CN106316825A - Preparing method for trans- 4- hydroxycyclohexanecarboxylic acid - Google Patents
Preparing method for trans- 4- hydroxycyclohexanecarboxylic acid Download PDFInfo
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- CN106316825A CN106316825A CN201610713999.3A CN201610713999A CN106316825A CN 106316825 A CN106316825 A CN 106316825A CN 201610713999 A CN201610713999 A CN 201610713999A CN 106316825 A CN106316825 A CN 106316825A
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- hydroxycyclohexanecarboxylate
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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
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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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
- C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
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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
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparing method for trans- 4- hydroxycyclohexanecarboxylic acid. The method comprises the steps of adding p-hydroxybenzoic acid, catalyst and solvent into the high pressure reactor to obtain cis- and trans- 4-hydroxycyclohexanecarboxylic acid, then adding the 4-hydroxycyclohexanecarboxylic acid into the solvent and adding a certain volume of sodium alkoxide as the catalyst, increasing the temperature and obtain trans- 4- hydroxycyclohexanecarboxylic acid with content of over 90% through isomerization reaction. Then obtaining pure trans- 4- isomerization reaction by recrystallization of petroleum ether ethyl acetate. Benefit of the invention: the invention provides a preparing method for trans- 4- hydroxycyclohexanecarboxylic acid. The raw material is easy to obtain and the product can be produced in large scale, which greatly reduces the cost.
Description
Technical field
The invention belongs to chemical field, be specifically related to the preparation method of a kind of trans-4-hydroxycyclohexanecarboxylate.
Background technology
The preparation method of trans 4-hydroxycyclohexanecarboxylate, document report is seldom.Only document report, is to pass through
Trans 4-hydroxycyclohexanecarboxylate ethyl ester hydrolysis obtains.And trans 4-hydroxycyclohexanecarboxylate ethyl ester be not one common former
Material, is difficult to obtain.Document is to utilize 4-oxocyclohex alkane Ethyl formate to do substrate, is reduced by the catalysis of selectivity enzyme and obtains.
The fatal defects of this method is, the price of enzyme is high, and severe reaction conditions, is not suitable for large-scale production.Trans-4-hydroxyl
Butylcyclohexanecarboxylic acid, as a kind of medicine intermediate, is applied to the synthesis of many medicines, and its importance is self-evident, therefore, needs
Want a preparation method being suitable for large-scale production.
Summary of the invention
In order to solve the problems referred to above, the invention provides the preparation method of trans-4-hydroxycyclohexanecarboxylate, concrete technology
Scheme is as follows:
Step one: by P-hydroxybenzoic acid, catalysts and solvents joins in autoclave, is passed through hydrogen, in High Temperature High Pressure
Under the conditions of, obtain 4-hydroxycyclohexanecarboxylate；
Step 2: join in solvent by 4-hydroxycyclohexanecarboxylate, adds appropriate sodium alkoxide, temperature rising reflux, obtains trans-4-
Hydroxycyclohexanecarboxylate crude product (content is more than 90%)；
Step 3: by trans-4-hydroxycyclohexanecarboxylate crude product, heavily tie with a certain proportion of ethyl acetate petroleum ether mixed solvent
Crystalline substance, obtains pure trans-4-hydroxycyclohexanecarboxylate.
Preferably, the catalyst of hydrogenation is ruthenium Pd/carbon catalyst；Solvent is water；Reaction temperature is 80-150 degree；Reaction
Pressure is 1-3MPa.
Preferably, in isomerization reaction, solvent for use is methanol, ethanol, propanol, n-butyl alcohol and the tert-butyl alcohol；Sodium alkoxide used
For Feldalat NM, Sodium ethylate, sodium propoxide and sodium tert-butoxide.
Preferably, the solvent used by recrystallization is the ratio of ethyl acetate petroleum ether mixed solvent, ethyl acetate and petroleum ether
Example is 1:1, and the ratio of the consumption (volume L) of mixed solvent and the amount (quality kg) of trans-4-hydroxycyclohexanecarboxylate crude product is
4:1 to 2:1.
