Application of LJ reaction in mitsunobu reaction

A reaction and new light technology, applied in compounds of group 5/15 elements of the periodic table, phosphorus halides/oxyhalides, organic chemistry, etc., can solve the problems of increasing the emission of "three wastes", production costs, and removal difficulties

Inactive Publication Date: 2012-05-09
WUHAN INSTITUTE OF TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The definition of Mitsunobu reaction refers to the redox coupling reaction of alcohol and acidic nucleophile precursor in the presence of trihydrocarbylphosphine and azodicarboxylate, and the phosphine reagent used in more than 90% of Mitsunobu reactions is PPh 3 ;For decades, the Mitsunobu reaction has been widely used, which can form a variety of chemical bonds, such as: C-OC-N C-S C-X and C-C bonds, etc., but the unreacted phosphine reagent and by-products are removed during post-treatment of the reaction Trihydrocarbyl phosphine oxide and hydrazine dicarboxylate are quite difficult, thus greatly increasing the discharge of "three wastes" and the cost of preparation

Method used

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  • Application of LJ reaction in mitsunobu reaction
  • Application of LJ reaction in mitsunobu reaction
  • Application of LJ reaction in mitsunobu reaction

Examples

Experimental program
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Effect test

Embodiment 1

[0045] Embodiment 1 Molecular ratio: N-hydroxyethylpropylenediamine: PCl 5 =1:1~2

[0046] Under the condition of isolating air and water, 30 grams of PCl 5 with 70 g CCl 4 Put it into the reaction bottle, start stirring, control the temperature at 30-60°C, add N-hydroxyethylpropylenediamine dropwise at the slowest speed, after the drop is finished, keep it warm for about 20 hours, and then azeotropically distill it under high vacuum Steam out phosphorus oxychloride as much as possible, add 50 grams of dichloroethane, and then wash excess PCl with 5% NaOH alkaline water 5 , separate layers, separate the water layer, distill the solvent of the organic layer, crystallize, filter, and dry to obtain homopiperazine with a content of 95% and a yield of 90%.

Embodiment 2

[0047] The synthesis of embodiment 2 benzoic acid (2-phenyl-2-butyl) ester

[0048] At 0°C under an argon atmosphere, phosphorus pentachloride (1.5 mol) in CCl 4Solution (30%) is dropped in reaction flask, drips the mixed n-hexane solution (40%) of 2-phenyl-2-butanol (0.6mol) and benzoic acid (0.6mol), insulation reaction 18~26 hours, then , under high vacuum as far as possible azeotropic steaming of phosphorus oxychloride, and then wash off excess phosphorus pentachloride with 5% NaOH alkaline water, layering, distillation, crystallization, filtration, drying to obtain the product, the content is 90%, the yield is 85% %.

Embodiment 3

[0049] The synthesis of embodiment 3 acetic acid 2-phenyl-2-benzyloxycarbonylaminopropylthioester

[0050] Under the condition of isolating air and water, and stirring at -10°C, the PCl 5 (10mol) of CCl 4 The solution (30%) is put into the reaction kettle, and the dry solution containing 2-phenyl-2-benzyloxycarbonylaminopropylthioester (5mol) and thioacetic acid (5mol) is added dropwise at the slowest speed, and continued at room temperature Stir and react for 3 to 6 hours, then try to azeotropically distill phosphorus oxychloride under high vacuum, and recycle it, then wash off excess phosphorus pentachloride with 5% NaOH alkaline water, separate layers, distill, crystallize, filter, The product was obtained by drying with a content of 92% and a yield of 90%.

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Abstract

The invention relates to application of a novel heterogeneous reaction in an LJ molecule in a mitsunobu reaction. Phosphorus pentahalide substitutes for a classic mitsunobu reaction coupling reagent, so that the yield in most of the mitsunobu reactions is improved, the cost is reduced, and the standard of clean production process is reached.

Description

[0001] The present invention relates to a new LJ intramolecular isomerization reaction, and its application in the Mitsunobu reaction. Phosphorus pentahalide is used to replace the classic Mitsunobu reaction coupling reagent, which can improve the yield of most Mitsunobu reactions, reduce costs, and achieve clean production standard of workmanship. Background technique [0002] On July 18, 2010, the applicant for the patent of this invention applied for an invention patent with the application number 201010237200.0 and the name "LJ isomerization reaction". A patent application fills it up. The Mitsunobu reaction is an organic reaction with great application value invented by the Japanese organic chemist Wangyang Mitsunobu in 1967. For this reason, the Japanese Society of Organic Synthetic Chemistry awarded Mitsunobu Wangyang the Achievement Award in recognition of his three-dimensional expertise in the activation of alcoholic hydroxyl groups. Discovery and development of the ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D243/08C01B25/10C07F9/42C07F9/30C07F9/38C07F9/6584
Inventor 李坚
Owner WUHAN INSTITUTE OF TECHNOLOGY
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