CN101381285A - High-purity 4-n-alkyl phenol preparation method - Google Patents
High-purity 4-n-alkyl phenol preparation method Download PDFInfo
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- CN101381285A CN101381285A CNA2008101558448A CN200810155844A CN101381285A CN 101381285 A CN101381285 A CN 101381285A CN A2008101558448 A CNA2008101558448 A CN A2008101558448A CN 200810155844 A CN200810155844 A CN 200810155844A CN 101381285 A CN101381285 A CN 101381285A
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- alkylphenol
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Abstract
The invention relates to a method for preparing high-purity 4-n-alkylphenol. The method comprises the following steps: mixing anisole and n-alkyl acyl chloride in the presence of a super acidic catalyst of ferric oxide-sulfuric acid solid, carrying out reaction of the mixture at a temperature of between 40 and 60 DEG C to generate p-acyl-anisole, and then reducing the p-acyl-anisole through hydrazine hydrate to obtain alkylphenol. The reaction in the method has specificity without ortho position and meta position products, recomposes side reaction, and the generation of carbon-carbon double bond, and directly obtains the high-purity alkylphenol, thus the method can reduce the cost and the environment pollution; besides, the yield is between 65 and 85 percent, and the prepared high-purity 4-n-alkylphenol can be used for preparing intermediates of liquid crystal materials.
Description
Invention field
The present invention relates to the preparation method of the positive alkylphenol of high purity 4-, this compound can be used for chemical intermediate, particularly the intermediate of synthesizing compound of liquid crystal.
Background technology
Liquid crystal material wherein shows with the nematic liquid crystal material it is a kind of liquid crystal material with fastest developing speed, market occupancy volume maximum along with the development of liquid-crystal display (LCD) develops rapidly.Nematic liquid crystal shows liquid-crystal displays (LCD) such as TN (twisted-nematic phase) pattern, STN (supertwist nematic phase) pattern, TFT (thin film transistor) pattern, PDLC (Polymer Dispersed Liquid Crystal) pattern, DS (dynamic scattering) pattern, GH (host and guest) pattern, ECB (electrically conerolled birefringence) pattern, OCB (light-operated double refraction) pattern DAP pattern.Wherein the TFT pattern is extremely many welcomes and attention.Particularly the TFT type has obtained remarkable development in the colored TV liquid-crystal display of high-resolution in recent years, and industrial scale constantly enlarges.Along with developing rapidly of information industry, the demand of liquid crystal indicator increases year by year, has higher requirement as the liquid crystal material that shows usefulness, and the research and development of new liquid crystal material makes fast progress.Develop into novel fluorinated liquid crystal compound from original various alkylphenol esters liquid crystal compounds gradually to alkyl-cyclohexyl (connection) benzene class liquid crystalline cpd, for example alkyl-cyclohexyl fluorine-containing (connection) benzene class, ethyl bridged bond class, alkene end group fluorine-containing aromatic ring class liquid crystalline cpd and various constitutionally stable difluoroethylene class liquid crystalline cpd, its molecular structure is more and more stable, more can satisfy the liquid-crystal display performance requriements.
At present, the fluorinated liquid crystal material mostly is alkyl-cyclohexyl fluorinated liquid crystal compound, and the synthetic of these liquid crystalline cpds need the positive alkylphenol of use 4-be basic intermediate mostly.
The synthetic method of the positive alkylphenol of 4-has multiple at present, and useful Acylphenol is directly used zinc amalgam and hydrochloric acid reduction method, the purity height of this method, and it is synthetic to be suitable for very much liquid crystal; But there is the serious environmental pollution problem in its cost height, and atom utilization is low.Useful alkylbenzene oxidation preparation method, its synthetic cost height is unfavorable for industrial production.
Utilized in recent years Fatty Alcohol(C12-C14 and C12-C18) or haloalkane or alkene and phenol Fu Ke alkylation process (CN1681758, CN1504445), but this method exists alkyl to reset and the ortho position product, the alkylphenol that obtains is not suitable for liquid crystal material and synthesizes.Also useful alkylbenzene methyl ether gets through the demethylation method, though this method productive rate height, cost is also high, (sees " petroleum journal ", 2008,24 (3): 294-298) so seldom use.
