A Convenient Synthesis of Esters of Diphenylphosphinic Acid. III<sup>1,2</sup>

Berlin, K. Darrell; Austin, T. Howard; Nagabhushanam, M.

doi:10.1021/jo01015a520

Cited by 15 publications

(8 citation statements)

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“…Dry (Fluka) chlorobenzene, 1,2-dichlorobenzene and toluene (H 2 O ≤ 15 ppm) were used. Alkyl diphenylphosphinates Ph 2 P(O)OR 1 − 4 were prepared by reacting diphenylphosphinyl chloride and the corresponding alcohol in the presence of triethylamine in CH 2 Cl 2 following a previously reported procedure …”

Section: Methodsmentioning

confidence: 99%

Dramatic Effect of the Metal Cation in Dealkylation Reactions of Phosphinic Esters Promoted by Complexes of Polyether Ligands with Metal Iodides

Albanese¹,

Landini²,

Maia³

2001

J. Org. Chem.

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Metal ion electrophilic catalysis has been revealed in dealkylation reactions of phosphinic esters 1-4 promoted by complexes of polyether ligands 5-7 with metal iodides MI(n) (M[n+] = Li(+), Na(+), K(+), Rb(+), Ca(2+), Sr(2+), Ba(2+)) in low polarity solvents (chlorobenzene, 1,2-dichlorobenzene, and toluene) at 60 degrees C. The catalytic effect increases with increasing the Lewis acid character of the cation, in the order Rb(+)< K(+)< Na(+)< Li(+) and Ba(2+)< Sr(2+)< Ca(2+). The results are interpreted in terms of a transition state where the complexed cation (M[n+] subset Lig) assists the departure of the leaving group Ph(2)P(O)O(-) and, at the same time, favors the attack at carbon of the nucleophile I(-) ("push-pull" mechanism). The rate sequence found for 1-4 (Me > Et >> i-Pr and t-Bu) shows that this reaction can be utilized for the selective dealkylation of these substrates.

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Section: Methodsmentioning

confidence: 99%

Dramatic Effect of the Metal Cation in Dealkylation Reactions of Phosphinic Esters Promoted by Complexes of Polyether Ligands with Metal Iodides

Albanese¹,

Landini²,

Maia³

2001

J. Org. Chem.

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“…Methyl diphenylphosphinate was prepared from diphenylphosphinic chloride and methanol in the presence of triethylamine (16) and purified by bulb-to-bulb distillation (oven temp. 25OoC/ 0.2 Torr; 1 Torr = 133.3 Pa).…”

Section: Methodsmentioning

confidence: 99%

Solvation and metal ion effects on structure and reactivity of phosphoryl compounds. Part 2. Alkali metal ion catalysis in the demethylation of methyl di(3-nitrophenyl)phosphinate by iodide ion

Modro¹,

Modro²

1993

Can. J. Chem.

