CN101811969A - Production method of trans-4-isopropyl hexahydrobenzoic acid-4'methoxy phenol ester - Google Patents
Production method of trans-4-isopropyl hexahydrobenzoic acid-4'methoxy phenol ester Download PDFInfo
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- CN101811969A CN101811969A CN200910264382A CN200910264382A CN101811969A CN 101811969 A CN101811969 A CN 101811969A CN 200910264382 A CN200910264382 A CN 200910264382A CN 200910264382 A CN200910264382 A CN 200910264382A CN 101811969 A CN101811969 A CN 101811969A
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- hexahydrobenzoic acid
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- methoxy phenol
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Abstract
The invention relates to a production method of trans-4-isopropyl hexahydrobenzoic acid-4'methoxy phenol ester, which is characterized in that trans-isopropyl hexahydrobenzoic acid, thionyl chloride, benzene, metoxyphenol, methylene dichloride, triethylamine and concentrated hydrochloric acid are used as raw materials. The production method comprises the following steps of: (1) carrying out acylation reaction by using the trans-isopropyl hexahydrobenzoic acid and the thionyl chloride as the raw materials, and compounding propyl cyclohexaformyl chloride through normal pressure, depressurization and distillation; (2) carrying out esterification on the propyl cyclohexaformyl chloride and the metoxyphenol by using the benzene as a solvent with a dripping method to produce the trans-4-isopropyl hexahydrobenzoic acid-4'methoxy phenol ester as an object product; and obtaining liquid crystal products of which each parameter meets standard requirements after purification. The invention has the advantages that the production rate of the compounded propyl cyclohexaformyl chloride is higher than and equal to 98%, and the production rate of the trans-4-isopropyl hexahydrobenzoic acid-4'methoxy phenol ester as an object product is higher than 80%.
Description
Technical field
What the present invention relates to is the trans propyl group hexahydrobenzoic acid-4 ' of a kind of 4--methoxy phenol ester production method, belongs to the trans propyl group hexahydrobenzoic acid-4 ' of 4--methoxy phenol ester preparing technical field.
Background technology
The report that the trans propyl group hexahydrobenzoic acid-4 ' of 4--methoxy phenol ester production method is not arranged at present as yet.
Summary of the invention
What the present invention proposed is the trans propyl group hexahydrobenzoic acid-4 ' of a kind of 4--methoxy phenol ester production method, and purpose is intended to improve the output and the productive rate of LCD product.
The trans propyl group hexahydrobenzoic acid-4 ' of technical solution of the present invention: 4--methoxy phenol ester production method, be to be raw material with trans propyl group hexahydrobenzoic acid, sulfur oxychloride, benzene, methoxyphenol, methylene dichloride, triethylamine and concentrated hydrochloric acid, material molar ratio is: trans propyl group hexahydrobenzoic acid 1, sulfur oxychloride 1.5, benzene 2.0, methoxyphenol 1.1, methylene dichloride 3.0, triethylamine 1.4, concentrated hydrochloric acid 2.0; Concrete production process: (1) is that raw material carries out acylation reaction and synthesizes propyl group cyclohexyl formyl chloride through normal pressure, decompression, distillation with trans propyl group hexahydrobenzoic acid and sulfur oxychloride; (2) adopting the dropping method by propyl group cyclohexyl formyl chloride and methoxyphenol is that solvent carries out esterification with benzene, generate the trans 4-propyl group of target product hexahydrobenzoic acid-4 '-methoxy phenol ester, through purifying, obtain the LCD product that the equal conformance with standard of parameters requires;
Advantage of the present invention: synthetic propyl group cyclohexyl formyl chloride, theoretical yield 18.85kg, productive rate 〉=98%, actual output 〉=18.47kg.The trans 4-propyl group of target product hexahydrobenzoic acid-4 '-methoxy phenol ester, white crystal, gas-chromatography+liquid chromatography purity＞99.50%.Theoretical yield 76.2kg, actual output＞61kg, productive rate＞80%.
Description of drawings
Accompanying drawing 1 is the trans propyl group hexahydrobenzoic acid-4 ' of 4--methoxy phenol ester technological process of production figure.
Embodiment
Embodiment
Operation (1)
In the 50L glass-lined kettle, add trans propyl group hexahydrobenzoic acid 17.0kg, sulfur oxychloride 23.8kg, benzene 10L opens HCl absorption unit valve.Be steam heated to backflow, return time 2 hours.Steam heating, clean benzene and sulfur oxychloride are steamed in decompression, take out under the negative pressure about 10mmHg 0.5 hour with oil pump under steam heating at last.Sulfur oxychloride that steams and benzole soln 15L are re-used in this technology when feeding intake, and add 1L benzene again, the 13kg sulfur oxychloride gets final product, and the acid amount is constant.Theoretical yield 18.85kg, productive rate 〉=98%, actual output 〉=18.47kg.
