The synthesis of some secondary amyl and hexyl homologues of dinitro ortho and paracresols
department or school: Science, Faculty of
department or school: Chemistry, Department of
data provider: DSpace
degree campus: UBCV
creator: Moffatt, John Gilbert
issued: 2012-02-21T21:00:07Z
issued: 1953
related degree: Master of Science - MSc
degree grantor: University of British Columbia
description: Eight new dinitro-sec.-amyl and hexylphenols of unequivocal structure were synthesized and characterized by their piperidine, morpholine and cyclohexylamine salts. The synthetic route followed involves the Fries rearrangement, of phenyl acetate and phenyl propionate to give the easily separated isomers o- and p-hydroxyacetophenone and o- and p-hydrcocypropiophenone. These compounds were then methylated to give the corresponding methoxyacetophenones and methoxypropiophenones. The methylated aryl-alkyl ketones were condensed through a Grignard reaction with various alkyl bromides to give tertiary alcohols which were dehydrated by the Dean and Stark method to the corresponding olefins and then hydrogenated to alkylanisoles. Demethylation was effected through the use of pyridine hydrobrondde for the p-alkylphenols, or 47% hydriodic acid and phenol for the o-alkylphenols. The alkyl phenols were then nitrated with fuming nitric acid in glacial acetic acid at -15⁰C., and the resulting dinitro-alkylphenols characterized as amine salts. The phenols prepared were: 3-(o- and p-hydroxyphenyl)-pentane, 2-(o- and p-hydroxyphenyl)-hexane, 2-(o- and p-hydroxyphenyl)-3-methylpentane, 2-(o- and p-hydroxyphenyl)-4-methylpentane. Of these, only 2-(p-methoxyphenyl)-3-mathylpentane has been reported prepared by an unequivocal synthesis. All other phenols, their intermediates and derivatives, and their dinitro derivatives, are previously unreported except in odd cases through questionable condensation methods.
aggregated CHO: https://circle.library.ubc.ca/rest/handle/2429/40831
note: THE SYNTHESIS OF SOME SECONDARY AMYL AND HEXYL HOMOLOGUES OF DDJITRO ORTHO AND PARA CRESOLS by JOHN GILBERT MDFFATT A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE -REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE IN THE DEPARTMENT OF CHEMISTRY. Me accept this Thesis as conforming to the standard required from candidates for the^Degree of MASTER OF SCIENCE Members of the Department of Chemistry THE UNIVERSITY OF BRITISH COLUMBIA July, 3953. ABSTRACT Eight new dinitro-sec.-amyl and hexylphenols of unequivocal structure were synthesized and characterized by their piperidine, morpholine and cyclohexylamine salts* The synthetic route followed involves the Fries rearrangement, of phenyl acetate and phenyl propionate to give the easily separated isomers o- and p-hydroxyacetophenone and o- and p-hydrcocypropiophenone. These compounds were then methylated to give the corresponding methoxyaceto-phenones and methoxypropiophenones. The methylated aryl-alkyl ketones were condensed through a Grignard reaction with various alkyl bromides to give tertiary alcohols which were dehydrated by the Dean and Stark method to the corresponding olefins and then hydrogenated to alkylanisoles. Demethylation was effected through the use of pyridine hydrobrondde for the p~alkylphen ols, or 47$ hydriodic acid and phenol for the o-alkylphenols. The alkyl phenols were then nitrated with fuming nitric acid in glacial acetic acid at -15°<'&-, and the resulting dinitro-alkylphenols characterized as amine salts. The phenols prepared were; 3-(o- and p-hydroxyphenyl)-pentane, 2-(o- and p-hydroxyphenyl)-hexane, 2-(o- and p-hydroxyphenyl)-3-methylpen-tane, 2-(o- and p-hydroxyphenyl)-4-methylpentane. Of these, only 2-(p-methoxyphenyl)-3-mathylpentane has been reported prepared by an unequivocal synthesis. A l l other phenols,. their intermediates and derivatives, and their dinitro derivatives, are previously unreported except in odd cases through questionable condensation methods. ACKNOWLEDGMENT Sincerest…
has type: Thesis/Dissertation
is shown at: 10.14288/1.0062326
language: eng
degree discipline: Chemistry
provider: Vancouver : University of British Columbia Library
publisher: University of British Columbia
rights: For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use.
scholar level: Graduate
type: Text
identifier URI: http://hdl.handle.net/2429/40831