CN1054584A - The preparing phenylacetic acid by chlorobenzyl carbonylation method - Google Patents
The preparing phenylacetic acid by chlorobenzyl carbonylation method Download PDFInfo
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- CN1054584A CN1054584A CN 90110384 CN90110384A CN1054584A CN 1054584 A CN1054584 A CN 1054584A CN 90110384 CN90110384 CN 90110384 CN 90110384 A CN90110384 A CN 90110384A CN 1054584 A CN1054584 A CN 1054584A
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Abstract
Normal pressure carbonylation of benzyl chloride system is the toluylic acid of general formula as above: R=H wherein, He, HeO, Cl, C
2H
5
Co
2(CO)
8Be catalyzer, alkali, alcohols and water are reaction medium, and CO or the industrial tail gas that is rich in CO are unstripped gas, and reaction pressure is a normal pressure, oxidation Co
2(CO)
8Reclaim and bore, alcohol is reclaimed in distillation, produces between the various toluylic acid yield 85-96% with method of the present invention, and purity is about 98%.It is simple that the present invention has technology compared to existing technology, easy to operate, with low cost, pollutes advantages such as few.
Description
The present invention relates to a kind of method by the logical formula II compound of logical formula I compound normal pressure carbonylation system
Wherein R is N, Ne, NeO, Cl, C
2N
5Deng.
Owing in industries such as medicine, agricultural chemicals, spices special purposes is arranged by the substituent toluylic acid that has shown in the formula II, the synthetic method of this compounds also is subjected to people's attention and attention always, sees that wherein work just reaches tens of kinds in the synthetic method of document.
The inventor also once on the existing methods basis, has proposed a kind of synthetic method of more simple economy and has registered patent in China.Therefore, the present invention is improvement and the expansion of CN88104172.6, Here it is, CN88104172.6 extended to from simple toluylic acid method for making be with substituent toluylic acid method for making, obviously the present invention can make full use of the device of described method of CN88104172.6 and foundation, according to different compounds, changes synthesis condition, just can on same set of device, produce dissimilar toluylic acids, and, have equally than US 3,928,429, US 4,060, and 690, clear 48-8094, the more easy and economic characteristics of method such as clear 55-271155 and CN85100362.
For making the public better understand the present invention, in the CN88104172.6 patent of the applicant's application, deficiency and the defective that prior art is existed done detailed narration, also point out simultaneously particularly US3 of above-mentioned prior art, 928,429 existing relatively technology have the reaction conditions gentleness, the product yield advantages of higher, but, as the inventor carefully after the selective reaction condition, obtained better reaction result, product yield substantially exceeds the example that above-mentioned patent exemplifies, and has exposed the not high defective of product yield that above-mentioned prior art exists again.
The present invention has avoided the deficiency of above-mentioned prior art, for the public provides the method for the preparing phenylacetic acid by chlorobenzyl carbonylation under normal pressure of the easier economy of a kind of technology, this place, order of the present invention just ground.
Order of the present invention ground is realized by following measure:
The present invention selects Co for use when the salt of the compound shown in the synthetic formula II
2(CO)
8Make catalyzer, alkali is made neutralizing agent, is reaction medium with the mixed solution of alkali, alcohol and water, and unstripped gas CO also can be selected from industrial tail gas, and the pH value of reaction solution is greater than 7,9-14 preferably, and reaction pressure is a normal pressure, back usefulness oxygenant oxidation Co is finished in reaction
2(CO)
8Oxidation-precipitation method reclaims cobalt, and distillating recovering solvent alcohol also makes the phenylacetate hydrolysis, and the terminal temperature that alcohol is reclaimed in distillation is controlled at below 100 ℃, treat that alcohol steams after, get thick product with hydrochloric acid or sulfuric acid acidation residue mother liquor.
Purpose of the present invention can realize by following measure.
The present invention notices: reaction medium has direct influence to reaction result.In entire reaction course, the composition of reaction medium, the variation of composition all are directly connected to the height of product yield.This means the composition that not only constitutes reaction medium benzyl chloride, be allowed a choice, and the composition of reaction medium to change in reaction process to some extent according to the benzyl chloride of different structure different structure.
