Trichloroisocyanuric acid: an efficient reagent for the synthesis of dialkyl chlorophosphates from dialkyl phosphites

Acharya, Jyotiranjan; Gupta, Arvind; Shakya, Purushottam; Kaushik, M. P.

doi:10.1016/j.tetlet.2005.06.024

Cited by 55 publications

(17 citation statements)

References 19 publications

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“…Presented in Tables and are the results of the benchmark calculations of 31 P NMR chemical shifts in a representative series of diverse organophosphorous compounds 1–53 including the most important classes – phosphines, phosphine oxides, phosphine sulfides, phosphorous acids and their derivatives, chlorophosphorous compounds, and phosphorous‐containing heterocycles, in comparison with available experimental data for 1 , 2–4 , and 10 ; 5 and 7–9 , 6 ; 11 ; 12 ; 13 and 16 ; 14 , 52 , and 53 ; 15 ; 17 ; 18 ; 19 ; 20 ; 21 ; 22 ; 23 ; 24 and 25 ; 26 and 27 ; 28 ; 29 ; 30 ; 31 ; 32 ; 33 ; 34 ; 35 and 38 ; 36 ; 37 ; 39 ; 40 ; 41 ; 42 and 43 ; 44 ; 45 ; 46 ; 47 ; 48 ; 49 ; 50 ; and 51 referenced to the 85% water solution of H 3 PO 4 . The last three compounds from this series, 51 , 52 , and 53 , presented a challenge task for this study because of their size of up to 35 atoms (including 20 second‐period elements and a third‐period phosphorous atom).…”

Section: Resultsmentioning

confidence: 99%

Towards the versatile DFT and MP2 computational schemes for³¹P NMR chemical shifts taking into account relativistic corrections

2014

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The main factors affecting the accuracy and computational cost of the calculation of (31)P NMR chemical shifts in the representative series of organophosphorous compounds are examined at the density functional theory (DFT) and second-order Møller-Plesset perturbation theory (MP2) levels. At the DFT level, the best functionals for the calculation of (31)P NMR chemical shifts are those of Keal and Tozer, KT2 and KT3. Both at the DFT and MP2 levels, the most reliable basis sets are those of Jensen, pcS-2 or larger, and those of Pople, 6-311G(d,p) or larger. The reliable basis sets of Dunning's family are those of at least penta-zeta quality that precludes their practical consideration. An encouraging finding is that basically, the locally dense basis set approach resulting in a dramatic decrease in computational cost is justified in the calculation of (31)P NMR chemical shifts within the 1-2-ppm error. Relativistic corrections to (31)P NMR absolute shielding constants are of major importance reaching about 20-30 ppm (ca 7%) improving (not worsening!) the agreement of calculation with experiment. Further better agreement with the experiment by 1-2 ppm can be obtained by taking into account solvent effects within the integral equation formalism polarizable continuum model solvation scheme. We recommend the GIAO-DFT-KT2/pcS-3//pcS-2 scheme with relativistic corrections and solvent effects taken into account as the most versatile computational scheme for the calculation of (31)P NMR chemical shifts characterized by a mean absolute error of ca 9 ppm in the range of 550 ppm.

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Section: Resultsmentioning

confidence: 99%

Towards the versatile DFT and MP2 computational schemes for³¹P NMR chemical shifts taking into account relativistic corrections

2014

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“…Those one at 4.23 ppm can be assigned to phosphorus atom in CH 3 OP(O)(Cl)OCH 2 CH 2 − end group. 27 The degree of polymerization of POECl is 28. This result revealed that during the oxidation the degree of polymerization is not changed.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

New Efficient Method of Oxidation of Poly(alkylene H-phosphonate)s: A Promising Route to Novel co-Polyphosphoesters

et al. 2012

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A novel method of oxidation of poly(alkylene Hphosphonate)s is presented here. Trichloroisocyanuric acid is used for the first time as a chlorination agent of poly(alkylene Hphosphonate)s. Poly(oxyethylene chlorophosphate) was obtained in quantitative yield at room temperature in 1 h from poly(oxyethylene H-phosphonate) and trichloroisocyanuric acid. Poly(alkylene chlorophosphate)s have been used as an efficient polymer carriers of low molecular biologically active substances bearing hydroxyl or amino groups. Using different molar ratio between trichloroisocyanuric acid and poly(alkylene H-phosphonate) can control the degree of oxidation, and novel co-polyphosphoesters with new properties can be obtained.

