CN104326914A - Preparation method of trans-4-methyl formate cyclohexanecarboxylic acid - Google Patents
Preparation method of trans-4-methyl formate cyclohexanecarboxylic acid Download PDFInfo
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- CN104326914A CN104326914A CN201410656632.3A CN201410656632A CN104326914A CN 104326914 A CN104326914 A CN 104326914A CN 201410656632 A CN201410656632 A CN 201410656632A CN 104326914 A CN104326914 A CN 104326914A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Abstract
The invention relates to the field of trans-4-methyl formate cyclohexanecarboxylic acid and specifically relates to a preparation method of trans-4-methyl formate cyclohexanecarboxylic acid. The preparation method of trans-4-methyl formate cyclohexanecarboxylic acid comprises the following steps: performing hydrolysis on trans-1, 4-dimethyl cyclohexanedicarboxylate and an equal molar amount of an alkali for alkaline hydrolysis in a methanol solution at the hydrolysis temperature of 40-45 DEG C for 12h, then recovering methanol, dissolving in water the mass of which is six times that of the mixed solution obtained from the former step, filtering to recover raw materials, then acidifying with hydrochloric acid till the pH value is 5-6, further filtering, washing with water and drying to obtain white solids, wherein the yield is above 80% and the purity is above 98% (HPLC (high-performance liquid chromatography)). The preparation method provided by the invention has the advantages of reasonable method, sufficient raw materials, low energy consumption and low pollution, is safe to operate, and can save cost, save energy and reduce emission.
Description
Technical field
The present invention relates to trans-4-methyl-formiate naphthenic acid field, be specifically related to a kind of preparation method of trans-4-methyl-formiate naphthenic acid.
Background technology
Trans-4-methyl-formiate naphthenic acid, as novel polyester monocase, is just progressively widely used in the middle of polyester, coating, novel high-quality polyester slice and high-quality liquid crystal material; The intermediate simultaneously synthesized as some newtype drugs.
The synthetic route of this compound has following two kinds at present:
One: take terephthalic acid as starting raw material
This route take terephthalic acid as raw material, in alkaline aqueous solution, hydrogenation prepares positive and negative mixing 1,4-cyclohexane cyclohexanedimethanodibasic, again by positive and negative mixing 1,4-cyclohexane cyclohexanedimethanodibasic tautomerization is separated and obtains anti-form-1,4-cyclohexane cyclohexanedimethanodibasic, then esterification obtains trans-4-methyl-formiate naphthenic acid under the vitriol oil.In this route, the reduction difficulty of the first benefit carboxylic acid is larger, needs higher temperature and pressure; The temperature needed in second step tautomerization is at about 250 degree, and industrialization difficulty is too high; Last esterification will use a large amount of vitriol oils, and spent acid amount is larger, seriously polluted.
Two: take dimethyl terephthalate (DMT) as starting raw material
This route take dimethyl terephthalate (DMT) as raw material, prepares positive and negative mixing 1,4 cyclohexanedicarboxylic acid dimethyl ester through hydrogenation, then tautomerization obtains pure trans 1,4 cyclohexanedicarboxylic acid dimethyl ester, obtains trans-4-methyl-formiate naphthenic acid in hydrolysis.Temperature in this technological process needed for hydrogenation, tautomerization, hydrolysis is not high, and another process energy consumption is lower relatively, pollutes few simultaneously.The first step benzene ring hydrogenation is an intermediate link of my company's (Jiangsu Kang Heng chemical industry) CHDM project, at present my this technique of company comparative maturity; Therefore abundant raw material source.
Summary of the invention
In order to solve the problem, the present invention proposes a kind of preparation method of trans-4-methyl-formiate naphthenic acid, technical maturity, observable index is lower, and pollute few, abundant raw material source, operational safety, reaches effects of energy saving and emission reduction.
In order to reach foregoing invention object, the present invention proposes following technical scheme:
A kind of preparation method of trans-4-methyl-formiate naphthenic acid, be hydrolyzed in methanol solution with the alkali that the alkaline hydrolysis of trans 1,4 cyclohexanedicarboxylic acid dimethyl ester and equimolar amount is used, hydrolysis temperature is 40-45 degree, after reaction 12h, after reclaiming methyl alcohol again, the water dissolution of about 6 times quality, after filtered and recycled raw material, hcl acidifying to pH value between 5-6, white solid is obtained, yield more than 80%, purity more than 98% (HPLC) after refiltering washing and drying.
Described alkaline hydrolysis alkali used can be the one in sodium hydroxide, potassium hydroxide, lithium hydroxide, and this patent requires that sodium hydroxide is good.
The temperature of described hydrolysis can at 30-70 degree, and present method requires that 40-45 is good.
The pH value of described acidifying can between 1-6, and present method requires that 5-6 is good.
Advantage of the present invention is that method is reasonable, operational safety, and raw material is sufficient, and energy consumption is low, pollutes few, cost-saving, and plays the effect of energy-saving and emission-reduction.
