CN1927801A - Preparation method of methylphenyl acetic acid - Google Patents
Preparation method of methylphenyl acetic acid Download PDFInfo
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- CN1927801A CN1927801A CN 200610124563 CN200610124563A CN1927801A CN 1927801 A CN1927801 A CN 1927801A CN 200610124563 CN200610124563 CN 200610124563 CN 200610124563 A CN200610124563 A CN 200610124563A CN 1927801 A CN1927801 A CN 1927801A
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Abstract
The present invention provides technological process of producing methyl phenylacetic acid. The technological process includes hydrolyzing corresponding methyl benzyl cyanide, such as o- methyl benzyl cyanide, p-methyl benzyl cyanide or m-methyl benzyl cyanide, in sulfuric acid solution to obtain course product; the subsequent neutralizing with alkali solution to obtain sodium salt; and final aciding out with inorganic acid, water washing and drying. The technological process of the present invention is simple, stable, and suitable for industrial production.
Description
Technical field
The present invention relates to the manufacture method of Chemicals, particularly prepare the method for methylphenyl acetic acid.
Background technology
The methylphenyl acetic acid thing as adjacent (to) methylphenyl acetic acid, its () is a kind of important organic chemical industry's fine chemicals intermediate, is mainly used in to make agricultural chemicals (as described in patent WO 03035636/2003 year, GR 3036239T/2001, US 6008381/1999 year, CN 1222150A/1999, WO 9748692A1/1997) and medicine and corresponding ester class etc.
The disclosed report document of the preparation of methylphenyl acetic acid thing is actually rare, but its similar compound---the synthetic and manufacture method of toluylic acid is then very many, and as known preparation method, for example, it can be by following method preparation; 1. oxo synthesis (comprising non-pressure process and high-pressure process)---with the Benzyl Chloride is raw material, gets (chemistry world, [1996] 4,360～362 with the reaction of CO and NaOH liquid under catalyzer; J.Org.Chem., [1985], 2134～3136 etc.); 2. benzyl cyanide hydrolysis method (comprising acid hydrolyzation and alkaline hydrolysis method)---with benzyl cyanide and aqueous sulfuric acid reaction and or benzyl cyanide and alkali lye reacted again get (Xu Kexun edits, meticulous Organic Chemicals and intermediate, [1998], 3～231) through acidifying; 3. the phenylacetamide hydrolysis method---by vinylbenzene is raw material, through making phenylacetamide with ammoniacal liquor, sulfur reaction, again through get (Liaoning chemical industry, [1994] 3,42～45 with sulphuric acid hydrolysis; CN1110677A); 4. phenylcarbinol method---by phenylcarbinol and CO reaction under high pressure and get (Anhui chemical industry, [2002] 4,19～20) under catalyzer; 5. benzene method---by benzene, formaldehyde and CO reaction under high pressure and getting under catalyzer; 6. benzene hexanone method---by the benzene hexanone is raw material, gets through hydrolysis after oxidation gets methyl phenylacetate (chemistry and biotechnology, [2005] 2,43～44) again; 7. electrochemical process---Benzyl Chloride is synthesized into (Speciality Petrochemicals, [1993] 3,36～39) with the anode electrolysis method in solvent and Tetrabutyl amonium bromide electrolytic solution.In above-mentioned method, the 2nd and the 1st kind of method study at most both at home and abroad at present, its technology is also ripe, and is applied in the suitability for industrialized production.
The hydrolysis of cyano group prepares this well-known process of organic hydroxy acid, it Duan Hangxin compile " practical Minute Organic Synthesis handbook has detailed description in (January calendar year 2001 first version, the 94th～100 page).
In above-mentioned technological process, cyano group can be with alkali or acid hydrolysis: (1) in reactor nitrile and NaOH water liquid in 100 ℃ of following back flow reaction 7～10h, the sodium salt that reaction generates dissolves in water layer, and remaining nitrile and other impurity can be used organic solvent extraction in the top oil reservoir; The water layer hcl acidifying leaches crystal, and washing gets product after the drying, and yield is 52～75%.For reaction is carried through to the end, commonly used excessive 10～20% alkali need add ethanol sometimes to improve reaction conditions.(2) acid hydrolysis 30～70% the H that is everlasting
2SO
4In carry out, under 100～130 ℃, nitrile joins fierce thermopositive reaction takes place in the reactor immediately, the carboxylic acid of generation is directly separated from reactant.The first step of acidolysis is to generate acid amides, continues hydrolysis again and generates carboxylic acid; For this reason, crude product need distill or smart agent such as recrystallization, and total recovery is 75～85%.In general adopt acidolysis process more more general than alkaline hydrolysis technology, unless have ether on the nitrile compound, hydrolysis also can take place in it in acid liquid.From another point of view, the hydrolysis of cyano group is one of important method of preparation organic carboxyl acid; Comparatively speaking, nitrile is easy to make from halohydrocarbon, also more easily purchases in market.In a word, there are shortcomings such as operation is complicated, cost is higher, efficient is lower in old technology.
