CN1271022C - Method for preparing 1,4-benzene dimethanol - Google Patents
Method for preparing 1,4-benzene dimethanol Download PDFInfo
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- CN1271022C CN1271022C CN 200310109034 CN200310109034A CN1271022C CN 1271022 C CN1271022 C CN 1271022C CN 200310109034 CN200310109034 CN 200310109034 CN 200310109034 A CN200310109034 A CN 200310109034A CN 1271022 C CN1271022 C CN 1271022C
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- phenyldicarbinol
- terephthaldehyde
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Abstract
The present invention discloses a preparation method of 1, 4-phenyldicarbinol. Phenyldimethyl dichloride, basic hydrolytic agents and water are added to emulsifying agents to carry out reflux reaction under the existence of phase transfer catalysts, and target products are obtained. After the 1, 4-phenyldicarbinol obtained by the preparation method is recrystallized, the purity of the 1, 4-phenyldicarbinol can reach more than 99%. The yield of the 1, 4-phenyldicarbinol is from 85 to 90%, and the melting point of the 1, 4-phenyldicarbinol is from 119 to 121 DEG C. Compared with the prior art, the present invention has the advantages of safe, simple and convenient operation and simple devices. The preparation method uses the phase transfer catalysts, the quality of products is stable, the yield is obviously increased, and the preparation method is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of 1, the preparation method of 4-xylyl alcohol.
Background technology
1, the 4-xylyl alcohol is a kind of organic synthesis intermediate commonly used.
In the prior art, " organic synthesis topical reference book " (the 395th page, Fan Nengting writes, press of Beijing Institute of Technology, 1992) reported that with terephthaldehyde's dichloro be raw material, react with alkaline hydrolysis agent yellow soda ash, water, reaction obtains 1,4-xylyl alcohol crude product is used ethyl alcohol recrystallization, productive rate 61.9%.Owing to carry out in two-phase, reaction is incomplete among this preparation method, and productive rate is not high.
" Fine Organic Chemical product technical manual " (first volume) (the 256th page, Zhang Si returns the chief editor, Science Press, 1992) reported that with terephthaldehyde's dichloro be raw material, make emulsifying agent with ethanol, react with alkaline hydrolysis agent yellow soda ash, water, obtain 1,4-xylyl alcohol crude product, productive rate 85%.This preparation method adopts ethanol as emulsifying agent, and two phase reaction is the result improve, and the crude product productive rate increases, but the recrystallization productive rate is not high.
US 2,939, and 886 have reported that with terephthaldehyde's dichloro be raw material, with alkaline hydrolysis agent salt of wormwood, water in autoclave 135 ℃ the reaction 11 hours, obtain 1,4-xylyl alcohol, productive rate 84.1%.This method productive rate is not low, but reaction needed carries out in autoclave, and the time is long, and industrial prospect is undesirable.
US 3,546, and 301 have reported that with terephthaldehyde's dichloro be raw material, make emulsifying agent with tetrahydrofuran (THF),, react with alkaline hydrolysis agent salt of wormwood, water under 9000 rev/mins of high-speed stirring more than 85 ℃, form homogeneous mixed solution (" Homomixer "), reacted productive rate 92.7% 3 minutes.This method reaction times is short, and the productive rate height needs carry out under the ultra-high speed condition but react, and to the requirement harshness of reaction unit, the value of application is little, and industrial prospect is undesirable.
Summary of the invention
It is a kind of 1 that the technical problem that the present invention solves provides, the preparation method of 4-xylyl alcohol, and to overcome in the prior art reaction not exclusively, productive rate is low, needs reaction under high pressure, need possess the shortcoming of ultra-high speed condition.
Technical conceive of the present invention is such: with terephthaldehyde's dichloro is raw material, in the presence of phase-transfer catalyst, react in emulsifying agent with alkaline hydrolysis agent, water, from reaction product, obtain 1,4-xylyl alcohol crude product carries out recrystallization, promptly obtains target product of the present invention.
Method of the present invention comprises the steps:
Terephthaldehyde's dichloro, alkaline hydrolysis agent, water are added in the emulsifying agent, in the presence of phase-transfer catalyst, 80-100 ℃ backflow 3-6 hour, collect 1 then from reaction product, 4-xylyl alcohol crude product adds organic solvent and carries out recrystallization, the white crystal that collection is separated out obtains target product.
Raw material terephthaldehyde dichloro used in the present invention be according to " organic synthesis topical reference book " (the 78th page, Fan Nengting writes, press of Beijing Institute of Technology, 1992) by p-Xylol under ultra violet lamp, feed that chlorine prepares; Alkaline hydrolysis agent used in the present invention is yellow soda ash, salt of wormwood, sodium bicarbonate commonly used,
Emulsifying agent used in the present invention is a kind of in tetrahydrofuran (THF), the ethyl acetate.
Phase-transfer catalyst used in the present invention is one or more in 15-hat-5,18-hat-6, the quaternary ammonium salt, preferred 18-hat-6.
The ratio of components of reactant of the present invention is terephthaldehyde's dichloro: water: emulsifying agent=1.0: 6.0-15.0: 0.5-1.5 (mass ratio)
According to the present invention, the ratio of components of reactant is terephthaldehyde's dichloro: the alkaline hydrolysis agent: phase-transfer catalyst=1.0: 1.2-2.0: 0.001-0.01 (mass ratio).
