Synthesis of Phosphonic Dichlorides and Correlation of Their P-31 Chemical Shifts

Grabiak, Raymond C.; Miles, J. A. L.; Schwenzer, Gretchen M.

doi:10.1080/03086648008078240

Cited by 33 publications

(17 citation statements)

References 12 publications

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“…After complete hydrolysis, the mixture was concentrated in vacuum to afford the products ( 3a–l ) in yields of 71–93% in a purity of at least 98%. From among the arylphosphonic acids, 3a, 3c, 3f, 3g , and 3k have been described and partially characterized , 3b and 3h–j were described and characterized only by a melting point , whereas the remaining products 3d, 3e , and 3l are new. Spectral parameters of the known species were compared with those of authentic samples.…”

Section: Resultsmentioning

confidence: 99%

“…(4‐Methylphenyl)Phosphonic Acid ( 3c ) . Yield: 85%; mp: 172–174°C (dec), mp : 185–187°C; 31 P NMR (DMSO) δ : 14.0; δ (D 2 O): 19.5; 13 C NMR (DMSO) δ : 20.9 (s, CH 3 ) 128.5 (d, J = 12.9, C 3 )*, 130.5 (d, J = 6.7, C 2 )*, 133.1 (d, J = 174.3, C 1 ), 140.5 (C 4 ), *may be reversed; 1 H NMR (DMSO) δ : 2.4 (s, 3H, CH 3 ); 7.2 (d, 2H, J = 1.8, ArH), 7.6 (d, 2H, J = 2.3, ArH); (M + H) + found = 173.0367, C 7 H 10 O 3 P requires 173.0368.…”

Section: Methodsmentioning

confidence: 99%

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Synthesis and Proton Dissociation Properties of Arylphosphonates: A Microwave‐Assisted Catalytic Arbuzov Reaction with Aryl Bromides

Keglevich

Grűn²,

Bölcskei

et al. 2012

Heteroatom Chemistry

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Synthesis and Proton Dissociation Properties of Arylphosphonates: A Microwave‐Assisted Catalytic Arbuzov Reaction with Aryl Bromides

Keglevich

Grűn²,

Bölcskei

et al. 2012

Heteroatom Chemistry

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“…rPCl 2 + II Supposedly, an increase in the d"-p n bond order was responsible for an increase in the d-orbital occupation on phosphorus and a shift of the 31 P signal to higher field (Grabiak et al, 1980;Tarasevich et al, 1971; see also Ionin, 1968). This common interpretation of the Letcher and Van Wazer theory, however, is much too simplistic because electron withdrawal from phosphorus can lead to shielding or deshielding.…”

Section: O-imentioning

confidence: 98%

Phosphorus-31 Chemical Shifts: Principles and Empirical Observations

Gorenstein

1984

Phosphorous-31 NMR

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“…Most of the arylphosphonic acids were prepared in good yields by a published method that involves the treatment of the aryl iodide or bromide with triethyl phosphite at 180°C in the presence of anhydrous nickel bromide (26,27). The diethyl arylphosphonates so produced were hydrolyzed to the corresponding acids by refluxing them with concentrated hydrochloric acid for 6-8 h. The 3-and 4-carboxyphenylphosphonic acids were prepared in quantitative yields by starting with the corresponding methyl iodobenzoates.…”

Section: Methodsmentioning

confidence: 99%

Arylphosphonic acids. I. Substituent effects on their first and second dissociations

Nagarajan¹,

Shelly²,

Perkins³

et al. 1987

Can. J. Chem.

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, 1729 (1987) Thermodynamic pK1 and pK2 values of 36 arylphosphonic acids have been determined. The pK values of the tneta and para compounds are correlated well by the a " parameter, suggesting that there is little conjugation between the phosphonic group and the aromatic ring; the p values of the first and second dissociations are 0.923 and 1.140, respectively. The -P03H-group itself appears to be electron donating, contrary to earlier literature reports. The effect of ortho groups has been examined using multivariate analysis; the steric component of the proximity effect is acid weakening and has a larger effect on the second dissociation than on the first, presumably because a greater change in degree of solvation accompanies the second dissociation than the first.K. NAGARAJAN, KEVIN P. SHELLY, R. R. PERKINS et Ross STEWART. Can. J. Chem. 65, 1729 (1987). On a dtterrnint les valeurs des pKI et pKz thermodynamiques de 36 acides arylphosphoniques. On a pu ttablir une bonne corrklation entre les valeurs des pK des composts meta et para et le parametre a"; ce resultat suggkre qu'il existe peu de conjugation entre le groupement phosphonique et le cycle aromatique; les valeurs de p pour les premiere et deuxieme dissociations sont respectivement 0,923 et 1,140. Contrairement i ce qui a pu &tre publie anttrieurement, le groupement -P03HF semble &tre Clectrodonneur. Faisant appel a une analyse multi-variable, on a aussi examint I'effet des groupements en ortho; la composante stkrique de l'effet de proximitt a pour effet de diminuer l'aciditt et cet effet est plus important sur la deuxieme dissociation que sur la premiere; ce resultat est probablement caust par le fait que le changement dans le degrt de solvatation qui accompagne la deuxikme dissociation est plus important que celui qui accompagne la premikre.[Traduit par la revue] Introduction As part of a study of general acid and general base catalysis of protolytic reactions we have prepared a series of arylphosphonic acids, ArP03H2, and examined the effectiveness of the three catalytic species, ArP03H2, ArPO3HP, and AI-PO~'-, on the enolization of acetone (1); the present paper deals with the acid dissociation constants of the first two of these species.There are a number of reports in the literature of the effect of substituents on the pK1 and pK2 values of arylphosphonic acids, most notably those of Jaff6 et al. (2, 3) and of Nuallain (4). We are particularly concerned with proximity effects in prototropic reactions and we needed pK data for ortho, meta, and para derivatives. The data of Jaff6 et al. include such compounds but the pK values are not thermodynamic values; the data of Nuallain, which are much less extensive, have been corrected for ionic strength effects but include only two ortho compounds. Since we needed a set of self-consistent pK values for our catalytic work we have measured the first and second dissociation constants of a considerable number of arylphosphonic acids and corrected them to the standard state. The effects of substituents on t...

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Synthesis of Phosphonic Dichlorides and Correlation of Their P-31 Chemical Shifts

Cited by 33 publications

References 12 publications

Synthesis and Proton Dissociation Properties of Arylphosphonates: A Microwave‐Assisted Catalytic Arbuzov Reaction with Aryl Bromides

Synthesis and Proton Dissociation Properties of Arylphosphonates: A Microwave‐Assisted Catalytic Arbuzov Reaction with Aryl Bromides

Phosphorus-31 Chemical Shifts: Principles and Empirical Observations

Arylphosphonic acids. I. Substituent effects on their first and second dissociations

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