Summary of the invention
The purpose of this invention is to provide that a kind of operating process is easy, stable, efficient is high, be easy to the manufacture method of the methylphenyl acetic acid of suitability for industrialized production.
Technical solution of the present invention is: under 90～150 ℃ temperature, the methylbenzene acetonitrile is slowly joined the 30～70%H for preparing in advance continuously
2SO
4In the liquid, the reinforced back insulation back flow reaction that finishes; The turnover ratio of control nitrile, when nitrile component concentration (GC) residual in the reaction mass but less than 0.1～1% the time stopped reaction.After reaction mass leaves standstill cooling slightly, emit lower floor's sour water and salt; The brown oil reservoir in upper strata---methylphenyl acetic acid is neutralized to pH=7.5～10 with alkali, and material leaves standstill after-filtration slightly in 50～90 ℃ of quantitative activated carbon adsorption of adding, decolouring then.The filtrate that obtains is acidified to pH=1～4 with mineral acid, stirs cooling down and separates out product; When temperature of charge is reduced to 20～60 ℃, emit product and carry out suction filtration.With clear water washed product 1～3 time, again behind the centrifugation moisture, dry, the film-making methylphenyl acetic acid that gets product.
Above-mentioned methylbenzene acetonitrile comprises the o-methyl-benzene acetonitrile, to a methylbenzene acetonitrile and a methylbenzene acetonitrile; The methylphenyl acetic acid thing comprises o-Tolylacetic acid, to methylphenyl acetic acid and m-Tolylacetic acid.
Selected neutralization comprises NaOH, KOH or Na with alkali in the above-mentioned technology
2CO
3And acidifying comprises hydrochloric acid and sulfuric acid with mineral acid.
Preferred acid hydrolysis process of the present invention prepares the methylphenyl acetic acid thing, is because the yield of basic hydrolysis technology on average is lower than 75%; In basic hydrolysis technology, the methylbenzene acetonitrile generates the height polymkeric substance impurity such as (III) that boils easily.Also finding in our research has ester (IV) to exist, and the acid generation esterification that trace methyl phenylcarbinol that this may be with from raw material methylbenzene acetonitrile and acid hydrolysis generate produces.Comparatively speaking, the acid hydrolysis process by-product impurities is handled easily than the impurity of basic hydrolysis technology, and the former production cycle much shorter.
(compound III) (compound IV)
Usually acid hydrolysis is the H 35～70%
2SO
4In carry out, acid concentration low more, speed of reaction is slow more, its transformation efficiency is also low; Then react hardly when following and carry out when the concentration of acid is lower than 20%.Our H of preferred 50 ~ 70% in technology
2SO
4Its main reaction formula is as follows:
Methylbenzene acetonitrile methylbenzene ethanamide
Methylbenzene ethanamide methylphenyl acetic acid
In above-mentioned reaction mass system, to react completely and improve product yield in order to impel, the amount of sulphuric acid soln needed 5～60% (mol than).
The refining general distillation or the recrystallization used of thick acid.For the material of toluylic acid class, because of its boiling point higher, during rectifying very easy cause acid decarboxylation and influence quality and yield, so many waters crystallization process is made with extra care in the present domestic production toluylic acid.Almost insoluble in water under the product methylphenyl acetic acid normal temperature of the present invention, the solubleness 2[g/100ml water of also only having an appointment near 100 ℃ the time], therefore can not select for use water to come recrystallized product.As for waiting recrystallization with organic solvent such as trichloromethane, pimelinketone or toluene, though can obtain high-quality product, but in the technology because of having used expensive inflammable and explosive organic solvent, first to bringing great safety and environmental protection hidden danger on the industrial production line, second increase the consumption of organic solvent and the production operation expense of recovery organic solvent, and then increased production cost.
