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Nitration of Oxo-pyramidines and Oxo-imidazoles
KTH, School of Chemical Science and Engineering (CHE), Chemistry.
2006 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

This thesis is mainly focused on the reactions of oxo-pyrimidines and oxo-imidazoles with nitric acid in sulfuric acid and properties of the gem-dinitro products formed in this process.

Low temperature nitrations of 2-methylimidazoles produced – in addition to the known 2-methyl-5(4)-nitroimidazole – 2-(dinitromethylene)-5,5-dinitro-4-imidazolidinone and parabanic acid. This tetranitro compound was also obtained via nitration of 2-methyl-4,4-dihydro-(1H)-5- imidazolone. Thermal decomposition of 2-(dinitromethylene)-5,5-dinitro-4-imidazolidinone yielded 2-(dinitromethylene)-4,5-imidazolidinedione, which also was the product from the nitration of the new compound 2-methoxy-2-methyl-4,5-imidazolidienedione. Treatment of 2- (dinitromethylene)-5,5-dinitro-4-imidazolidinone with aqueous ammonia resulted in the previously unknown 1,1-diamino-2,2-dinitroethylene (Paper I).

The nitration of some 2-substituted pyrimidine-4,6-diones in sulfuric acid, which afforded previously unknown 5,5-gem-dinitro-pyrimidine-4,6-diones in high yields, was studied. Alloxane was prepared in a one-step procedure by thermal decomposition of 5,5-dinitrobarbituric acid in hot acetic acid. The gem-dinitro products were found to be easily attacked by nucleophiles with concomitant formation of gem-dinitroacetyl derivatives, which in turn could be further hydrolysed to salts of dinitromethane and triureas (Papers II and III).

Nitration of 4,6-dihydroxypyrimidine in sulfuric acid yielded nitroform as the sole product. This behaviour was tentatively explained by the formation of an intermediate, 5,5-dinitro-4,6- dihydroxypyrimidine, which underwent hydrolysis in the nitrating acid into gem-dinitroacetyl formamidine. This compound was further nitrated in the same reaction mixture into trinitroacetylformamidine, which finally underwent hydrolytic cleavage into nitroform. It was also demonstrated that gem-dinitroacetylureas could produce nitroform upon nitration. The structures of the proposed trinitroacetylureas were confirmed by the isolation of one of their derivatives (Paper IV).

Place, publisher, year, edition, pages
Stockholm: KTH , 2006. , 34 p.
Keyword [en]
explosives, gem-Dinitro compounds, Dinitromethane, Nitroform
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-601ISBN: 91-7178-255-9 (print)OAI: oai:DiVA.org:kth-601DiVA: diva2:14577
Public defence
2006-02-10, Sal K2, Teknikringen 28, Stockholm, 10:00
Opponent
Supervisors
Note
QC 20100907Available from: 2006-01-26 Created: 2006-01-26 Last updated: 2010-09-07Bibliographically approved
List of papers
1. Synthesis and Reactions of 1,1-dinitro-2,2-dinitroethylene
Open this publication in new window or tab >>Synthesis and Reactions of 1,1-dinitro-2,2-dinitroethylene
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1998 (English)In: Tetrahedron, ISSN 0040-4020, E-ISSN 1464-5416, Tetrahedron, Vol. 54, no 38, 11525-11536 p.Article in journal (Refereed) Published
Abstract [en]

Low temperature nitrations of 2-methylimidazole gave in addition to the known 2-methyl-5(4)-nitroimidazole (1), 2-(dinitromethylene)-5,5-dinitro-4-imidazolidinone (3) and parabanic acid (2). The tetranitro compound 3 was also obtained by nitration of 2-methyl-4,5-dihydro-(1H)-5-imidazolone (8). Thermal decomposition of 3 gave 2-(dinitromethylene)-4,5-imidazolidinedione (4) which also was the product from nitration of the new compound 2-methoxy-2-methyl-4,5-imidazolidinedione. Treatment of 4 with aqueous ammonia gave the previously unknown 1,1-diamino-2,2-dinitroethylene (5). The physical properties and chemical behaviour of (5) are described.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-9033 (URN)10.1016/S0040-4020(98)00673-5 (DOI)
Note
QC 20100907Available from: 2006-01-26 Created: 2006-01-26 Last updated: 2010-09-07Bibliographically approved
2. Nitration of 2-substituted pyrimidine-4,6-diones, structure and reactivity of 5,5-gem-dinitropyrimidine-4,6-diones
Open this publication in new window or tab >>Nitration of 2-substituted pyrimidine-4,6-diones, structure and reactivity of 5,5-gem-dinitropyrimidine-4,6-diones
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2002 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 67, no 22, 7833-7838 p.Article in journal (Refereed) Published
Abstract [en]