Operation (2)
Add the 34.2kg methoxyphenol in the 200L glass-lined kettle, the 30kg triethylamine, the 90L methylene dichloride installs kettle cover, begins to stir;
Stir crack steam heating down, begin about 40 ℃ to reflux, the trans propyl group cyclohexyl of beginning Dropwise 5 4.0kg formyl chloride, exothermic heat of reaction stops to heat when obvious backflows arranged, and adds in about about 1.5 hours;
The high-order jar that drips of suction 20L dichloromethane rinse splashes in the reactor fast again, after dropwising, stirs, and crack steam heating refluxed 3 hours, and heating steam pressure is no more than 0.1MPa, and temperature in the kettle is controlled at 47 ± 5 ℃;
After reaction finishes, stop to heat after 15 minutes to not refluxing, (120L deionized water and 4L concentrated hydrochloric acid preparation washed twice is used 60L * 6 deionized water wash six times again, stirs 10 minutes at every turn with 60L * 2 dilute hydrochloric acid solutions, behind the standing demix, lower floor's gas producing formation branch is gone in the bucket, behind the branch vibration layer, with gas producing formation again in the suction still, carry out separatory next time again, washing time is no less than 3 hours;
Washing finishes, and reaction solution is changed in the 300L glass-lined kettle, stirs down that normal pressure steams methylene dichloride, reaches 80 ℃ to temperature in the kettle, crude product; Add the 240L dehydrated alcohol, stirred 10 minutes, refrigerating fulid is cooled to-15 ℃ and also keeps-15 ± 2 ℃ of stirrings 1 hour, and temperature fall time is no less than 6 hours;
The material that freezes divides evenly to be put into drier for three times and dries, and dries time 10-15 minute at every turn, and product is a white solid;
Product after weighing dries is got 60kg and is changeed in the 300L glass-lined kettle, adds the 240L dehydrated alcohol, stirs 10 minutes, and refrigerating fulid is cooled to-15 ℃, and keeps-15 ± 2 ℃ to stir 1 hour, and temperature fall time is no less than 6 hours;
The material that freezes divides evenly to be put into drier for three times and dries, and dries about 10 minutes time at every turn.After each the drying, with the freezing dehydrated alcohol flushing of 10L product, dry 5-10 minute one time recrystallization ethanol mother liquor again and concentrate respectively in addition, steam 3/4ths solvent, residuum is refrigerated to-15 ℃ of dryings, uses four times of ethyl alcohol recrystallizations 2 times again, be refrigerated to-15 ℃ of dryings, get the part qualified product.
White crystal, gas-chromatography+liquid chromatography purity＞99.50%.Theoretical yield 76.2kg, actual output＞61kg, productive rate＞80%.
Main raw material
| Sequence number | Main raw material | Index request |
| ??1 | Trans propyl group hexahydrobenzoic acid | The pure white crystal, molten point＞40 ℃ |
| ??2 | Sulfur oxychloride | The yellow-green colour transparent liquid |
| ??3 | Benzene | Colourless transparent liquid, water content≤0.05% |
| ??4 | Methoxyphenol | Brown yellow transparent liquid |
| ??5 | Methylene dichloride | Colourless transparent liquid, GC purity 〉=99.0% |
| ??6 | Triethylamine | Colourless transparent liquid, GC 〉=99.0% |
| Sequence number | Main raw material | Index request |
| ??7 | Concentrated hydrochloric acid | Colourless transparent liquid (SILVER REAGENT) |
Major equipment
Claims (3)
1.4-trans propyl group hexahydrobenzoic acid-4 '-methoxy phenol ester production method, it is characterized in that with trans propyl group hexahydrobenzoic acid, sulfur oxychloride, benzene, methoxyphenol, methylene dichloride, triethylamine and concentrated hydrochloric acid be raw material, material molar ratio is: trans propyl group hexahydrobenzoic acid 1, sulfur oxychloride 1.5, benzene 2.0, methoxyphenol 1.1, methylene dichloride 3.0, triethylamine 1.4, concentrated hydrochloric acid 2.0; Concrete production process: (1) is that raw material carries out acylation reaction and synthesizes propyl group cyclohexyl formyl chloride through normal pressure, decompression, distillation with trans propyl group hexahydrobenzoic acid and sulfur oxychloride; (2) adopting the dropping method by propyl group cyclohexyl formyl chloride and methoxyphenol is that solvent carries out esterification with benzene, generate the trans 4-propyl group of target product hexahydrobenzoic acid-4 '-methoxy phenol ester, through purifying, obtain the LCD product that the equal conformance with standard of parameters requires.
2. the trans propyl group hexahydrobenzoic acid-4 ' of 4-according to claim 1-methoxy phenol ester production method; it is characterized in that production process (1) acylation reaction adds trans propyl group hexahydrobenzoic acid 17.0kg in the 50L glass-lined kettle; sulfur oxychloride 23.8kg; benzene 10L opens HCl absorption unit valve.Be steam heated to backflow, return time 2 hours.Steam heating, clean benzene and sulfur oxychloride are steamed in decompression, take out under the negative pressure about 10mmHg 0.5 hour with oil pump under steam heating at last.Sulfur oxychloride that steams and benzole soln 15L are re-used in this technology when feeding intake, and add 1L benzene again, the 13kg sulfur oxychloride gets final product, and the acid amount is constant.