At above-mentioned difficult point of the prior art, the invention provides the refining technique that a kind of production cost is low, be easy to suitability for industrialized production: crude product is used liquid caustic soda again, and (20～48%NaOH) neutralizations obtain corresponding sodium salts, under 50～90 ℃, add the organic impurity and the decolouring of quantitative activated carbon adsorption trace, mother liquor after the filtration obtains crystal or solid through the mineral acid acid out, removes inorganic salt solution (Na
2SO
4), solid again through washing, desalination, dry after and obtain finished acid.
The used alkali of neutralization has NaOH, KOH or Na in the technology of the present invention
2CO
3From quality guarantee and cost, our preferred liquid caustic soda---20～48%NaOH.The mineral acid available that acidifying is used has hydrochloric acid and sulfuric acid, consider hydrochloric acid to equipment corrosion greatly and to the operation site environmental pollution, still preferably come acidifying with sulfuric acid (20～50%).
Not only require its main content to reach 99% (GC) as commodity with sour quality index, but also other various impurity individual events of special requirement all must not be big or small by 0.1%, and this is to descend degradation because some impurity can greatly influence next step utilization significantly as making catalyst deactivation, reaction conversion rate.Behind the organic impurity and decolouring with the activated carbon treatment trace in this technology, the content of product can be stabilized in more than 99% (GC), and other requirement also all can be satisfied; The consumption of activated carbon by 1～5% (massfraction) of throwing nitrile raw materials quality.
In the same finished product ash content---inorganic salt also are one of important indicators that influences quality.In order to guarantee the purity of finished product, after acidifying, need to reduce as far as possible the product of separating out and carry salt secretly, for this reason we control product acid in water the cooling precipitation rate and the size of solids, make its dispersion as far as possible.
In order to reduce discharge of wastewater in the technological process, wherein the salt solution after the washing can recycle as removing dilute acid or alkali behind cooling, sedimentation desalination.
In sum, operational process of craft of the present invention is easy, stable, and cost is low, is suitable for suitability for industrialized production.
Embodiment
The present invention can further specify its technological process in conjunction with following embodiment, and the following example is usefulness as an illustration only, and unrestricted protection scope of the present invention.
Embodiment 1,
In the four-hole boiling flask of 500ml, add 100 gram water earlier, under agitation slowly add 98% vitriol oil, 240 grams (2.40mol).Be warming up to 90 ℃ after a while, and restrain 90～150 ℃ of slow down droppings 200 (98%, 1.50mol) o-methyl-benzene acetonitrile; Control rate of addition in the dropping process, guarantee that temperature of reaction is not less than 90 ℃.Dropwise, insulation back flow reaction 5～6 hours, the timing sampling analysis, the o-methyl-benzene ethane nitrile content (GC) in material in the flask is formed but less than 0.2% the time stopped reaction.Add warm water 50 grams then, stirred 10 minutes, make monoammonium sulfate dissolving and cooling, pour out reaction solution to beaker, the insulation left standstill 15 minutes, incline upper strata light brown red oily material pour into be equipped with 400 the gram water 1000 ml beakers in, the limit is stirred following slowly cooling and is separated out product, filter wet crude product of lurid o-Tolylacetic acid particle or crystal, about 260 grams, content (GC) 97.58%.
Above-mentioned crude product is put into 2000 ml beakers, drop into 600～800g clear water, be warming up to 60～90 ℃, under agitation slowly add 30%NaOH liquid to pH=8～9 and obtain corresponding o-Tolylacetic acid sodium salt.Add activated carbon (1～5%wt is in the crude product o-Tolylacetic acid) after a while, stirred 10 minutes, suction filtration was left standstill in insulation 10 minutes.Filtrate places 2000 ml beakers again, under agitation slowly adds 40%H
2SO
4Liquid is to pH=2～3; Insulation was left standstill 10～15 minutes, incline and upper strata light yellow oil material and pour into and stir down slowly cooling in 1000 ml beakers that 400 gram water are housed and separate out product, filter and wash 2 times and get yellowish wet granulation with distilled water or clear water, after 30 ~ 50 ℃ of following dryings, get o-Tolylacetic acid finished product 202.8g, content (GC) 99.62%; 87.8～89.9 ℃ of fusing points (literature value: 87～90 ℃); Yield: 90.05%.
Embodiment 2,
In the four-hole boiling flask of 500ml, add 90 gram water earlier, under agitation slowly add 98% vitriol oil, 135 grams (1.35mol).Be warming up to 90 ℃ after a while, and (98%, 1.12mol) to the methylbenzene acetonitrile, other operation is the same slowly to drip 150 grams down at 90～150 ℃.Must be white to methylphenyl acetic acid finished product 145.2g, content (GC) 99.80%; 91.5～92.5 ℃ of fusing points (literature value: 90～93 ℃); Yield: 86.10%.
