Hunsdiecker Reaction
Hunsdiecker Reaction
Bunsdiecker Reaction also known as Borodine-Hunsdiecker
reaction. Hunsdiecker et al. (1935) found that silver salts of the
carboxylic acids in carbon tetrachloride solution are decomposed by chlorine or
bromine to form the alkyl halide, e.g.,
RCO2Ag
+ Br → RBr + CO2 + AgBr
The yield of halide is primary > secondary > tertiary, and
bromine is generally used, chlorine giving a poorer yield of alkyl chloride. The
mechanism is uncertain, but a favorable theory is that the first step is the
formation of an acyl hypohalite which then decomposes into free radicals. The details
of the later steps are less certain:
RCO2Ag
+ Br2 → RCOOBr +
AgBr
RCOOBR → Br. +
RCOO. → R. + CO2
R. + Br2 → RBr + Br.
R. + RCOOBr → RBr
+ RCOO., etc.
Cristol et al. (1963) have obtained very good yields of
alkyl bromide by adding bromine to a refluxing carbon tetrachloride solution of
the acid in the presence of an excess of red mercuric oxide.
2RCO2H
+ 2Br2 +
HgO → 2RBr
+ 2CO2 +
HgBr2
Iodine forms esters with the silver slats;
this is known as the Birnbaun-Simonini reaction (1892).
2RCO2Ag + I2 → RCO2R + CO2 +
2AgI
Cristol et
al. (1964), however, have shown that acids form alkyl iodides if iodine and red
mercuric oxide are used.
On the
other hand, Bachman et al. (1963) have shown that aliphatic carboxylic acids
may be converted into esters and alkyl halides as follows:
RCO2H → (RCO2)4Pb (X2)→ RCO2R + 2RX
Alkyl chlorides
may be prepared without simultaneous ester formation by the action of lead
tetra-acetate and lithium chloride on the carboxylic acid in benzene solution. This
reaction is applicable to primary, secondary and tertiary acids, and occurs
without rearrangement, e.g.,
Me3CCH2CO2H → Me3CCH2Cl
The reaction
is believed to proceed by a free-radical mechanism.
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