Reactions of 1,3 dienes with active hydrogen compounds, catalysed by transition metal complexes
Reactions of 1,3 dienes with active hydrogen compounds, catalysed by transition metal complexes
Reactions of myrcene with acetylacetone, ethyl acetoacetate and diethyl malonate have been studied in order to assess the reactivity of myrcene in systems catalysed by nickel and palladium complexes, and to examine methods of producing terpenoid derivatives. In the presence of catalytic quantities of nickel complexes new terpenoid compounds were produced from addition of myrcene and diethyl malonate, while the use of palladium salts as catalysts resulted in formation of both the new terpenoid compounds and geranyl derivatives of acetylacetone, ethyl acetoacetate and diethyl malonate. With acetylacetone, ketones including geranyl acetone were also formed. Further treatment of this ketone led, in low yield, to formation of pseudoionone.The reaction of myrcene and the amines: morpholine, pyrrolidine, diethylamine and di-n-propylamine with nickel salt has also been studied. In contrast to nickel catalysed reactions of myrcene and active methylene reagents, the products formed in reactions with amines included geranyl derivatives. The use of ethanol as solvent in this system was examined and its effect on yield and product distribution is discussed.Reaction of myrcene with acetone and stoichiometric quantities of bis(1,5-cyclooctadiene)rickel, followed by treatment with water, has been shown to give two products, an alcohol derived from 1:1 addition and a di-alcohol arising from addition of two molecules of acetone and one of myrcene. With acetaldehyde under similar conditions a low yield, unselective reaction was obtained. Addition of ethanol to the reaction, however, resulted in formation of essentially one product, an alcohol derived from 1:1 addition of myrcene and acetaldehyde.In all the reactions of myrcene and active hydrogen compounds, catalysed by transition metal complexes, the products are considered to arise through n -allyl intermediates.Reactions of butadiene with primary aromatic amines in the presence of iridium chloride have also been studied and shown to yield mixtures of butenyl and octadienyl adducts of the amines together with substituted quinolines. The alkylations are discussed in terms of it-allyl and bis-7T-allyl intermediates while the formation of quinolines is considered to arise from cyclisation of branched adducts. Reactions were carried out with branched butenyl adduct in order to investigate the mechanism of cyclisation, and mechanisms involving iridium-catalysed cyclisation are discussed.
University of Southampton
1977
Popplestone, Roger John
(1977)
Reactions of 1,3 dienes with active hydrogen compounds, catalysed by transition metal complexes.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
Reactions of myrcene with acetylacetone, ethyl acetoacetate and diethyl malonate have been studied in order to assess the reactivity of myrcene in systems catalysed by nickel and palladium complexes, and to examine methods of producing terpenoid derivatives. In the presence of catalytic quantities of nickel complexes new terpenoid compounds were produced from addition of myrcene and diethyl malonate, while the use of palladium salts as catalysts resulted in formation of both the new terpenoid compounds and geranyl derivatives of acetylacetone, ethyl acetoacetate and diethyl malonate. With acetylacetone, ketones including geranyl acetone were also formed. Further treatment of this ketone led, in low yield, to formation of pseudoionone.The reaction of myrcene and the amines: morpholine, pyrrolidine, diethylamine and di-n-propylamine with nickel salt has also been studied. In contrast to nickel catalysed reactions of myrcene and active methylene reagents, the products formed in reactions with amines included geranyl derivatives. The use of ethanol as solvent in this system was examined and its effect on yield and product distribution is discussed.Reaction of myrcene with acetone and stoichiometric quantities of bis(1,5-cyclooctadiene)rickel, followed by treatment with water, has been shown to give two products, an alcohol derived from 1:1 addition and a di-alcohol arising from addition of two molecules of acetone and one of myrcene. With acetaldehyde under similar conditions a low yield, unselective reaction was obtained. Addition of ethanol to the reaction, however, resulted in formation of essentially one product, an alcohol derived from 1:1 addition of myrcene and acetaldehyde.In all the reactions of myrcene and active hydrogen compounds, catalysed by transition metal complexes, the products are considered to arise through n -allyl intermediates.Reactions of butadiene with primary aromatic amines in the presence of iridium chloride have also been studied and shown to yield mixtures of butenyl and octadienyl adducts of the amines together with substituted quinolines. The alkylations are discussed in terms of it-allyl and bis-7T-allyl intermediates while the formation of quinolines is considered to arise from cyclisation of branched adducts. Reactions were carried out with branched butenyl adduct in order to investigate the mechanism of cyclisation, and mechanisms involving iridium-catalysed cyclisation are discussed.
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Published date: 1977
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Local EPrints ID: 458620
URI: http://eprints.soton.ac.uk/id/eprint/458620
PURE UUID: fffb8beb-ebd2-4099-8c2d-7841894a6e8b
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Date deposited: 04 Jul 2022 16:52
Last modified: 04 Jul 2022 16:52
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Author:
Roger John Popplestone
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