CN108383719B - Production process of cyclohexanecarboxylic acid - Google Patents
Production process of cyclohexanecarboxylic acid Download PDFInfo
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- CN108383719B CN108383719B CN201810422657.5A CN201810422657A CN108383719B CN 108383719 B CN108383719 B CN 108383719B CN 201810422657 A CN201810422657 A CN 201810422657A CN 108383719 B CN108383719 B CN 108383719B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention discloses a production process of cyclohexanecarboxylic acid, and belongs to the field of chemical synthesis. The process takes cyclohexene oxide as a starting material to react with carbon dioxide, Mg powder and TMSCl to generate 2-hydroxycyclohexanecarboxylic acid, and then the cyclohexanecarboxylic acid is obtained by Pd/C catalytic hydrogenation in the presence of acid. The production process is safe, simple and convenient to operate and suitable for industrial production.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a production process of cyclohexanecarboxylic acid.
Background
The cyclohexanecarboxylic acid is an important organic synthesis intermediate, can be used for synthesizing the photoinitiator 184 and the pyroquine, and can also be used as a petroleum clarifier and a vulcanized rubber solubilizer.
At present, the synthesis methods of the cyclohexanecarboxylic acid are more, and the methods such as a benzoic acid catalytic hydrogenation method and a Grignard reagent method (firstly, the cyclohexanol is chlorinated into chlorocyclohexane, then the chlorocyclohexane is prepared into the Grignard reagent, carbon dioxide is introduced into the Grignard reagent, and finally the cyclohexanecarboxylic acid is obtained through acidic hydrolysis) are preferred industrially.
But the benzoic acid catalytic hydrogenation method needs high-pressure hydrogenation, the reaction conditions are harsh, and the operation risk is large; the Grignard reagent method has long steps, a plurality of operation steps and low yield.
Therefore, it is necessary to develop a safe and easy-to-operate process for producing cyclohexanecarboxylic acid.
Disclosure of Invention
The invention aims to provide a safe and simple-operated cyclohexanecarboxylic acid production process which is suitable for industrial production. The process comprises the following steps of reacting cyclohexene oxide serving as a starting raw material with carbon dioxide, Mg powder and TMSCl to generate 2-hydroxycyclohexanecarboxylic acid, and then carrying out Pd/C catalytic hydrogenation in the presence of acid to obtain the cyclohexanecarboxylic acid, wherein the process route is as follows:
the specific process steps of the process route of the invention are as follows:
the first step is as follows: dissolving epoxy cyclohexane in an organic solvent, adding Mg powder while stirring, cooling to-150 ℃ to 0 ℃, introducing carbon dioxide gas, and simultaneously adding TMSCl to react to obtain 2-hydroxycyclohexanecarboxylic acid; the second step is that: dissolving 2-hydroxycyclohexanecarboxylic acid in ethanol, and carrying out Pd/C catalytic hydrogenation reaction under the catalysis of acid to obtain the cyclohexanecarboxylic acid.
Further, in the above technical solution, in the first step, the organic solvent is DMF or NMP. The organic solvent is preferably NMP.
Further, in the technical scheme, in the first step, the molar ratio of the cyclohexene oxide, the Mg powder and the TMSCl is 1:1-1.5: 1.5-2.
Further, in the above technical solution, in the second step, the acid is selected from perchloric acid and boron trifluoride-solvent complex. In the process of simple acid catalysis, different position selectivities of double bonds exist after hydroxyl groups are eliminated, and the same product can be obtained after in-situ hydrogenation.
Further, in the above technical scheme, in the second step, the pressure of palladium-carbon catalytic hydrogenation is 3-4 kg, the reaction temperature is 40-55 ℃, after the reaction is finished, the palladium-carbon is filtered for continuous hydrogenation in the next batch, and after circulation is carried out for 8-10 times, new palladium-carbon is replaced.
Compared with the prior art, the invention has the following advantages:
1. the method has the advantages of short steps, high yield and easy realization of industrial production.
