CN109369349B - Preparation method of 1, 2-bis (3-methylphenoxy) ethane - Google Patents
Preparation method of 1, 2-bis (3-methylphenoxy) ethane Download PDFInfo
- Publication number
- CN109369349B CN109369349B CN201811257762.4A CN201811257762A CN109369349B CN 109369349 B CN109369349 B CN 109369349B CN 201811257762 A CN201811257762 A CN 201811257762A CN 109369349 B CN109369349 B CN 109369349B
- Authority
- CN
- China
- Prior art keywords
- cooling
- heating
- hours
- cresol
- methylphenoxy
- 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
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of thermosensitive sensitizers, in particular to a preparation method of a 1, 2-bis (3-methylphenoxy) ethane thermosensitive sensitizer. The method comprises the following steps: (1) adding m-cresol and potassium hydroxide into a high-pressure reaction vessel, stirring, heating to 130-150 ℃, completely dissolving, cooling to 70-80 ℃, and adding dichloroethane; (2) after the addition is finished, closing the high-pressure kettle, introducing nitrogen for replacing for 3 times, introducing a small amount of nitrogen, heating to 130-150 ℃, and carrying out heat preservation reaction for 15 hours; (3) cooling to 70-80 ℃, adding water, heating to 80-100 ℃, stirring for 1 hour, cooling to room temperature, separating out for more than 3 hours, filtering, washing with water, and drying to obtain a white 1, 2-bis (3-methylphenoxy) ethane thermosensitive sensitizer product. The method has simple process, is suitable for industrial large-scale production, and the product is widely applied to the production of the thermal sensitive paper.
Description
Technical Field
The invention relates to the field of thermosensitive sensitizers, in particular to a preparation method of a 1, 2-bis (3-methylphenoxy) ethane thermosensitive sensitizer.
Background
The structural formula of the 1, 2-bis (3-methylphenoxy) ethane thermosensitive sensitizer is as follows:
the compound is usually generated by the reaction of m-cresol and dichloroethane under the action of alkali liquor. Wherein, the hydrolysis side reaction of dichloroethane under alkaline condition is the main reason for influencing the reaction yield. The previous synthetic methods report that the research direction is mainly how to avoid the side reaction and improve the yield. The method mainly comprises the following steps:
the method of using excessive m-cresol at the beginning has the disadvantages of more m-cresol usage, higher cost, difficult post-treatment of excessive m-cresol, and yield up to 72 percent; later, a batch alkali adding method is adopted, the method needs to monitor and control the alkali concentration for a long time, is not easy to control and complex to operate, hydrolysis side reaction still occurs, and the yield can reach 72.8%; and then, by adopting a method of excessive dichloroethane and adding a phase transfer catalyst, the yield of the method can reach 80-85%, the dichloroethane hydrolysis cannot be completely avoided, the amount of the dichloroethane is increased, the phase transfer catalyst needs to be added, an isopropanol solvent needs to be added for aftertreatment, and the cost is high.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the preparation method of the 1, 2-bis (3-methylphenoxy) ethane, which has high yield and simple post-treatment and is suitable for large-scale production, and solves the problems of dichloroethane hydrolysis, low yield, difficult post-treatment and the like in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention relates to a preparation method of 1, 2-bis (3-methylphenoxy) ethane, which comprises the following steps:
(1) adding m-cresol and potassium hydroxide into a high-pressure reaction vessel, stirring, heating to 130-150 ℃, completely dissolving, cooling to 70-80 ℃, and adding dichloroethane;
(2) after the addition is finished, closing the autoclave, introducing nitrogen for replacement, introducing a small amount of nitrogen to ensure that the pressure reaches 0.1-0.2 Mpa, heating to 130-150 ℃, and carrying out heat preservation reaction for 15-20 hours;
(3) cooling to 70-80 ℃, adding water, heating to 80-100 ℃, stirring for 1-2 hours, cooling to room temperature, separating out for more than 3 hours, filtering, washing with water, and drying to obtain a white product.
Further, the mol ratio of m-cresol, dichloroethane and potassium hydroxide in the step (1) is 2:1: 2.2-2.5.