Beneficial effects of the present invention: the invention provides the preparation method of a kind of trans-4-hydroxycyclohexanecarboxylate, its
In, this raw material of P-hydroxybenzoic acid is easy to get, and can be used to large-scale production target product, and cost is greatly reduced.
Accompanying drawing explanation
Fig. 1 is course of reaction figure in the present invention.
Detailed description of the invention
Embodiment 1
The preparation of 4-hydroxycyclohexanecarboxylate, in 50L autoclave, adds 10 kilograms of P-hydroxybenzoic acid, 30 kg of water,
0.3 kilogram of 5% ruthenium C catalyst, nitrogen replace once, hydrogen exchange three times.Opening stirring, pressurized with hydrogen, to 1MPa, is warming up to
80 degree, start to inhale hydrogen, be progressively warming up to 120 degree, keep constant temperature till not inhaling hydrogen.Sampling monitoring, high performance liquid chromatography
(HPLC) analyzing, the reaction of raw material P-hydroxybenzoic acid is completely.Being down to room temperature, hydrogen of draining, nitrogen is replaced once.Filter out catalysis
Agent, is evaporated off the water in reactant liquor, obtains thick thing, adds 10L methanol, stirring to pulp, obtains dispersibility the whitest
Color powder.Filtering, be dried, obtain 9 kilograms of 4-hydroxycyclohexanecarboxylate, trans content is 60%.
The preparation of trans-4-hydroxycyclohexanecarboxylate crude product, by 9 kilograms of 4-hydroxycyclohexanecarboxylate, 30L methanol joins
In 50L reactor, open stirring, be dividedly in some parts 3.5 kilograms of Feldalat NMs.After be warming up to 60 degree, back flow reaction 3-hour, be cooled to
0 degree.Dripping 10% dilute hydrochloric acid in reactant liquor to PH is 2.Solid filters, and dries, obtains 8 kilograms of Lycoperdon polymorphum Vitt powder, the most trans-4-hydroxyl
Butylcyclohexanecarboxylic acid crude product (containing 5% cis-4-hydroxycyclohexanecarboxylate).
The preparation of trans-4-hydroxycyclohexanecarboxylate fine work, will appeal 8 kilograms of trans-4-hydroxycyclohexanecarboxylate crude products,
Joining (ethyl acetate: petroleum ether=1:1) in the mixed solvent of 32L ethyl acetate and petroleum ether, be warming up to 80 degree, stirring 2 is little
Time, system is molten clearly.Slow cooling, to 0 degree, is incubated 2 hours, separates out large quantities of white powder.Filter, dry, obtain 7.2 kilograms instead
Formula-4-hydroxycyclohexanecarboxylate, content 99%.
In the present embodiment, the raw material being easily easy to get by some, carry out series reaction, obtain highly purified mesh
Mark product, cost has obtained the biggest reduction, is suitable for large-scale production.
Claims (4)
1. a preparation method for trans-4-hydroxycyclohexanecarboxylate, it specifically comprises the following steps that
Step one: by P-hydroxybenzoic acid, catalysts and solvents joins in autoclave, is passed through hydrogen, in High Temperature High Pressure
Under the conditions of, obtain 4-hydroxycyclohexanecarboxylate；
Step 2: join in solvent by 4-hydroxycyclohexanecarboxylate, adds appropriate sodium alkoxide, temperature rising reflux, obtains trans-4-
Hydroxycyclohexanecarboxylate crude product；
Step 3: by trans-4-hydroxycyclohexanecarboxylate crude product, heavily tie with a certain proportion of ethyl acetate petroleum ether mixed solvent
Crystalline substance, obtains pure trans-4-hydroxycyclohexanecarboxylate.
