Alcohols and phenols are phosphorylated in
high yield by reaction with various 2-chloroalkylphosphonic acids at 20-50�C in
the presence of three or more molar equivalents of cyclohexylamine or
triethylamine, the other products being the corresponding alk-1-ene and
chloride ion. The reaction probably proceeds by attack of an ROH molecule on
the phosphorus atom of a doubly-ionized phosphonate group.
2-Chlorodecyl-, 10-carboxy-2-chlorodecyl-,
and 2-chloro-octylphosphonic acid decompose rapidly in neutral solution giving
chloride ion, phosphate ion, and the corresponding alk-1-ene. In the absence of
hydroxylic compounds, 2-chlorodecylphosphonic acid is decomposed by
cyclohexylamine to dec-1-ene and a product which appears to be
N-cyclohexylphosphoramidate; t-amines and also aniline cause
dehydrohalogenation to dec-1-enylphosphonic acid.
The proton magnetic resonance spectra of
most of the phosphorus-containing substances described herein are recorded.
2-(4?-Thiazolyl)benzimidazole
(thiabendazole) is alkylated at a benzimidazole nitrogen by reaction with
sodium hydride and an alkyl halide. With 1,3-dibromo-propane and
1,2-dibromoethane, the thiazole nitrogen is also alkylated to give quaternary
salts containing the 6,7- dihydro-5H-thiazolo[3?,4?:1.2][1,4]diazepino-[8,9-a]benzimidazole
and 5,6-dihydrothiazolo[3?,4?:1,2]pyrazino[7,8-a]benzimidazole ring systems
respectively. The structures proposed for these tetracyclic products are
supported by spectroscopic examination of the products formed by alkali fission
of their thiazole rings.
A kinetic study has been made of the coupling of diazotised sulphanilic acid with glyoxaline. It is suggested that the rate-determining step is the reaction between the diazonium ion and the glyoxaline anion, the latter being formed from glyoxaline by ionisation of the N-H bond.
Mono- and diesters of phosphonic acids are
conveniently prepared by reaction of a phosphonic acid with appropriate
quantities of NN'-dicyclohexylcarbodiimide and an alcohol or phenol in pyridine
solution.
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