2. The invention has safe reaction conditions and simple and convenient operation.
Detailed Description
Example 1
Firstly, dissolving 9.8kg (100mol) of epoxy cyclohexane in 50L of DMF, adding 2.4kg (100mol) of Mg powder while stirring, cooling to-15 ℃ to-5 ℃, introducing carbon dioxide gas into the solution, adding 16.3kg (150mol) of TMSCl, reacting for 6-8h, controlling the temperature to be below 0 ℃ after the detection reaction is finished, adding the filtrate into 1N hydrochloric acid solution, adjusting the pH to be 3-4, extracting twice by using 80L of ethyl acetate, washing with half-saturated common salt, distilling the organic layer to obtain 13.25kg (92mol) of 2-hydroxycyclohexanecarboxylic acid, wherein the yield is 92%, and the cis-trans ratio is determined to be 2.2:7.8 by nuclear magnetism; the column chromatography gave a sample, trans-H NMR (400MHz, CDCl3+ D2O) 3.70-3.78(m,1H),2.22-2.32(m,1H),1.12-2.01(m, 8H). Cis H NMR (400MHz, CDCl3+ D2O) 4.18-4.22(m,1H),2.50-2.58(m,1H),1.22-1.98(m, 8H).
Secondly, dissolving 13.25kg (92mol) of 2-hydroxycyclohexanecarboxylic acid in 30L of ethanol, adding 0.66kg of 10% Pd/C and 0.13kg of perchloric acid, replacing the gas in the kettle with nitrogen for three times, and then introducing H2Heating to 40-45 ℃ under the pressure of 3-4 kg, reacting for 4h, filtering to remove Pd/C, evaporating most of solvent, adding 15% hydrochloric acid to adjust pH to 2-3, extracting and layering ethyl acetate, adding heptane into an oil layer, dehydrating, distilling under reduced pressure to obtain 11.44kg (89.24mol) of cyclohexanecarboxylic acid, cooling to obtain a white solid with a melting point of 28-30 ℃ and a yield of 97%. HNMR (400MHz, CDCl3):11.82(brs,1H),2.29-2.36(m,1H),1.91-1.95(m,2H),1.74-1.78(m,2H),1.62-1.66(m,1H),1.40-1.50(m,2H),1.20-1.34(m,3H).
Example 2
Firstly, dissolving 9.8kg (100mol) of epoxy cyclohexane in 50L of NMP, adding 2.4kg (100mol) of Mg powder while stirring, cooling to-15 ℃ to-5 ℃, introducing carbon dioxide gas into the solution, adding 16.3kg (150mol) of TMSCl, reacting for 8h, detecting that the reaction is finished, controlling the temperature to be below 0 ℃, adding the filtrate into 1N hydrochloric acid solution, adjusting the pH to be 3-4, extracting twice by using ethyl acetate 80L, washing with half-saturated common salt, distilling an organic layer to obtain 13.6kg (94.5mol) of 2-hydroxycyclohexane carboxylic acid, wherein the yield is 94.5%, and the cis-trans ratio is 2.6:7.4 by nuclear magnetism;
secondly, 13.6kg (94.5mol) of 2-hydroxycyclohexanecarboxylic acid is dissolved in 30L of ethanol, 0.68kg of 10% Pd/C and 0.25kg of perchloric acid are added, the gas in the kettle is replaced by nitrogen for three times, and then H is introduced2Heating to 40-45 ℃ under the pressure of 3-4 kg, reacting for 5h, filtering to remove Pd/C, evaporating most of solvent, adding 15% hydrochloric acid to adjust the pH value to 2-3, extracting and layering ethyl acetate, adding toluene into an oil layer, dehydrating, then distilling under reduced pressure, cooling the obtained liquid to separate out 11.9kg (92.9mol) of cyclohexanecarboxylic acid solid, wherein the melting point is 29-30 ℃, and the yield is 98.3%. HNMR (400MHz, CDCl3):11.82(brs,1H),2.29-2.36(m,1H),1.91-1.95(m,2H),1.74-1.78(m,2H),1.62-1.66(m,1H),1.40-1.50(m,2H),1.20-1.34(m,3H).
