79812-47-8Relevant academic research and scientific papers
DERIVATIVES OF CYCLOHEXANE-1,2-DIOL-PHOSPHOROCHLORIDATE AND 1-CHLOR-4,5-BENZ-2,6-DIOXAPHOSPHORINANONE-(3) 1-OXIDE
Cremlyn, Richard,Ruddock, Keith,Obisesan, Oluyemisi
, p. 333 - 338 (2007/10/02)
Cyclohexane 1,2-diol (1) has been phosphorylated to the cyclic phosphorochloridate (2; X=O) and chloridothioate (2; X=S).Hydrolysis of the former with boiling aqueous acetone gave 2-hydroxycyclohexyl dihydrogen phosphate (3; X=O, R=H) and excess isopropyl alcohol gave the diisopropyl phosphate (3; X=O, R=(CH3)2CH).Reaction of the chloridate (2; X=O) with aniline, diethylamine, and morpholine gave the corresponding amidates (4-6).The chloridothioate (2; X=S) similarly gave amidates (8, 9) with morpholine and aniline, but with isopropyl alcohol the cyclic isopropyl phosphate (10) was obtai ned.Attempted hydrolysis (aqueous acetone) of the chloridothioate (2; X=S) resulted in decomposition.Salicylic acid (11) with phosphorus oxychloride gave the cyclic phosphorochloridate (12) which reacted with ethanol, propanol, isopropyl alcohol and benzyl alcohol to give the alkoxy derivatives (13-16).The highly sterically hindered alcohols, t-butanol and benzhydrol did not react.The alkoxy derivatives were hydrolyzed to the corresponding 2-carboxyphenyl phosphates (17-20).Attempted reaction of the chloridate (12) with aniline gave complex mixtures of unidentified products.The proton n.m.r., i.r. and ms. of the compounds (12-20) are briefly discussed.
