Preparation method of beta-ketone substituted phosphate ester compound

A technology for phosphate esters and compounds, which is applied in the field of preparation of phosphate ester compounds, can solve the problems of harsh reaction conditions, limited range of substrate substituents, etc., and achieves the effects of simple operation, cheap reaction raw materials, and reasonable design.

Inactive Publication Date: 2016-08-10
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, in the currently reported methods, either the reaction conditions are harsh or the range of substrate substituents is limited. These factors have prompted the development of a new class of methods for the construction of β-keto-substituted phosphate compounds.

Method used

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  • Preparation method of beta-ketone substituted phosphate ester compound
  • Preparation method of beta-ketone substituted phosphate ester compound
  • Preparation method of beta-ketone substituted phosphate ester compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] Embodiment 1: the preparation of (2-oxo-2-phenylethyl) diethyl phosphite

[0033] Add (1-azidovinyl)benzene (1mmol, 145mg) and diethyl phosphite (1.0mmol, 138mg) into a sealed glass tube, then add 2.0mL of DMF, after the addition, react at room temperature, TLC The reaction was detected (ethyl acetate:petroleum ether=1:5), and the reaction ended after 6 hours. The reaction solution was concentrated in vacuo, and the concentrated solution was extracted with ethyl acetate (20mL×3). The combined organic phases were washed twice with water and once with saturated brine, dried over anhydrous sodium sulfate, filtered, and spin-dried to obtain a residue, which was subjected to column chromatography. Analysis and separation (eluent: ethyl acetate:petroleum ether=1:4) gave a yellow liquid with a yield of 92%.

[0034] Its structural formula is:

[0035]

[0036] Yellow oil, 236mg, yield 92%. 1 H NMR (500MHz, CDCl 3 )δ8.01(d,J=7.0Hz,2H),7.80-7.57(m,1H),7.48(t,J=8.0Hz,2H),4...

Embodiment 2

[0037] Embodiment 2: Preparation of (2-(4-methylphenyl)-2-oxoethyl) diethyl phosphite

[0038] The synthesis method is the same as in Example 1, except that the raw material 1-azidenylbenzene is replaced with 1-azidoenyl-4-methylbenzene. Pale yellow liquid, yield 88%, its structural formula is:

[0039]

[0040] Yellow oil, yield 88%. 1 H NMR (500MHz, CDCl 3 )δ7.91(d, J=8.0Hz, 2H), 7.28-7.27(m, 2H), 4.17-4.11(m, 4H), 3.61(d, J=22.5Hz, 2H), 2.42(s, 3H ),1.28(t,J=7.0Hz,6H). 13 C NMR (125MHz, CDCl 3 )δ191.6(d, J=7.5Hz), 144.8, 134.2, 129.4, 129.3, 62.8(d, J=6.25Hz), 38.5(d, J=130Hz), 21.81, 16.4(d, J=6.25Hz ).HRMS(ESI):m / z calcd for(C 13 h 19 o 4 P+H) + :271.1094; found: 271.1090.

Embodiment 3

[0041] Embodiment 3: Preparation of (2-(3-bromo-4-ethoxyphenyl) 2-oxoethyl) diethyl phosphite

[0042] The synthesis method is the same as in Example 1, except that the raw material 1-azidenylbenzene is replaced with 1-azidonyl-(3-bromo-4-ethoxyl)benzene. Yellow liquid, yield 79%, its structural formula is:

[0043]

[0044] Yellow oil, yield 79%. 1 H NMR (500MHz, CDCl 3 )δ8.21(d, J=2.0Hz, 1H), 7.96(dd, J=8.5, 2.0Hz, 2H), 6.91(d, J=9.0Hz, 2H), 4.20-4.11(m, 4H), 3.55(d, J=22.5Hz, 2H), 1.50(t, J=7.0Hz, 3H), 1.29(t, J=7.0Hz, 6H). 13 C NMR (125MHz, CDCl 3 )δ189.4(d, J=6.25Hz), 159.8, 134.7, 130.6, 130.5, 112.4, 112.0, 65.3, 62.8(d, J=6.25Hz), 38.6(d, J=129Hz), 16.4(d, J=6.25Hz), 14.62. HRMS (ESI): m / z calcd for (C 14 h 20 BrO 5 P+H) + :379.0304; found: 379.0306.

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Abstract

The invention provides a preparation method of a beta-ketone substituted phosphate ester compound. The beta-ketone substituted phosphate ester compound is generated through a reaction of initial materials comprising alkenyl azide and phosphite ester in an organic solvent with manganese acetate as an oxidant. The preparation method has the advantages of reasonable design, easily available raw materials, mild reaction conditions, no high temperature reflow, high safety and convenience, and high yield, and allows the yield of most of products to be 70% or above. The preparation method is a method for constructing the beta-ketone substituted phosphate ester compound and having the advantages of simple operation, fastness, mildness and diversification; and the two initial raw materials are obtained through a one-step technology, so reaction raw materials are cheap and can be easily obtained. The general formula (I) of the beta-ketone substituted phosphate ester compound is shown in the description.

Description

technical field [0001] The invention belongs to the field of compound synthesis, and mainly relates to a preparation method of β-keto-substituted phosphate compounds. Background technique [0002] Organophosphates are an important class of chemical intermediates, widely used in organic synthesis, materials chemistry, medicinal chemistry, and ligand chemistry. Among them, β-keto-substituted phosphates are mainly used in the construction of C-C bonds in chemical synthesis to obtain corresponding alkenes, cyclopropanes or straight-chain ketones, etc., which are currently reported in the literature for the synthesis of β-keto-substituted Phosphates mainly include the substitution reaction between methylphosphonate and ethyl acetate under strong alkali conditions, the substitution reaction between α-chloroketone and triethyl phosphite, etc. However, in the currently reported methods, either the reaction conditions are harsh or the range of substrate substituents is limited. Thes...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/40C07F9/32
CPCC07F9/3241C07F9/4059
Inventor 陈文腾唐湃舒可陈斌辉邵加安俞永平
Owner ZHEJIANG UNIV
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