A new synthesis of phosphorofluoridates of biological interest. The reaction of phosphoroazolides with benzoyl fluoride

Dąbkowski, Wojciech; Cramer, Friedrich; Michalski, Jan

doi:10.1016/s0040-4039(00)95535-7

Cited by 29 publications

(7 citation statements)

References 7 publications

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“…The polymer/plasticizer ratios of the cellulose acetate/triethylcitrate films were varied and the P(OEt) 2 (O)X, X ) Cl, F, 28 and CN detection times monitored (Table 2). 25 For the CA/TEC films, the time required for both minimum detection of the phosphate as well as for complete conversion of 1 to 2 drops with increasing plasticizer (TEC) content.…”

mentioning

confidence: 99%

Rapid Luminescent Detection of Phosphate Esters in Solution and the Gas Phase Using (dppe)Pt{S₂C₂(2-pyridyl)(CH₂CH₂OH)}

1998

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Organophosphate inhibitors of acetylcholine esterase (including phosphinates and phosphonates) are used as pesticides and as chemical warfare agents. [1][2][3][4][5][6][7] As such, their detection over a range of concentrations and conditions is required and has attracted considerable attention. [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] Several detection methods rely on an immobilized acetylcholine esterase detector coupled to a transducer (i.e., pH electrodes, 5,9,[11][12][13]15,16,22 fiber optics, 10,21 and piezoelectric crystals 14 ). Although the immobilized enzymes are sensitive and detect a broad spectrum of acetylcholine esterase inhibitors, they lack selectivity and are prone to false positives when exposed to choline mimics. 15,23,24 The rapid detection of volatile fluoro and cyano phosphates is of particular interest since these are major constituents in the chemical warfare arsenal. Reported is a new selective method for the rapid detection of these esters. The method uses a new platinum 1,2-enedithiolate complex with an appended alcohol that upon exposure to selected phosphate esters is converted to a roomtemperature lumiphore. 25 Complex, 1, was prepared by the literature procedure (eq 1). 26a,dThe chemical conversion of 1 to [(dppe)Pt{S 2 C 2 (CH 2 CH 2 -N-2-pyridinium)}] + , 2, by activated phosphate esters (eq 2) can be monitored by the emissions from 2 which have been assigned to a thiolate to heterocycle π* intraligand charger-transfer singlet, 1 ILCT*, and triplet, 3 ILCT*. While 1, and 1H + , are nonemissive (φ < 0.00001), 2 is emissive in room-temperature solution ( 1 φ ) 0.002, 3 φ ) 0.01, DMSO) and when immobilized in cellulose acetate/triethylcitrate films ( 1 φ ≈ 0.01, 3 φ ≈ 0.2). 26 Neutral pyridine-substituted complexes such as (dppe)Pt{S 2 C 2 -(2-pyridyl)(R)} R ) H, and CH 2 CH 2 OH, are not emissive due to a lowest lying d to d transition which leads to rapid nonradiative decay of emissive excited states. 26 However, the emissive properties of 2 are similar to those of [(dppe)Pt{S 2 C 2 (2-pyridinium)(H)}] + suggesting that either the steric bulk or solution dynamics of the [(dppe)Pt{S 2 C 2 (2-pyridinium)(CH 2 CH 2 OH)}] + side-chain increases the nonradiative decay rate. The gross differences in the photophysical properties of 2 and [(dppe)Pt-{S 2 C 2 (2-pyridinium)(H)}] + from those of 1H + could arise from the necessity for the 1,2-enedithiolate and heterocycle to be coplanar for emission from the ILCT excited states. 26d Whereas in 2 the 1,2-enedithiolate and heterocycle are held coplanar in the ground state, 26d the ability of the 1,2-enedithiolate and heterocycle to be coplanar in the [(dppe)Pt{S 2 C 2 (2-pyridinium)(R)}] + complexes depends on the bulk of the R group, and this could account for the emission from R ) H and not R ) CH 2 CH 2 OH.Given the chemical reactivity of 1 and combined photophysical properties of 1 and 2, activated phosphate esters serve to turn on the emission in this family of complexes. The reaction of 1 with phosphate, thiophosphate...