Embodiment
Example one:
Trans 1,4 cyclohexanedicarboxylic acid dimethyl ester 40g, sodium hydroxide 8g join in 200g methyl alcohol, are slowly warming up to 40-45 degree, after reaction 12h, recycling design methyl alcohol, then add water 250g, after stirring, filtered and recycled raw material 8g, between obtained aqueous solution hcl acidifying to 5-6, obtain white solid trans-4-methyl-formiate naphthenic acid after refiltering washing and drying, 24.8g, yield more than 83%, purity 98.4%(HPLC).
Example two:
Trans 1,4 cyclohexanedicarboxylic acid dimethyl ester 80g, sodium hydroxide 16g join in 400g methyl alcohol, are slowly warming up to 40-45 degree, after reaction 12h, recycling design methyl alcohol, then add water 500g, after stirring, filtered and recycled raw material 16.5g, between obtained aqueous solution hcl acidifying to 5-6, obtain white solid trans-4-methyl-formiate naphthenic acid after refiltering washing and drying, 50g, yield more than 83.9%, purity 98.5%(HPLC).
Example three:
Trans 1,4 cyclohexanedicarboxylic acid dimethyl ester 100g, sodium hydroxide 20g join in 500g methyl alcohol, are slowly warming up to 40-45 degree, after reaction 12h, recycling design methyl alcohol, then add water 625g, after stirring, filtered and recycled raw material 20g, between obtained aqueous solution hcl acidifying to 5-6, obtain white solid trans-4-methyl-formiate naphthenic acid after refiltering washing and drying, 63g, yield more than 84.5%, purity 98.7%(HPLC).
Example four:
Trans 1,4 cyclohexanedicarboxylic acid dimethyl ester 120g, sodium hydroxide 24g join in 600g methyl alcohol, are slowly warming up to 40-45 degree, after reaction 12h, recycling design methyl alcohol, then add water 750g, after stirring, filtered and recycled raw material 24g, between obtained aqueous solution hcl acidifying to 5-6, obtain white solid trans-4-methyl-formiate naphthenic acid after refiltering washing and drying, 75.2g, yield more than 84.9%, purity 98.7%(HPLC).
Claims (4)
1. the preparation method of a trans-4-methyl-formiate naphthenic acid, it is characterized in that with trans 1, the alkali that the alkaline hydrolysis of 4-dimethyl hexahydrophthalate and equimolar amount is used is hydrolyzed in methanol solution, hydrolysis temperature is 40-45 degree, after reaction 12h, then after reclaiming methyl alcohol, the water dissolution of about 6 times quality, after filtered and recycled raw material, hcl acidifying between 5-6, obtains white solid after refiltering washing and drying to pH value.
2. the preparation method of a kind of trans-4-methyl-formiate naphthenic acid according to claim 1, it is characterized in that described alkaline hydrolysis alkali used can for the one in sodium hydroxide, potassium hydroxide, lithium hydroxide, this patent requires that sodium hydroxide is good.
3. the preparation method of a kind of trans-4-methyl-formiate naphthenic acid according to claim 1, it is characterized in that the temperature of described hydrolysis can at 30-70 degree, present method requires that 40-45 is good.
4. the preparation method of a kind of trans-4-methyl-formiate naphthenic acid according to claim 1, it is characterized in that the pH value of described acidifying can between 1-6, present method requires that 5-6 is good.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410656632.3A CN104326914A (en) | 2014-11-18 | 2014-11-18 | Preparation method of trans-4-methyl formate cyclohexanecarboxylic acid |
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| CN201410656632.3A CN104326914A (en) | 2014-11-18 | 2014-11-18 | Preparation method of trans-4-methyl formate cyclohexanecarboxylic acid |
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| CN201410656632.3A Pending CN104326914A (en) | 2014-11-18 | 2014-11-18 | Preparation method of trans-4-methyl formate cyclohexanecarboxylic acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129307A (en) * | 2017-12-08 | 2018-06-08 | 和夏化学(太仓)有限公司 | A kind of preparation method of trans- 1,4 cyclohexanedicarboxylic acid mono-methyl |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101238127A (en) * | 2005-05-20 | 2008-08-06 | 艾伦托斯制药控股公司 | Pyrimidine or triazine fused bicyclic metalloprotease inhibitors |
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2014
- 2014-11-18 CN CN201410656632.3A patent/CN104326914A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101238127A (en) * | 2005-05-20 | 2008-08-06 | 艾伦托斯制药控股公司 | Pyrimidine or triazine fused bicyclic metalloprotease inhibitors |
Non-Patent Citations (2)
| Title |
|---|
| H. VAN，BEKKUM ET AL.: "Cyclohexane derivatives. I. A chemical proof of the configuration of the two 1,4-dimethylcyclohexanes", 《RECUEIL DES TRAVAUX CHIMIQUES DES PAYS-BAS》 * |
| N.B.CHAPMAN ET AL.: "Conformation and reactivity. III. Kinetics of the acid-catalyzed hydrolysis of the methyl cyclohexanemono- and -dicarboxylates and 4-tert-butylcyclohexanecarboxylates", 《JOURNAL OF THE CHEMICAL SOCIETY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129307A (en) * | 2017-12-08 | 2018-06-08 | 和夏化学(太仓)有限公司 | A kind of preparation method of trans- 1,4 cyclohexanedicarboxylic acid mono-methyl |
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Application publication date: 20150204 |