Abstract
The flash vacuum pyrolysis (FVP, 450-600 oC/10 -3 mmHg) of 3,4-diaryl- and 3,4-dialkyl-1,2,5oxadiazole 2-oxides (furoxans) has been investigated. In all cases the 1,2,5-oxadiazole ring cleaved cleanly at O(1)-N(2) and C(3)-C(4) to afford two nitrile oxide fragments, which were trapped in high yield (75-97%) as their isoxazoline cycloadducts by reaction with alk-1-enes. At higher temperatures (700-800 oC) isocyanates were formed as by-products. The dimerisation of acetonitrile oxide to dimethylfuroxan was followed by 1 H NMR spectroscopy, and the rate constant for the 2 nd order reaction determined. The furoxans were converted into isocyanates in good yield (61-95%) by FVP, followed by sulfur dioxide-mediated isomerisation of the resulting nitrile oxides. 2,4,5-Trisubstituted-1,2,3-triazole 1-oxides showed greater thermal stability, but at 700-800 oC decomposition of the 4,5-dimethyl compound 25b lead to 1,2-di(5-methyl-2-phenyl1,2,3-triazol-2-yl)ethane as the major product; attempts to trap acetonitrile oxide were unsuccessful.
Highlights
1,2,5-Oxadiazole 2-oxides 1 have often been regarded as unwanted by-products formed during the 1,3-dipolar cycloaddition reactions of nitrile oxides 2.1 when isolated nitrile oxides are used, or even when they are generated in situ, the nitrile oxide dimer 1 may be formed in addition to the target cycloadduct, with less reactive dipolarophiles (Scheme 1)
We have recently described the use of flash vacuum pyrolysis (FVP) technique[7,8] to study the corresponding furazans (1,2,5-oxadiazoles) and found that under these conditions they cleaved cleanly at O(1)−N(2) and C(3)−C(4) to afford the nitrile oxide and nitrile fragments.[9]
We report on the thermal stability of the related 4,5-disubstituted 1,2,3-triazole 1-oxides under Flash vacuum pyrolysis (FVP) conditions
Summary
1,2,5-Oxadiazole 2-oxides (furoxans) 1 have often been regarded as unwanted by-products formed during the 1,3-dipolar cycloaddition reactions of nitrile oxides 2.1 when isolated nitrile oxides are used, or even when they are generated in situ, the nitrile oxide dimer 1 may be formed in addition to the target cycloadduct, with less reactive dipolarophiles (Scheme 1).
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