Recrystallization solvent used in the present invention is one or more in methyl alcohol, ethanol, the ethyl acetate.
According to the present invention, the consumption of recrystallization solvent is 1,4-xylyl alcohol crude product: solvent=1.0: 2.0-5.0 (mass ratio).
Reaction formula of the present invention is as follows:
With preparation method of the present invention obtain 1, behind the 4-xylyl alcohol recrystallization, purity reaches more than 99%, productive rate is 85-90%, fusing point is 119-121 ℃.
The present invention is compared with prior art: simple and safe operation, equipment are simple; The present invention has adopted phase-transfer catalyst, and constant product quality, productive rate are significantly improved, and is suitable for suitability for industrialized production.
Embodiment
The invention will be further described below by embodiment, but embodiment does not limit protection scope of the present invention.
Embodiment 1
Having heating, thermometer, mechanical stirring, in the reaction unit of reflux exchanger, the heating of terephthaldehyde's dichloro-4,4 00 gram is dissolved in tetrahydrofuran (THF) 200 grams, adds yellow soda ash 560 grams, water 2400 grams, 18-hat-6 2 grams successively, 95 ℃ of following stirring and refluxing 3 hours.The back steaming that refluxes removes tetrahydrofuran (THF), and cool overnight is separated out white needle-like crystals, purity (HPLC) 98.1%, and productive rate 90%, with 600 gram recrystallizing methanol, purity (HPLC) 99.0%, overall yield: 85%, fusing point: 119.0-121.0 ℃.
Embodiment 2
Having heating, thermometer, mechanical stirring, in the reaction unit of reflux exchanger, the 00 gram heating of terephthaldehyde's dichloro-4,4 is dissolved in tetrahydrofuran (THF) 400 grams, adds yellow soda ash 600 grams, water 4000 grams, 18-hat-64 grams successively.90 ℃ of following stirring and refluxing 5 hours.The back steaming that refluxes removes tetrahydrofuran (THF), and cool overnight is separated out white needle-like crystals, purity (HPLC) 98.3%, and productive rate 95%, with 700 gram ethyl alcohol recrystallizations, purity (HPLC) 99.3%, total yield: 90%, fusing point: 119.8-121.4 ℃.
Embodiment 3
The 00 gram heating of terephthaldehyde's dichloro-4,4 is dissolved in tetrahydrofuran (THF) 600 grams, adds yellow soda ash 700 grams, water 5000 grams, 18-hat-64 grams successively.85 ℃ of following stirring and refluxing 6 hours.The back steaming that refluxes removes tetrahydrofuran (THF), and cool overnight is separated out white needle-like crystals, purity (HPLC) 98.3%, and productive rate 94%, with 650 gram re-crystallizing in ethyl acetate, purity (HPLC) 99.2%, overall yield: 88%, fusing point: 119.6-121.3 ℃.
Claims (8)
1. one kind 1, the preparation method of 4-xylyl alcohol is characterized in that comprising the steps:
Terephthaldehyde's dichloro, alkaline hydrolysis agent, water are added in the emulsifying agent, in the presence of phase-transfer catalyst, 80-100 ℃ backflow 3-6 hour, from reaction product, collect 1 then, 4-xylyl alcohol crude product, the white crystal that recrystallization obtains is target product.
2. method according to claim 1 is characterized in that, said emulsifying agent is a kind of in tetrahydrofuran (THF), the ethyl acetate.
3. method according to claim 1 is characterized in that said phase-transfer catalyst is one or more in 15-hat-5,18-hat-6, the quaternary ammonium salt.
4. method according to claim 3 is characterized in that said phase-transfer catalyst is a 18-hat-6.
5. according to each described method of claim 1-4, it is characterized in that ratio of components is a mass ratio, terephthaldehyde's dichloro: water: emulsifying agent=1.0: 6.0-15.0: 0.5-1.5.
6. according to each described method of claim 1-4, it is characterized in that ratio of components is a mass ratio, terephthaldehyde's dichloro: alkaline hydrolysis agent: phase-transfer catalyst=1.0: 1.2-2.0: 0.001-0.01.
7. method according to claim 1 is characterized in that recrystallization solvent is one or more in methyl alcohol, ethanol, the ethyl acetate.
8. method according to claim 1, the consumption that it is characterized in that recrystallization solvent is a mass ratio, 1,4-xylyl alcohol crude product: solvent=1.0: 2.0-5.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310109034 CN1271022C (en) | 2003-12-03 | 2003-12-03 | Method for preparing 1,4-benzene dimethanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310109034 CN1271022C (en) | 2003-12-03 | 2003-12-03 | Method for preparing 1,4-benzene dimethanol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1623969A CN1623969A (en) | 2005-06-08 |
| CN1271022C true CN1271022C (en) | 2006-08-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310109034 Expired - Fee Related CN1271022C (en) | 2003-12-03 | 2003-12-03 | Method for preparing 1,4-benzene dimethanol |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060668B (en) * | 2010-11-29 | 2014-01-08 | 武汉有机实业有限公司 | Method for preparing o-xylene-alpha, alpha'-diol |
| CN107778129A (en) * | 2016-08-24 | 2018-03-09 | 李长荣化学工业股份有限公司 | The preparation system and preparation method of fragrance derivatives |
| CN109851478B (en) * | 2019-02-27 | 2022-08-12 | 武汉有机实业有限公司 | Dibenzyl alcohol extraction purification method |
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Granted publication date: 20060823 Termination date: 20101203 |