Chloroform, boiling point hydrolysis

Phosphorus(V) sulfochloride is a colorless, fuming liquid with boiling point 125° and specific gravity 1.635. The alpha form solidifies at —40.8°, while the beta form solidifies at —36.2°.7 The compound hydrolyzes slowly in water and rapidly in alkaline solution. In water, the hydrolysis products are orthophosphoric acid, hydrochloric acid, and hydrogen sulfide. Phosphorus (Y) sulfochloride is soluble in benzene, carbon tetrachloride, carbon disulfide, and chloroform. It reacts with ethanol, yielding O-ethyl dichlorothiophosphate8 (synthesis 25). 

It was possible to racemize bulbocapnine 0-methyl ether and 0-benzoyl-bulbocapnine by first oxidizing with iodine and subsequently reducing with zinc in dilute acid. The dZ-O-methyl ether melted at 136° and was resolvable into the I- and d-derivatives ([a] d 247° in chloroform) by means of d- and Z-tartaric acid, respectively. Hydrolysis of the dZ-O-benzoylbulbo-capnine (m.p. 201-202°) with sodium methylate yielded dZ-bulbocapnine (m.p. 209-210°). As in other aporphines, it was possible to effect scission of the nitrogen ring in bulbocapnine by treatment with benzoyl chloride at its boiling point. 

Other derivatives can be prepared by reaction of the alcohol with an acid anhydride. For example, phthalic or 3-nitrophthalic anhydride (I mol) and the alcohol (Imol) are refluxed for half to one hour in a non-hydroxylic solvent, e.g. toluene or alcohol-free chloroform, and then cooled. The phthalate ester crystallises out, is precipitated by the addition of low boiling petroleum ether or is isolated by ev toration of the solvent. It is recrystallised from water, 50% aqueous ethanol, toluene or low boiling petroleum ether. Such an ester has a characteristic melting point and the alcohol can be recovered by acid or alkaline hydrolysis. 

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