Method for preparing 2-phosphonic acid ester base-1, 3-dicarbonyl derivative

A technology of phosphonate-based and derivatives, which is applied in the field of preparation of organic compounds, can solve the problems of heavy pollution and difficulty in obtaining raw materials, and achieve the effects of low pollution, short reaction time, and favorable production safety

Active Publication Date: 2016-04-20
KUNSHAN KAIZHOU ENVIRONMENTAL PROTECTION MACHINERY CO LTD
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] The above synthetic route has raw materials that are difficult to obtain, such as ethyl 2-diethoxyphosphoryl acetate, which is an unconventional product, and is difficult to obtain; the reaction conditions are strict, and hexanoyl chloride is used in the reaction. Therefore, strict personal protection measures must be taken during the reaction, and the substance cannot be inhaled or touched; at the same time, the reaction environment, solvents, and reactants should be kept dry; the pollution is relatively large; therefore, it is simple to find a raw material source that is in line with green chemistry. Requirements, mild reaction conditions, and a universal preparation method are necessary to efficiently synthesize 2-phosphonate-1,3-dicarbonyl derivatives

Method used

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  • Method for preparing 2-phosphonic acid ester base-1, 3-dicarbonyl derivative
  • Method for preparing 2-phosphonic acid ester base-1, 3-dicarbonyl derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] Example 1: Synthesis of 2-dimethylphosphonate-1,3-diphenyl-1,3-propanedione

[0038] Using 1,3-diphenyl-1,3-propanedione and trimethyl phosphite as raw materials, the reaction steps are as follows:

[0039] Add 1,3-diphenyl-1,3-propanedione (0.224g, 1.0mmol), trimethylphosphite (0.124g, 1.0mmol), cuprous chloride (0.010g, 0.1mmol), tert-butyl hydroperoxide (0.09g, 1mmol), and ethanol (5ml), react at 70°C;

[0040] TLC tracking reaction until complete completion;

[0041] The crude product obtained after the reaction was separated by column chromatography (petroleum ether:ethyl acetate=4:1) to obtain the target product (yield 54%). The analytical data of the product are as follows: 1 HNMR (400MHz, DMSO-d 6 ):δ8.09(d,J=7.4Hz,4H),7.71(t,J=7.4Hz,2H),7.58(t,J=7.7Hz,4H),7.17(d,1H),3.71(d ,6H).

Embodiment 2

[0042] Example 2: Synthesis of 2-dimethylphosphonate-1-(4-methylphenyl)-3-phenyl-1,3-propanedione

[0043] Using 1-(4-methylphenyl)-3-phenyl-1,3-propanedione and trimethylphosphite as raw materials, the reaction steps are as follows:

[0044] Add 1-(4-methylphenyl)-3-phenyl-1,3-propanedione (0.238g, 1.0mmol), trimethylphosphite (0.248g, 2.0mmol), Cuprous chloride (0.010g, 0.1mmol), tert-butyl hydroperoxide (0.18g, 2mmol) and acetonitrile (5ml), react at 70°C;

[0045] TLC tracking reaction until complete completion;

[0046] The crude product obtained after the reaction was separated by column chromatography (petroleum ether:ethyl acetate=4:1) to obtain the target product (yield 64%). The analytical data of the product are as follows: 1 HNMR (400MHz, DMSO-d 6 ):δ8.03(dd,J=25.2,7.9Hz,4H),7.70(s,1H),7.57(d,J=7.7Hz,2H),7.38(d,J=8.0Hz,2H),3.84 –3.64 (m, 6H), 2.49 – 2.33 (m, 3H).

Embodiment 3

[0047] Example 3: Synthesis of 2-dimethylphosphonate-1,3-bis(4-methylphenyl)-1,3-propanedione

[0048] Using 1,3-bis(4-methylphenyl)-1,3-propanedione and trimethylphosphite as raw materials, the reaction steps are as follows:

[0049] Add 1,3-bis(4-methylphenyl)-1,3-propanedione (0.252g, 1.0mmol), trimethylphosphite (0.372g, 3.0mmol), chloride Copper (0.013g, 0.1mmol), tert-butyl hydroperoxide (0.27g, 3mmol) and acetic acid (5ml) were reacted at 70°C;

[0050] TLC tracking reaction until complete completion;

[0051] The crude product obtained after the reaction was separated by column chromatography (petroleum ether: ethyl acetate = 4:1) to obtain the target product (yield 90%). The analytical data of the product are as follows: 1 HNMR (400MHz, DMSO-d 6 ):δ8.05(d,J=7.9Hz,4H),7.08(d,J=7.9Hz,4H),6.98(d,J=7.8Hz,1H),3.87(s,6H),3.71(d , J=11.2Hz, 6H).

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Abstract

The invention discloses a method for preparing a 2-phosphonic acid ester base-1, 3-dicarbonyl derivative. A 1, 3-dicarbonyl derivative and trialkyl phosphite ester are used as starting materials, and a great variety of raw materials are easy to obtain. Varied types of products are obtained through the method, can be directly used, and can also be used for other further reactions. In addition, the reaction is performed in air, the condition is mild, the reaction time is short, the target product yield is high, pollution is small, the reaction operation and aftertreatment process is simple, and the method is suitable for industrial production.

Description

technical field [0001] The invention belongs to the technical field of preparation of organic compounds, and in particular relates to a preparation method of 2-phosphonate-1,3-dicarbonyl derivatives. Background technique [0002] 2-Phosphonate-1,3-dicarbonyl derivatives are widely used in witting and Horner-Wardsworth-Emmons (HWE) reactions to react with aldehydes or ketones to prepare various important α, β-unsaturated carbonyl compounds. Such as 4-hydroxy-2(E)-nonenal (4-hydroxy-2(E)-nonenal(HNE)) and 4-oxo-2(E)-nonenal (4-oxo-2(E) )-nonenal(ONE)), which are the products of lipid peroxidation in organisms, have important biological activities, and their structures are as follows: [0003] [0004] Wherein HNE can effectively inhibit the activity of many biological enzymes, such as proteinase C (proteinkinase C), adenylate cyclase (adenylatecyclase), glyceraldehyde-3-phosphate dehydrogenase (glyceraldehyde-3-phosphate dehydrogenase) etc.; Induce apoptosis, change gene ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/40
CPCC07F9/4006C07F9/4018C07F9/4059
Inventor 邹建平周少方周志豪
Owner KUNSHAN KAIZHOU ENVIRONMENTAL PROTECTION MACHINERY CO LTD
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