The Synthesis of Arylphosphonic and Diarylphosphinic Acids by the Diazo Reaction<sup>1</sup>

Doak, G. O.; Freedman, Leon D.

doi:10.1021/ja01156a049

Cited by 54 publications

(18 citation statements)

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“…The halo and 4-nitro phenylphosphonic acids were prepared from the corresponding diazonium fluoroborates (30). In the case of 2-bromophenylphosphonic acid, phosphorus tribromide was employed, since the use of phosphorus trichloride, as suggested by Freedman et al (3 I), produced a mixture containing a significant amount of 2-chlorophenylphosphonic acid impurity.…”

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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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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“…The acid was prepared by an acid-catalyzed hydrolysis of 4-sulfamoylphenylphosphonic acid (NH 2 SO 2 C 6 H 4 PO 3 H 2 ), which was prepared according to [4]. The reaction layout is given in Fig.…”

Section: Preparation Of 4-sulfophenylphosphonic Acidmentioning

confidence: 99%

Synthesis and characterization of new zirconium 4-sulfophenylphosphonates

et al. 2010

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“…4-Carboxyphenylphosphonic acid monohydrate was prepared according to a previously published procedure. 31 The preparation of 4-sulfophenylphosphonic acid was carried out by the acid catalyzed hydrolysis of 4-sulfamoylphenylphosphonic acid (NH 2 SO 2 C 6 H 4 PO 3 H 2 ), which was prepared according to the literature. 31 A reaction mixture containing NH 2 SO 2 C 6 H 4 PO 3 H 2 (1 g, 4.2 mmol), 35% wt.…”

Section: Methodsmentioning

confidence: 99%

“…31 The preparation of 4-sulfophenylphosphonic acid was carried out by the acid catalyzed hydrolysis of 4-sulfamoylphenylphosphonic acid (NH 2 SO 2 C 6 H 4 PO 3 H 2 ), which was prepared according to the literature. 31 A reaction mixture containing NH 2 SO 2 C 6 H 4 PO 3 H 2 (1 g, 4.2 mmol), 35% wt. hydrochloric acid (6.5 mL, 63 mmol) and water (2.5 mL) was placed in a Teflon-lined 23 mL Parr acid digestion bomb and heated under autogeneous pressure at 160 C for 8 h. 30 The reaction mixture was evaporated to dryness, 20 mL of distilled water was added and the solution was eluted by column chromatography with an acid form of Amberlite IR120 ion exchanger.…”

Section: Methodsmentioning

confidence: 99%

New copper aryl phosphonates with auxiliary nitrogen ligands

Zima

Svoboda

Yang³

et al. 2012

CrystEngComm

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The Synthesis of Arylphosphonic and Diarylphosphinic Acids by the Diazo Reaction¹

Cited by 54 publications

References 0 publications

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

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

Synthesis and characterization of new zirconium 4-sulfophenylphosphonates

New copper aryl phosphonates with auxiliary nitrogen ligands

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The Synthesis of Arylphosphonic and Diarylphosphinic Acids by the Diazo Reaction1

Cited by 54 publications

References 0 publications

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

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

Synthesis and characterization of new zirconium 4-sulfophenylphosphonates

New copper aryl phosphonates with auxiliary nitrogen ligands

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The Synthesis of Arylphosphonic and Diarylphosphinic Acids by the Diazo Reaction¹