Decomposition of alkene adducts of thianthrene cation radical in nitrile solvents. Formation of alkyl-2-oxazolines and a new class of four-component products

5-[(1-alkoxyalkylidene) ammonio]alkylthianthrenium diperchlorates

Henry J. Shine, Bing Jun Zhao, John N. Marx, Teyeb Ould-Ely, Kenton H. Whitmire

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

The monoadducts (4a-d) of thianthrene cation radical perchlorate (1a) and isobutene, 2-methyl-butene, 2-methyl-2-butene, and 2-methylpentene decompose spontaneously in acetonitrile (MeCN) solution, with the formation of thianthrene (Th). Decomposition of 4a (1,2-(5,10-thianthreniumdiyl)-2-methylpropane diperchlorate) and 4a', the corresponding dihexafluorophosphate, was studied in depth and extensively with 1H and 13C NMR spectroscopy. Decomposition of 4a was found to involve the solvent itself as well as water in the solvent, remaining from incomplete drying, and gave, apart from Th, successively, the perchlorate salts of 2,4,4-trimethyl-2-oxazoline (6) and 2-amino-2-methylpropyl acetate (7). These salts, 6-HCIO 4 and 7-HCIO 4, respectively, were prepared and used in understanding the reactions of 4a as well as the relationships among 6, 7, and 2-(acetylamino)-2-methyl propanol (8) in acidified MeCN solution. Decompositions of 4a-d in MeCN and other nitriles (RCN) containing an added alcohol (ROH) led to new products, 5-[(1-alkoxyalkylidene)ammonio]alkylthianthrenium diperchlorates (5a-u). These compounds were identified with 1H and 13C NMR spectroscopy and, in part, with X-ray crystallography and elemental analysis. The mechanisms of formation of 5-7 are discussed.

Original languageEnglish
Pages (from-to)9255-9261
Number of pages7
JournalJournal of Organic Chemistry
Volume69
Issue number26
DOIs
Publication statusPublished - Dec 24 2004
Externally publishedYes

Fingerprint

Nitriles
Alkenes
Cations
Decomposition
Nuclear magnetic resonance spectroscopy
Salts
1-Propanol
X ray crystallography
Drying
Acetates
Alcohols
Water
Chemical analysis
thianthrene
perchlorate
2-butene

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Decomposition of alkene adducts of thianthrene cation radical in nitrile solvents. Formation of alkyl-2-oxazolines and a new class of four-component products : 5-[(1-alkoxyalkylidene) ammonio]alkylthianthrenium diperchlorates. / Shine, Henry J.; Zhao, Bing Jun; Marx, John N.; Ould-Ely, Teyeb; Whitmire, Kenton H.

In: Journal of Organic Chemistry, Vol. 69, No. 26, 24.12.2004, p. 9255-9261.

Research output: Contribution to journalArticle

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AB - The monoadducts (4a-d) of thianthrene cation radical perchlorate (1a) and isobutene, 2-methyl-butene, 2-methyl-2-butene, and 2-methylpentene decompose spontaneously in acetonitrile (MeCN) solution, with the formation of thianthrene (Th). Decomposition of 4a (1,2-(5,10-thianthreniumdiyl)-2-methylpropane diperchlorate) and 4a', the corresponding dihexafluorophosphate, was studied in depth and extensively with 1H and 13C NMR spectroscopy. Decomposition of 4a was found to involve the solvent itself as well as water in the solvent, remaining from incomplete drying, and gave, apart from Th, successively, the perchlorate salts of 2,4,4-trimethyl-2-oxazoline (6) and 2-amino-2-methylpropyl acetate (7). These salts, 6-HCIO 4 and 7-HCIO 4, respectively, were prepared and used in understanding the reactions of 4a as well as the relationships among 6, 7, and 2-(acetylamino)-2-methyl propanol (8) in acidified MeCN solution. Decompositions of 4a-d in MeCN and other nitriles (RCN) containing an added alcohol (ROH) led to new products, 5-[(1-alkoxyalkylidene)ammonio]alkylthianthrenium diperchlorates (5a-u). These compounds were identified with 1H and 13C NMR spectroscopy and, in part, with X-ray crystallography and elemental analysis. The mechanisms of formation of 5-7 are discussed.

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