- REACTION OF HALOMETHYLFURANS WITH SODIUM DIMETHYL PHOSPHITE AND TRIMETHYL PHOSPHITE
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Phosphorylation of 2- and 3-chloromethylfurans with sodium dimethyl phosphite in a methanol-benzene medium leads to formation of two products, a methoxy derivative and phosphonate, the first being predominant.Using sodium tert-butoxide as a metalating agent in benzene allows as to drive the process to the formation of phosphonates, but the yields are poor.Phase-transfer catalytic systems based on potassium hydroxide and fluoride are ineffective. 2- and 3-Mono and 2,3- and 2,5-bis(bromomethyl)furancarboxylates are phosphorylated with trimethyl phosphite under conditions of the Arbuzov reaction; however, in the presence of an additional acceptor substituent, such as an acetoxymethyl group, dehalogenation occurs.With 2,5-bis(halomethyl)-furan-3-carboxylates the Arbuzov reaction with trimethyl phosphite proceeds stepwise, the halomethyl group in position 5 reacting first, regardless of the halogen nature.The resulting intermediate products are not halomethyl phosphonates, which was proved by independent synthesis of the latter and by studying their chemical properties.
- Pevzner, L. M.,Ignat'ev, V. M.,Ionin, B. I.
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p. 1754 - 1763
(2007/10/03)
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