Chlorination of biphenylene with molecular chlorine and sulphuryl chloride

Siala, Fadel Yousef

(1975)

Siala, Fadel Yousef (1975) Chlorination of biphenylene with molecular chlorine and sulphuryl chloride.

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Abstract

The non-catalysed reaction of chlorine with biphenylene yields 2-chlorobiphenylene as the main product, and tetra-chloro-, and trichlorohydroxy-tetrahydrobiphenylenes. Dechlorination of the tetrachloride and hydroxychloride gives biphenylene.

The reaction of biphenylene with sulphuryl chloride also gives 2-chlorobiphenylene and tetrachlorotetrahydro-biphenylene in very poor yield.

An attempt to chlorinate biphenylene with phosphorus pentachloride was unsuccessful.

Methoxybiphenylene has been made by combined hydrolysis and methylation of 2-benzoyloxybiphenylene. Mono-substitution occurs at the 3-position on chlorination of 2-methoxy-biphenylene with molecular chlorine, giving 2-methoxy-3-chlorobiphenylene, but no chlorination occurs with sulphuryl chloride, either on standing or on reflux. Direct chlorination of 2-nitrobiphenylene gives 2-nitro-6-chlorobiphenylene in poor yield, but nitration of 2-chlorobiphenylene gave a comjilex mixture.

Attempts to chlorinate 2 ,6-dimethoxybipheiiyleiie, 2-chlorobiphenylene and 2-bromobiphenylene did not give identified substitution products, but chlorination of 2-chlorobiphenvlene with large excess of chlorine in acetic acid gave a tetrachlorobiphenylene.

Direct chlorination of both 2-benzoyl- and 2-acetyl-biphenylenes, and chlorination after sulpl.onation, gave an inseparable mixture of mono- and dichloro-derivatives.

2-Benzoyl-7-chloro- and 2-acety 1-6-clilorobiphenylones were made by Friodel-Crafts benzoylation and acetylatiou respectively, of 2-chlorobiphenylene-Chlorobiphenylene has been made by pyrolysis of 2- and 3-chlorobiphenylone iodonium iodide with cuprous oxide in poor yield.

Finally, pyrolysis of -4-chlorobiphenylene iodonium iodide and 2,4-dichlorobiphenylene iodonium iodide with cuprous oxide gave 1-chlorobiphenylene and 1,3-dichloro-biphenylene respectively.

The comparative study of the N.M.R., U.V. and I.R. spectra of the chlorobiphenyleneSand those of their bromo-analogues was extensively and successfully used to distinguish between structural isomers.

Information about this Version

This is a Accepted version
This version's date is: 1975
This item is not peer reviewed

Link to this Version

https://repository.royalholloway.ac.uk/items/c0a0f201-8a33-4dd5-92dd-bf3e57bdf0ab/1/

Item TypeThesis (Doctoral)
TitleChlorination of biphenylene with molecular chlorine and sulphuryl chloride
AuthorsSiala, Fadel Yousef
Uncontrolled KeywordsMolecular Chemistry; Pure Sciences; Biphenylene; Chloride; Chlorination; Chlorine; Chlorination; Molecular; Sulphuryl
Departments

Identifiers

ISBN978-1-339-62346-7

Deposited by () on 31-Jan-2017 in Royal Holloway Research Online.Last modified on 31-Jan-2017

Notes

Digitised in partnership with ProQuest, 2015-2016. Institution: University of London, Bedford College (United Kingdom).


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