Ring expansion in the addition of dichlorocarbene to 2,5-dihydro-1H-phosphole 1-oxides

György Keglevich, Imre Petneházy, Péter Miklós, Attila Almásy, Gábor Tóth, László Töke, Louis D. Quin

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Abstract

While the addition of dichlorocarbene to 2,5-dihydro-3-methyl-1H-phosphole 1-oxides (1a-d) carried out under phase-transfer catalytic conditions gave 6,6-dichloro-1-methyl-3-phosphabicyclo[3.1.0]hexane 1-oxides (2a-d), the 3 4-dimethyl-1-phenyl analogue (3a) yielded, via four consecutive steps including two ring expansions, 4 5-dichloro-3,6-dimethyl-1-phenylphosphacyclohepta-2,4,6-triene 1-oxide (7a). In the reaction of 2,5-dihydro-1-methoxy-3,4-dimethyl-1H-phosphole 1-oxide (3d) the dichlorocarbene adduct (4d), 4-chloro-1,2-dihydro-1-methoxy-3,5-dimethylphosphorin 1-oxide (5d), the corresponding phosphinic acids (8, 9), and 4,5-dichloro-1-methoxy-3,6-dimethylphosphacyclohepta-2,4,6-triene 1-oxide (7d) were formed by a combination of dichlorocarbene addition, ring expansion, and hydrolysis. The primary dichlorocarbene adducts (4d, 8) were unstable and rearranged on standing with loss of hydrogen chloride to 1,6-dihydrophosphorins (5d, 9).

Original languageEnglish
Pages (from-to)3983-3986
Number of pages4
JournalJournal of Organic Chemistry
Volume52
Issue number18
Publication statusPublished - 1987

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Oxides
Phosphinic Acids
Hydrochloric Acid
Hexanes
dichlorocarbene
Hydrolysis

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Keglevich, G., Petneházy, I., Miklós, P., Almásy, A., Tóth, G., Töke, L., & Quin, L. D. (1987). Ring expansion in the addition of dichlorocarbene to 2,5-dihydro-1H-phosphole 1-oxides. Journal of Organic Chemistry, 52(18), 3983-3986.

Ring expansion in the addition of dichlorocarbene to 2,5-dihydro-1H-phosphole 1-oxides. / Keglevich, György; Petneházy, Imre; Miklós, Péter; Almásy, Attila; Tóth, Gábor; Töke, László; Quin, Louis D.

In: Journal of Organic Chemistry, Vol. 52, No. 18, 1987, p. 3983-3986.

Research output: Contribution to journalArticle

Keglevich, G, Petneházy, I, Miklós, P, Almásy, A, Tóth, G, Töke, L & Quin, LD 1987, 'Ring expansion in the addition of dichlorocarbene to 2,5-dihydro-1H-phosphole 1-oxides', Journal of Organic Chemistry, vol. 52, no. 18, pp. 3983-3986.
Keglevich, György ; Petneházy, Imre ; Miklós, Péter ; Almásy, Attila ; Tóth, Gábor ; Töke, László ; Quin, Louis D. / Ring expansion in the addition of dichlorocarbene to 2,5-dihydro-1H-phosphole 1-oxides. In: Journal of Organic Chemistry. 1987 ; Vol. 52, No. 18. pp. 3983-3986.
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AU - Quin, Louis D.

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AB - While the addition of dichlorocarbene to 2,5-dihydro-3-methyl-1H-phosphole 1-oxides (1a-d) carried out under phase-transfer catalytic conditions gave 6,6-dichloro-1-methyl-3-phosphabicyclo[3.1.0]hexane 1-oxides (2a-d), the 3 4-dimethyl-1-phenyl analogue (3a) yielded, via four consecutive steps including two ring expansions, 4 5-dichloro-3,6-dimethyl-1-phenylphosphacyclohepta-2,4,6-triene 1-oxide (7a). In the reaction of 2,5-dihydro-1-methoxy-3,4-dimethyl-1H-phosphole 1-oxide (3d) the dichlorocarbene adduct (4d), 4-chloro-1,2-dihydro-1-methoxy-3,5-dimethylphosphorin 1-oxide (5d), the corresponding phosphinic acids (8, 9), and 4,5-dichloro-1-methoxy-3,6-dimethylphosphacyclohepta-2,4,6-triene 1-oxide (7d) were formed by a combination of dichlorocarbene addition, ring expansion, and hydrolysis. The primary dichlorocarbene adducts (4d, 8) were unstable and rearranged on standing with loss of hydrogen chloride to 1,6-dihydrophosphorins (5d, 9).

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