Furylmethyl chloride

A Hylic rearrangements occur in the carbonation of Grignard reagents from 3-furylmethyl chloride and w-methylbenzyl bromide part of the product in each case contains a nuclear carboxyl group. 

A similar rearrangement occurs with a-(l-chloroethyl)-furan 5-ethylfuryl cyanide is formed. Also, 3-furylmethyl chloride and aqueous potassium cyanide furnish an isomeric mixture of nitriles, a 9 1 ratio of 3-furylaceto-nitrile and 3-methyl-2-furonitrile. Tetrahydrofurfuryl chloride behaves normally although its halogen is mote firmly held. As expected, the halides of pyridine, quinoline, and isoquinoline react satisfactorily without a solvent-promoter. 

A more extended version of the same idea accounts for the regioselectivity of attack by cyanide ion on the cation 4.168, derived from furylmethyl chloride 4.167, which leads, counter to the thermodynamics, to the product 4.169 of an SnT" reaction, and hence to the re-aromatised product 4.170.396... 

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