52372-89-1Relevant articles and documents
Tf2O/DMSO-Promoted P-O and P-S Bond Formation: A Scalable Synthesis of Multifarious Organophosphinates and Thiophosphates
Shen, Jian,Li, Qi-Wei,Zhang, Xin-Yue,Wang, Xue,Li, Gui-Zhi,Li, Wen-Zuo,Yang, Shang-Dong,Yang, Bin
supporting information, p. 1541 - 1547 (2021/04/05)
A Tf2O/DMSO-based system for the dehydrogenative coupling of a wide range of alcohols, phenols, thiols, and thiophenols with diverse phosphorus reagents has been developed. This metal- and strong-oxidant-free strategy provides a facile approach to a great variety of organophosphinates and thiophosphates. The simple reaction system, good functional-group tolerance, and broad substrate scope enable the application of this method to the modification of natural products and the direct synthesis of bioactive molecules and flame retardants.
An Alternative Metal-Free Aerobic Oxidative Cross-Dehydrogenative Coupling of Sulfonyl Hydrazides with Secondary Phosphine Oxides
Cheng, Feixiang,Liu, Jianjun,Liu, Teng,Yu, Rong,Zhang, Yanqiong
, p. 253 - 262 (2019/12/28)
An alternative metal-free, efficient and practical approach for the preparation of phosphinothioates is established via the aerobic oxidative cross-dehydrogenative coupling (CDC) of sulfonyl hydrazides with secondary phosphine oxides catalyzed by tetrabutylammonium iodide (TBAI) in the presence of atmospheric oxygen. The strategy provides an array of diverse phosphinothioates in good to excellent yields. Furthermore, two representative bioactive molecules are synthesized on up to gram scale by utilizing this method.
Novel method for preparing thiophosphonate through oxidative dehydrogenation coupled reaction of copper-catalyzed diarylphosphine oxide and mercaptan
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Paragraph 0008; 0014, (2020/12/14)
The invention provides a method for efficiently and highly selectively synthesizing thiophosphonate derivatives containing different substituted functional groups. According to the method, cuprous iodide is used as a catalyst, 2,2 '-dipyridyl is used as a ligand, pyridine is used as alkali, oxygen is used as an oxidizing agent, diarylphosphine oxide and a mercaptan compound are used as reaction substrates, and an organic solvent is added into a reaction system. The method has the advantages that the catalyst and the oxidant are cheap and easily available; substrate applicability is high; reaction conditions are mild, safe and reliable; the selectivity of the obtained target product is close to 100%; and the yield of the target products is as high as 90% or above. The method overcomes the defects of poor reaction selectivity, complex reaction steps, low yield, need for reagents harmful to the environment and the like in traditional synthesis of thiophosphonate derivatives, and has goodindustrial application prospects. The invention also provides the corresponding thiophosphonate derivatives containing different substituted functional groups at the same time.
Preparation method of compound containing P-O bond or P-S bond
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Paragraph 0093-0097, (2020/09/12)
The invention discloses a preparation method of a compound containing a P-O bond or a P-S bond. The method comprises the following steps: a compound containing hydroxyl or sulfydryl and a phosphorus reagent are taken as initial raw materials; then, the initial raw materials are put into an inert gas atmosphere; and under the action of trifluoromethanesulfonic anhydride (Tf2O) and dimethyl sulfoxide (DMSO), the compound containing hydroxyl or sulfydryl, the phosphorus reagent, the trifluoromethanesulfonic anhydride and the dimethyl sulfoxide in a molar ratio of (1-5): (1-2.5): (2-3): 2 react inan organic solvent at the reaction temperature of 25-100 DEG C for 6-20 hours to obtain the compound with the structural general formula (I). The reagents used in the method are low in toxicity and environmentally friendly, and use of precious metal catalysts high in price and toxicity is avoided. The reagents trifluoromethanesulfonic anhydride (Tf2O) and dimethyl sulfoxide (DMSO) used in the method are low in toxicity and very low in cost, so that the method is green, environment-friendly, high in economy and suitable for large-scale production.
