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Method for preparing alpha-replacing malonic acid diacetoxyiodo derivative

A technology of diethyl malonate and diethyl oxosuccinate, which is applied in the field of preparing diethyl malonate derivatives, can solve the problems of complex process, large environmental pollution, harsh reaction conditions, etc. The effect of stable conditions, safe process and simple operation

Active Publication Date: 2012-07-04
ASYMCHEM LAB TIANJIN +4
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In contrast, the catalytic carbonylation process is advanced in technology, but the process is complicated, the reaction conditions are harsh, and there are certain difficulties in industrialization.
[0006] 3. Transesterification method: using dibutyl tin oxide as a catalyst, dimethyl malonate and ethanol are refluxed, methanol is removed to obtain diethyl malonate, and then diethyl malonate is used as a parent to carry out alkylation Alkylation, acylation, alkoxylation, and hydroxyalkylation to obtain diethyl malonate derivatives. This method uses heavy metals as catalysts, which is not only expensive, but also pollutes the environment and is not suitable for industrial production.

Method used

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  • Method for preparing alpha-replacing malonic acid diacetoxyiodo derivative
  • Method for preparing alpha-replacing malonic acid diacetoxyiodo derivative
  • Method for preparing alpha-replacing malonic acid diacetoxyiodo derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Embodiment 1: Preparation of diethyl 2-fluoromalonate

[0026](1) Condensation: In a 1000L reactor, add 614.0kg tetrahydrofuran (1kg / 6L) at one time, add 156.3kg sodium tert-butoxide (1.5eq) and 136.5kg diethyl oxalate (1.3eq) in batches, and control the temperature 25±2°C, add 115kg of main raw material ethyl fluoroacetate (1.0eq) dropwise to the system, and keep it warm for reaction. 6kg) to adjust pH=2, then extract and wash, in addition, add 17.3kg silica gel (1g / 0.15g) to remove tar, finally dry, press filter, and concentrate to obtain the product 2-fluoro-3-oxosuccinic acid Diethyl ester 217.2kg, yield 72.9%, external standard (Wt%): 75%, liquid chromatography purity (HPLC): 91.2%.

[0027] (2) Oxidation: Add 240.0kg of purified water (1kg / 2kg) to the 1000L reaction kettle, add 286.0kg of concentrated sulfuric acid (5eq) and 283.1kg of potassium persulfate (1.8eq) to the kettle in batches, and then add 134.0 kg co-solvent absolute ethanol (5eq), strictly contr...

Embodiment 2

[0028] Embodiment 2: prepare diethyl methylmalonate

[0029] (1) Condensation: In a 500L reactor, add 555.3kg methyl tert-butyl ether (1kg / 15L) at one time, add 57.5kg potassium tert-butoxide (1.2eq) and 124.7kg diethyl oxalate (2.0 eq), temperature control 20±2°C, add 50kg main raw material ethyl propionate (1.0eq) dropwise to the system, heat preservation reaction, after the reaction is complete, carry out post-treatment with temperature control 20±2°C, use 500kg10% hydrochloric acid solution (1kg / 10kg) to adjust the pH=1, then extract and wash, in addition, add 15.0kg silica gel (1kg / 0.3kg) to remove tar, finally dry, press filter, and concentrate to obtain the product 2-methyl-3-oxo Diethyl succinate 80.5kg, yield 65.3%, external standard (Wt%): 70%, liquid chromatography purity (HPLC): 91%.

[0030] (2) Oxidation: Add 400kg of purified water (1kg / 8kg) to the 500L reactor, add 90.3kg of concentrated hydrochloric acid (10eq) and 76.5kg of sodium persulfate (1.3eq) to the...

Embodiment 3

[0031] Embodiment 3: Preparation of 2-hydroxydiethyl malonate

[0032] (1) Condensation: In a 500L reactor, add 206.5kg 2-methyltetrahydrofuran (1kg / 4L) at one time, add 86.3kg sodium ethoxide (2.2eq) and 92.7kg diethyl oxalate (1.1eq) in batches, Control the temperature at 28±2°C, add 60kg of main raw material 2-hydroxyacetate ethyl ester (1.0eq) dropwise to the system, and keep it warm for reaction. 10% hydrochloric acid solution (1kg / 4kg) to adjust the pH=3, then extract and wash, add 3.0kg silica gel (1g / 0.05g) to remove tar, finally dry, press filter and concentrate to obtain the product 2-hydroxyl -Diethyl 3-oxosuccinate 110.7kg, yield 68.0%, external standard (Wt%): 72%, liquid chromatography purity (HPLC): 90.8%.

[0033] (2) Oxidation: Add 82.5kg of purified water (1kg / 1.5kg) to the 500L reaction kettle, add 30.0kg of concentrated hydrochloric acid (3eq) and 153.6kg of ammonium persulfate (2.5eq) to the kettle in batches, and then add 156.5kg cosolvent acetone (10...

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Abstract

The invention relates to a method for preparing an alpha-a replacing malonic acid diacetoxyiodo derivative. Replacing ethyl acetate and oxalic acid diacetoxyiodo which are already commercialized raw materials on the market or easy to produce are selected as initial raw materials, and after the two steps of condensation and oxidation, target products are synthesized. The method for preparing alpha-the replacing malonic acid diacetoxyiodo derivative is easy in obtaining raw materials, high in conversion rate of raw materials, high in purity yield, stable in process condition, simple in operation and suitable for large-scale production, and provides a novel idea and method for preparing alpha-the replacing malonic acid diacetoxyiodo derivative.

Description

(1) Technical field: [0001] The invention relates to a method for preparing diethyl malonate derivatives, in particular to a method for preparing α-substituted diethyl malonate derivatives. (two) background technology: [0002] Diethyl malonate derivatives are the standard additives with the maximum allowable usage amount and the maximum allowable residue amount in food additives; at the same time, they are widely used in organic synthesis, the production of medicines, pesticides, spices, dyes, etc., and can also be used for the preparation of amino acids, Widely used in biochemical research. In addition, diethyl malonate derivatives can also be used in the synthesis of phytochemical insecticides, hydroxyquinoline or pyrazole carboxylates, and quinoline antimalarials. Therefore, diethyl malonate derivatives have extremely wide fields and very broad development prospects, and it is of great significance to develop a high-efficiency, low-cost synthesis process of diethyl malo...

Claims

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Application Information

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IPC IPC(8): C07C69/63C07C69/34C07C69/675C07C67/313
Inventor 洪浩陈朝勇李江顺
Owner ASYMCHEM LAB TIANJIN
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