CN107879933B - Preparation method of thermosensitive material p-methylbenzyl alcohol oxalic acid diester - Google Patents
Preparation method of thermosensitive material p-methylbenzyl alcohol oxalic acid diester Download PDFInfo
- Publication number
- CN107879933B CN107879933B CN201711129823.4A CN201711129823A CN107879933B CN 107879933 B CN107879933 B CN 107879933B CN 201711129823 A CN201711129823 A CN 201711129823A CN 107879933 B CN107879933 B CN 107879933B
- Authority
- CN
- China
- Prior art keywords
- oxalic acid
- preparation
- mass ratio
- benzyl alcohol
- methyl benzyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of a thermosensitive material p-methylbenzyl alcohol oxalic acid diester, which comprises the steps of dissolving, synthesizing and alkali washing; the preparation method comprises the following steps of preparing p-methyl benzyl alcohol and oxalic acid as raw materials; the catalyst is p-methyl benzene sulfonic acid and stannous chloride. The yield of the product prepared by the invention reaches 90.65-93%; the product is white powder in appearance and has good color; the purity is 99.58-99.8%; the drying weight loss is 0.06-0.13%; the melting point is 102.4-103.4 ℃. According to the invention, inorganic acids such as sulfuric acid are not used as catalysts, so that the side reaction is less, the reaction efficiency is high, and meanwhile, the problem that a large amount of sulfuric acid-containing wastewater pollutes the environment in the post-treatment process is avoided; the invention greatly reduces the self-decomposition characteristic of the material and greatly improves the yield of superior products after treatment.
Description
Technical Field
The patent relates to a synthesis process of p-methylbenzyl alcohol oxalate diester as a thermosensitive dye, belonging to the technical field of chemical synthesis.
Background
P-methylbenzyl alcohol oxalic acid diester products are typical of the preparation of diphenylsulfone compounds, and the preparation methods of such compounds have been disclosed in japanese patent publications for a long time, such as patents WO2009025316a1, WO2005087503a1, and the like. It is also published in the European and American patent office, and the synthesis routes such as patent EP1674543A1, EP1764399A1, and US2007112113A1 mostly adopt oxalic acid and p-methyl benzyl alcohol as raw materials.
The prior art generally has the following defects: firstly, inorganic acids such as sulfuric acid are used as catalysts, so that the side reactions of the reaction are more, the post-treatment is difficult, and the color of the product is poorer; meanwhile, a large amount of sulfuric acid-containing wastewater is generated in the post-treatment process to pollute the environment; secondly, high boiling point solvents such as toluene and xylene are used in the synthesis process, the temperature is not easy to control, the product p-methyl benzyl alcohol oxalic acid diester is decomposed, and the process stability is not high. Thirdly, the sulfuric acid is used in the process, the requirement on equipment is high under the high-temperature condition, the equipment maintenance difficulty is high, and safety accidents are easy to happen; fourth, the existing process generally has the disadvantages of low yield, mostly 80-85%, and high cost. Fifthly, the material obtained under the acidic condition has the problem of easy decomposition.
Disclosure of Invention
Aiming at the defects of the prior art, the invention takes oxalic acid and p-methylbenzyl alcohol as raw materials, and selects a catalyst under the action of p-methylbenzene sulfonic acid and stannous chloride; the preparation method of the thermosensitive material p-methyl benzyl alcohol oxalic acid diester is provided by using a low-boiling-point solvent cyclohexane as a water-carrying agent, adopting a mixed dripping method of oxalic acid and cyclohexane and combining alkali washing, so as to realize the following purposes:
(1) side reactions are reduced, and the color of the product is improved;
(2) the yield is improved;
(3) the decomposition of the product is reduced.
The synthesis route of the patent is as follows:
in order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a thermosensitive material p-methylbenzyl alcohol oxalic acid diester comprises the steps of dissolving, synthesizing and alkali washing; the preparation method comprises the following steps of preparing p-methyl benzyl alcohol and oxalic acid as raw materials; the catalyst is p-methyl benzene sulfonic acid and stannous chloride.
The following is a further improvement of the above technical solution:
the mass ratio of the p-methyl benzyl alcohol to the oxalic acid is as follows: 1.5-2.5: 1; the mass ratio of the p-toluenesulfonic acid to the p-methylbenzyl alcohol is 0.006-0.01: 1; the mass ratio of the stannous chloride to the p-methyl benzyl alcohol is 0.001-0.006: 1.
