Reactions of Ethyl Phosphites with β-Nitrostyrenes. The Role of Nitrosoalkenes as Intermediates

Glen A. Russell, Ching Fa Yao

Research output: Contribution to journalArticle

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Abstract

3-Phenyl-2-substituted-indoles are formed in high yields in the reaction of Ph2C=C(R)NO2 (R = H, Me, Ph) with (EtO)3P at 150 °C while reaction with (EtO)2PO-/(EtO)2P(O)H at room temperature forms the aziridines 1 with R = H, Me, Ph. 2,2-Diphenyl-3-substituted-2H-azirines formed by deoxygenation of the Michael-type adducts are postulated as intermediates. Reactions of PhCH=C(R)NO2 (R = H, Me, Ph) with (EtO)3P at 150 °C or (EtO)2PO-/(EtO)2P(O)H at room temperature give products resulting from the addition of the phosphorus nucleophile at the benzylidene carbon atom. Evidence for the formartion of cyclic structures with pentacoordinated phosphorus atoms is presented for the reaction of Ph2C=C(Me)NO2 with (EtO)2PO-/EtO)2P(O)H and for PhCH=C(R)NO2 (R = H, Me, Ph) with (EtO)O3P. The Michael-type adducts PhCH[P(O)(OEt)2]CH(R)NO2 (R = Me, Ph) undergo reaction upon treatment with aqueous base at 80–100 °C followed by acidification to yield the 3-(diethoxyphosphinyl)-2-R-N-hydroxyindoles. 4-(Diethoxyphosphinyl)-3-R-4H-1,2-benzoxazines (13, R = Me, Ph) are formed by reaction with 85% H2SO4 of the adducts of PhCH=C(R)NO2 with (EtO)2PO- (R = Me) or (EtO)3P (R = Ph).

Original languageEnglish
Pages (from-to)6508-6513
Number of pages6
JournalJournal of Organic Chemistry
Volume57
Issue number24
DOIs
Publication statusPublished - 1992 Nov 1

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Phosphites
Phosphorus
Azirines
Aziridines
Benzoxazines
Indoles
Atoms
Nucleophiles
Acidification
Carbon
Temperature
diphenyl

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Reactions of Ethyl Phosphites with β-Nitrostyrenes. The Role of Nitrosoalkenes as Intermediates. / Russell, Glen A.; Yao, Ching Fa.

In: Journal of Organic Chemistry, Vol. 57, No. 24, 01.11.1992, p. 6508-6513.

Research output: Contribution to journalArticle

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abstract = "3-Phenyl-2-substituted-indoles are formed in high yields in the reaction of Ph2C=C(R)NO2 (R = H, Me, Ph) with (EtO)3P at 150 °C while reaction with (EtO)2PO-/(EtO)2P(O)H at room temperature forms the aziridines 1 with R = H, Me, Ph. 2,2-Diphenyl-3-substituted-2H-azirines formed by deoxygenation of the Michael-type adducts are postulated as intermediates. Reactions of PhCH=C(R)NO2 (R = H, Me, Ph) with (EtO)3P at 150 °C or (EtO)2PO-/(EtO)2P(O)H at room temperature give products resulting from the addition of the phosphorus nucleophile at the benzylidene carbon atom. Evidence for the formartion of cyclic structures with pentacoordinated phosphorus atoms is presented for the reaction of Ph2C=C(Me)NO2 with (EtO)2PO-/EtO)2P(O)H and for PhCH=C(R)NO2 (R = H, Me, Ph) with (EtO)O3P. The Michael-type adducts PhCH[P(O)(OEt)2]CH(R)NO2 (R = Me, Ph) undergo reaction upon treatment with aqueous base at 80–100 °C followed by acidification to yield the 3-(diethoxyphosphinyl)-2-R-N-hydroxyindoles. 4-(Diethoxyphosphinyl)-3-R-4H-1,2-benzoxazines (13, R = Me, Ph) are formed by reaction with 85{\%} H2SO4 of the adducts of PhCH=C(R)NO2 with (EtO)2PO- (R = Me) or (EtO)3P (R = Ph).",
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N2 - 3-Phenyl-2-substituted-indoles are formed in high yields in the reaction of Ph2C=C(R)NO2 (R = H, Me, Ph) with (EtO)3P at 150 °C while reaction with (EtO)2PO-/(EtO)2P(O)H at room temperature forms the aziridines 1 with R = H, Me, Ph. 2,2-Diphenyl-3-substituted-2H-azirines formed by deoxygenation of the Michael-type adducts are postulated as intermediates. Reactions of PhCH=C(R)NO2 (R = H, Me, Ph) with (EtO)3P at 150 °C or (EtO)2PO-/(EtO)2P(O)H at room temperature give products resulting from the addition of the phosphorus nucleophile at the benzylidene carbon atom. Evidence for the formartion of cyclic structures with pentacoordinated phosphorus atoms is presented for the reaction of Ph2C=C(Me)NO2 with (EtO)2PO-/EtO)2P(O)H and for PhCH=C(R)NO2 (R = H, Me, Ph) with (EtO)O3P. The Michael-type adducts PhCH[P(O)(OEt)2]CH(R)NO2 (R = Me, Ph) undergo reaction upon treatment with aqueous base at 80–100 °C followed by acidification to yield the 3-(diethoxyphosphinyl)-2-R-N-hydroxyindoles. 4-(Diethoxyphosphinyl)-3-R-4H-1,2-benzoxazines (13, R = Me, Ph) are formed by reaction with 85% H2SO4 of the adducts of PhCH=C(R)NO2 with (EtO)2PO- (R = Me) or (EtO)3P (R = Ph).

AB - 3-Phenyl-2-substituted-indoles are formed in high yields in the reaction of Ph2C=C(R)NO2 (R = H, Me, Ph) with (EtO)3P at 150 °C while reaction with (EtO)2PO-/(EtO)2P(O)H at room temperature forms the aziridines 1 with R = H, Me, Ph. 2,2-Diphenyl-3-substituted-2H-azirines formed by deoxygenation of the Michael-type adducts are postulated as intermediates. Reactions of PhCH=C(R)NO2 (R = H, Me, Ph) with (EtO)3P at 150 °C or (EtO)2PO-/(EtO)2P(O)H at room temperature give products resulting from the addition of the phosphorus nucleophile at the benzylidene carbon atom. Evidence for the formartion of cyclic structures with pentacoordinated phosphorus atoms is presented for the reaction of Ph2C=C(Me)NO2 with (EtO)2PO-/EtO)2P(O)H and for PhCH=C(R)NO2 (R = H, Me, Ph) with (EtO)O3P. The Michael-type adducts PhCH[P(O)(OEt)2]CH(R)NO2 (R = Me, Ph) undergo reaction upon treatment with aqueous base at 80–100 °C followed by acidification to yield the 3-(diethoxyphosphinyl)-2-R-N-hydroxyindoles. 4-(Diethoxyphosphinyl)-3-R-4H-1,2-benzoxazines (13, R = Me, Ph) are formed by reaction with 85% H2SO4 of the adducts of PhCH=C(R)NO2 with (EtO)2PO- (R = Me) or (EtO)3P (R = Ph).

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