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AGNES M. MODRO and TOMASZ A. MODRO. Can. J. Chem. 71, 469 (1993) Second-order rate constants for the demethylation of methyl di(3-nitropheny1)phosphinate by iodide in acetone-d6 at 25°C have been measured. For a series of iodide salts the rate increased in the order: NBu,I < KI 5 NaI < LiI. The addition of crown ethers or D 2 0 has a retarding effect on the reaction rate. The results are discussed in terms of the increase of the nucleofugality of the phosphinate group via the complexation of metal ions with the phosphoryl function. On a mesure les constantes de vitesse du deuxikme ordre de la reaction de dCmCthylation du di(3-nitrophkny1)-phosphinate de mkthyle par l'iodure dans l'acetone-d6, i 25°C. Pour une sCrie d'iodures, la vitesse augmente dans l'ordre NBu,I < KI 5 NaI < LiI. L'addition dlCthers couronnes ou de DzO diminue la vitesse de la rkaction. On discute des rksultats en fonction de l'augmentation du caractkre nucltofuge du groupe phosphinate via une complexation des ions metalliques par la fonction phosphoryle.[Traduit par la rkdaction]Methyl phosphotriester analogues of polynucleotides attract increasing attention (2), while nucleophilic removal of the methyl group from the POMe function (see, for example, ref.3) represents the final step in the "phosphotriester" method of oligonucleotide synthesis. Various nucleophiles can be employed in the dealkylation, and the utility of halide ions as reagents for selective removal of alkyl groups in phosphate esters was recognised 40 years ago by Zervas and Dilaris (4), as well as by Todd in his classic studies on phosphorylation (5). Although the effect of the counterion of the halide salt on the reaction rate was never the subject of an investigation, it was reported in one of Todd's papers (6) that the yield of debenzylation of benzyl diphenylphosphate by M+I-increases in the order: M' = C6H,,NH3' < Na+ < Li+. The participation of the Li' ion in the demethylation of phosphoric esters was postulated by van Lier and co-workers (7), followed by their nmr spectroscopic study of the interactions between Li' and phosphoryl substrates (8). On the other hand, Winstein (9) and others (10) demonstrated that the rate of dealkylation of alkyl arenesulfonates by halide ions in acetone or HMPTA is independent of the cation used.In a recent series of papers on the nucleophilic displacement at phosphorus and sulfur centers, Buncel and coworkers demonstrated for the first time, and quantitatively assessed, alkali metal ion catalysis in the displacement at the phosphoryl centre by oxygen nucleophiles (1 1). The catalysis, increasing in the order: K+ < ~a ' < Li+, was interpreted in terms of the association of the metal ion and the transition state. Our own studies on the effect of metal ions (K', Na', Li', M~' + ) on nmr spectroscopic parameters and the conformational preferences of phosphonic esters (1) gave evidence for strong interactions between the metal ion and the P03R, group. In this work we report our results on the 0-demethylation of methyl di(3-nitropheny1)pho...

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“…The residue was chromatographed on a column filled with silica gel. Yield of ester I, 76%; m.p., 55-57~ (ether-pentane); reported b.p., 1780C/2 Torr [4]. Esters 0091-150X/97/3112-0638518.00 9 1998 Plenum Publishing Corporation III -XIV and XVIII were obtained using analogous procedures.…”

Section: Experimental Chemical Partmentioning

confidence: 99%

“…Yield, 74%; m.p., 98-99~ (benzene-hexane); reported m.p., 97-99~ [4]. Diphenylphosphinic acid phenyl ester (XI).…”

Section: Experimental Chemical Partmentioning

confidence: 99%

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Synthesis and study of the antiinflammatory and analgesic activity of some phosphinic acid esters

et al. 1997

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A Convenient Synthesis of Esters of Diphenylphosphinic Acid. III^1,2

Cited by 15 publications

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Dramatic Effect of the Metal Cation in Dealkylation Reactions of Phosphinic Esters Promoted by Complexes of Polyether Ligands with Metal Iodides

Dramatic Effect of the Metal Cation in Dealkylation Reactions of Phosphinic Esters Promoted by Complexes of Polyether Ligands with Metal Iodides

Solvation and metal ion effects on structure and reactivity of phosphoryl compounds. Part 2. Alkali metal ion catalysis in the demethylation of methyl di(3-nitrophenyl)phosphinate by iodide ion

Synthesis and study of the antiinflammatory and analgesic activity of some phosphinic acid esters

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A Convenient Synthesis of Esters of Diphenylphosphinic Acid. III1,2

Cited by 15 publications

References 0 publications

Dramatic Effect of the Metal Cation in Dealkylation Reactions of Phosphinic Esters Promoted by Complexes of Polyether Ligands with Metal Iodides

Dramatic Effect of the Metal Cation in Dealkylation Reactions of Phosphinic Esters Promoted by Complexes of Polyether Ligands with Metal Iodides

Solvation and metal ion effects on structure and reactivity of phosphoryl compounds. Part 2. Alkali metal ion catalysis in the demethylation of methyl di(3-nitrophenyl)phosphinate by iodide ion

Synthesis and study of the antiinflammatory and analgesic activity of some phosphinic acid esters

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A Convenient Synthesis of Esters of Diphenylphosphinic Acid. III^1,2