Substituted Aryl Phosphonic and Phosphinic Acids<sup>1,2</sup>

Denham, Joseph M.; Ingham, Robert K.

doi:10.1021/jo01103a016

Cited by 7 publications

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“…The colorless, crystalline dichloro compound 4 was described previously, and its melting point [39] was confirmed. The present synthesis is much more convenient than the process used earlier [39]. Compounds 4 and 5 were obtained as thin needles or colorless plates (resembling boric acid), respectively.…”

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confidence: 96%

(Benzene-1,3,5-triyl)tris[phosphine] (C6H3(PH2)3) and (Benzene-1,3,5-triyl)tris[phosphonic Acid] (C6H3[P(O)(OH)2]3). Absence of Hydrogen Bonding in Solid Primary Phosphines

Reiter

Assmann

Nogai

et al. 2002

HCA

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The prolonged photo-Arbuzov reaction (3 weeks, Hg lamp) of 1,3,5-trichloro-benzene with a large excess of trimethyl phosphite (as a solvent) at 508 gives moderate yields of dimethyl (3,5-dichlorophenyl)phosphonate (1; 14.5%), tetramethyl (5-chloro-1,3-phenylene)bis[phosphonate] (2; 35.4%), and hexamethyl (benzene-1,3,5-triyl)tris[phosphonate] (3; 30.1%). The products can be separated by fractional distillation. Acid hydrolysis of the esters gives almost quantitative yields of the corresponding phosphonic acids 4 ± 6. Reduction of the esters 1 ± 3 by LiAlH 4 in tetrahydrofuran affords the primary phosphines (3,5-dichlorophenyl)phosphine (7; 46.5%), (5-chloro-1,3-phenylene)bis[phosphine] (8; 34.5%) and (benzene-1,3,5-triyl)tris[phosphine] (9; 25.2% yield). In the crude reduction products from 2 (preparation of 8) and from 3 (preparation of 9), (3-chlorophenyl)phosphine and (1,3-phenylene)bis[phosphine], respectively, are observed as by-products. All compounds are characterized by standard analytical, spectroscopic, and (for 1, 7, and 8) structural techniques. The arrangement of the molecules in the crystal structures of 7 and 8 suggest that H-bonding between the primary arylphosphines is virtually insignificant for the packing of the components. This is in marked contrast to the importance of H-bonding for the supramolecular chemistry of arylamines. The new primary polyphosphines and polyphosphonic acids are to be employed in the construction of extended arrays.Introduction. ± Arylphosphines play an important role in many areas of contemporary chemistry. Tertiary phosphines Ar 3 P are the most prominent class of ligands for transition metals, and their complexes are used as homogeneous catalysts in a large variety of reactions [1]. They are also the base chemicals for many reagents in organic synthesis including phosphonium salts [2], phosphonium ylides [2 ± 4], phosphine boranes [2] [5], and phosphine oxides and sulfides [2]. Secondary phosphines Ar 2 PH are less common in catalysts and also as reagents, but their PÀH group offers an additional functionality for the design of more sophisticated substitution patterns and for oxidation products. Finally, primary phosphines ArPH 2 are the least developed series of arylphosphines with still very limited areas of application [6 ± 8]. However, their potential as synthons is even greater owing to two reactive PÀH functions in addition to the nucleophilic/donor center at the P-atom.Only a relatively small number of primary arylphosphines has been prepared and fully characterized [9 ± 11], and this is particularly true for aromatic hydrocarbons with more than one primary phosphine function [6] [12 ± 23]. For benzene itself, the complete set of primary phosphines has the general formula C 6 H n (PH 2 ) 6Àn comprising a total of 12 species, of which only less than half are known (Fig. 1).Current interest in advanced materials with tailored structures and properties has attracted increasing attention to polyphosphinoarenes with a rigid skeleton, on which new structural motifs...

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confidence: 96%

(Benzene-1,3,5-triyl)tris[phosphine] (C6H3(PH2)3) and (Benzene-1,3,5-triyl)tris[phosphonic Acid] (C6H3[P(O)(OH)2]3). Absence of Hydrogen Bonding in Solid Primary Phosphines

Reiter

Assmann

Nogai

et al. 2002

HCA

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“…Literature data for TEPO. ○, ref ; △, ref ; ◇, refs − ; – – – , correlation, ref ; - - -, correlation, ref extrapolated; ―, correlation, this work.…”

Section: Resultsmentioning

confidence: 72%

“…Figure shows a plot of the Antoine equation calculated from the new data for TEPO superimposed on Cavalier’s 1899 data and the 1930 data from Evans et al along with numerous ambient- and reduced-pressure boiling points reported in the literature. − Both of the earlier data sets , were measured at temperatures above T = 363 K and overlap to a large extent. Evans’ Clausius–Clapeyron equation, shown in Figure , has been extrapolated beyond the experimental range into the ambient region with a calculated vapor pressure at T = 298.15 K of P = 34.4 Pa.…”

