Synthesis and chemistry of novel bridged polyamines
Synthesis and chemistry of novel bridged polyamines
Reaction of the bishydrazine 4,9-dimethyl-2,3,7,8-tetraazatetracyclo-[7.3.1.04,1206,10]trideca-1,6-diene with potassium carbonate in ethanol results in a base catalysed rearrangement to give a tetracyclic bisazoalkane. Photolysis of the bisazoalkane in either acetone or methanol affords a triasterane by a double extrusion of nitrogen. The azo groups in the bisazoalkane can be reduced to give the bishydrazine, 1,6-di-methyl-2,3,7,8-tetraazatetracyclo[7.3.1.04,1206,10] tridecane. Reductions of tetraacyl derivatives of this bishydrazine afford the tetramethyl and tetraethyl bishydrazines and differences in the conformations of these systems have been noted by the use of NMR and PE spectroscopy. The reductive cleavage of the hydrazine bonds in the above bishydrazine has been studied and in connection with this an investigation into the optimum conditions for the cleavage of a number of 1,2-diacyl substituted hydrazine derivatives has been carried out. As an extension of this work elaboration of the Diels-Alder adduct obtained from cyclopentadiene and diethyl azodicarboxylate affords oxidised products. The hydrazine bond in these systems can be reduced to give highly functionalised cyclopentadiamine derivatives. Reduction of the tetratrifluoroacetyl derivative of the above bishydrazine using aluminium amalgam gives a tetra(trifluoro-acetamido)bicyclo[3.3.1]nonane, although attempted hydrolysis of the trifluoroacetyl groups to give an unsubstituted tetraamine was unsuccessful. Reaction of the tetraacetyl derivative of the bishydrazine with borane successfully reduces the N-N bonds to give a tetraethyl tetraamine system. The chemistry of the bishydrazine and this tetraamine with aldehydes, ketones and acid derivatives has been investigated and a number of caged condensation products have been obtained. (D71545/87)
University of Southampton
1986
Smith, Neil Michael
(1986)
Synthesis and chemistry of novel bridged polyamines.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
Reaction of the bishydrazine 4,9-dimethyl-2,3,7,8-tetraazatetracyclo-[7.3.1.04,1206,10]trideca-1,6-diene with potassium carbonate in ethanol results in a base catalysed rearrangement to give a tetracyclic bisazoalkane. Photolysis of the bisazoalkane in either acetone or methanol affords a triasterane by a double extrusion of nitrogen. The azo groups in the bisazoalkane can be reduced to give the bishydrazine, 1,6-di-methyl-2,3,7,8-tetraazatetracyclo[7.3.1.04,1206,10] tridecane. Reductions of tetraacyl derivatives of this bishydrazine afford the tetramethyl and tetraethyl bishydrazines and differences in the conformations of these systems have been noted by the use of NMR and PE spectroscopy. The reductive cleavage of the hydrazine bonds in the above bishydrazine has been studied and in connection with this an investigation into the optimum conditions for the cleavage of a number of 1,2-diacyl substituted hydrazine derivatives has been carried out. As an extension of this work elaboration of the Diels-Alder adduct obtained from cyclopentadiene and diethyl azodicarboxylate affords oxidised products. The hydrazine bond in these systems can be reduced to give highly functionalised cyclopentadiamine derivatives. Reduction of the tetratrifluoroacetyl derivative of the above bishydrazine using aluminium amalgam gives a tetra(trifluoro-acetamido)bicyclo[3.3.1]nonane, although attempted hydrolysis of the trifluoroacetyl groups to give an unsubstituted tetraamine was unsuccessful. Reaction of the tetraacetyl derivative of the bishydrazine with borane successfully reduces the N-N bonds to give a tetraethyl tetraamine system. The chemistry of the bishydrazine and this tetraamine with aldehydes, ketones and acid derivatives has been investigated and a number of caged condensation products have been obtained. (D71545/87)
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Published date: 1986
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Local EPrints ID: 460723
URI: http://eprints.soton.ac.uk/id/eprint/460723
PURE UUID: aa6bddc3-cc2e-4d9c-82d8-b4f152bbbb1b
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Date deposited: 04 Jul 2022 18:28
Last modified: 04 Jul 2022 18:28
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Author:
Neil Michael Smith
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