21713-55-3Relevant academic research and scientific papers
Electrochemical Enabled Cascade Phosphorylation of N?H/O?H/S?H Bonds with P?H Compounds: An Efficient Access to P(O)-X Bonds
Abdukader, Ablimit,Dong, Xiaojuan,Jin, Weiwei,Liu, Chenjiang,Wang, Bin,Wang, Ruige,Xia, Yu,Xue, Fei,Zhang, Yonghong
supporting information, p. 14931 - 14935 (2021/10/06)
An electrochemical three component cascade phosphorylation reaction of various heteroatoms-containing nucleophiles including carbazoles, indoles, phenols, alcohols, and thiols with Ph2PH has been established. Electricity is used as the “traceless” oxidant and water and air are utilized as the “green” oxygen source. All kinds of structurally diverse organophosphorus compounds with P(O)-N/P(O)-O/P(O)-S bonds are assembled in moderate to excellent yields (three categories of phosphorylation products, 50 examples, up to 97 % yield). A tentative free radical course is put forward to rationalize the reaction procedure.
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.
Base-promoted selective O-phosphorylation of aryl triflates with P(O)-H compounds
Wang, Mingyue,Yang, Jia,Wang, Shuai,Zhong, Hong
, (2020/05/05)
Compared to previous transition metal-catalyzed C-phosphorylation reactions for constructing C–P bonds, in the absence of transition metal catalysts and ligands, a direct O-phosphorylation of aryl triflates selectively occurred with P(O)-H compounds in the presence of a base via the construction of O–P bonds. This transformation proceeds under simple and mild conditions, and provides a new method for the preparation of valuable organophosphoryl compounds from readily available P(O)-H compounds and triflates.
Phosphonate compound, preparation method and application thereof
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Paragraph 0086-0088, (2020/04/02)
The invention provides a phosphonate compound, a preparation method and application thereof. The method includes the steps of: in a nitrogen atmosphere, mixing a P(O)-H compound, an aryl trifluoromethanesulfonate compound, an alkali reagent and an organic solvent, carrying out stirring reaction at 80-130DEG C for 15-24h, and conducting cooling, washing and extraction at the end of reaction to obtain an organic phase; drying and distilling the obtained organic phase to obtain the phosphonate compound; wherein the molar ratio of the P(O)-H compound, the aryl trifluoromethanesulfonate compound and the alkali reagent is 1-3:1:2-3. The method has the advantages of simple and easily available raw materials, simple reaction conditions, wide functional group compatibility, high yield and wide applicability, the structural formula of the obtained phosphonate compound is shown as formula (I) in the specification, and the extraction rate of the phosphonate compound applied to the field of lithiumion extraction is 53% or above.
Highly Efficient and Convenient Access to Phosphinates via CHCl3-Assisted Direct Phosphorylation between R2P(O)H and ROH by Phosphonium Salt Catalysis
Jiang, Zhiyu,Wang, Tianli,Yu, Xiaojun,Zhang, Hong-Su,Zhang, Song
supporting information, (2020/05/25)
A mild, efficient, convenient and scalable method to synthesize phosphinates via direct phosphorylation between R2P(O)H and ROH was developed. All aromatic substrates completed this transformation with excellent yields (up to 98 %), and preliminary mechanistic studies suggest that a carbene-involving process from CHCl3 to CH2Cl2 facilitates the phosphorylation.
Preparation method of compound containing P-O bond or P-S bond
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Paragraph 0307-0311, (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.
A phosphoryl radical-initiated Atherton-Todd-type reaction under open air
Ou, Yingcong,Huang, Yuanting,He, Zhenlin,Yu, Guodian,Huo, Yanping,Li, Xianwei,Gao, Yang,Chen, Qian
supporting information, p. 1357 - 1360 (2020/02/11)
A phosphoryl radical-initiated Atherton-Todd-type reaction using air as the radical initiator and CHCl3 as the halogenating reagent for the phosphorylation of alcohols, phenols, and amines has been developed. This novel transformation provides a highly efficient route to important phosphinates, phosphinic amides, and phosphoramidates in up to 99% yield with a broad substrate scope under very mild conditions (48 examples).
A scalable electrochemical dehydrogenative cross-coupling of P(O)H compounds with RSH/ROH
Li, Yujun,Yang, Qi,Yang, Liquan,Lei, Ning,Zheng, Ke
supporting information, p. 4981 - 4984 (2019/05/21)
A practical, scalable electrochemical dehydrogenative cross-coupling of P(O)H compounds with thiols, phenols and alcohols in both an undivided cell and a continuous-flow setup is disclosed. Its broad substrate scope (>50 examples), good functional-group tolerance and scalability (>10 g) show potential for practical synthesis. A preliminary mechanistic study suggests that the phosphorus radicals are involved in the catalytic cycle.
Method for preparing organophosphate compound through efficient esterification of P(O)-OH-containing compound and phenol
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Paragraph 0036, (2017/09/01)
The invention provides a method for preparing an organophosphate compound through efficient esterification of a P(O)-OH-containing compound and phenol. The method realizes efficient and highly selective synthesis of organophosphate derivatives containing
Kinetic study on nucleophilic substitution reactions of aryl diphenylphosphinates with butane-2,3-dione monoximate and aryloxide anions: Reaction mechanism and origin of the α-effect
Um, Ik-Hwan,Han, Jeong-Yoon
, p. 1180 - 1184 (2016/08/12)
A kinetic study is reported for nucleophilic substitution reactions of X-substituted-phenyl diphenylphosphinates (3a-3f) with butane-2,3-dione monoximate (Ox-) and a series of Y-substituted-phenoxide (Y-PhO-) ions in 50 mol % H2O/50 mol % DMSO at 25.0 ± 0.1°C. The reactions of 3a-3f with Ox- and 4-chlorophenoxide (4-ClPhO-) result in linear Br?nsted-type plots with βlg = -0.70 and -0.64, respectively, a typical βlg value for reactions reported previously to proceed through a concerted mechanism. The Br?nsted-type plots for the reactions of 4-chloro-2-nitrophenyl diphenylphosphinate (3a), 4-nitrophenyl diphenylphosphinate (3b), and 4-acetylphenyl diphenylphosphinate (3d) with Y-PhO- are also linear with βnuc = 0.15-0.35. The current reactions have been concluded to proceed through a concerted mechanism in which the bond formation is much less advanced than the bond rupture in the TS on the basis of the βlg and βnuc values. The α-effect observed in this study is very small (i.e., the kOx-/kp-ClPhO- ratio=4.61-43.5) and is independent of the leaving-group basicity. It has been concluded that the α-effect shown by Ox- in the current reactions is mainly due to desolvation of Ox- in the reaction medium (ground-state contribution) rather than stabilization of the transition-state (TS contribution) on the basis of the kinetic results.
