Unsubstituted 1- and 2-phosphabutadienes: preparation and spectroscopic characterization

Guillemin, Jean‐Claude; Cabioch, J.-L.; Morise, Xavier; Denis, Jean Marc; Lacombe, Sylvie; Gonbeau, Danielle; Pfister‐Guillouzo, G.; Guénot, Pierre; Savignac, Philippe

doi:10.1021/ic00075a013

Cited by 15 publications

(12 citation statements)

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“…In this case, propene elimination during flash vacuum thermolysis generates the parent 1-phosphabutadiene 16 (R = H), as well as derivatives bearing only a phosphorus substituent. [26][27][28][29] The highly reactive products 16 could be characterized by IR spectroscopy, MS and PES, as well as by chemical trapping when R = H, Me. 27 In the case of R = t-Bu, Ph, the 1phosphabutadienes 16 were observed by low-temperature 31 P NMR spectroscopy, and were isolated as diphosphacyclohexadiene isomers formed by dimerization in a [4+2] cycloaddition upon warming.…”

Section: Methodsmentioning

confidence: 99%

“…[26][27][28][29] The highly reactive products 16 could be characterized by IR spectroscopy, MS and PES, as well as by chemical trapping when R = H, Me. 27 In the case of R = t-Bu, Ph, the 1phosphabutadienes 16 were observed by low-temperature 31 P NMR spectroscopy, and were isolated as diphosphacyclohexadiene isomers formed by dimerization in a [4+2] cycloaddition upon warming. 26,28 Starting from vinyldiallylphosphine (15, R = CH=CH 2 ) or triallylphosphine (15, R = CH 2 CH=CH 2 ), the initially formed phosphabutadienes 16 undergo further rearrangement and fragmentation reactions to yield almost exclusively l 3phosphinine in the former case; in the latter case, phosphaethyne is the major product, with several l 3 -phosphinines formed as byproducts.…”

Section: Methodsmentioning

confidence: 99%

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The Ene Reaction in the Chemistry of Low-Coordinate Phosphorus

Mackewitz¹,

Regitz²

1998

Synthesis

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The ene reaction belongs to one of the simplest and most versatile reaction categories in organic chemistry. Recently ene reactions involving compounds of low-coordinate phosphorus, phospha-ene reactions, have found wide application in the synthesis of different classes of organophosphorus compounds. For phospha-ene reactions four main types are currently known which involve the employment of phosphaalkenes, iminophosphines and phosphaalkynes. Also included are retro-phospha-ene reactions, which reveal access to short-lived and highly reactive phosphaalkenes. The experimentally observed regiochemistry is in agreement with MO calculations, carried out on the simplest parent reactions of type I-IV. Neilson has recently shown that 5 avoids the also feasible [2+2] cycloaddition in reactions with 1,1-dimethylallene, Table 1. Products and reaction conditions for type I phospha-ene reactions of 5 with all-carbon enes (entries 1-5, 21 6-7 19 and 8 20)

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

The Ene Reaction in the Chemistry of Low-Coordinate Phosphorus

Mackewitz¹,

Regitz²

1998

Synthesis

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“…1), where the coupling constants to the two vinyl protons have identical values. 15 The primary phosphines are highly unstable and must be handled under an inert atmosphere. Chloroform as solvent should be avoided, because the release of acid induces degradation of the compounds within a few hours.…”

Section: Synthesis Of the Phosphine Porphyrinsmentioning

confidence: 99%

Ru(ii) and Rh(iii) porphyrin complexes of primary phosphine-substituted porphyrinsDedicated to the memory of Bhaskar G. Maiya.

et al. 2004

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“…These problems may be overcome if it is replaced by POCl 3 being used as solvent and reagent. [44][45][46][47]91,92] Only one of the chlorines of this reagent is used in the phosphonate-phosphonochloridate conversion and the monochlorination reactions render it a safe and convenient substitute to PCl 5 . The by-product is one equivalent of the corresponding alkyl dichlorophosphate 30 (Scheme 17).…”

Section: Scheme 15mentioning

confidence: 99%

Phosphonate–phosphonochloridate conversion

Iorga¹,

Carmichael²,

Savignac³

2000

Comptes Rendus de l'Académie des Sciences - Series IIC - Chemis

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This review deals with the phosphonate-phosphonochloridate conversion. The different phosphorus-chlorine bond forming reagents (COCl 2 , (COCl) 2 , SOCl 2 , PCl 5 , POCl 3 , Ph 3 PCl 2 , trichloro(o-phenylenedioxy)phosphorane) and the reaction conditions which they impose are considered. Phosphonates / Phosphonochloridates / Chlorinating Agents Version française abrégée -Conversion des dialkyl alkylphosphonates en alkyl chloroalkylphosphonates. La transformation des alkylphosphonates en chloroalkylphosphonates est une réaction très utile en chimie du phosphore. Les chloroalkylphosphonates sont de précieux intermédiaires dans la préparation de dérivés phosphorés plus élaborés tels que, fluoroalkylphosphonates, diesters mixtes, phosphoramideester, thiophosphonates et phosphinates. Plusieurs agents de chloration ont été introduits pour réaliser cette transformation: le phosgène, COCl 2 , le chlorure d'oxalyle, (COCl) 2 , le chlorure de thionyle, SOCl 2 , le pentachlorure de phosphore, PCl 5 , l'oxychlorure de phosphore, POCl 3 , Ph 3 PCl 2 et le trichloro(ο-phenylenedioxy)phosphorane. Les avantages et inconvénients de chaque réactif sont examinés en fonction des critères suivants: disponibilité, efficacité, tolérance, conditions d'emploi, solvant, température, nature des sous-produits. Trois réactifs se détachent, le chlorure d'oxalyle, le pentachlorure et l'oxychlorure de phosphore. Ils réalisent la transformation alkylphosphonates-chloroalkylphosphonates avec efficacité dans des conditions non destructrices et avec des phosphonates d'une grande variété structurale.

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Unsubstituted 1- and 2-phosphabutadienes: preparation and spectroscopic characterization

Cited by 15 publications

References 1 publication

The Ene Reaction in the Chemistry of Low-Coordinate Phosphorus

The Ene Reaction in the Chemistry of Low-Coordinate Phosphorus

Ru(ii) and Rh(iii) porphyrin complexes of primary phosphine-substituted porphyrinsDedicated to the memory of Bhaskar G. Maiya.

Phosphonate–phosphonochloridate conversion

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