Metal- and base-free reductive coupling reaction of P(O)-H with aryl/alkyl sulfonyl chlorides: a novel protocol for the construction of P-S-C bonds
Wang, Dungai,Zhao, Jinlong,Xu, Weigang,Shao, Changwei,Shi, Zheng,Li, Liang,Zhang, Xinghua
supporting information, p. 545 - 549 (2017/01/25)
Novel and efficient synthesis of S-aryl/alkyl phosphinothioates from P(O)-H and aryl/alkyl sulfonyl chlorides under metal- and base-free conditions is described. This reaction provides an alternative strategy for the construction of P-S-C bonds in moderate to excellent yields. Moreover, this method can be readily applied to gram-scale preparation.
Direct synthesis of thiophosphates by reaction of diphenylphosphine oxide with sulfonyl chlorides
He, Wei,Wang, Zhiming,Li, Xinjin,Yu, Qing,Wang, Zhongwei
supporting information, p. 7594 - 7598 (2016/11/11)
A new method for the synthesis of thiophosphates by reductive coupling reaction of diphenylphosphine oxide and sulfonyl chlorides has been developed. The reaction is metal-free and needs no additives, affording various aryl and alkyl substituted thiophosphates in good to excellent yields under mild conditions.
TBPB-promoted metal-free synthesis of thiophosphinate/phosphonothioate by direct P-S bond coupling
Wang, Jichao,Huang, Xin,Ni, Zhangqin,Wang, Sichang,Wu, Jun,Pan, Yuanjiang
, p. 314 - 319 (2018/04/16)
An efficient method for the direct coupling of thiol/thiophenol with H-phosphine oxides or H-phosphinate esters is reported. Without using any metallic catalyst, the direct sulfur-phosphorus bond coupling reaction was promoted using tert-butyl peroxybenzo
Studies on Organophosphorous Compounds XXXIII. Chemoselective Phase-Transfer Catalytic S-Alkylation of Dialkyl/diarylthiophosphinic Acids; A New Facile Route to S-Alkyl Dialkyl/diarylthiophosphinates
Yuan, Chengye,Feng, Hanzhen,Lin, Qiang
, p. 48 - 50 (2007/10/02)
A phase-transfer catalytic (PTC) alkylation involving the reaction of alkyl bromide and dialkyl/diarylthiophosphinic acids in the presence of potassium carbonate and tetrabutylammonium bromide is described.The reaction proceeds by SN2 mechanism
PHOSPHORORGANISCHE VERBINDUNGEN 96. DIE SELECTIVE VERKNUEPFUNG BIOLOGISCH WICHTIGER FUNKTIONELLER GRUPPEN MIT PHOSPHORORGANISCHEN SAEUREN
Horner, L,Gehring, R.
, p. 157 - 176 (2007/10/02)
Derivatives of phosphinic, phosphonic, and phosphoric acids of the general type R1R2P(O)X show selectivity in their reactions with nucleophiles RYH (R = n-C4H9; Y = O, NR or S) according the Eq. (1); the selectivity depends on the nature of the leaving group (X = Cl, F, CN, N3 or OC6H4NO2(p)) and the base used.The nature of the ligands R1 and R2, exert a comparatively minor influence on the reaction.Method: (a) The phosphylating agent R1R2P(O)X was allowed to react with mixture of two nucleophiles RYH and RY'H in competition (Reagent ratio 1:1:1).The product mixture (R1R2P(O)YR + R1R2P(O)Y'R was then analyzed. (b) Compounds of the type HY-CH2-CH2-Y'H (serine-n-butylamide L-cysteinmethylester) were reacted with the phosphylating agent R1R2P(O)X (reagent ratio 1:1) according the Eqs. (3) and (4) respectively.The products were isolated, identified and the yields quantitatively determined.Results: For X = F, CN, OC6H4NO2 (p), the O-ester is formed virtually exclusively.For X = Cl, only amides are formed.Azides (X = N3) show no selectivity.In competition reactions using n-butylamine and n-butylthiol, the organophosphorus chlorides (X = Cl) were found to be N-selective,, whereas the corresponding cyanides (X = CN) were S-selective.In competition reactions using n-butanol and n-butylthiol, the organophosphorus fluorides (X = F) p-nitrophenylesters (X = OC6H4NO2(p)) and cyanides (X = CN) were all O-selective.
