Clay-supported iron(III) nitrate: A multifunctional reagent. Oxidation and nitration of nitrogen bridgehead compounds

Mária Balogh, I. Hermecz, István Hermecz, André Gerstmans

Research output: Contribution to journalArticle

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Abstract

Ethyl 9-(hydroxyimino)-4-oxo-6,7,8,9-tetrahydro-4H-pyrido[1,2-a]Pyrimidine-3- carboxylate (1) is oxidized to the 9-nitro derivative 2 at ambient temperature with K-10 montmorillonite clay-supported iron(III) nitrate (Clayfen). The reaction involves direct oxidation of the hydroxyimino group, as shown by mass spectral analysis of 15N-labeled compounds. The 9,9-dinitro derivative 3 was prepared from either 2 or 1 and Clayfen in refluxing methylene chloride. Analogues of 1 with a 9-formyl group (4) or a 9-((dimethylamino)methylene) group (5) were also converted into 2 and 3 by Clayfen. Similar nitration of pyridoquinazolinone 7 to 8 was accompanied by some dehydrogenation of the starting compound to 9. Nitration of the oxazepino[1,2-a]pyrimidine-3-carboxylate 10 with an equimolar quantity of Clayfen gave the 10,10-dinitro compound 11, whereas use of 0.5 equiv of Clayfen led to ring contraction, giving 2.

Original languageEnglish
Pages (from-to)6198-6202
Number of pages5
JournalJournal of Organic Chemistry
Volume55
Issue number25
Publication statusPublished - 1990

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Nitrogen Compounds
Nitration
Nitrates
Iron
Derivatives
Oxidation
Methylene Chloride
Dehydrogenation
Spectrum analysis
Temperature
clay
pyrimidine
montmorillonite K-10

ASJC Scopus subject areas

  • Organic Chemistry

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Clay-supported iron(III) nitrate : A multifunctional reagent. Oxidation and nitration of nitrogen bridgehead compounds. / Balogh, Mária; Hermecz, I.; Hermecz, István; Gerstmans, André.

In: Journal of Organic Chemistry, Vol. 55, No. 25, 1990, p. 6198-6202.

Research output: Contribution to journalArticle

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AB - Ethyl 9-(hydroxyimino)-4-oxo-6,7,8,9-tetrahydro-4H-pyrido[1,2-a]Pyrimidine-3- carboxylate (1) is oxidized to the 9-nitro derivative 2 at ambient temperature with K-10 montmorillonite clay-supported iron(III) nitrate (Clayfen). The reaction involves direct oxidation of the hydroxyimino group, as shown by mass spectral analysis of 15N-labeled compounds. The 9,9-dinitro derivative 3 was prepared from either 2 or 1 and Clayfen in refluxing methylene chloride. Analogues of 1 with a 9-formyl group (4) or a 9-((dimethylamino)methylene) group (5) were also converted into 2 and 3 by Clayfen. Similar nitration of pyridoquinazolinone 7 to 8 was accompanied by some dehydrogenation of the starting compound to 9. Nitration of the oxazepino[1,2-a]pyrimidine-3-carboxylate 10 with an equimolar quantity of Clayfen gave the 10,10-dinitro compound 11, whereas use of 0.5 equiv of Clayfen led to ring contraction, giving 2.

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