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 It involves migration of a substituent to
 an uncharged, electron deficient, carbon
 atom called carbene
  That is a molecule containing a neutral
   carbon atom with two unshared valence
   electrons. The general formula is RR'C:
   The term "carbene" may also refers to the
    compound H2C:, also called methylene
   Carbenes are classified as either singlets or triplets
    depending upon their electronic structure
   Most of the carbenes are very short lived, although
    persistent carbenes are known
 In this rearrangement α-diazoketones
 lose nitrogen to form highly reactive
 ketenes
R   C   CHN2

    O

                       R
                           C   CH N    N
                               ** +
                       O               -N2

                   R           R
        C      C                   C    CH
                                           **
                   H
    O                          O
 - Synthesis of analogues of carboxylic
  acids
 - Synthesis of acid amides from
  carboxylic acids
 - Synthesis of esters from carboxylic
  acids
SOCl2
         R   C   OH             R    C        Cl           Diazomethane
             O                       O                      CH2N2

                                         R
                                              C    CH        N   N
                                                   **        +
                                         O                       -N2

                            R                       R
                 C      C                                   C      CH
                                                                     **
                            H
             O                                         O
 CH OH




                                    NH
                      H2O
   3




                                     3
                                                   O
                            O
         O                                   R-CH2-C-NH2
                      R-CH2-C-OH
R-CH2-C-O CH3

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Wolf rearrangement

  • 1.  It involves migration of a substituent to an uncharged, electron deficient, carbon atom called carbene  That is a molecule containing a neutral carbon atom with two unshared valence electrons. The general formula is RR'C:
  • 2. The term "carbene" may also refers to the compound H2C:, also called methylene  Carbenes are classified as either singlets or triplets depending upon their electronic structure  Most of the carbenes are very short lived, although persistent carbenes are known
  • 3.  In this rearrangement α-diazoketones lose nitrogen to form highly reactive ketenes
  • 4. R C CHN2 O R C CH N N ** + O -N2 R R C C C CH ** H O O
  • 5.  - Synthesis of analogues of carboxylic acids  - Synthesis of acid amides from carboxylic acids  - Synthesis of esters from carboxylic acids
  • 6. SOCl2 R C OH R C Cl Diazomethane O O CH2N2 R C CH N N ** + O -N2 R R C C C CH ** H O O CH OH NH H2O 3 3 O O O R-CH2-C-NH2 R-CH2-C-OH R-CH2-C-O CH3