Synthesis of Bis(Phospha-λ5-Azenes) by a Redox-Condensation Reaction. Formation of an Anomalous N-Cyanophospha-λ5-Azene from Urea

Shmuel Bittner; Yonit Assaf; Penina Krief; Martin Pomerantz; Shikang Xi; Malgorzata K. Witczak

doi:10.1021/jo00236a001

Synthesis of Bis(Phospha-λ⁵-Azenes) by a Redox-Condensation Reaction. Formation of an Anomalous N-Cyanophospha-λ⁵-Azene from Urea

Shmuel Bittner, Yonit Assaf, Penina Krief, Martin Pomerantz, Shikang Xi, Malgorzata K. Witczak

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

33 Scopus citations

Abstract

The reaction of diphosphines [Ph₂P(CH₂)_nPPh₂; n = 1, 2] with sulfonamides, a phosphinamide, and cyanamide as well as of a dicarboxamide, a disulfonamide, urea, thiourea, and sulfamide with triphenylphosphine in the presence of diethyl azodicarboxylate has been shown to produce bis(phospha-λ⁵-azenes). In the case of cyanamide with bis(diphenylphosphino)methane a mono-(10) as well as a bis(phospha-λ⁵-azene) (9) could be prepared. Further, the monophospha-λ⁵-azene monooxide 11 was also isolated. In the case of thiourea, the monophospha-λ⁶-azene intermediate was also isolated. The reaction of urea with bis(diphenylphosphino)methane gave the mono-N-cyanophospha-λ⁵-azene monooxide (11) along with bis(diphenylphosphino)methane dioxide. This is the first observation of a nitrile produced in the reaction of an amide, a phosphine, and diethyl azodicarboxylate at room temperature.

Original language	English
Pages (from-to)	1-5
Number of pages	5
Journal	Journal of Organic Chemistry
Volume	53
Issue number	1
DOIs	https://doi.org/10.1021/jo00236a001
State	Published - 1 Jan 1988

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Organic Chemistry

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title = "Synthesis of Bis(Phospha-λ5-Azenes) by a Redox-Condensation Reaction. Formation of an Anomalous N-Cyanophospha-λ5-Azene from Urea",

abstract = "The reaction of diphosphines [Ph2P(CH2)nPPh2; n = 1, 2] with sulfonamides, a phosphinamide, and cyanamide as well as of a dicarboxamide, a disulfonamide, urea, thiourea, and sulfamide with triphenylphosphine in the presence of diethyl azodicarboxylate has been shown to produce bis(phospha-λ5-azenes). In the case of cyanamide with bis(diphenylphosphino)methane a mono-(10) as well as a bis(phospha-λ5-azene) (9) could be prepared. Further, the monophospha-λ5-azene monooxide 11 was also isolated. In the case of thiourea, the monophospha-λ6-azene intermediate was also isolated. The reaction of urea with bis(diphenylphosphino)methane gave the mono-N-cyanophospha-λ5-azene monooxide (11) along with bis(diphenylphosphino)methane dioxide. This is the first observation of a nitrile produced in the reaction of an amide, a phosphine, and diethyl azodicarboxylate at room temperature.",

author = "Shmuel Bittner and Yonit Assaf and Penina Krief and Martin Pomerantz and Shikang Xi and Witczak, {Malgorzata K.}",

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T1 - Synthesis of Bis(Phospha-λ5-Azenes) by a Redox-Condensation Reaction. Formation of an Anomalous N-Cyanophospha-λ5-Azene from Urea

AU - Bittner, Shmuel

AU - Assaf, Yonit

AU - Krief, Penina

AU - Pomerantz, Martin

AU - Xi, Shikang

AU - Witczak, Malgorzata K.

PY - 1988/1/1

Y1 - 1988/1/1

N2 - The reaction of diphosphines [Ph2P(CH2)nPPh2; n = 1, 2] with sulfonamides, a phosphinamide, and cyanamide as well as of a dicarboxamide, a disulfonamide, urea, thiourea, and sulfamide with triphenylphosphine in the presence of diethyl azodicarboxylate has been shown to produce bis(phospha-λ5-azenes). In the case of cyanamide with bis(diphenylphosphino)methane a mono-(10) as well as a bis(phospha-λ5-azene) (9) could be prepared. Further, the monophospha-λ5-azene monooxide 11 was also isolated. In the case of thiourea, the monophospha-λ6-azene intermediate was also isolated. The reaction of urea with bis(diphenylphosphino)methane gave the mono-N-cyanophospha-λ5-azene monooxide (11) along with bis(diphenylphosphino)methane dioxide. This is the first observation of a nitrile produced in the reaction of an amide, a phosphine, and diethyl azodicarboxylate at room temperature.

AB - The reaction of diphosphines [Ph2P(CH2)nPPh2; n = 1, 2] with sulfonamides, a phosphinamide, and cyanamide as well as of a dicarboxamide, a disulfonamide, urea, thiourea, and sulfamide with triphenylphosphine in the presence of diethyl azodicarboxylate has been shown to produce bis(phospha-λ5-azenes). In the case of cyanamide with bis(diphenylphosphino)methane a mono-(10) as well as a bis(phospha-λ5-azene) (9) could be prepared. Further, the monophospha-λ5-azene monooxide 11 was also isolated. In the case of thiourea, the monophospha-λ6-azene intermediate was also isolated. The reaction of urea with bis(diphenylphosphino)methane gave the mono-N-cyanophospha-λ5-azene monooxide (11) along with bis(diphenylphosphino)methane dioxide. This is the first observation of a nitrile produced in the reaction of an amide, a phosphine, and diethyl azodicarboxylate at room temperature.

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Synthesis of Bis(Phospha-λ⁵-Azenes) by a Redox-Condensation Reaction. Formation of an Anomalous N-Cyanophospha-λ⁵-Azene from Urea

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