Nitration of some 2-substituted pyrimidine-4,6-diones in sulfuric acid was studied, which afforded previously unknown 5,5-gem-dinitropyrimidine-4,6-diones in high yields. The gem-dinitro products were easily attacked by nucleophiles with concomitant formation of gem-dinitroacetyl derivatives, which in turn could be further hydrolyzed to salts of dinitromethane and triureas.

Keyword
Hydrolysis, Methane, Molecular structure, Nitration, Substitution reactions, Sulfuric acid, Urea
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-9034 (URN)10.1021/jo025952x (DOI)000178820200035 ()12398510 (PubMedID)
Note
Tidigare titel: Nitration of 2-Substituted Pyrimidine-4,6-diones, Structure and Reactivity of 5,5-gem-Dinitropyrimidine QC 20100907Available from: 2006-01-26 Created: 2006-01-26 Last updated: 2010-09-07Bibliographically approved
3. Synthesis and reaction of 5,5-dinitrobarbituric acid
Open this publication in new window or tab >>Synthesis and reaction of 5,5-dinitrobarbituric acid
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2000 (English)In: Tetrahedron Letters, ISSN 0040-4039, E-ISSN 1873-3581, Tetrahedron letters, Vol. 41, no 12, 2011-2013 p.Article in journal (Refereed) Published
Abstract [en]

Nitration of barbituric acid at 40°C gave the previously unknown 5,5- dinitrobarbituric acid (3), which readily underwent hydrolysis to dinitroacetylurea (5), which in turn could be hydrolysed in basic media to the potassium salt of dinitromethane. Alloxane was prepared in a one step procedure by thermal decomposition of 5,5-dinitrobarbituric acid in hot acetic acid.

Keyword
Nitration, Nitro compounds, Nitrogen heterocycles
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-9035 (URN)10.1016/S0040-4039(00)00086-1 (DOI)000086086100036 ()
Note
QC 20100907Available from: 2006-01-26 Created: 2006-01-26 Last updated: 2010-09-07Bibliographically approved
4. Formation of Nitroform in the Nitration of gem-Dinitro Compounds
Open this publication in new window or tab >>Formation of Nitroform in the Nitration of gem-Dinitro Compounds
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2004 (English)In: Propellants, explosives, pyrotechnics, ISSN 0721-3115, E-ISSN 1521-4087, Propellants, Explosives, Pyrotechnics, Vol. 29, no 6, 344-348 p.Article in journal (Refereed) Published
Abstract [en]

Nitration of 4,6-dihydroxypyrimidine in sulphuric acid gave nitroform as the sole product. This behaviour was tentatively explained by the formation of an intermediate, 5,5-dinitro-4,6-dihydroxypyrimidine, that underwent hydrolysis in the nitrating acid to gem-dinitroacetyl formamidine. This compound was further nitrated in the same reaction mixture to trinitroacetylformamidine which finally underwent hydrolytic cleavage to nitroform. It was also demonstrated that gem-dinitroacetyl ureas were able to produce nitroform on nitration. The structures of the proposed trinitroacetylureas were confirmed by the isolation of one of their derivatives.

Keyword
nitration, nitroform, explosive, gem-dinitro
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-9036 (URN)10.1002/prep.200400064 (DOI)000226187600004 ()
Note
QC 20100907Available from: 2006-01-26 Created: 2006-01-26 Last updated: 2010-09-07Bibliographically approved

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