122-52-1Relevant articles and documents
Nucleophilic Activation of Red Phosphorus for Controlled Synthesis of Polyphosphides
Dragulescu-Andrasi, Alina,Jo, Minyoung,Miller, L. Zane,Pak, Chongin,Shatruk, Michael
, p. 5483 - 5489 (2020)
Reactions between red phosphorus (Pred) and potassium ethoxide in various organic solvents under reflux convert this rather inert form of the element to soluble polyphosphides. The activation is hypothesized to proceed via a nucleophilic attack by ethoxide on the polymeric structure of Pred, leading to disproportionation of the latter, as judged from observation of P(OEt)3 in the reaction products. A range of solvents has been probed, revealing that different polyphosphide anions (P73-, P162-, P213-, and P5-) can be stabilized depending on the combination of the boiling point and dielectric constant (polarity) of the solvent. The effectiveness of activation also depends on the nature of nucleophile, with the rate of reaction between Pred and KOR increasing in the order t-Bu red and NaSR yielded exclusively P162- as a soluble polyphosphide product.
A simple and efficient synthesis of [2H10]deuterated bromfenvinphos by the Perkow reaction
Huras, Bogumiaa,Konopski, Leszek,Zakrzewski, Jerzy
, p. 399 - 400 (2011)
(E,Z)-2-bromo-1-(2,4-dichlorophenyl)vinyl bis[ethyl-2H 5] phosphate ([2H10]bromfenvinphos), a regiospecifically deuterium-labelled pesticide, was synthesized in two steps starting from [2H6]ethanol, phosphorus trichloride and 2,4-dichlorophenacylidene bromide, and fully characterized. The deuterated biologically active bromfenvinphos is an important compound for the advancement of environmental degradation testing and some mass spectrometric studies.
Autoxidation of Ethyl Phosphinite, Phosphonite, and Phosphite Esters
Hwang, Wen-Shu,Yoke, John T.
, p. 2088 - 2091 (1980)
The AIBN-initiated autoxidations in benzene of triethyl phosphite P(OEt)3, diethyl ethylphosphonite, EtP(OEt)2, and ethyl diethylphosphinite, Et2POEt, were studied at 50 deg C.The quantitative conversion of P(OEt)3 to triethyl phosphate obeys the rate law rate = (2.0 x 1E-4 atm-1s-1)PO2 and is zero order in phosphite.Autoxidation of EtP(OEt)2 and Et2POEt gives the complete mixture of intermediates and products predicted by Buckler's mechanism for the autoxidation of trialkylphosphines.At 1 atm of oxygen pressure and 0.02 M AIBN the pseudo-first-order rate law is rate = k', with k'= 7.49 x 1E-4 s-1 for EtP(OEt)2 and 2.37 x 1E-4 s-1 for Et2POEt.
Flash production of organophosphorus compounds in flow
Nagaki, Aiichiro,Tamaki, Takashi
supporting information, (2021/09/09)
Flow synthesis techniques have received a significant amount of attention due to their high productivity. However, when reaction condition is heterogeneous, it is usually difficult to adapt it to flow synthesis. Herein, by selecting appropriate reagents, the synthesis of phosphate esters, which is commonly heterogeneous, was made homogeneous, enabling synthesis in flow systems. In addition, reaction rate was accelerated compared to the batch system. It was demonstrated that not only can the high productivity of flow synthesis be achieved in flow, but also high productivity can be achieved by accelerating the reaction. Finally, we demonstrated the synthesis of the Akiyama-Terada catalyst, a chiral organocatalysts, in a short period.
Silver-Catalyzed Regioselective Phosphorylation of para-Quinone Methides with P(III)-Nucleophiles
Liu, Yu,Tang, Ke-Wen,Wong, Wai-Yeung,Xie, Jun,Xiong, Biquan,Xu, Shipan,Xu, Weifeng
, p. 14983 - 15003 (2021/11/12)
A simple and efficient method for the silver-catalyzed regioselective phosphorylation of para-quinone methides (p-QMs) with P(III)-nucleophiles (P(OR)3, ArP(OR)2, Ar2P-OR) has been established via Michaelis-Arbuzov-type reaction. A broad range of P(III)-nucleophiles and para-quinone methides are well tolerated under the mild conditions, giving the expected diarylmethyl-substituted organophosphorus compounds with good to excellent yields. Moreover, a series of corresponding enantiomers can be obtained by employing dialkyl arylphosphonite (ArP(OR)2) as substrates. The control experiments and 31P NMR tracking experiments were also performed to gain insights for the plausible reaction mechanism. This protocol may have significant implications for the formation of C(sp3)-P bonds in Michaelis-Arbuzov-type reactions.