And the synthesis comprises the step of dropwise adding a mixed solution of oxalic acid and cyclohexane into a reaction kettle, wherein the mass ratio of the oxalic acid to the cyclohexane is 1: 3.5-7.5.
The alkali washing is carried out by dripping 2-3% of sodium carbonate aqueous solution with the temperature of 45 ℃ into a reaction kettle for washing, settling and layering; the mass ratio of the added alkali to the p-methyl benzyl alcohol is 0.015-0.03: 1.
The synthesis adopts a mode of dripping and dividing water; the dropping time is controlled to be 4-7h, and the proportion of the dropping speed and the water dividing speed is controlled to be 1: 0.8-0.9.
And after the synthesis and the dropwise addition are finished, continuously refluxing and dividing water, and after the water division is finished, continuously refluxing for 3-6 h.
And (3) dissolving, namely putting the p-methyl benzyl alcohol, the catalyst and part of cyclohexane into a reaction kettle, and heating to 70-80 ℃ to dissolve.
The mass ratio of the p-methyl benzyl alcohol to the cyclohexane is 1: 3-5.
The alkali is one or more of sodium carbonate, sodium bicarbonate, liquid alkali and potassium carbonate.
The method further comprises refining; refining, cooling, suction filtering to obtain solid material, adding the solid material into a reaction kettle, refining with ethanol, washing, and drying.
Due to the adoption of the technical scheme, the invention achieves the technical effects that:
(1) the yield of the product prepared by the invention reaches 90.65-93%; the product is white powder in appearance and has good color; the purity is 99.58-99.8%; the drying weight loss is 0.06-0.13%; the melting point is 102.4-103.4 ℃.
(2) According to the invention, inorganic acids such as sulfuric acid are not used as catalysts, so that the side reaction is less, the reaction efficiency is high, and meanwhile, the problem that a large amount of sulfuric acid-containing wastewater pollutes the environment in the post-treatment process is avoided;
(3) the invention greatly reduces the self-decomposition characteristic of the material and greatly improves the yield of superior products after treatment.
(4) The invention has simple process and convenient operation; the reaction operation unit is safe, the solvent recovery rate is high, and the method is more suitable for industrial production.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
Example 1 preparation method of thermosensitive material p-methylbenzyl alcohol oxalic acid diester
The method comprises the following steps:
(1) dissolution
P-methylbenzyl alcohol (81 g), p-methylbenzenesulfonic acid/stannous chloride (1.0 g, mass ratio 1: 1) and cyclohexane (250 g) were put into a three-necked flask, and the temperature of the three-necked flask was raised to 70 ℃ to prepare a mixed solution of oxalic acid (38 g) and cyclohexane (150 g).
(2) Synthesis of
Dripping a mixed solution of oxalic acid and cyclohexane in a manner of dripping while dividing water; the dropping time was controlled to 3.5 hours, and the dropping speed and the water-dividing speed were controlled to be equivalent in the whole process (the dropping speed/water-dividing speed was maintained at 1: 0.8). After dripping, continuously refluxing and distributing water; and after water diversion is finished, continuously refluxing for 3.0 h.
(3) Alkali washing
The prepared 2% sodium carbonate (1.5g) aqueous solution at 45 ℃ is dropped into a reaction kettle for washing, sedimentation and delamination.
(4) Refining
Cooling to about 20 deg.C, vacuum filtering to obtain crude product, washing with 90% cold ethanol 125 (ml); and (5) carrying out suction filtration and drying to obtain 90.5g of refined product.
TABLE 1 indices of the products prepared in inventive example 1
Example 2 preparation method of thermosensitive material p-methylbenzyl alcohol oxalic acid diester
The method comprises the following steps:
(1) dissolution
P-methylbenzyl alcohol (81 g), p-methylbenzenesulfonic acid/stannous chloride (1.0 g, mass ratio 1: 0.8) and cyclohexane (300 g) were put into a three-necked flask, and a mixed solution of oxalic acid (48 g) and cyclohexane (350 g) was prepared by heating the three-necked flask to 75 ℃.
(2) Synthesis of
Dripping a mixed solution of oxalic acid and cyclohexane while distributing water; the dropping time was controlled to 5.0h, and the dropping speed and the water-dividing speed were controlled to be equivalent in the whole process (the dropping speed/water-dividing speed was maintained at 1: 0.9). After dripping, continuously refluxing and distributing water; and after water diversion is finished, continuously refluxing for 4.0 h.
