4237-00-7

Magnetic nanoparticles of CuFe2O4 were applied as catalyst system for one-pot thiophosphate synthesis via the reaction of aryl sulfonyl chlorides with H-phosphonates under conventional heating conditions. This is an extremely efficient and green method for thiophosphate synthesis under base- and solvent-free conditions. Various thiophosphates were obtained in good to excellent yields under the optimized reaction conditions in a short time. The catalyst can be easily recycled from the reaction by an external magnetic field and reused for the next run. In this study, TD-DFT B3LYP/6-31 + G(d) calculations are in good accord with the experimental results. A comparison between experimental and theoretical UV-vis absorption spectra of the thiophosphate 3k has been carried out; and a small hypsochromic shift (only ～ 2 nm) was displayed at maximum absorption. The aim of this work is to investigate the best method and basis set for thiophosphate compounds; therefore, predictions for these compounds can be performed in theoretical studies.

Fe(Pc)-Catalyzed aerobic oxidation of thiols for the synthesis of disulfides has been developed under mild reaction conditions. In addition, an aerobic oxidative cross-dehydrogenative coupling (CDC) reaction of thiols with P(O)-H compounds (H-phosphonates and H-phosphine oxide) for the formation of S-P(O) bonds has been demonstrated under the Fe(Pc) catalysis system with a base additive. Control experiments revealed that the use of a base (DIPA) in this system controls the synthetic pathways in which thiophosphates are formed.

A Cu-BTC@Fe3O4 composite was prepared and exhibited good catalytic activity toward the synthesis of S-aryl phosphorothioates. The three-component reaction involved the coupling of in situ generated aryl diazonium salts from aniline, R2P(O)H, and sulfur powder, allowing the facile and direct formation of C(aryl)-S-P bonds. A broad scope of substrates survived the reaction conditions to afford the corresponding products in good to excellent yields. Moreover, this heterogeneous catalyst could be magnetically recovered and reused without significant loss of its activity after six cycles.

Background: Although the exploitation of facile and efficient preparation for S-aryl phosphorothioates has gained considerable interest, there is still great demand for the development of a direct, convenient and especially environmentally benign protocol

Green methods for the synthesis of S-aryl phosphorothioates have been developed based on copper-catalyzed multicomponent reactions involving diaryliodonium/arenediazonium salts, elemental sulfur, and R2P(O)H compounds. Most target products are obtained with these two methods in good to high yields at room temperature. These transformations allow the direct formation P-S and C-S bonds in one reaction.

The invention discloses a preparation method of S-aryl phosphorothioate. The preparation method comprises the following steps of (1) adding a copper catalyst, an aryl sulfonyl chloride and phosphite in an organic solvent, reacting for 12-24 h at a temperature of 60-150 DEG C and cooling to a room temperature to obtain a reaction liquid; and (2) concentrating the reaction liquid, separating and purifying to obtain S-aryl phosphorothioate. According to the preparation method of S-aryl phosphorothioate, a one-pot method is adopted; copper is used as the catalyst; economical and easily available aryl sulfonyl chloride and phosphite are used as the raw materials; and a coupling reaction is carried out directly to generate corresponding S-aryl phosphorothioate, without adding alkali in air. A synthetic system has a relatively wide application scope, is compatible with a plurality of groups such as alkoxy, aryl, halogen and acyloxy. The preparation method provided by the invention is simple in process, convenient for operations and mild in reaction conditions, has a wide substrate range and relatively high yield, and is suitable for popularization and application.

A metal-free oxidative P-S bonds coupling method for the synthesis of thiophosphates with DTBP as the oxidant is established. A wide range of functionalities are tolerated in the method. This method provides a facile way to synthesize thiophophates from readily available thiophenols/disulfides and phosphites.

A very simple N-chlorosuccinimide-promoted synthesis of thiophosphates through the coupling of thiols and phosphonates is reported. Notably, the reactions were carried out in the absence of a base. Functional groups including fluoro, bromo and trifluoromethyl are all tolerated by the reaction conditions employed. Both aryl and alkyl thiols are coupled smoothly with a broad spectrum of phosphonates to afford the corresponding thiophosphates in good to excellent yields.

An efficient protocol for copper-catalyzed reductive cross-coupling of aryl sulfonyl chlorides with H-phosphonates has been developed. The various S-aryl phosphorothioates were afforded in up to 86% yield for 20 examples. This protocol features high effic

In the presence of a catalytic amount of cesium hydroxide, the corresponding S-aryl phosphorothioates can be obtained by the reactions of dialkyl phosphites with diaryldisulfides in excellent yields at room temperature, using DMSO as a solvent. The reaction mechanism was discussed. The method provides a new and expedient path for the preparation of S-aryl phosphorothioates.

Kinetic studies for the reactions of O,O-dimethyl Z-S-aryl phosphorothioates with X-pyridines have been carried out in dimethyl sulfoxide at 85.0 °C. The Hammett and Broensted plots for substituent X variations in the nucleophiles are biphasic concave upwards with a break point at X = H, while those for substituent Z variations in the leaving groups are linear. The negative sign of the cross-interaction constant (ρXZ) implies that the reaction proceeds through a concerted mechanism for both the strongly and weakly basic pyridines. The magnitude of ρXZ (= .0.35) for the strongly basic pyridines is greater than that (ρXZ = .0.15) for the weakly basic pyridines, indicating a change of the nucleophilic attacking direction from frontside for the strongly basic pyridines to backside for the weakly basic pyridines. The early transition state is proposed on the basis of the absence of positive deviations from both the Hammett and Bronsted plots for the strong π-acceptor, X = 4-Ac, and small values of ρXZ and βX.

A new and efficient method for the synthesis of alkyl and aryl phosphorothioates in high yields via the reaction of (5,5-dimethyl-2-thioxo-1,3, 2-dioxaphosphorin-2-yl)disulfanyl derivatives with trimethyl phosphite is described. Georg Thieme Verlag Stuttg

Azobisisobutyronitrile-initiated free radical reaction of dialkyl phosphites with diaryl diselenides afforded arylselenophosphates in high yields. Arylthiophosphates and aryltellurophosphates can also be synthesized by similar reaction of diaryl disulfide

Phosphoric thiol esters are conveniently prepared by the treatment of phosphorous triesters with thiols in the presence of tellurium(IV) chloride in a redox-type reaction.

Benzenesulfenyl chloride reacts with trialkylphosphite to give O,O-dialkyl S-phenyl phosphorothiolates 3 in high yield.Compounds 3 are thiated using 1,3-dithia 2,4-diphosphetane 2,4-disulfides 6 to produce O,O-dialkyl S-phenyl phosphorodithiolates 7 in ne

Various S-substituted thiosuccinimides 1a-d and thiophthalimides 2a-d were found to react with trialkylphosphites according to a Michaelis-Arbuzov type mechanism. This provides an efficient way to prepare thiophosphoric acid esters, particularly thiophospholipids, with a C-S-P bond.

Regioselective attack of the trivalent phosphorus atom of dialkyl and trialkyl phosphites on either nitrogen or sulfur atom of sulfenamides has been found.The reaction of phenylsulfenamides with dialkyl phosphites yielded phosphorothiolates, whereas the treatment of (2-benzothiazolyl)sulfenamides with dialkyl and trialkyl phosphites gave phosphoramidates in excellent yields.