10061-48-0Relevant academic research and scientific papers
Fragmentation-Rearrangement of 2-Acyloxyalkylphosphonates - a Novel Route to Alkyl Metaphosphate Extrusion
Jongh, Connie P. de,Modro, Tomasz A.
, p. 1003 - 1004 (1992)
Thermolysis of dialkyl 2-acyloxyalkylphosphonates, resulting in the fragmentation to an alkene, ester and alkyl metaphosphate, represents the first example of a reaction in which alkyl group migration has to occur before the metaphosphate species can be extruded from the system.
The mechanism of fragmentation of alky α-(oxyimino)benzylphosphonates; use of silica gel as a novel hydroxylic trapping reactant for an intermediate alkyl metaphosphate
Quin, Louis D.,Wu, Xiao-Ping,Breuer, Eli,Mahajna, Mahmoud
, p. 6281 - 6282 (2007/10/02)
Silica gel was employed to react with the suspected metaphosphate intermediate of the acid-promoted cleavage of monoalkyl α-(oxyimino)benzylphosphonates. The silica gels displayed CP-MAS 31P NMR signals at about δ-8. A similar value was obtained for silica gel phosphorylated with ethyl metaphosphate from a different source (thermolysis of a P-ethoxy 2,3-oxaphosphabicyclo[2.2.2]octene derivative.
Phosphoryl to carbonyl migration of amino groups in mixed anhydrides
Symes, Jill,Modro, Tomasz A.
, p. 1702 - 1708 (2007/10/02)
Mixed anhydrides derived from carboxylic and aminophosphoric acids, (RO)(R'2N)P(O)OC(O)R'' (1), undergo unimolecular fragmentation yielding carboxyamides, R''C(O)NR'2, and metaphosphate esters, ROPO2.The mechanism of the amino group transfer was studied for substrate 1a (1, R = R' = Me; R'' = Ph); solvent as well as substituent effects indicate little (if any) charge development in the transition state.The effects of solvents and Lewis acids on the reaction rate and the activation parameters determined for 1a can be explained best in terms of stabilizing interactions with either carboxyamide or metaphosphate being formed in the course of reaction.The transfer of a functional group from one acyl center to another was investigated for other anhydride systems and the relative contributions of the fragmentation vs. disproportionation of substrates are discussed.