(3) Alkali washing
The prepared 2 percent sodium carbonate (2.0g) aqueous solution with the temperature of 45 ℃ is dripped into a reaction kettle for washing, sedimentation and delamination.
(4) Refining
Cooling to about 20 deg.C, vacuum filtering to obtain crude product, washing with 90% cold ethanol 125 (ml); and (5) carrying out suction filtration and drying to obtain 91.25g of fine product.
TABLE 2 indices of the products prepared in example 2 of the invention
Example 3 preparation method of thermosensitive material p-methylbenzyl alcohol oxalic acid diester
The method comprises the following steps:
(1) dissolution
P-methylbenzyl alcohol (81 g), p-methylbenzenesulfonic acid/stannous chloride (1.0 g, mass ratio 1: 0.6) and cyclohexane (350 g) were put into a three-necked flask, and the temperature of the three-necked flask was raised to 78 ℃ to prepare a mixed solution of oxalic acid (38 g) and cyclohexane (250 g).
(2) Synthesis of
Dripping a mixed solution of oxalic acid and cyclohexane while distributing water; the dropping time was controlled at 7 hours, and the dropping speed and the water-dividing speed were controlled to be equivalent throughout the whole process (the dropping speed/water-dividing speed was maintained at 1: 0.9). After dripping, continuously refluxing and distributing water; and after water diversion is finished, continuously refluxing for 6.0 h.
(3) Alkali washing
The prepared 3 percent sodium carbonate (1.8g) aqueous solution with the temperature of 45 ℃ is dripped into a reaction kettle for washing, settling and layering.
(4) Refining
Cooling to about 20 deg.C, vacuum filtering to obtain crude product, washing with 90% cold ethanol 125 (ml); and (5) carrying out suction filtration and drying to obtain 89.75g of competitive products.
TABLE 3 indices of the products prepared in example 3 of the invention
Unless otherwise stated, the percentages used in the present invention are percentages by weight, and the proportions described in the present invention are proportions by mass.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. A preparation method of a thermosensitive material p-methylbenzyl alcohol oxalic acid diester is characterized by comprising the following steps: the preparation method comprises the steps of dissolving, synthesizing and alkali washing; the preparation method comprises the following steps of preparing p-methyl benzyl alcohol and oxalic acid as raw materials; the catalyst is p-toluenesulfonic acid and stannous chloride;
the mass ratio of the p-methyl benzyl alcohol to the oxalic acid is as follows: 1.5-2.5: 1; the mass ratio of the p-toluenesulfonic acid to the p-methylbenzyl alcohol is 0.006-0.01: 1; the mass ratio of the stannous chloride to the p-methyl benzyl alcohol is 0.001-0.006: 1;
the synthesis comprises the steps of dropwise adding a mixed solution of oxalic acid and cyclohexane into a reaction kettle, wherein the mass ratio of the oxalic acid to the cyclohexane is 1: 3.5-7.5;
the alkali washing is carried out by dripping 2-3% of sodium carbonate aqueous solution with the temperature of 45 ℃ into a reaction kettle for washing, settling and layering; adding alkali and p-methyl benzyl alcohol in the mass ratio of 0.015-0.03 to 1;
the synthesis adopts a mode of dripping and dividing water; the dripping time is controlled to be 4-7h, and the ratio of the dripping speed to the water distribution speed is controlled to be 1: 0.8-0.9; after the dropwise addition is finished, continuously refluxing and dividing water, and after the water division is finished, continuously refluxing for 3-6 h;
dissolving, namely putting the p-methyl benzyl alcohol, the catalyst and part of cyclohexane into a reaction kettle, and heating to 70-80 ℃ to dissolve; the mass ratio of the p-methyl benzyl alcohol to the cyclohexane is 1: 3-5.
2. The method for preparing p-methylbenzyl alcohol oxalic acid diester as thermal sensitive material according to claim 1, wherein: the alkali is one or more of sodium carbonate, sodium bicarbonate, liquid alkali and potassium carbonate.
