Alkylation of phosphine PH3 generated from red phosphorus

Semenzin, Delphine; Etemad‐Moghadam, Guita; Albouy, Dominique; Koenig, Max

doi:10.1016/s0040-4039(00)76889-4

Cited by 25 publications

(18 citation statements)

References 8 publications

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“…[27] Thus, the electrochemical synthesis of reaction mixture exhibited the presence of the potassium (α-hydroxyalkyl)phosphane oxides from white phosphorus salt of mono(α-hydroxybenzyl)phosphinic acid (2a) [3] we have demonstrated that the one-pot synthesis of (α-hydroxybenzyl)-driodic acid, the reaction gives phosphoric acid and only traces of 4a as minor product are observed by 31 P NMR. phosphinic acid (2a) from red phosphorus and 1a involves the in situ generation of PH 3 as phosphorylating agent.…”

Section: Reactivity Of Red Phosphorus Towards Aldehydes I Reactimentioning

confidence: 99%

“…[1] [2] ous medium Our previous studies have been focused on the investigation of the reactivity of amorphous red phosphorus. [3] [4] Therefore, the stability of phosphane and hypophosphorWe have demonstrated that its basic hydrolysis allows the ous acid in water is dependent upon the acidity of the megeneration of PH 3 , hydrogen and hypophosphite ion dium. [5] In strong acidic media (pH < 2), the hypophos-(Scheme 1; pathway 1).…”

Section: Introductionmentioning

confidence: 99%

“…[5] In strong acidic media (pH < 2), the hypophos-(Scheme 1; pathway 1). [3] Thus, the synthesis of aliphatic phorous acid is stable and can appear as the preferential and vinylic phosphane derivatives can be realized by a onereducing agent while for other pH acidities, a competition pot reaction from red phosphorus and terminal alkenes and between the phosphane and hypophosphite ion can arise. alkynes in basic media under sonication.…”

Section: Introductionmentioning

confidence: 99%

“…alkynes in basic media under sonication. [3] The reaction inPursuing our investigation into the reactivity of red phosvolves the addition of the in situ generated PH 3 to unsatuphorus [3,4] and PϪH-labile derivatives, [6] and in view of the rated compounds and occurs by a Michael-like reaction preparation of (α-hydroxyalkyl)phosphorus derivatives, we mechanism (Pudovik reaction).…”

Section: Introductionmentioning

confidence: 99%

“…[4] In ditions, [14Ϫ19] or under anhydrous strongly acidic conspite of the complexity of the hydrolysis reaction of elemen-ditions. [20Ϫ21] In contrast to the well-documented reactivity of red [a] Laboratoire des IMRCP (UMR 5623), Université Paul Sabatier, phosphorus in basic medium, [3] The rearrangement α-hydroxyphosphonate to phosphate in basic media is not observed, [16a,24,25] and the isolated (α-to the corresponding organophosphates. [2a,23] In order to determine the nature of the phosphorus inter-hydroxybenzyl)phosphinic acid (2a), kept in the presence of KOH/H 2 O/DMSO, remains unchanged at room temperamediate which is present in each medium, and to estimate their synthetic interest as cheap and safe raw materials upon ture for two weeks.…”

Section: Introductionmentioning

confidence: 99%

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Phosphorylating Power of Red Phosphorus towards Aldehydes in Basic and in Acidic Media

Albouy¹,

Etemad‐Moghadam²,

Koenig³

1999

Eur. J. Org. Chem.

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The reactivity of red phosphorus towards aldehydes was investigated under basic and acidic media. It was demonstrated that the real phosphorylating agent involved in the reaction was phosphane (PH3) in basic media, and hypophosphorous acid (H3PO2) in acidic media. A convenient one‐pot synthesis of (α‐hydroxyalkyl)phosphinic acids from red phosphorus and aldehydes in basic media was realized under sonication. The same reaction under acidic media in the presence of hydriodic acid led to the corresponding phosphonic acids. The (α‐hydroxyalkyl)phosphinic acids were readily prepared under sonication from hypophosphorous acid and aldehydes in the presence of catalytic amounts of hydrochloric acid. The mechanism of the addition reaction of PH3 to benzaldehyde was elucidated and shows the complexity of the reaction as a function of the experimental conditions.

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Section: Reactivity Of Red Phosphorus Towards Aldehydes I Reactimentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Phosphorylating Power of Red Phosphorus towards Aldehydes in Basic and in Acidic Media

Albouy¹,

Etemad‐Moghadam²,

Koenig³

1999

Eur. J. Org. Chem.

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An Efficient One-Pot Synthesis of New Polyfunctional Phosphorus Acid Amphiphiles

et al. 2000

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The addition reaction between the P‐H bond of tetraoxyspirophosphoranes 1‐2 and long‐chain imines 3a‐h (decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and oleyl imines) occurs instantaneously at room temperature. It is diastereoselective, and quantitatively leads to the corresponding (α‐aminoalkyl)spirophosphoranes 4a‐h and 5e. The influence of the pentacoordinated phosphorus atom on the stereoselectivity of the Pudovik reaction might be attributed to the involvement of the rigid spirophosphoranide (PV) intermediate in the addition reaction. Selective and one‐pot hydrolysis of these P‐C bond spirophosphoranes readily proceeds either at room temperature in the presence of moist solvents to give the corresponding carboxyalkyl (α‐aminoalkyl)phosphonic acid monoesters 6a‐h and 7e, or the reaction may be carried out in the presence of 20% aqueous hydrochloric acid under reflux, to afford the free (α‐aminoalkyl)phosphonic acid amphiphiles 8a‐h in high yields. In contrast to their sodium salts, these single‐ and double‐chained free and monoester phosphonic acid amphiphiles exist as zwitterions and are not soluble in water.

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