F. D. Mills, B. G. Baker, J. Hodge
Nov 1, 1970
Citations
0
Influential Citations
18
Citations
Journal
Carbohydrate Research
Abstract
Abstract Crystalline 1-deoxy-1-piperidino- d -fructose ( 1 ) was pyrolyzed in a sublimation apparatus at 106° and 0.1 torr. The sublimate-distillate collected consisted of piperidine acetate (43%); two piperidino derivatives of C -methyl reductone (28%); 4-hydroxy-2-piperidino-butanolactone (1.4%); and the piperidine amides of carbonic (6.5%), formic (1.6%), and acetic (5.1%) acids. Trace proportions of other volatile compounds were identified as 4-hydroxy-2,5-dimethyl-3(2 H )-furanone; 2,5-dimethyl-3-piperidinofuran; 2-acetyl-3-piperidinofuran; 2-acetyl-3-piperidino-4,5-dihydrofuran; and the piperidides of glycolic, lactic, and butyric acids. Under the same pyrolysis conditions the piperidino C -methyl reductones isolated were degraded to carbonic, formic, and acetic piperidides. After separation of these compounds by preparative g.l.c., the products were identified by mass, i.r., and p.m.r. spectra; almost all were positively identified with compounds separately synthesized. The results indicate that piperidine is eliminated from C-1 and recombines at C-3 of the hexose carbon-skeleton before the primary C 4 , C 2 fission occurs.