3. The method for preparing p-methylbenzyl alcohol oxalic acid diester as thermal sensitive material according to claim 1, wherein: the method further comprises refining; refining, cooling, suction filtering to obtain solid material, adding the solid material into a reaction kettle, refining with ethanol, washing, and drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711129823.4A CN107879933B (en) | 2017-11-15 | 2017-11-15 | Preparation method of thermosensitive material p-methylbenzyl alcohol oxalic acid diester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711129823.4A CN107879933B (en) | 2017-11-15 | 2017-11-15 | Preparation method of thermosensitive material p-methylbenzyl alcohol oxalic acid diester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107879933A CN107879933A (en) | 2018-04-06 |
| CN107879933B true CN107879933B (en) | 2021-08-03 |
Family
ID=61777308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711129823.4A Active CN107879933B (en) | 2017-11-15 | 2017-11-15 | Preparation method of thermosensitive material p-methylbenzyl alcohol oxalic acid diester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107879933B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03275650A (en) * | 1990-03-26 | 1991-12-06 | Dainippon Ink & Chem Inc | Production of dibasic acid di(alkylbenzyl) ester |
| CN101654511A (en) * | 2009-08-12 | 2010-02-24 | 吴江鹰翔万信化纤有限公司 | Polymerization catalysis stabilization method for polybutylene terephthalate |
| CN102492524A (en) * | 2011-11-15 | 2012-06-13 | 中国科学院新疆理化技术研究所 | Synthesis method for liquid phenolic ester type antioxidants |
-
2017
- 2017-11-15 CN CN201711129823.4A patent/CN107879933B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03275650A (en) * | 1990-03-26 | 1991-12-06 | Dainippon Ink & Chem Inc | Production of dibasic acid di(alkylbenzyl) ester |
| CN101654511A (en) * | 2009-08-12 | 2010-02-24 | 吴江鹰翔万信化纤有限公司 | Polymerization catalysis stabilization method for polybutylene terephthalate |
| CN102492524A (en) * | 2011-11-15 | 2012-06-13 | 中国科学院新疆理化技术研究所 | Synthesis method for liquid phenolic ester type antioxidants |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107879933A (en) | 2018-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3805196B1 (en) | Preparation method for high optical indoxacarb intermediate | |
| CN103058845A (en) | Dibenzoylmethane preparation method | |
| CN111018749A (en) | Phenolsulam and calcium dobesilate impurities as well as preparation method and application thereof | |
| CN107879933B (en) | Preparation method of thermosensitive material p-methylbenzyl alcohol oxalic acid diester | |
| CN101830764A (en) | Method for synthesizing Stilbene compound by utilizing Pfitzner-moffatt oxidizing reaction | |
| CN110746281B (en) | Preparation method of 3-bromo-4-hydroxybenzaldehyde | |
| CN105175317B (en) | A kind of method for preparing picosulfate sodium | |
| CN104326915A (en) | Method for synthesizing ethyl p-hydroxybenzoate through catalysis of modified metal oxide type solid super acid | |
| CN106146457B (en) | 5-chloro-2-acyl chloride thiophene intermediate and preparation method thereof | |
| CN110845443A (en) | Method for preparing high-purity tolperisone hydrochloride | |
| CN101723925B (en) | Preparation method of 7-hydroxy-4-methylcoumarin | |
| CN106699523A (en) | Synthetic method of o-phenyl phenoxyethanol | |
| CN112094189B (en) | Synthesis method of dimethyl succinylsuccinate | |
| CN106699504A (en) | Preparation method of 2,2-bis(3,4-dimethylphenyl)hexafluoropropane | |
| CN1508127A (en) | High-purity 4,4'-dihydroxy diphenyl sulfone preparing method | |
| CN113234055B (en) | Synthesis method of lactide | |
| CN105566223A (en) | Crude iminostilbene product recrystallization method | |
| CN105175316B (en) | A kind of method for preparing laxative picosulfate sodium | |
| CN110655479A (en) | Method for synthesizing BP-4 by microreactor | |
| CN109928951B (en) | Preparation method of 2-isopropyl thioxanthone | |
| WO2021218275A1 (en) | Method for synthesizing and refining 4-fluorobenzoylacetonitrile | |
| CN104028310A (en) | Preparation method for synthesizing dimethoxy bisphenol A carbonate catalyst | |
| CN104945234B (en) | The preparation method of the methoxy benzophenone of 2,2 ' dihydroxy 4 | |
| CN110272451B (en) | Preparation method of tetraphenylphenol phosphonium salt | |
| CN106278824A (en) | A kind of method using modified eutectic solvent alkaline hydrolysis to prepare cresol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211115 Address after: 262700 No. 5 Xueyuan East Street, Shouguang City, Weifang City, Shandong Province Patentee after: Shandong Ruikang Fine Chemicals Co., Ltd Patentee after: Shouguang Fukang Pharmaceutical Co., Ltd Address before: 262700 No. 666, East Ring Road, Shouguang City, Weifang City, Shandong Province Patentee before: Shouguang Fukang Pharmaceutical Co., Ltd |