Thermal degradation of 1-deoxy-1-piperidino-d-fructose
1970; Elsevier BV; Volume: 15; Issue: 2 Linguagem: Inglês
10.1016/s0008-6215(00)88005-2
ISSN1873-426X
AutoresFrank D. Mills, B.G. Baker, John E. Hodge,
Tópico(s)Enzyme Catalysis and Immobilization
ResumoCrystalline 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(2H)-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 C4, C2 fission occurs.
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