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Dandegaonker, S. H. (1957) Reactions of organoboron chlorides. Doctoral thesis, Northern Polytechnic.
For investigation of the arylboronic series arylboron dichlorides were required as synthetic intermediates. Simple methods of preparation have been developed. Arylboron chlorides have been characterised by hydrolysis and alcoholysis.
A number of new phenylchloroboronites Ph-B-OR phenylboronates Ph-B(OR)2 have been prepared. Simple Arylboron chlorides Hitherto undescribed aryl phenylchloroboronites and diaryl aryl phenylchloroboronites and diaryl phenylboronaten have been prepared. The proportionation on reaction of phenylboronates with phenylboron dichloride, and the complexes of aryl esters with pyridine are reported. The reactions of phenylchloroboronites with water, alcohol, phenols, ethers and pyridine are described. Phenylchloroboronites, except the benzyl ester, were thermally stable. The effect of constitutional, environmental and stereochemical factors on the decomposition into alkyl chloride was investigated using the methyl series of esters. By contrast, aryl phenylchloroboronitesed disproportionated when heated in a vacuum.
The reaction of phenylboron dichoride with ethers have been studied. It did not react with ethers at 20 degree, but at the reflux temperature of the ether, carbonoxygen fission was effected, to produce alkyl chlorides and alkyl (or aryl) phenylchloroboronites (Ph-B-OR). The reactions with 16 mixed ethers were shown to be stoicheiometrically specific, being alkychloride produced exclusively from alkyl aryl ethers and from the more electron releasing of the two alkyl groups in dialkyl ethers; n-butyl isobutyl ether gave iso- and tert-butyl chlorides. Fission of ethyl sec-octyl ether produced 2-chlore-octane, of predominantly ethers inverted configuration, but with much loss in rotatory power. Mechanisms of the reactions are discussed. Diphenyl and bis-2-chloroethyl ethers did not react.
Claisen rearrangement of allyl and substituted allyl phenyl ethers with phenylboron dichloride, boron trichloride and other Lewis acids have been investigated.
Infra-red spectroscopic examination of phenylboranates and phenylchloroboronites were carried out. The frequencies for B - 0 absorption were confirmed, whereas an assignment of 890-916 cm-1 has been made for the B-Cl stretching frequency.
A series of new piperidine complexes with certain organic boron compounds were prepared for spectroscopic investigation.
A polymetic product has been obtained by pyrolysis of p-methoxyphenylboron dichloride; an attempt to elucidate its structure has been made.
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