Example 3
Firstly, dissolving 9.8kg (100mol) of epoxy cyclohexane in 50L of NMP, adding 2.88kg (120mol) of Mg powder while stirring, cooling to-15 ℃ to-5 ℃, introducing carbon dioxide gas into the solution, adding 19.5kg (180mol) of TMSCl, reacting for 10h, detecting the completion of the reaction, controlling the temperature to be below 0 ℃, adding the filtrate into 1N hydrochloric acid solution, adjusting the pH to be 3-4, extracting twice by using ethyl acetate 80L, washing with half-saturated common salt water, distilling an organic layer to obtain 13.8kg (95.8mol) of 2-hydroxycyclohexanecarboxylic acid, wherein the yield is 95.8%, and the cis-trans ratio is 2.3: 7.7;
secondly, 13.8kg (95.8mol) of 2-hydroxycyclohexanecarboxylic acid is dissolved in 30L of ethanol, 0.6kg of 10% Pd/C and 0.2kg of perchloric acid are added, the gas in the kettle is replaced by nitrogen for three times, and then H is introduced2Heating to 40-45 ℃ under the pressure of 3-4 kg, reacting for 5h, filtering to remove Pd/C, evaporating most of solvent, adding 15% hydrochloric acid to adjust pH to 2-3, extracting with ethyl acetate 45L twice, adding heptane into the oil layer for dehydration, then distilling under reduced pressure, cooling the obtained oily liquid to separate out 11.8kg (92.4mol) of cyclohexanecarboxylic acid solid, wherein the melting point is 29-31 ℃ and the yield is 96.5%. HNMR (400MHz, CDCl3):11.82(brs,1H),2.29-2.36(m,1H),1.91-1.95(m,2H),1.74-1.78(m,2H),1.62-1.66(m,1H),1.40-1.50(m,2H),1.20-1.34(m,3H).
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (7)
1. A production process of cyclohexanecarboxylic acid is obtained through two-step reaction, and is characterized in that the reaction route is as follows: the method comprises the following steps:
the first step is as follows: dissolving epoxy cyclohexane in an organic solvent, adding Mg powder while stirring, cooling to below 0 ℃, introducing carbon dioxide gas and adding TMSCl at the same time, and reacting to obtain 2-hydroxycyclohexanecarboxylic acid;
the second step is that: dissolving 2-hydroxycyclohexanecarboxylic acid in ethanol, and carrying out Pd/C catalytic hydrogenation reaction in the presence of acid to obtain the cyclohexanecarboxylic acid.
2. The process for producing cyclohexanecarboxylic acid according to claim 1, wherein: in the first step, the organic solvent is selected from DMF or NMP.
3. The process for producing cyclohexanecarboxylic acid as claimed in claim 2, wherein: in the first step, the organic solvent is selected from NMP.
4. The process for producing cyclohexanecarboxylic acid according to claim 1, wherein: in the first step, the molar ratio of the cyclohexene oxide, the Mg powder and the TMSCl is 1:1-1.5: 1.5-2.
5. The process for producing cyclohexanecarboxylic acid according to claim 1, wherein: in the second step, the acid is selected from hydrochloric acid or perchloric acid.
6. The process for producing cyclohexanecarboxylic acid according to claim 1 or 5, wherein: in the second step, the acid is selected from perchloric acid.
7. The process for producing cyclohexanecarboxylic acid according to claim 1, wherein: in the second step, the catalytic hydrogenation is carried out under the pressure of 3-4 kg of hydrogen, and the reaction temperature is 40-55 ℃.
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Denomination of invention: A Production Process for Cyclohexanoic Acid Effective date of registration: 20230711 Granted publication date: 20200915 Pledgee: Bank of China Limited Xiangyang Branch Pledgor: HUBEI JINGHONG CHEMICAL Co.,Ltd. Registration number: Y2023980047966 |