Method for preparing novel alkynyl phosphate

A new type of alkynyl phosphate, which is applied in the field of preparation of new alkynyl phosphate, and achieves the effect of simple reaction conditions and high reaction efficiency

Active Publication Date: 2019-01-11
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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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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  • Method for preparing novel alkynyl phosphate
  • Method for preparing novel alkynyl phosphate
  • Method for preparing novel alkynyl phosphate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Embodiment 1: the preparation of phenylethynyl diethyl phosphate

[0022] Under nitrogen protection, 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, and then filter and transfer In addition to 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] Embodiment 2: the preparation of phenylethynyl phosphate dimethyl

[0026] Under nitrogen protection, 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, and then filter and transfer Remove 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, and separated by column chromatography to obtain 174.3mg of a colorless liquid product with a yield of 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] Embodiment 3: the preparation of di-n-butyl phenylethynyl phosphate

[0030] Under nitrogen protection, 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, and then filter and transfer Remove 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 220.5mg of a colorless liquid product 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 a novel alkynyl phosphate. Background technique [0002] Phosphorus-containing compounds are widely used in ligands, asymmetric catalysis and other fields, and can be converted into various important intermediates of pharmaceuticals or fine chemical products through wittig reactions, coupling reactions, and cyclization reactions. Alkynyl phosphate, as an important phosphorus-containing compound, has potential biological activity and can participate in various organic transformation reactions, and 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 for preparing alkynyl phosphates: as copper catalyzed in dry air, the oxidative coupling reaction of terminal alkynes and phosphite diesters; the coupling reaction of aryl propiolic acid and phosphite dies...

Claims

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Application Information

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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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