“…The prevailing method for the synthesis of diazetine dioxides is via oxidation of the corresponding 1,2-bishydroxylamines. ,, We found one brief report, however, on the direct oxidation of a 1,2-diamine (i.e., 2,3-dimethyl-1,2-diaminobutane) to diazetine dioxide 1c with use of the strong oxidizing agent dimethyldioxirane …”
Diazetine dioxide 1a has been synthesized in a single step via oxidation of meso-2,3-diphenyl-1,2-ethanediamine with dimethyldioxirane, albeit in low yield (7%). Thermal decomposition of 1a afforded predominantly either trans-stilbene or diphenyl glyoxime depending on solvent, temperature, and the presence of an amine catalyst. Reaction in chloroform at 69 degrees C favored elimination of NO and formation of trans-stilbene. The stereospecific formation of trans-stilbene suggests a mechanism of decomposition in which C-N bond cleavage leads to a diradical intermediate stabilized by the phenyl group. Bond rotation followed by cleavage of the second C-N bond accounts for the trans-stilbene. At 25 degrees C in chloroform, while trans-stilbene was still the major product, some diphenyl glyoxime was also observed (4% yield). However, 1a as a solution in chloroform in the presence of Et3N, or 1a as a solution in DMSO-d6, afforded predominantly diphenyl glyoxime. These results are interpreted in terms of two closely competing reactions subject to the effects of entropic contributions.
“…The prevailing method for the synthesis of diazetine dioxides is via oxidation of the corresponding 1,2-bishydroxylamines. ,, We found one brief report, however, on the direct oxidation of a 1,2-diamine (i.e., 2,3-dimethyl-1,2-diaminobutane) to diazetine dioxide 1c with use of the strong oxidizing agent dimethyldioxirane …”
Diazetine dioxide 1a has been synthesized in a single step via oxidation of meso-2,3-diphenyl-1,2-ethanediamine with dimethyldioxirane, albeit in low yield (7%). Thermal decomposition of 1a afforded predominantly either trans-stilbene or diphenyl glyoxime depending on solvent, temperature, and the presence of an amine catalyst. Reaction in chloroform at 69 degrees C favored elimination of NO and formation of trans-stilbene. The stereospecific formation of trans-stilbene suggests a mechanism of decomposition in which C-N bond cleavage leads to a diradical intermediate stabilized by the phenyl group. Bond rotation followed by cleavage of the second C-N bond accounts for the trans-stilbene. At 25 degrees C in chloroform, while trans-stilbene was still the major product, some diphenyl glyoxime was also observed (4% yield). However, 1a as a solution in chloroform in the presence of Et3N, or 1a as a solution in DMSO-d6, afforded predominantly diphenyl glyoxime. These results are interpreted in terms of two closely competing reactions subject to the effects of entropic contributions.
“…Diazetine dioxides are prepared by the oxidation of the corresponding bishydroxyamines with NaOBr in aqueous base. [452][453][454][455][456] 3-Bromo-3,4,4-trimethyl-3,4-dihydrodiazete 1,2-dioxide (43) and 3-bromo-4-methyl-3,4-hexamethylene-3,4-dihydro-diazete 1,2-dioxide (44) are commercially available.…”
Section: Diazetine Dioxidesmentioning
confidence: 99%
“…Compound 42 has been extensively used as a triplet quencher. − Recently, the biological activity and NO release mechanism of DD have been studied. Diazetine dioxides are prepared by the oxidation of the corresponding bishydroxyamines with NaOBr in aqueous base. − 3-Bromo-3,4,4-trimethyl-3,4-dihydrodiazete 1,2-dioxide ( 43 ) and 3-bromo-4-methyl-3,4-hexamethylene-3,4-dihydro-diazete 1,2-dioxide ( 44 ) are commercially available. 18 19 …”
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