Further, the weight of the added water in the step (3) is 3-5 times of the weight of the m-cresol.
Compared with the prior art, the invention has the following advantages:
1. the invention does not use water to dissolve potassium hydroxide during reaction, and the potassium hydroxide can be dissolved in m-cresol at high temperature. No water is added in the reaction process, so that the side reaction of dichloroethane hydrolysis can be thoroughly avoided.
2. In the reaction process, the potassium hydroxide of the cresol is mutually soluble with the dichloroethane, and a phase transfer catalyst is not required to be added.
3. In the reaction process of the invention, no water is added, so that the dichloroethane is not needed to be hydrolyzed at high temperature and is carried out in a high-pressure closed reaction kettle; therefore, the temperature can be raised to 130-150 ℃ for reaction, thereby improving the conversion rate.
4. The reaction process is carried out in a high-pressure closed reaction kettle and is protected by nitrogen, so that the dark color of the product caused by the oxidation of m-cresol can be avoided, the product is not refined by a solvent, and the white product can be directly separated out in water.
5. The method is simple to operate, and the yield is high and can reach 90-95%.
Detailed Description
In a specific embodiment, the preparation method of the 1, 2-bis (3-methylphenoxy) ethane thermosensitive sensitizer comprises the following steps: (1) adding m-cresol and potassium hydroxide into a high-pressure reaction container, stirring, heating to 130-150 ℃, completely dissolving, cooling to below 80 ℃, and adding dichloroethane; (2) after adding, closing the autoclave, introducing nitrogen for 3 times of replacement, introducing a small amount of nitrogen to ensure that the pressure reaches 0.1-0.2 Mpa, heating to 130-150 ℃, and carrying out heat preservation reaction for 15-20 hours; (3) cooling to 70-80 ℃, adding water, heating to 80-100 ℃, stirring for 1-2 hours, cooling to room temperature, separating out for more than 3 hours, filtering, washing with water, and drying to obtain a white product. Wherein the content of the first and second substances,
the reaction formula in the process of preparing the 1, 2-bis (3-methylphenoxy) ethane thermosensitive sensitizer is as follows:
the mol ratio of the m-cresol to the dichloroethane to the potassium hydroxide is 2:1: 2.2-2.5.
And (4) adding water which is 3-5 times of the weight of the m-cresol into the post-treatment in the step (3).
The present invention will be further described with reference to the following examples.
Example 1
Adding 400 g of m-cresol and 254 g of potassium hydroxide with the content of 90% into a 2L high-pressure autoclave, heating to 130-150 ℃, stirring for dissolving, cooling to the temperature below 80 ℃, adding 184 g of 1, 2-dichloroethane, sealing the high-pressure autoclave after adding, replacing with nitrogen for three times, introducing a small amount of nitrogen, heating to 130 ℃, carrying out heat preservation reaction for 15 hours, cooling to the temperature below 80 ℃, adding water, and carrying out heat preservation for 1 hour at the temperature of 80-100 ℃. And cooling to 5-25 ℃, separating out for more than 3 hours, filtering, leaching with a small amount of water, and drying a filter cake to obtain 419.0 g of a white solid product with the content of 99.3% and the yield of 93.5%.
Example 2
Adding 400 g of m-cresol and 276 g of potassium hydroxide with the content of 90% into a 2L high-pressure autoclave, heating to 130-150 ℃, stirring for dissolving, cooling to 80 ℃, adding 184 g of 1, 2-dichloroethane, sealing the high-pressure autoclave after adding, replacing with nitrogen for three times, introducing a small amount of nitrogen, heating to 150 ℃, carrying out heat preservation reaction for 15 hours, cooling to 70 ℃, adding 1200 ml of water, and carrying out heat preservation for 1.5 hours at 80-100 ℃. And cooling to 5-25 ℃, separating out for more than 3 hours, filtering, leaching with a small amount of water, and drying a filter cake to obtain 423.5 g of a white solid product with the content of 99.5% and the yield of 94.5%.
