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A kind of method for preparing 2-oxaphosphorolane

A technology of oxopentane and oxaphosphine, which is applied in the field of catalytic preparation of 2-oxaphosphine, can solve the problems of unsafe reaction route, low yield and the like, and achieves easy acquisition and high yield. , post-processing simple effects

Inactive Publication Date: 2015-11-18
SUZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] U.S. Patent No. 4,042,649 discloses a method for synthesizing 2-oxaphosphorolane, that is, in an alkaline system, the reaction of phosphite diester and α,β-unsaturated ketone is used to prepare 2-oxaphosphorane Pentane, the participation of active metal sodium is required in the process, thus making the reaction route unsafe, and the yield of the reaction is also low

Method used

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  • A kind of method for preparing 2-oxaphosphorolane
  • A kind of method for preparing 2-oxaphosphorolane
  • A kind of method for preparing 2-oxaphosphorolane

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Embodiment 1

[0030] Embodiment one: catalyst [(Me 3 Si) 2 N] 3 La( mu -Cl)Li(THF) 3 Synthesis

[0031] -10°C, the n - BuLi hexane solution (60mmol, 2.52M) was slowly added to the (Me 3 Si) 2 NH (60mmol) in 100mL Schlenk reaction flask, reacted at room temperature for 30 minutes. The above reaction solution was added to anhydrous LaCl 3 (20mmol) in THF (30mL), stirred overnight at room temperature. The solvent was removed under reduced pressure, and the obtained solid powder was extracted with hot toluene to remove LiCl, concentrated, placed at 0°C, and a large number of crystals were precipitated, which was the desired silicon ammonia rare earth compound, with a yield of 84%.

[0032] Other catalysts can refer to the preparation method of Example 1.

Embodiment 2

[0033] Embodiment two: [(Me 3 Si) 2 N] 3 La( mu -Cl)Li(THF) 3 Synthesis of 2-Oxaphospholane by Catalytic Reaction of Diethyl Phosphite and Chalcone

[0034] In the reaction flask treated with dehydration and deoxygenation, weigh [(Me 3 Si) 2 N] 3 La( mu -Cl)Li(THF) 3 (0.18g, 0.2mmol), sequentially added toluene / HMPA (20mL, volume ratio 5:1), diethyl phosphite (3.88mL, 30mmol), chalcone (2.1g, 10mmol), stirred at 40°C for 5 Add 10mL (0.1mol / L) acetic acid aqueous solution to terminate the reaction after 1 hour, extract with ethyl acetate three times, the extract is dried with anhydrous sodium sulfate, filtered, the solvent is removed under reduced pressure, and finally through silica gel column flash column chromatography (eluent: Ethyl acetate:petroleum ether=1:1) to obtain a colorless oil which is the corresponding 2-oxaphospholane with a yield of 71%.

[0035] The theoretical molecular formula of the obtained product and the main NMR test data are as follows. It ca...

Embodiment 3

[0038] Embodiment three: [(Me 3 Si) 2 N] 3 La( mu -Cl)Li(THF) 3 Synthesis of Oxaphospholanes by Catalytic Reaction of Diethyl Phosphite and Chalcone

[0039] In the reaction flask treated with dehydration and deoxygenation, weigh [(Me 3 Si) 2 N] 3 La( mu -Cl)Li(THF) 3 (0.35g, 0.4mmol), sequentially added toluene / HMPA (20mL, volume ratio 5:1), diethyl phosphite (3.88mL, 30mmol), chalcone (2.1g, 10mmol), stirred at 40°C for 5 Add 10mL (0.1mol / L) acetic acid aqueous solution to terminate the reaction after 1 hour, extract with ethyl acetate three times, the extract is dried with anhydrous sodium sulfate, filtered, the solvent is removed under reduced pressure, and finally through silica gel column flash column chromatography (eluent: Ethyl acetate:petroleum ether=1:1) to obtain a colorless oil which is the corresponding 2-oxaphospholane with a yield of 80%.

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Abstract

The invention discloses a method for preparing dioxaphospholane, which uses silicon amino rare earth compound [(Me3Si)2N]3Ln(mu-Cl)Li(THF)3 as a catalyst to catalyze an addition reaction of phosphite ester and Alpha, Beta-unsaturated ketone to prepare the dioxaphospholane, wherein Ln represents plus three rare earth metal ions selected from one kind of lanthanum, samarium and ytterbium; (Me3Si)2N represents trimethylsilyl amide; mu represents a bridge bond; THF represents tetrahydrofuran; the chemical structural formula of the Alpha, Beta-unsaturated ketone is shown in the specification; and phosphate is dietyl phosphate. The method provided by the invention has the advantages of good regioselectivity of catalyst, high reaction activity, mild reaction condition and high yield of a target product.

Description

technical field [0001] The invention belongs to the technical field of preparation of phosphorus-containing organic compounds, and in particular relates to a catalytic preparation method of 2-oxaphospholane. Background technique [0002] 2-Oxaphosphorolane is a class of phosphorus-containing physiologically active substances. It can be used as a flame retardant for epoxy resins in addition to applications in the fields of biochemistry and pharmacy. [0003] U.S. Patent No. 4,042,649 discloses a method for synthesizing 2-oxaphosphorolane, that is, in an alkaline system, the reaction of phosphite diester and α,β-unsaturated ketone is used to prepare 2-oxaphosphorane Pentane requires the participation of active metal sodium in the process, thus making the reaction route unsafe, and the yield of the reaction is also low. [0004] Therefore, it is necessary to find a catalytic system with simple source, high activity, good selectivity, safety and good universality to effectively...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/6574
Inventor 徐凡蔡礼健张艾娇姚志刚张骏
Owner SUZHOU UNIV