Embodiment 3,
In the four-hole boiling flask of 500ml, add 100 gram water earlier, under agitation slowly add 98% vitriol oil, 240 grams (2.40mol).Be warming up to 90 ℃ after a while, and restrain 90～150 ℃ of slow down droppings 200 (98%, 1.50mol) o-methyl-benzene acetonitrile, other is operated with embodiment 1.When reaction is finished, be cooled to 80 ℃, add toluene 300ml then, stirred 10 minutes, tell organic phase, water is used 2 * 100ml toluene extracting twice respectively again, merges organic phase, washs 2 times with distilled water or clear water.Organic phase is stirred bottom slowly to be cooled to 3～5 ℃ and to make it to separate out the sheet white crystal; It is air-dry down in room temperature (20～30 ℃) to filter the back, gets o-Tolylacetic acid finished product 180.3g, content (GC) 99.73%; 88.0～90.0 ℃ of fusing points (literature value: 87～90 ℃); Yield: 80.14%.
Claims (4)
1, a kind of manufacture method of methylphenyl acetic acid is characterized in that: under 90～150 ℃ temperature, the methylbenzene acetonitrile is slowly joined the 30～70%H for preparing in advance continuously
2SO
4In the liquid, the reinforced back insulation back flow reaction that finishes; The turnover ratio of control nitrile, but when nitrile component concentration residual in reaction mass stopped reaction less than 0.1～1% time; After the quiet slightly cooling of reaction mass, emit lower floor's sour water and salt; Brown oil reservoir-the methylphenyl acetic acid in upper strata is neutralized to PH=7.5～10 with alkali, and material adds quantitative activated carbon adsorption, decolouring, static slightly after-filtration for 50～90 ℃ in temperature then; The filtrate that obtains is acidified to PH=1～4 with mineral acid, stirs cooling down and separates out product; When temperature of charge is reduced to 20～60 ℃, emit product and carry out suction filtration; With clear water washed product 1～3 time, again behind the centrifugation moisture, dry, the film-making methylphenyl acetic acid that gets product.
2, by the manufacture method of the described methylphenyl acetic acid of claim 1, it is characterized in that: above-mentioned selected material methylbenzene acetonitrile includes the o-methyl-benzene acetonitrile, to a methylbenzene acetonitrile and a methylbenzene acetonitrile.
3, by the manufacture method of the described methylphenyl acetic acid of claim 1, it is characterized in that: above-mentioned selected neutralization includes NaOH, KOH or Na with alkali
2CO
3
4, by the manufacture method of the described methylphenyl acetic acid of claim 1, it is characterized in that: above-mentioned selected acidifying comprises hydrochloric acid and sulfuric acid with mineral acid.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643192A (en) * | 2012-03-29 | 2012-08-22 | 常熟市新港农产品产销有限公司 | Preparation method of methoxyphenylacetic acid |
| CN106278861A (en) * | 2016-08-24 | 2017-01-04 | 河北诚信有限责任公司 | A kind of method preparing substituted phenylacetic acid |
| CN113861011A (en) * | 2021-10-15 | 2021-12-31 | 江苏鸣翔化工有限公司 | Production process of o-methylphenylacetic acid |
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| CS169541B1 (en) * | 1974-09-20 | 1976-07-29 | ||
| CS169546B1 (en) * | 1974-09-26 | 1976-07-29 | ||
| RO86313B1 (en) * | 1983-05-07 | 1985-03-31 | Institutul De Cercetari Chimico-Farmaceutice | Process for preparing phenylacetic acid |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643192A (en) * | 2012-03-29 | 2012-08-22 | 常熟市新港农产品产销有限公司 | Preparation method of methoxyphenylacetic acid |
| CN106278861A (en) * | 2016-08-24 | 2017-01-04 | 河北诚信有限责任公司 | A kind of method preparing substituted phenylacetic acid |
| CN106278861B (en) * | 2016-08-24 | 2019-05-14 | 河北诚信集团有限公司 | A method of preparing substituted phenylacetic acid |
| CN113861011A (en) * | 2021-10-15 | 2021-12-31 | 江苏鸣翔化工有限公司 | Production process of o-methylphenylacetic acid |
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| CN100455557C (en) | 2009-01-28 |
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