A kind of preparation method of alkynyl phosphate

A technology of alkynyl phosphate and terminal alkyne is applied in the field of preparation of alkynyl phosphate to achieve the effects of high reaction efficiency and simple reaction conditions

Active Publication Date: 2020-08-14
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Alkynyl halides can also be used as reaction substrates to prepare alkynyl phosphates through coupling reactions with phosphates or phosphites, but the preparation of alkynyl phosphates using alkynyl halides as an alkynyl source has not been reported yet.

Method used

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  • A kind of preparation method of alkynyl phosphate
  • A kind of preparation method of alkynyl phosphate
  • A kind of preparation method of alkynyl phosphate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Example 1: Preparation of phenylethynyl diethyl phosphate

[0022] Under the protection of nitrogen, dissolve phenylacetylene (1mmol, 102mg) in acetone (1mL), then add silver nitrate (0.1mmol, 16.8mg) and NBS (1.2mmol, 211mg), stir the reaction mixture, react for 1h, filter and remove Remove the insoluble matter, spin dry, add diethyl phosphite (1mmol, 138mg), copper sulfate pentahydrate (0.1mmol, 24.8mg), 1,10-phenanthroline (0.2mmol, 36.0mg), potassium carbonate (2mmol 276mg), toluene (2mL), reacted at 65°C for 12 hours, filtered, the filter residue was washed with dichloromethane, spin-dried, and separated by column chromatography to obtain 204.7mg of a colorless liquid product with a yield of 86%.

[0023]

[0024] 1 H NMR(500MHz, CDCl 3 ): δ7.56(d,J=10.0Hz,2H),7.46-7.40(m,1H),7.39-7.36(m,2H),4.25-4.21(m,4H),1.41(t,J=5.0 Hz, 6H).

Embodiment 2

[0025] Example 2: Preparation of phenylethynyl dimethyl phosphate

[0026] Under the protection of nitrogen, dissolve phenylacetylene (1mmol, 102mg) in acetone (1mL), then add silver nitrate (0.1mmol, 16.8mg) and NBS (1.2mmol, 211mg), stir the reaction mixture, react for 1h, filter and remove Remove the insoluble matter, spin dry, add dimethyl phosphite (1mmol, 110mg), copper sulfate pentahydrate (0.1mmol, 24.8mg), 1,10-phenanthroline (0.2mmol, 36.0mg), potassium carbonate (2mmol 276mg), toluene (2mL), reacted at 65°C for 12 hours, filtered, the filter residue was washed with dichloromethane, spin-dried, column chromatography to obtain a colorless liquid product 174.3mg, the yield was 83%.

[0027]

[0028] 1 H NMR(500MHz, CDCl 3 ): δ7.58(d,J=10.0Hz,2H), 7.48-7.45(m,1H), 7.40-7.37(m,2H), 3.88(s,3H), 3.85(s,3H).

Embodiment 3

[0029] Example 3: Preparation of di-n-butyl phenylethynyl phosphate

[0030] Under the protection of nitrogen, dissolve phenylacetylene (1mmol, 102mg) in acetone (1mL), then add silver nitrate (0.1mmol, 16.8mg) and NBS (1.2mmol, 211mg), stir the reaction mixture, react for 1h, filter and remove Remove the insoluble matter, spin dry, add di-n-butyl phosphite (1mmol, 194mg), copper sulfate pentahydrate (0.1mmol, 24.8mg), 1,10-phenanthroline (0.2mmol, 36.0mg), potassium carbonate ( 2mmol, 276mg), toluene (2mL), reacted at 65°C for 12 hours, filtered, the filter residue was washed with dichloromethane, spin-dried, and separated by column chromatography to obtain a colorless liquid product 220.5mg with a yield of 75%.

[0031]

[0032] 1 H NMR(400MHz, CDCl 3 ): δ7.54(d,J=8.0Hz,2H),7.46-7.40(m,1H),7.39-7.35(m,2H),4.16-4.08(m,4H),1.75-1.68(m,4H) ),1.48-1.40(m,4H),0.94(t,J=8.0Hz,6H).

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Abstract

The invention belongs to the technical field of organic synthesis, and provides a method for preparing novel alkynyl phosphate. The method comprises the following steps: in an organic solvent, under the action of a silver nitrate catalyst, using 1.2 equivalent amount of N-bromo-succinimide as a brominating agent, under room temperature condition, performing in-situ formation of an alkynyl bromide,adding copper sulfate pentahydrate as a catalyst, taking 1,10-phenanthroline as a ligand, reacting 2 equivalent amount of potash in toluene at the temperature of 65 DEG C for 12-24 hours, and obtaining the alkynyl phosphate compounds with the yield being 75%-86%. The method prepares the alkynyl phosphate compound, and the product yield is not less than 75%. The preparation method has simple reaction conditions and high reaction efficiency, and is more suitable for large-scale production requirements, and the prepared alkynyl phosphate compound has potential physiological activity and can be converted into various heterocyclic compounds.

Description

Technical field [0001] The invention belongs to the technical field of organic synthesis and relates to a preparation method of alkynyl phosphate. Background technique [0002] Phosphorus-containing compounds are widely used in ligands, asymmetric catalysis and other fields, and can be transformed into various important pharmaceutical or fine chemical product intermediates through wittig reaction, coupling reaction, cyclization reaction, etc. Alkynyl phosphate, as an important phosphorus-containing compound, has potential biological activity and can participate in various organic transformation reactions. It has always been a research hotspot (Org. Lett. 2004, 6, 3461 and Chem. Res .Toxicol. 1996, 9, 241). [0003] At present, people have developed some methods to prepare alkynyl phosphates: such as copper-catalyzed oxidative coupling reaction of terminal alkynes and phosphite diesters in dry air; coupling reaction of aryl propioic acid and phosphite diesters, etc. ( J. Org. Chem...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/40
CPCC07F9/4056C07F9/4075
Inventor 宋汪泽郑楠郑玉斌
Owner DALIAN UNIV OF TECH
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