SYNTHESIS OF 2-ARYLOXY-6-METHYL-4-TRICHLOROMETHYL-4H-1,3,2-BENZODIOXAPHOSPHORIN 2-OXIDES/SULFIDES

Abstract

Synthesis of 2-aryloxy-6-methyl-4-trichloromethyl-4H-1,3,2-benzodioxaphosphorin 2-oxides and corresponding 2-sulfides and their IR, ¹H, ¹³C and ¹³P NMR spectral analyses were reported. Long-range 3J _H–P, 2J _PDC and 3 J _POCC couplings were determined. An X-ray diffraction analysis of a crystal of 2(2′,6′dimethylphenoxy)-6-methyl-4-trichloromethyl-4H-1,3,2-benzodioxaphosphorin 2-oxide suggested distorted-boat conformation for the dioxaphosphorin ring with P[dbnd]O directed away from the ring. Electron impact mass spectra exhibited M⁺, (M[sbnd]Cl) +, (M[sbnd]Cl)[sbnd]-HCl)⁺ and (M[sbnd]CCl₃)⁺ as major ions with the dioxaphosphorin ring intact supporting the proposed structures of these esters. Toxicity of some of the compounds against the insect, P. americana, was evaluated and their LD₅₀ values were reported.

Key Words:

• 2-Aryloxy-6-methyl-4-trichloromethyl-1,3,2-benzodioxaphosphorin 2-oxides/sulfides
• NMR and mass spectral analysis
• X-ray diffraction of 2(2′,6′-dimethylphenoxy)-6-methyl-4-trichloromethyl-4H-1,3,2-benzodioxaphosphorin 2-oxide
• toxicity evaluation