Reactions of tert-Butylperoxy Esters. XV. Decomposition of Dialkyl tert-Butylperoxy Phosphates

Abstract

The thermal decomposition of dialkyl £er£-butylperoxy phosphates, in the presence and absence of solvents, yields the corresponding dialkyl phosphate, acetone, methanol, 2,2-dimethoxypropane, and methyl isopropenyl ether as the primary products. Prolonged heating of the product mixture produces trialkyl phosphates, (R0)3P(0), which arise from the thermal decomposition of dialkyl phosphates. Data are presented to support a mechanism involving the heterolytic cleavage of the peroxide linkage.

Benzimidazolyl phosphates as anti‐wear additives in poly(ethylene glycol) for steel/steel contacts

“…Four compounds were synthesized according to Carl and Allan, Sosnovsky and Zaret and Shono et al . Figure presents the chemical structures of BPs and TCP as reference.…”

The Chemistry of Peresters

“…In an analog of the Kharasch–Sosnovky reaction, peroxyphosphates react with substrates possessing an activated C‐H to furnish phosphonates;, the transformation has also been achieved photochemically . Curiously, investigations into the thermolysis of tert ‐butyl peroxyphosphates failed to find strong evidence for the generation of radicals …”

Chemistry of organophosphorus compounds containing the peroxide bond

“…Decomposition in Solvents Other Than n-Nonane In addition to the decomposition reaction of tert-butylperoxy phosphates 3, R = C2HB, n-C4H9, in nonane, the decomposition reaction was also studied in polar solvents. 78,91,97,98 Unlike in n-nonane, in which the decomposition proceeds by both homolytic and heterolytic cleavage of the peroxide bond, in solvents with either a high dielectric constant or favorable solvation properties, heterolytic rearrangement of 3, R = C2HB, occurs to give a nonperoxidic derivative, which then decomposes into diethylphosphoric acid (105, R = C2Hb) and a-methylvinyl methyl ether (122). 97 The decomposition of 3, R = C2HB, in nitrobenzene, nitromethane, n-butyl alcohol, ethyl alcohol, methyl alcohol, acetic acid, valeric acid, and water is a firstorder reaction, and the composition of the final product is independent of the solvent.…”

“…102 However, these results had to be revised several years later. 98 The thermal decomposition of peroxy esters 3 proceeds under reduced pressure to give the corresponding dialkyl phosphates 105, which, on heating are readily transformed to the trialkyl phosphates 123 (Table XXV). The mixture of 105 and 123 can simu-(R0)2P(0)00C(CH3)3 -(R0)2P(0)0H -3 105 (R0)3P=0 123 late properties, such as boiling point under vacuum of the corresponding pyrophosphate,98 and, hence, on the basis of this observation, the original102 misinterpretation of preliminary data is explained.…”

“…Both neat and in the presence of the solvent, the yields of methane and acetone are virtually the same. Isobutylene presumably arises from dehydration of terf-butyl alcohol by the phosphorus acid(s) formed during the decompositions, i.e., methylphosphonic acid (95, R = CH3) and tert-butyl hydrogen methylphosphonate (98). Acid 98 presumably is CH3P(0)(0H)2 H0(CH3)P(0)0C(CH3)3 formed by the reaction of isobutylene or tort-butyl alcohol with acid 95.…”