Preparation method of triethyl phosphite
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Paragraph 0031-0043; 0047, (2020/12/15)
The invention relates to the field of production of organic chemical intermediates, and particularly discloses a preparation method of triethyl phosphite. The preparation method comprises the steps ofuniformly mixing absolute ethyl alcohol, an organic solvent, a catalyst trioctylamine and an acid-binding agent to obtain a mixed solution; cooling the mixed solution, keeping the temperature of thesystem at 0-10 DEG C, dropwise adding a phosphorus trichloride solution into the mixed solution with the molar ratio of phosphorus trichloride to absolute ethyl alcohol being 1:(3-6), continuously conducting heat preservation for 1-4h after adding is completed, and obtaining a reaction solution; and separating and purifying to obtain triethyl phosphite, wherein the molar ratio of trioctylamine tothe acid-binding agent is 2:(3-5). The preparation method has the advantages that under the condition that the product yield is not lower than 90% and the purity is not lower than 95%, the content ofammonium chloride in the reaction waste liquid is reduced, and the waste liquid treatment cost is reduced.
Synthesis process of antioxidant 618
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Paragraph 0027; 0028-0041; 0047-0051; 0047-0051, (2019/08/06)
The invention belongs to the synthesis technology of phosphite antioxidants, in particular to a synthesis technology of antioxidant 618. Triethyl phosphite is synthesized through a microreactor, pentaerythritol diphosphite is synthesized, and the antioxidant 618 is finally synthesized. The synthesis process of the antioxidant 618 has the advantages of good sealing performance, easy control of reaction conditions, reflux utilization of solvents and products, and cost saving.
Continuous production method for triethyl phosphite
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Paragraph 0036; 0037; 0038; 0039; 0040; 0041, (2016/10/31)
The invention discloses a continuous production method for triethyl phosphite. The method comprises the steps that absolute ethyl alcohol and phosphorus trichloride are taken as reaction raw materials, dimethylaniline and o-dichlorobenzene are taken as reaction solvent, ammonia is introduced while reacting is performed, and after reacting is finished, a product is directly delivered into a continuous distillation column to be processed through reduced pressure distillation to obtain crude triethyl phosphite; the rest materials are delivered into a washing column to be washed by adding hot water and then layered, an organic layer is delivered into a distillation column to be processed through distillation dewatering to be recycled by serving as solvent, a water layer is delivered into a cooling kettle to be cooled, ammonium chloride solids are crystallized out, and mother liquor is continuously used for washing the rest materials of distillation. After the obtained triethyl phosphite is rectified through a rectifying column, the purity is 99.5%-99.9%, and the obtained ammonium chloride can serve as an ammonium fertilizer raw material. The continuous production method has the advantages that a decomposition reaction can be prevented from occurring in the process that the triethyl phosphite participates washing, dewatering can be achieved only by simply distilling the mother liquor, a salt column does not need to be introduced for dewatering, generation of secondary solid waste can be avoided, pollution to the environment is greatly reduced, the labor intensity is low, and the production cost is low.
Method for preparing triethyl phosphite
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Paragraph 0043; 0044; 0045; 0046; 0047, (2017/01/26)
The invention discloses a method for preparing triethyl phosphate .The method comprises the following steps that phosphorus trichloride and absolute ethyl alcohol are adopted as raw materials, methylbenzene is adopted as a solvent, a synthetic reaction is carried out under the action of an acid absorbent, the product is subjected to filtering and vacuum distillation, and refined triethyl phosphate is obtained .Compared with the prior art, 90% or above of a byproduct hydrogen chloride can be removed under the micro-negative pressure condition, the product conversion rate is high, the quality is stable, the quantity of adopted acid absorbent can be reduced, cost can be reduced, recycled hydrogen chloride can be used for other fields, environmental pollution is reduced, and effective resources are reasonably reused; the method for preparing triethyl phosphate is simple, operate is convenient, productivity is high, and the obtained product is high in purity and yield.
Synthesis of cyclopropane-containing phosphorus compounds by radical coupling of butenylindium with iodo phosphorus compounds
Kiyokawa, Kensuke,Suzuki, Itaru,Yasuda, Makoto,Baba, Akio
supporting information; experimental part, p. 2163 - 2171 (2011/05/16)
The radical coupling of α- or β-iodo phosphorus compounds such as iodo phosphonate, iodo phosphane oxide, and iodo phosphonothioate with butenylindium species, prepared by transmetalation between a (cyclopropylmethyl)stannane and InBr3, afforded the corresponding cyclopropylmethylated products. The radical reaction was initiated by the radical species generated from butenylindium assisted by a small amount of oxygen. Butenylindium works not only as a cyclopropylmethylating reagent, but also as a radical initiator. For successful coupling, a tin/indium transmetalation was used, where it was important for the tin halide by-product to be inert to the reaction system. In addition, the transmetalation of a (cyclopropylmethyl)stannane and InBr3 provided the dibutenylindium bromide as a single product, which smoothly coupled with the unstable phosphonyl radical species from the iodo phosphorus compound. A photochemical method (UV irradiation) was also applied and accelerated the coupling reaction. The cyclopropylmethylated phosphonate produced was a good intermediate in the Horner-Wadsworth-Emmons reaction and gave functionalized olefins bearing the cyclopropane moiety. Copyright
