O-Phenylene phosphorochloridite

The very high accuracy which may be obtained by the pulsed Fourier transform method has been demonstrated using o-phenylene phosphorochloridite.1... 

The mono- to tetraethylene glycol modified phosphites 14a-d have been synthesized according to the first-described method starting from commercially available (o-phenylene) phosphorochloridite 13 in > 90% yield (Scheme 2). 

Reaction of an alcohol with the reagent o-phenylene phosphorochloridite followed by treatment of the alkyl o-phenylene phosphite so obtained with iodine in dichloromethane at room temperature results in a good yield of alkyl iodide. This method, exemplified by the preparation of 1-iodoheptane (Expt 5.60), is the preferred procedure when acid-sensitive functional groups are present. 

Heptyl o-phenylene phosphite. Place 87.0 g (0.5 mol) of o-phenylene phosphorochloridite, 39.5 g (0.05 mol) of dry redistilled pyridine and 500 ml of dry ether, in a 2-litre conical flask and cool to 0 °C. Add 58.1 g (0.5 mol) of heptan-l-ol dissolved in 400 ml of dry ether during about 5 minutes with occasional shaking. Stopper the flask and allow the reaction to proceed at room temperature overnight. Filter off the precipitated pyridinium chloride under suction, wash well with dry ether and remove the ether from the combined filtrate and washings on a rotary evaporator to obtain 127.0 g (100%) of heptyl o-phenylene phosphite as a colourless oil of sufficient purity for use in the next stage. 

Synthesis of olefins. In a new synthesis of olefins, a nonenolizable aldehyde or ketone, for example benzophenone, is treated with dimsyllithium in THF o-phenylene phosphorochloridite (2, 321-322) is added to the solution at -80°. The reaction is... 

Iodination (-Butyl hypoiodite. Iodine-periodic acid. Iodine monobromide, I-Iodohepta-fluoropropane. o-Phenylene phosphorochloridite. 

Cyclohexanol in ether added with stirring at 0° to o-phenylene phosphorochloridite (prepn. s. Synth. Meth. 14, 159) and pyridine in ether, stoppered, allowed to warm to 25°, and the product isolated after 12 hrs. cyclohexyl o-phenylene phosphite (Y 95.4%) dissolved in methylene diloride, treated with iodine, stirred 6 hrs. at 25°, and extracted successively with 5%-NaOH-soln., NaHSOg-soln., and satd. NaCl-soln. -> cyclohexyl iodide (Y 87.4%). Overall Y 83.2%. F. e. s. E. J. Corey and J. E. Anderson, J. Org. Chem. 32, 4160 (1967). 

Hydroxy-2,2-diphenylethyl phenyl sulfide allowed to react with methyllithium in tetrahydrofuran, then at 0 with o-phenylene phosphorochloridite, and the intermediate crude phosphorous ester refluxed 3 hrs. in dioxane 1,1-diphenyl-ethylene. Y 83%. F. e. s. I. Kuwajima, S. Sato, and Y. Kurata, Tetrah. Let. 1972, 737 f. method cf. R. M. Coates and R. L. Sowerby, Am. Soc. 94, 5386 (1972). 

There are several procedures for conversion of alcohols to iodides which are based on alkoxyphosphonium intermediates. One involves preparation of a cyclic phosphite ester from the alcohol and o-phenylene phosphorochloridite. Treatment of the cyclic phosphite ester with iodine then generates the alkyl iodide ... 

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