Example 3
Adding 400 g of m-cresol and 288 g of potassium hydroxide with the content of 90% into a 2L high-pressure autoclave, heating to 130-150 ℃, stirring for dissolving, cooling to 75 ℃, adding 184 g of 1, 2-dichloroethane, sealing the high-pressure autoclave after adding, replacing with nitrogen for three times, introducing a small amount of nitrogen, heating to 140 ℃, carrying out heat preservation reaction for 15 hours, cooling to 78 ℃, adding 1300 ml of water, and carrying out heat preservation for 2 hours at 80-100 ℃. And cooling to 5-25 ℃, separating out for more than 3 hours, filtering, leaching with a small amount of water, and drying a filter cake to obtain 425.7 g of a white solid product with the content of 99.6% and the yield of 95.0%.
Comparative example
Adding 400 g of m-cresol and 415 g of 50% potassium hydroxide solution into a 2L four-neck bottle, heating to 80 ℃, reacting for half an hour, adding 367 g of 1, 2-dichloroethane and 40 g of PEG1000, refluxing, preserving heat, reacting for 7 hours, then adding 415 g of 50% potassium hydroxide solution, and preserving heat for 13 hours at 87-93 ℃. Heating and concentrating to ensure that the temperature gradually reaches 120 ℃ within 3 hours, and preserving the heat for 1 hour at 118-120 ℃. Adding 1400 ml of water, heating to 100 ℃, stirring for 0.5 hour, cooling to 80 ℃, filtering, leaching with a small amount of water, and vacuum-drying a filter cake to obtain a dark brown product. Recrystallizing with isopropanol, and drying to obtain 385 g of white solid product with the content of 99.0 percent and the yield of 85.0 percent.
The results of the examples and the comparative examples show that the method has simple process and high yield of the obtained product, and is suitable for industrial large-scale production.
Claims (2)
- A process for the preparation of 1, 2-bis (3-methylphenoxy) ethane, characterized in that it comprises the following steps:(1) adding m-cresol and potassium hydroxide into a high-pressure reaction vessel, stirring, heating to 130-150 ℃, completely dissolving, cooling to 70-80 ℃, and adding dichloroethane; the mol ratio of the m-cresol to the dichloroethane to the potassium hydroxide is 2:1: 2.2-2.5;(2) after the addition is finished, closing the autoclave, introducing nitrogen for replacement, introducing a small amount of nitrogen to ensure that the pressure reaches 0.1-0.2 Mpa, heating to 130-150 ℃, and carrying out heat preservation reaction for 15-20 hours;(3) cooling to 70-80 ℃, adding water, heating to 80-100 ℃, stirring for 1-2 hours, cooling to room temperature, separating out for more than 3 hours, filtering, washing with water, and drying to obtain a white product.
- 2. The method for producing 1, 2-bis (3-methylphenoxy) ethane as claimed in claim 1, wherein the weight of the added water in the step (3) is 3 to 5 times the weight of m-cresol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811257762.4A CN109369349B (en) | 2018-10-26 | 2018-10-26 | Preparation method of 1, 2-bis (3-methylphenoxy) ethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811257762.4A CN109369349B (en) | 2018-10-26 | 2018-10-26 | Preparation method of 1, 2-bis (3-methylphenoxy) ethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109369349A CN109369349A (en) | 2019-02-22 |
| CN109369349B true CN109369349B (en) | 2021-08-03 |
Family
ID=65389877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811257762.4A Active CN109369349B (en) | 2018-10-26 | 2018-10-26 | Preparation method of 1, 2-bis (3-methylphenoxy) ethane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109369349B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110204429A (en) * | 2019-05-10 | 2019-09-06 | 江苏理工学院 | A kind of preparation method of 1,2- biphenoxyl ethane |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041604A (en) * | 1986-12-22 | 1991-08-20 | Sanko Kaihatsu Kagaku Kenkyusho | Process for producing di(aryloxy)alkane |