3. the trans propyl group hexahydrobenzoic acid-4 ' of 4-according to claim 1-methoxy phenol ester production method is characterized in that production process (2) esterification, adds the 34.2kg methoxyphenol in the 200L glass-lined kettle, the 30kg triethylamine, the 90L methylene dichloride installs kettle cover, begins to stir; Stir crack steam heating down, begin about 40 ℃ to reflux, the trans propyl group cyclohexyl of beginning Dropwise 5 4.0kg formyl chloride, exothermic heat of reaction stops to heat when obvious backflows arranged, and adds in about about 1.5 hours; The high-order jar that drips of suction 20L dichloromethane rinse splashes in the reactor fast again, after dropwising, stirs, and crack steam heating refluxed 3 hours, and heating steam pressure is no more than 0.1MPa, and temperature in the kettle is controlled at 47 ± 5 ℃; After reaction finishes, stop to heat after 15 minutes to not refluxing, with 60L * 2 dilute hydrochloric acid solutions, this dilute hydrochloric acid solution is with 120L deionized water and the preparation of 4L concentrated hydrochloric acid, use the dilute hydrochloric acid solution washed twice, use 60L * 6 deionized water wash again six times, stirred 10 minutes at every turn, behind the standing demix, lower floor's gas producing formation branch is gone in the bucket, behind the branch vibration layer, with gas producing formation again in the suction still, carry out separatory next time again, washing time is no less than 3 hours; Washing finishes, and reaction solution is changed in the 300L glass-lined kettle, stirs down that normal pressure steams methylene dichloride, reaches 80 ℃ to temperature in the kettle, crude product; Add the 240L dehydrated alcohol, stirred 10 minutes, refrigerating fulid is cooled to-15 ℃ and also keeps-15 ± 2 ℃ of stirrings 1 hour, and temperature fall time is no less than 6 hours; The material that freezes divides evenly to be put into drier for three times and dries, and dries time 10-15 minute at every turn, and product is a white solid; Product after weighing dries is got 60kg and is changeed in the 300L glass-lined kettle, adds the 240L dehydrated alcohol, stirs 10 minutes, and refrigerating fulid is cooled to-15 ℃, and keeps-15 ± 2 ℃ to stir 1 hour, and temperature fall time is no less than 6 hours; The material that freezes divides evenly to be put into drier for three times and dries, and dries about 10 minutes time at every turn.After each the drying, with the freezing dehydrated alcohol flushing of 10L product, dry 5-10 minute one time recrystallization ethanol mother liquor again and concentrate respectively in addition, steam 3/4ths solvent, residuum is refrigerated to-15 ℃ of dryings, uses four times of ethyl alcohol recrystallizations 2 times again, be refrigerated to-15 ℃ of dryings, get qualified LCD product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910264382A CN101811969A (en) | 2009-12-21 | 2009-12-21 | Production method of trans-4-isopropyl hexahydrobenzoic acid-4'methoxy phenol ester |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910264382A CN101811969A (en) | 2009-12-21 | 2009-12-21 | Production method of trans-4-isopropyl hexahydrobenzoic acid-4'methoxy phenol ester |
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| CN101811969A true CN101811969A (en) | 2010-08-25 |
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| CN200910264382A Pending CN101811969A (en) | 2009-12-21 | 2009-12-21 | Production method of trans-4-isopropyl hexahydrobenzoic acid-4'methoxy phenol ester |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108463452A (en) * | 2016-01-26 | 2018-08-28 | 日本瑞翁株式会社 | The manufacturing method of acyl halide solution and the manufacturing method of monoester compound |
-
2009
- 2009-12-21 CN CN200910264382A patent/CN101811969A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108463452A (en) * | 2016-01-26 | 2018-08-28 | 日本瑞翁株式会社 | The manufacturing method of acyl halide solution and the manufacturing method of monoester compound |
| CN108463452B (en) * | 2016-01-26 | 2021-07-20 | 日本瑞翁株式会社 | Method for producing acid halide solution and method for producing monoester compound |
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Owner name: JIANGSU LIANHE CHEMICAL INDUSTRY CO., LTD. Free format text: FORMER OWNER: JIANGSU KANGXIANG GROUP CORP. Effective date: 20121204 |
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Inventor after: Zhu Kangyang Inventor after: Liu Shitong Inventor before: Zhu Kangyang |
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Effective date of registration: 20121204 Address after: 212212 east side of Yangzhong, Jiangsu, Yangtze River Bridge Applicant after: Jiangsu Combined chemical co., Ltd Address before: 212212 east side of Yangzhong, Jiangsu, Yangtze River Bridge Applicant before: Jiangsu Kangxiang Group Company |
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Application publication date: 20100825 |