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“…As a result, intensive research and studies have been carried out over a long period of time on their chlorination, oxidation, and miscellaneous properties. 1 The most commonly used reagents are N-chlorosuccinimide (NCS), 2-7 trichloroisocyanuric acid, [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23] 1,3-dichloro-5,5-dimethylhydantoin, [24][25][26] chloramine-T, [27][28][29][30][31][32][33][34][35][36][37][38][39] N-chlorosaccharin, [40][41][42][43][44][45][46] 1-chlorobenzotriazole, [47][48][49][50][51] and N,N¢-dichloro-N,N¢-bis (2,4,6-trichlorophenyl)urea (CC-2) 52-56 ( Figure 1). These compounds are often prepared by the direct chlorination of amines or amides usi...…”

Section: Introductionmentioning

confidence: 99%

tert-Butyl-N-chlorocyanamide: A Novel and Versatile Reagent in Organic Synthesis

Kumar¹,

Kaushik²

2007

Synlett

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The chemistry and applications of tert-butyl-N-chlorocyanamide in a variety of organic transformations is discussed in this account. The reagent was found to be highly versatile for chlorination and oxidation reactions in organic synthesis. tert-Butyl-Nchlorocyanamide is reactive and possesses a high active chlorine content; it is also safe, soluble in all organic solvents, and recyclable. The reagent is stable, in terms of its active chlorine content, under ambient conditions for a period of more than two years. tertButyl-N-chlorocyanamide is able to generate a high level of positive chlorine that is mainly responsible for its involvement in many useful organic transformations, including the conversion of sulfides into sulfoxides, ketoximes into gem-chloronitroso compounds, aldoximes into hydroximoyl chlorides and 2-isoxazolines, dialkyl and diaryl phosphites into dialkyl and diaryl chlorophosphates, and secondary alcohols into ketones, as well as the coupling of thiols to give disulfides and the oxidative decontamination of sulfur mustard (a chemical warfare agent) and its simulants. In addition, the reagent can undergo photolytic addition to various olefins.

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Trichloroisocyanuric acid: an efficient reagent for the synthesis of dialkyl chlorophosphates from dialkyl phosphites

Cited by 55 publications

References 19 publications

Towards the versatile DFT and MP2 computational schemes for³¹P NMR chemical shifts taking into account relativistic corrections

Towards the versatile DFT and MP2 computational schemes for³¹P NMR chemical shifts taking into account relativistic corrections

New Efficient Method of Oxidation of Poly(alkylene H-phosphonate)s: A Promising Route to Novel co-Polyphosphoesters

tert-Butyl-N-chlorocyanamide: A Novel and Versatile Reagent in Organic Synthesis

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Trichloroisocyanuric acid: an efficient reagent for the synthesis of dialkyl chlorophosphates from dialkyl phosphites

Cited by 55 publications

References 19 publications

Towards the versatile DFT and MP2 computational schemes for31P NMR chemical shifts taking into account relativistic corrections

Towards the versatile DFT and MP2 computational schemes for31P NMR chemical shifts taking into account relativistic corrections

New Efficient Method of Oxidation of Poly(alkylene H-phosphonate)s: A Promising Route to Novel co-Polyphosphoesters

tert-Butyl-N-chlorocyanamide: A Novel and Versatile Reagent in Organic Synthesis­

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Towards the versatile DFT and MP2 computational schemes for³¹P NMR chemical shifts taking into account relativistic corrections

Towards the versatile DFT and MP2 computational schemes for³¹P NMR chemical shifts taking into account relativistic corrections

tert-Butyl-N-chlorocyanamide: A Novel and Versatile Reagent in Organic Synthesis