Preparation method of D,L-2-hydroxy-4-methylthio butyric ester

A technology of methylthiobutyrate and methylthiobutyric acid, which is applied in the field of preparation of D,L-2-hydroxy-4-methylthiobutyrate chemical products, can solve the problem of increasing production costs and equipment corrosion Serious, complicated process and other problems, to achieve the effects of saving production costs, reducing waste generation, and high catalytic activity

Inactive Publication Date: 2014-01-08
NINGXIA UNISPLENDOUR TIANHUA METHIONINE CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Existing D,L-2-hydroxy-4-methylthiobutyrate preparation technology scheme can be roughly divided into three categories: the first category is to use D,L-2-hydroxy-4-methylthiobutyrate salt as raw material, such as U.S. Patent No. 3761518 and U.S. No. 3850987 disclose that under the catalysis of hydrogen chloride gas, D, L-2-hydroxyl-4-methylthiobutyrate (calcium salt, sodium salt, potassium salt, ammonium salt etc.) react with alcohol (methanol, ethanol, isopropanol, butanol, etc.) to prepare D,L-2-hydroxy-4-methylthiobutyrate; the preparation process is cumbersome and the cost is high , not conducive to industrialization and large-scale production
The second type is to use 2-hydroxy-4-methylthiobutyronitrile as a raw material, hydrolyze it under the action of sulfuric acid, and obtain D, L-2-hydroxy-4-methylthiobutyrate through esterification , such as Chinese patent CN1166630C discloses that 2-hydroxy-4-methylthiobutyronitrile is used as a raw material to obtain 2-hydroxy-4-methylthiobutyronitrile by hydrolysis with sulfuric acid, and then esterified with alcohol under the action of sulfuric acid , to obtain D, L-2-hydroxyl-4-methylthiobutyrate; the yield of this process method is low, and the consumption of reaction medi...

Method used

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  • Preparation method of D,L-2-hydroxy-4-methylthio butyric ester

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Embodiment 1

[0030] The preparation of embodiment one silica gel sulfonic acid

[0031] Add 1000 grams of 200-300 mesh dry silica gel into the reactor, then add 2000 grams of dichloromethane, stir at room temperature, and slowly add a certain amount of chlorosulfonic acid. After the addition was complete, stirring was continued at room temperature for 2 hours, and the hydrogen chloride gas released was absorbed with water. Stand still and remove dichloromethane to obtain silica gel sulfonic acid with a certain amount of immobilized sulfonic acid, dry and analyze the immobilized amount of sulfonic acid to obtain catalyst silica gel sulfonic acid for future use. The mass ratio of the sulfonic acid to the silica gel by weight of chlorosulfonic acid is 15-40%. The mass ratio of the chlorosulfonic acid to silica gel is 15%, 25% and 40% as shown in the table below.

[0032] catalyst

Embodiment 2

[0033] Embodiment two D, the preparation of L-2-hydroxyl-4-methylthiobutyric acid isopropyl ester

[0034] Hydroxymethionine (a mixture of 65% D,L-2-hydroxy-4-methylthiobutyric acid monomer, 20% dimer, 3% polymer and 12% water) 682 gram and 1442 grams of isopropanol were added in the three-necked flask, and the molar ratio of D, L-2-hydroxyl-4-methylthiobutyric acid and isopropanol was controlled to be 1:6, filled with nitrogen, stirred and heated, and the three-necked bottle When the temperature of the inner liquid reaches 70°C, add 60 grams of self-made silica gel sulfonic acid A catalyst, and then heat to reflux for 8 hours. After the reaction, filter out the catalyst, dry and circulate to the next esterification reaction, distill the product of the esterification reaction to remove unreacted isopropanol under normal pressure, and obtain a light yellow oily liquid after cooling. Obtain D, L-2-hydroxyl-4-methylthiobutyrate isopropyl 744.9 grams, yield is 95%, D, the purity ...

Embodiment 3

[0036] Embodiment three D, the preparation of L-2-hydroxyl-4-methylthiobutyric acid methyl ester

[0037] Hydroxymethionine (a mixture of 65% D,L-2-hydroxy-4-methylthiobutyric acid monomer, 20% dimer, 3% polymer and 12% water) 682 and 1280 grams of methanol were added to the three-necked flask, the molar ratio of D, L-2-hydroxy-4-methylthiobutyric acid to methanol was controlled to be 1:10, filled with nitrogen, stirred and heated until the temperature of the liquid in the three-necked flask reached At 60°C, 60 grams of self-made silica gel sulfonic acid B catalyst was added, and then heated to reflux for 8 hours. After the reaction, filter out the catalyst, dry and circulate to the next esterification reaction, distill the product of the esterification reaction to remove unreacted methanol under normal pressure, and obtain a light yellow oily liquid after cooling. 649.3 grams of methyl D,L-2-hydroxy-4-methylthiobutyrate were obtained, the yield was 97%, and the purity of met...

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Abstract

The invention belongs to the field of chemical industry, relates to preparation of D,L-2-hydroxy-4-methylthio butyric ester chemical products, and in particular relates to a preparation method of D,L-2-hydroxy-4-methylthio butyric ester based on silicone sulfonic acid as a catalyst. The method comprises the following step: performing an esterification reaction on D,L-2-hydroxy-4-methylthio butyric acid and an alcohol which are taken as raw materials so as to obtain the D,L-2-hydroxy-4-methylthio butyric ester, wherein the silicone sulfonic acid is taken as the catalyst and the alcohol contains 1 to 12 carbon atoms during the esterification reaction. The silicone sulfonic acid taken as the catalyst is simple to synthesize; and the raw material of the silicone sulfonic acid is cheap and easily-available and high in catalytic activity. The catalyst can be repeatedly recycled in a simple filtration mode, so that the production cost is saved; the corrosion of equipment, caused by sulfuric acid, phosphoric acid and the like, is avoided. The process is high in yield, wherein the conversion rate can reach 95% or more; the subsequent treatment is simple after the reaction is finished; the atom economy of the whole reaction is high, namely, other wastes except water are not generated.

Description

technical field [0001] The invention belongs to the field of chemical industry and relates to the preparation of D,L-2-hydroxy-4-methylthiobutyrate chemical products. Background technique [0002] Methionine is the first limiting amino acid for poultry. Methionine additives commonly used in feed mainly include powdered D,L-methionine (DLM) and methionine hydroxyl analog (HMB). Methionine additives can fully provide protein synthesis, decomposition and growth in animals. Required L-Methionine. Methionine hydroxy analogs are divided into liquid methionine hydroxy analogs and solid methionine hydroxy analogs calcium. Methionine hydroxy analogue is a substance with methionine biological activity, besides the function of methionine, it also has functions such as acidifier. Although the liquid methionine hydroxy analog has no amino group, it can still be metabolized into L-methionine in vivo to participate in in vivo metabolism. [0003] The chemical name of the methionine hydr...

Claims

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Application Information

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IPC IPC(8): C07C323/52C07C319/20B01J27/02
CPCY02P20/584
Inventor 吴传隆朱小莉秦岭朱丽利王用贵杨帆任星宇陈宏杨李欧
Owner NINGXIA UNISPLENDOUR TIANHUA METHIONINE CO LTD
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