A kind of preparation method of alkenyl phosphonate compound

A technology of alkenyl phosphonate and compounds, which is applied in the field of preparation of alkenyl phosphonate compounds, can solve problems such as poor regioselectivity, harsh reaction conditions, and limited substrate range, and achieve good tolerance, low reaction cost, The effect of high reaction efficiency

Active Publication Date: 2017-04-19
PEKING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the disadvantages of these methods include: (1) harsh reaction conditions; (2) low yield; (3) raw materials are not easy to obtain; (4) limited range of substrates; (5) poor regioselectivity

Method used

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  • A kind of preparation method of alkenyl phosphonate compound
  • A kind of preparation method of alkenyl phosphonate compound
  • A kind of preparation method of alkenyl phosphonate compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Synthesis of (E)-1,2-Diphenylvinyl Phosphate Dimethyl Ester

[0031] Add 45.2 mg (i.e. 0.20 mmol) dimethyl diazo (phenylmethyl) phosphate, 9.2 mg tris (2-furyl) phosphine (i.e. diazo (phenyl methyl) phosphate di 20mol% of methyl ester), then weighed 2.2mg (5mol% of diazo (phenylmethyl) dimethyl phosphate) palladium acetate, replaced the system with nitrogen environment after the reaction tube was sealed, and added 2mL of toluene , and then added 40.4 mg of diisopropylamine (ie 0.40 mmol), and finally added 42.8 mg (ie 0.25 mmol) of benzyl bromide, and reacted at 80° C. for 5 hours. After the reaction, filter, rinse with ethyl acetate, concentrate, and purify by thin-plate chromatography with an eluent with a volume ratio of petroleum ether:ethyl acetate of 1:1 to obtain (E)-1,2-diphenylvinyl phosphoric acid Dimethyl ester, the compound is a colorless liquid with a yield of 88%. When the reaction temperature is 100°C, the yield is 62%; when the reaction temperature is ...

Embodiment 2

[0036] Synthesis of (E)-((1-phenyl)(2-(4-methylphenyl))vinyl)phosphate dimethyl ester

[0037]Add 45.2 mg (i.e. 0.20 mmol) dimethyl diazo (phenylmethyl) phosphate, 9.3 mg tris (2-furyl) phosphine (i.e. diazo (phenyl methyl) phosphate di 20mol% of methyl ester), then weighed 2.2mg (ie 5mol% of diazo (phenylmethyl) dimethyl phosphate) palladium acetate, replaced the inside of the system with nitrogen atmosphere after the reaction tube was sealed, and added 2mL of toluene , and then added 40.4 mg of diisopropylamine (ie 0.40 mmol), and finally added 46.3 mg (ie 0.25 mmol) of 4-methylbenzyl bromide, and reacted at 80° C. for 5 hours. After the reaction, it was filtered, washed with ethyl acetate and concentrated, and purified by thin-plate chromatography with petroleum ether: ethyl acetate volume ratio of 1:1 eluent to obtain (E)-((1-phenyl)(2- (4-methylphenyl)) vinyl) dimethyl phosphate, its structure is shown in the following formula:

[0038]

[0039] The compound is a col...

Embodiment 3

[0042] Synthesis of (E)-((1-phenyl)(2-(4-phenylphenyl))vinyl)phosphate dimethyl ester

[0043] Add 45.2 mg (i.e. 0.20 mmol) dimethyl diazo (phenylmethyl) phosphate, 9.3 mg tris (2-furyl) phosphine (i.e. diazo (phenyl methyl) phosphate di 20mol% of methyl ester), then weighed 2.2mg (5mol% of diazo (phenylmethyl) dimethyl phosphate) palladium acetate, and finally added 61.8mg (0.25mmol) of 4-phenylbenzyl bromide After sealing the reaction tube, replace the system with a nitrogen atmosphere, add 2 mL of toluene, and then add 40.4 mg of diisopropylamine (0.40 mmol), and react at 80° C. for 5 hours. After the reaction, it was filtered, washed with ethyl acetate and concentrated, and purified by thin-plate chromatography with petroleum ether: ethyl acetate volume ratio of 1:1 eluent to obtain (E)-((1-phenyl)(2- (4-phenylphenyl)) vinyl) dimethyl phosphate, its structure is shown in the following formula:

[0044]

[0045] The compound is a colorless liquid with a yield of 76%, a...

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Abstract

The invention discloses a preparation method for an alkenyl phosphate compound. By taking palladium acetate or tetra(triphenylphosphine) palladium as a catalyst, an alkali, a ligand, a diazo compound and a halide or an alkali, tosylhydrazone and a halide react under protection of an N2 atmosphere in an organic solvent to obtain the alkenyl phosphate compound RR'C=C(Ar)(P(O)(OMe)2), wherein Ar represents substituted or unsubstituted aryl comprising phenyl, naphthyl and heterocyclic rings; R and R' represent substituted or unsubstituted aryl, alkyl, alkenyl or hydrogen. According to the reaction referred to the invention, an E-configuration alkenyl phosphate compound can be smoothly obtained. The preparation method is convenient and simple to operate and has good tolerance and universality on functional groups. Moreover, the use level of the catalyst is relatively small, neither the reagent nor the solvent is specially treated, and the reaction cost is relatively low, so that the preparation method can be widely used for preparing the alkenyl phosphate compound.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a preparation method of an alkenyl phosphonate compound. Background technique [0002] Phosphorus-containing organic compounds have received extensive attention due to their important applications in biochemistry, medicinal chemistry, and agricultural chemistry. Among them, alkenyl phosphonate compounds are important structural units and synthetic precursors, which can be transformed into molecules with biological activities or functions. Therefore, organic chemists have been committed to exploring the synthesis methods of such compounds. In the currently known synthetic methods, alkenyl phosphonate compounds with definite geometric configuration can be prepared by Wittig reaction, Wittig-Horner reaction or metal-catalyzed Michaelis-Arbusov reaction, or simple alkenyl phosphonate The Heck reaction or the cross-coupling reaction of P(O)H compounds with alkenyl halides...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/40C07F9/572C07F9/6553
Inventor 王剑波周钰静叶飞王兮徐帅张艳
Owner PEKING UNIV
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