Summary of the invention
The purpose of this invention is to provide a kind of productive rate height, cost is lower, a kind of novel synthesis of the positive alkylphenol of 4-that atom utilization is higher.
The present invention prepares the positive alkyl phenol processes of 4-; in the presence of Indian red-sulfuric acid solid super acid catalyst, be that the positive alkyl acyl chloride of 3-12 mixes with methyl-phenoxide and carbon number, under 40-60 ℃ condition, react again; generation aligns the acyl group methyl-phenoxide, then obtains alkylphenol through hydrazine hydrate reduction.
Said temperature of reaction is preferably 45-50 ℃, reacts 4-5 hour.
In the said hydrazine hydrate reduction process, after 4-acyl group methyl-phenoxide and hydrazine hydrate refluxed 6 hours, add potassium hydroxide and a small amount of methyl-sulphoxide; 140 ℃-170 ℃ of temperature controls; react after 4-6 hour temperature of reaction is brought up to 200 ℃-210 ℃, reacted 3-4 hour, obtain the 4-alkylphenol.
Present method alkylbenzene methyl ether in the reduction reaction process removes methyl, directly generates product 4-alkylphenol.Reaction has specificity, does not have ortho position and metacompaund, does not reset side reaction, does not have carbon-carbon double bond to produce, and obtains high-purity alkylphenol.
Present method prepares the 4-alkylphenol and can reduce cost, and reduces environmental pollution; Productive rate reaches 65%-85%, and the positive alkylphenol of the 4-that makes can be used for the industrial production of liquid crystal material.
Specific embodiment
Synthesizing of embodiment 1 pentanoyl methyl-phenoxide
In the 500mL there-necked flask, add 3g ferric oxide-sulfuric acid solid acid catalyst and 16.7g methyl-phenoxide fast, start and stir and heating, begin to drip the 20g valeryl chloride, controlled temperature 45-50 ℃, after dropwising in about 1 hour, about 45 ℃ of holding temperatures continue to stir 4 hours.Remove by filter catalyzer, add the 50mL methylene dichloride, reaction solution is slowly poured in the 10ml saturated sodium bicarbonate solution, stirred 5-10 minutes, add 50ml water flushing there-necked flask again and pour wherein static layering into.Separate water layer and use the 50ml dichloromethane extraction more once, merge organic layer.Organic layer is used the water washing secondary of 50ml * 2 again, separates the water purification layer.With 2g anhydrous sodium sulfate drying 3 hours; Filter back normal pressure steaming vibrating dichloromethane.Carry out underpressure distillation with water pump again, collect 200-205 ℃/0.09Mpa fraction, obtain the 25.3g white solid and be pentanoyl methyl-phenoxide, gas chromatographic purity 98.5%, be provided with down embodiment and use.
One of embodiment 2 amyl phenol synthesis examples
In three mouthfuls of glass flask of 100mL, add 19.2g pentanoyl methyl-phenoxide, the hydrazine hydrate of 13ml (80%), 50ml one condensed ethandiol.Reflux 6 hours, temperature is about 120 ℃.The hydrazine hydrate that distillation water outlet and unreacted are intact is to about 160 ℃ of fluid temperatures.Be cooled to again about 80 ℃, add 6 gram potassium hydroxide and 5ml exsiccant methyl-sulphoxides.Be stirred and heated to 145 ℃, have a large amount of bubbles to emit, continue the heating temperature control, stirred 5-8 hours at 150-170 ℃.Add thermal distillation and make temperature of reaction reach 210 ℃, stirred 3-4 hour, stop heating and stirring.
Cold water is cooled to below 100 ℃, adds 100ml water, adds 50ml * 2 methylbenzene extraction twice again, and toluene liquid is placed, and focuses on.
In water layer, add the 10ml concentrated hydrochloric acid, stirred static layering 5 minutes.After product told, water layer was used 50ml * 2 methylbenzene extraction twice again, merged gas producing formation.Gas producing formation is washed three times with 20ml * 3, divides the water purification layer.After 3 hours, boil off toluene with the 2g anhydrous sodium sulfate drying after the filtration.Carry out underpressure distillation again, collection 13.9g colourless liquid (120-125 ℃/1mmHg), productive rate 80%; Gas chromatographic purity 99.3%.