Section: Discussionmentioning

confidence: 99%

“…Previous TEPO vapor pressure literature includes two primary source articles containing data measured by Cavalier at T = (376.15 to 484.65) K and by Evans et al, at T = (363.15 to 488.15) K . Many ambient- and reduced-pressure boiling points have also been reported. − Cavalier and Prost and Evans et al have reported vapor pressure data for TPPO at T = (406.65 to 411.15) K and at T = (394.15 to 525.15) K, respectively. Many ambient- and reduced-pressure boiling points have also been reported for TPPO. − Early literature on the vapor pressure of DEM consists of two points over a relatively wide range from Anschutz and Reitter at T = (360.25 to 471.05) K and a larger data set at T = (314.7 to 463.8) K by Heiber and Riendl .…”

Section: Introductionmentioning

confidence: 99%

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Vapor Pressure of Triethyl and Tri-n-Propyl Phosphates and Diethyl Malonate

et al. 2014

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Triethyl phosphate (TEPO,, tri-npropyl phosphate (TPPO,, and diethyl malonate (DEM, are of considerable interest to the chemical defense community as nontoxic simulants for toxic chemical warfare agents. Vapor pressure data have been measured for TEPO at T = (271.25 to 480.15) K, for TPPO at T = (263.15 to 527.61) K, and for DEM at T = (265.15 to 471.25) K using a variety of standard methods that have been modified as necessary. The new data extend the range of vapor pressure data previously reported in the literature for each of the title compounds to subambient temperatures and to lower pressures by approximately 3 orders of magnitude for TEPO, 5 orders of magnitude for TPPO, and 1 order of magnitude for DEM. Vapor pressure data and derived properties, including volatility and temperature-dependent heats of vaporization are reported for TEPO, TPPO, and DEM along with comparisons to chemical warfare agent materials.

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The Synthesis of Phosphonic and Phosphinic Acids and their Derivatives: Non‐Functionalized Acids

Edmundson¹

2009

Patai's Chemistry of Functional Groups

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Introduction The Formation of P  C ( sp 3 ) Bonds. Syntheses of Alkyl, Cycloalkyl and Aralkyl Phosphonic and Phosphinic Acids The Formation of P  C ( sp 2 ) Bonds. Syntheses of Alkenyl and Alkadienyl Phosphonic and Phosphinic Acids The Formation of P  C ( sp ) Bonds. Syntheses of Alkynyl Phosphonic and Phosphinic Acids The Formation of P  C (Aromatic) Bonds. Syntheses of Aryl Phosphonic and Phosphinic Acids Syntheses of Phosphonic and Phosphinic Acids by Modification Procedures

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Substituted Aryl Phosphonic and Phosphinic Acids^1,2

Cited by 7 publications

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(Benzene-1,3,5-triyl)tris[phosphine] (C6H3(PH2)3) and (Benzene-1,3,5-triyl)tris[phosphonic Acid] (C6H3[P(O)(OH)2]3). Absence of Hydrogen Bonding in Solid Primary Phosphines

(Benzene-1,3,5-triyl)tris[phosphine] (C6H3(PH2)3) and (Benzene-1,3,5-triyl)tris[phosphonic Acid] (C6H3[P(O)(OH)2]3). Absence of Hydrogen Bonding in Solid Primary Phosphines

Vapor Pressure of Triethyl and Tri-n-Propyl Phosphates and Diethyl Malonate

The Synthesis of Phosphonic and Phosphinic Acids and their Derivatives: Non‐Functionalized Acids

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Substituted Aryl Phosphonic and Phosphinic Acids1,2

Cited by 7 publications

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(Benzene-1,3,5-triyl)tris[phosphine] (C6H3(PH2)3) and (Benzene-1,3,5-triyl)tris[phosphonic Acid] (C6H3[P(O)(OH)2]3). Absence of Hydrogen Bonding in Solid Primary Phosphines

(Benzene-1,3,5-triyl)tris[phosphine] (C6H3(PH2)3) and (Benzene-1,3,5-triyl)tris[phosphonic Acid] (C6H3[P(O)(OH)2]3). Absence of Hydrogen Bonding in Solid Primary Phosphines

Vapor Pressure of Triethyl and Tri-n-Propyl Phosphates and Diethyl Malonate

The Synthesis of Phosphonic and Phosphinic Acids and their Derivatives: Non‐Functionalized Acids

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Substituted Aryl Phosphonic and Phosphinic Acids^1,2