2. according to the preparation method of a kind of trans-4-hydroxycyclohexanecarboxylate described in claim 1, it is characterised in that: hydrogen
The catalyst changing reaction is ruthenium Pd/carbon catalyst；Solvent is water；Reaction temperature is 80-150 degree；Reaction pressure is 1-3MPa.
3. according to the preparation method of a kind of trans-4-hydroxycyclohexanecarboxylate described in claim 1, it is characterised in that: different
In structureization reaction, solvent for use is methanol, ethanol, propanol, n-butyl alcohol and the tert-butyl alcohol；Sodium alkoxide used is Feldalat NM, ethanol
Sodium, sodium propoxide and sodium tert-butoxide.
4. according to the preparation method of a kind of trans-4-hydroxycyclohexanecarboxylate described in claim 1, it is characterised in that: weight
Solvent used by crystallization be the ratio of ethyl acetate petroleum ether mixed solvent, ethyl acetate and petroleum ether be 1:1, mixed solvent
The ratio of the amount (quality kg) of consumption (volume L) and trans-4-hydroxycyclohexanecarboxylate crude product is 4:1 to 2:1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610713999.3A CN106316825A (en) | 2016-08-24 | 2016-08-24 | Preparing method for trans- 4- hydroxycyclohexanecarboxylic acid |
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| CN201610713999.3A CN106316825A (en) | 2016-08-24 | 2016-08-24 | Preparing method for trans- 4- hydroxycyclohexanecarboxylic acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108290813A (en) * | 2015-11-27 | 2018-07-17 | 住友化学株式会社 | The manufacturing method of trans-cyclohexane formic acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4013582A (en) * | 1976-06-17 | 1977-03-22 | Rca Corporation | Liquid crystal compounds and electro-optic devices incorporating them |
| JP2007091612A (en) * | 2005-09-27 | 2007-04-12 | Fujifilm Corp | Cyclohexyl group-having diester compound, and composition, retardation film, and display device containing the compound |
| CN103539660A (en) * | 2013-09-25 | 2014-01-29 | 江苏康恒化工有限公司 | Method of preparing trans-1,4-cyclohexane dicarboxylic acid from hybrid 1,4-cyclohexane dicarboxylic acid |
| CN103769089A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst preparation method, and synthesis method of catalyst and trans-1,4-cyclohexane dicarboxylic acid |
-
2016
- 2016-08-24 CN CN201610713999.3A patent/CN106316825A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4013582A (en) * | 1976-06-17 | 1977-03-22 | Rca Corporation | Liquid crystal compounds and electro-optic devices incorporating them |
| JP2007091612A (en) * | 2005-09-27 | 2007-04-12 | Fujifilm Corp | Cyclohexyl group-having diester compound, and composition, retardation film, and display device containing the compound |
| CN103769089A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst preparation method, and synthesis method of catalyst and trans-1,4-cyclohexane dicarboxylic acid |
| CN103539660A (en) * | 2013-09-25 | 2014-01-29 | 江苏康恒化工有限公司 | Method of preparing trans-1,4-cyclohexane dicarboxylic acid from hybrid 1,4-cyclohexane dicarboxylic acid |
Non-Patent Citations (3)
| Title |
|---|
| SAMUEL SIEGEL ET AL.: "Quantitative Relationships in the Reactions of trans-4-X-Cyclohexanecarboxylic Acids and their Methyl Esters", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| TOMOHIRO MAEGAWA ET AL.: "Efficient and Practical Arene Hydrogenation by Heterogeneous Catalysts under Mild Conditions", 《CHEM. EUR. J.》 * |
| WILLIAM J. BAILEY ET AL.: "RING-OPENING POLYMERIZATION OF CYCLIC KETENE ACETALS AND UNSATURATED CYCLIC SPIRO ORTHO ESTERS", 《MAKROMOL. CHEM., MACROMOL. SYMP.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108290813A (en) * | 2015-11-27 | 2018-07-17 | 住友化学株式会社 | The manufacturing method of trans-cyclohexane formic acid |
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Application publication date: 20170111 |