Embodiment 3: two of amyl phenol synthesis example
In three mouthfuls of glass flask of 100mL, add 19.2g pentanoyl methyl-phenoxide, the hydrazine hydrate of 13ml (80%), the 50ml glycol ether, reflux 6 hours, temperature is about 120 ℃.The hydrazine hydrate that distillation water outlet and unreacted are intact, about 180 ℃ of temperature.When treating that temperature drops to below 120 ℃, add 6 gram potassium hydroxide.Add about thermal distillation to 210 ℃, begin to emit a large amount of nitrogen bubble, temperature of reaction was controlled at about 210-220 ℃ backflow 5-6 hour.Stop heating, cold water cools to below 100 ℃, adds 100ml water, adds 50ml * 2 methylbenzene extraction twice again, and toluene liquid focuses on after collecting.
In water layer, add the 10ml concentrated hydrochloric acid, stirred static layering 5 minutes.After product told, water layer was used 100ml * 2 methylbenzene extraction twice again, merged gas producing formation.Gas producing formation is washed three times with 50ml * 3, divides the water purification layer.Behind the 2g anhydrous sodium sulfate drying, boil off toluene after the filtration.Carry out underpressure distillation again, collection 10.7g product (120-125 ℃/1mmHg), productive rate 65%.Gas chromatographic purity 99.0%.
Claims (4)
1. the preparation method of the positive alkylphenol of high purity 4-; it is characterized in that in the presence of Indian red-sulfuric acid solid super acid catalyst, methyl-phenoxide is mixed with positive alkyl acyl chloride, under 40-60 ℃ condition, react again; generation aligns the acyl group methyl-phenoxide, then obtains alkylphenol through hydrazine hydrate reduction.
2. the preparation method of the positive alkylphenol of high purity 4-according to claim 1; it is characterized in that in the said hydrazine hydrate reduction process; after 4-acyl group methyl-phenoxide and hydrazine hydrate refluxed 6 hours; add potassium hydroxide and a small amount of methyl-sulphoxide; 140 ℃-170 ℃ of temperature controls; react after 4-6 hour temperature of reaction is brought up to 200 ℃-210 ℃, reacted 3-4 hour, obtain the 4-alkylphenol.
3. the preparation method of the positive alkylphenol of high purity 4-according to claim 1 is characterized in that said methyl-phenoxide and positive alkyl acyl chloride reaction temperature are 45-50 ℃, reacts 4-5 hour.
4. according to the preparation method of claim 1 or the positive alkylphenol of 2 or 3 described high purity 4-, it is characterized in that positive alkyl acyl chloride carbon number is 3-12.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008101558448A CN101381285A (en) | 2008-10-17 | 2008-10-17 | High-purity 4-n-alkyl phenol preparation method |
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| CNA2008101558448A CN101381285A (en) | 2008-10-17 | 2008-10-17 | High-purity 4-n-alkyl phenol preparation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159596A (en) * | 2011-12-14 | 2013-06-19 | 南京华狮化工有限公司 | Preparation method for 4-butylresorcinol |
| CN105016979A (en) * | 2015-08-07 | 2015-11-04 | 湖北荆洪生物科技股份有限公司 | Synthesis method of 4-n-alkyl substituted phenol |
| CN110272747A (en) * | 2018-03-15 | 2019-09-24 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal composition containing from orientation compound and its application |
-
2008
- 2008-10-17 CN CNA2008101558448A patent/CN101381285A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159596A (en) * | 2011-12-14 | 2013-06-19 | 南京华狮化工有限公司 | Preparation method for 4-butylresorcinol |
| CN105016979A (en) * | 2015-08-07 | 2015-11-04 | 湖北荆洪生物科技股份有限公司 | Synthesis method of 4-n-alkyl substituted phenol |
| CN110272747A (en) * | 2018-03-15 | 2019-09-24 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal composition containing from orientation compound and its application |
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Application publication date: 20090311 |