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Rapid Luminescent Detection of Phosphate Esters in Solution and the Gas Phase Using (dppe)Pt{S₂C₂(2-pyridyl)(CH₂CH₂OH)}

1998

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“…[1,2] The second approach is based on the replacement of active hydrogen of dialkyl phosphite either with alkali metals or with trimethyl silylchloride, followed by reaction with an activated source of fluorine atom. [3] The first protocol has drawbacks such as use of an expensive reagent such as crown ethers, excess reagent, high temperature (200 C), and variable yield (12-77%). In the second method, dialkylphosphites were converted to their alkali metal salts followed by reaction with sulfuryl chloride fluoride.…”

Section: Trichloroisocyanuric Acid-kf As An Efficient Reagent For Onementioning

confidence: 99%

“…In the second method, dialkylphosphites were converted to their alkali metal salts followed by reaction with sulfuryl chloride fluoride. [3] Though this method apparently looks better, it gives a mixture of chloridates and fluoridates, and isolation of pure fluoridates becomes very difficult. Another major drawback of these methods is that they require reaction conditions that are difficult to maintain, such as temperature of À50 C. In addition, these reactions make use of dialkyl chlorophosphates as starting materials, which in turn need to be prepared from dialkyl phosphites.…”

Section: Trichloroisocyanuric Acid-kf As An Efficient Reagent For Onementioning

confidence: 99%

Trichloroisocyanuric Acid–KF as an Efficient Reagent for One-Pot Synthesis of Dialkylfluorophosphates from Dialkylphosphites

Acharya

Gupta

Pardasani

et al. 2008

Synthetic Communications

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“…1 For instance, benzoyl fluoride has been used in the syntheses of antibiotics, 2 antitumor agents, 3 and enzyme inhibitors. 4 Acyl fluorides have also been widely employed for peptide bond formation since they are stable to moisture and are easy to handle. 5 Several approaches for preparing acyl fluorides are available in the literature; these can be classified by the use of either carboxylic acid or acyl chloride as the starting material.…”

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confidence: 99%

“…Recently, Kim et al reported the use of tetrabutylammonium tetra(tert-butyl alcohol) coordinated fluoride [TBAF(t-BuOH) 4 ] as a fluoride source, which has low hygroscopicity for easy handling and has good solubility in organic solvents. 18 Herein, we report an efficient and practical procedure for the synthesis of acyl fluorides from carboxylic acids with trichloroacetonitrile, triphenylphosphine, and TBAF(t-BuOH) 4 .…”

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confidence: 99%

A Convenient, One-Pot Procedure for the Preparation of Acyl and Sulfonyl Fluorides Using Cl3CCN, Ph3P, and TBAF(t-BuOH)4

Kim¹,

Jang²

2010

Synlett

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A new synthesis of phosphorofluoridates of biological interest. The reaction of phosphoroazolides with benzoyl fluoride

Cited by 29 publications

References 7 publications

Rapid Luminescent Detection of Phosphate Esters in Solution and the Gas Phase Using (dppe)Pt{S₂C₂(2-pyridyl)(CH₂CH₂OH)}

Rapid Luminescent Detection of Phosphate Esters in Solution and the Gas Phase Using (dppe)Pt{S₂C₂(2-pyridyl)(CH₂CH₂OH)}

Trichloroisocyanuric Acid–KF as an Efficient Reagent for One-Pot Synthesis of Dialkylfluorophosphates from Dialkylphosphites

A Convenient, One-Pot Procedure for the Preparation of Acyl and Sulfonyl Fluorides Using Cl3CCN, Ph3P, and TBAF(t-BuOH)4

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A new synthesis of phosphorofluoridates of biological interest. The reaction of phosphoroazolides with benzoyl fluoride

Cited by 29 publications

References 7 publications

Rapid Luminescent Detection of Phosphate Esters in Solution and the Gas Phase Using (dppe)Pt{S2C2(2-pyridyl)(CH2CH2OH)}

Rapid Luminescent Detection of Phosphate Esters in Solution and the Gas Phase Using (dppe)Pt{S2C2(2-pyridyl)(CH2CH2OH)}

Trichloroisocyanuric Acid–KF as an Efficient Reagent for One-Pot Synthesis of Dialkylfluorophosphates from Dialkylphosphites

A Convenient, One-Pot Procedure for the Preparation of Acyl and Sulfonyl Fluorides Using Cl3CCN, Ph3P, and TBAF(t-BuOH)4

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Rapid Luminescent Detection of Phosphate Esters in Solution and the Gas Phase Using (dppe)Pt{S₂C₂(2-pyridyl)(CH₂CH₂OH)}

Rapid Luminescent Detection of Phosphate Esters in Solution and the Gas Phase Using (dppe)Pt{S₂C₂(2-pyridyl)(CH₂CH₂OH)}