| CN1544406A (en) * | 2003-11-27 | 2004-11-10 | 山西大学 | Ethylene glycol diarylether preparation method |
| JP2004330588A (en) * | 2003-05-07 | 2004-11-25 | Sanko Kk | Sensitizer composition for thermosensitive recording body and thermosensitive recording body employing the same |
| CN102276432A (en) * | 2011-05-17 | 2011-12-14 | 潍坊大有生物化工有限公司 | Synthetic method of 1,2-bis(3-methyllphenoxy)ethane thermosensitive sensitizer |
| CN104710287A (en) * | 2013-12-13 | 2015-06-17 | 北京北朋科技有限公司 | Industrial preparation method of 1,2-diphenoxyl ethane and its analog |
-
2018
- 2018-10-26 CN CN201811257762.4A patent/CN109369349B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041604A (en) * | 1986-12-22 | 1991-08-20 | Sanko Kaihatsu Kagaku Kenkyusho | Process for producing di(aryloxy)alkane |
| JP2004330588A (en) * | 2003-05-07 | 2004-11-25 | Sanko Kk | Sensitizer composition for thermosensitive recording body and thermosensitive recording body employing the same |
| CN1544406A (en) * | 2003-11-27 | 2004-11-10 | 山西大学 | Ethylene glycol diarylether preparation method |
| CN102276432A (en) * | 2011-05-17 | 2011-12-14 | 潍坊大有生物化工有限公司 | Synthetic method of 1,2-bis(3-methyllphenoxy)ethane thermosensitive sensitizer |
| CN104710287A (en) * | 2013-12-13 | 2015-06-17 | 北京北朋科技有限公司 | Industrial preparation method of 1,2-diphenoxyl ethane and its analog |
Non-Patent Citations (1)
| Title |
|---|
| 双甲苯氧即烷烃双季铵盐;嵇汝运;《化学学报》;19590430;第25卷(第2期);第100-105页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109369349A (en) | 2019-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104557801B (en) | Method for preparing gamma-valerolactone from furfural on metal/solid acid catalyst | |
| CN107721913B (en) | A kind of preparation method of 2,3- dichloropyridine | |
| CN109369349B (en) | Preparation method of 1, 2-bis (3-methylphenoxy) ethane | |
| CN110845424B (en) | Preparation method of 5-acetoacetylaminobenzimidazolone | |
| CN113372227A (en) | Synthesis process of high-purity benzethonium chloride | |
| CN109503513B (en) | One-pot synthesis method of febuxostat intermediate | |
| CN114524771A (en) | Preparation method of 6-hydroxy-2,4,5-triaminopyrimidine sulfate | |
| CN109897019B (en) | Method for preparing furfuryl alcohol by furfural liquid-phase hydrogenation by using copper-based catalyst | |
| CN112062671A (en) | Preparation method of R- (+) -2- (4-hydroxyphenoxy) propionic acid | |
| CN112300102A (en) | Synthetic method of furan ammonium salt | |
| CN112707848A (en) | Preparation method of guanidine hydrochloride | |
| CN105254611A (en) | Preparation method for benzothiophene-2-carboxylic acid | |
| CN114835661A (en) | Industrial preparation method of a-acetyl-r-butyrolactone | |
| CN114346251A (en) | Preparation method of rhodium powder | |
| CN113999171A (en) | Synthesis method of high-content dipyrithione | |
| CN109824629B (en) | Method for preparing 3-amino-5- (alpha-aminoethyl) tetrahydrofuran by using N-acetylglucosamine | |
| CN111620812A (en) | Synthetic method of 2, 3-dichloropyridine | |
| CN111675671A (en) | Preparation method of venlafaxine impurity E | |
| CN113816949B (en) | Preparation method of arotinolol hydrochloride | |
| CN107721864B (en) | Preparation method of thermosensitive material N, N-di-N-amyl m-aminophenol | |
| CN110615799B (en) | Preparation method of EDOT intermediate | |
| CN112574020B (en) | Preparation method of high-quality 1, 3-cyclohexanedione product | |
| CN115819304B (en) | Preparation method of molybdenum disulfide catalyzed tetraethyl thiuram disulfide | |
| CN114369069B (en) | Preparation method of quizalofop-p-ethyl compound intermediate | |
| CN103374081A (en) | Method for preparing high-viscosity and high-deacetylation-degree chitosan |
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 |