH3 CH2CH3 Cl

Cl C c OH

Cl Cl - Cl - Cl OH H + + +

CH CHS-「HH3scH--cHH3→ CH3 Br CH3 C--「HCH→ Product CH3 CH3 Stable cation CHPh SNI 3 CH-C CH CHPh 关 CH CHPh CH2 Br CH 3 CH3 CH3 Stable cation Product CH3O /> > >>CH2=CH >R2C->R2CH->CH3->H-

CH3 C CH3 CH3 CHCH3 Br SN1 CH3 C CH3 CH3 CHCH3 CH3 C CH3 CHCH3 CH3 Product CH3 C CH3 CH3 CHPh CH SN1 3 C CH3 CH3 CHPh Br Product CH3 C CH3 CHPh CH3 CH3O ＞ ＞ Cl ＞ CH2 =CH ＞ R3 C ＞ R2CH ＞CH3 ＞H Stable cation Stable cation

HNO CHa-C-Choh CH CH 2 CH3 CH3-C-CH2CH3-20 OH F-CH2CH3 CH3 CHNH HNO 2 H,OHOH CH HO Ht

CH3 C CH3 CH3 CH2 OH N2 HNO2 CH3 C CH3 CH3 CH2 CH3 C CH3 CH2CH3 H + H2O CH3 C CH3 CH2CH3 OH CH2NH2 NH2 HNO2 N2 CH2 + + H + H2 O H + CH OH 2OH CH2

CHNH HO HNO2 CHOH H+ 2 32 H H H2o OH 2 58% NH HNO HO Dt HO H CH,=CHCH2OH

N2 HNO2 CH2 NH2 H + H2 O H + CH2 + CH2 OH 32% + H2 O H + OH 58% H + 2% NH2 HNO2 N2 + + H + H2O H + H2O CH2 =CHCH2OH