In this manual, we are referred to as reaction medium to the solution that alkali, alcohol and water are made into for sake of convenience.The present invention is said, reaction medium is made up of two portions, a part is to make the alkaline solution of neutralizing agent, another part is to make the alcohol of solvent or the mixed solution of alcohol and water, neutralizing agent solution can (being before the reactant benzyl chloride adds the people) be made into reaction medium with solvent earlier in proportion before the reaction beginning, also can in reaction process, join synchronously-go in solvent-reaction medium with reaction mass, obviously, synchronous adding along with neutralizing agent solution and reaction mass (benzyl chloride), in entire reaction course, the composition of reaction medium is constantly to change, and beginning may only be the mixed solution of alcohol or alcohol and water.
When the substituent phenylacetate of anamorphic zone, at first in reactor, add certain part of reaction medium, feed reaction gas CO then, in above-mentioned reaction medium, add CATALYST Co again
2(CO)
8Be heated to about 55 ℃ and constantly and stir, under constantly stirring, add the compound shown in the formula I or add another part reaction medium simultaneously at last, in whole CARBONYLATION PROCESSES, the temperature of reaction system remains on 45-65 ℃, is preferably in 50-60 ℃, and keep the full atmosphere of carbon monoxide or carbon monoxide and rare gas element, the pressure of reaction system is normal pressure, and pressure boost is to instead producing detrimentally affect, if pressure boost more helps reaction or more economical words easily certainly.
When synthetic benzene acetate, the concentration of used alkali lye is 20-40%, is preferably 30 ± 5%, alkali lye can be selected oxyhydroxide, oxide compound or the carbonate preparation of basic metal or alkaline-earth metal for use, but preferably alkali-metal oxyhydroxide, and this alkali is preferably cheap and easy to get, NaON for example, Na
2CO
3, the consumption of alkali is by reaction mol ratio, slightly excessive being advisable.Alcohol or alcohol-water mixture are made reaction solvent, pure optional methyl alcohol, ethanol, Virahol or propyl alcohol, water accounts for 0-15%(weight in alcohol-water mixture), be preferably in 0-10%(weight) between.The add-on of catalyzer is with Co
2(CO)
8And the mol ratio between the halogen benzyl 1: 30-1: 100 are advisable, be preferably in 1: 43-1: between 86, CO can select pure CO or industrial tail gas for use, when CO selects industrial tail gas for use, the purity of CO obviously has tangible influence to reaction, therefore, the content of CO preferably is not less than 85%(weight in the tail gas), when the content of CO unstripped gas is lower than 80%, preferably the content of CO is raise through gas processing, oxious components such as oxygen, sulphur and arsenic in the industrial tail gas, the most handy ordinary method is handled, and can improve reaction yield like this and reduce catalyst consumption.Usually the industrial tail gas of selecting for use has: phosphorus production tail gas, and the cuprammonium resurgent gases, silicon carbide is produced tail gas, and generally between 85-98%, content of harmful gas such as oxygen preferably are no more than 0.1% to the CO content of these industrial tail gas, CO
2Content is no more than 5%, for example: phosphorus production tail gas CO85-97%, CO
22-5%, O
20.1-0.5%; Cuprammonium resurgent gases CO90-99%; Silicon carbide is produced tail gas CO90-97%, and in whole oxonation, the temperature of reaction system should remain on 45-65 ℃, be preferably in 50-60 ℃, and keep carbon monoxide or carbon monoxide and the full atmosphere of rare gas element, and the pressure of reaction system is normal pressure, obviously pressure boost does not have detrimentally affect to reaction.
Above-mentioned reaction can be finished in 3-6 hour, and question response finishes back (CO no longer absorbs), added oxygenant precipitated catalyst Co to reaction solution
2(CO)
8The oxygenant that adds is air or oxygen, obviously bubbling air is more economical, convenient, reasonable, along with air or oxygen constantly feed reaction solution, the color of reaction solution becomes tawny by white powder, show, catalyzer has become cobaltous hydroxide by cobalt-carbonyl, after filtration, and calcination, the rate of recovery of cobalt is more than 90%, the Co that obtains
2O
3Can directly make Co
2(CO)
8
Filtrate (reaction solution) heating, distillation method reclaims solvent alcohol, ester hydrolysis in still-process, terminal temperature is looked different alcohol, is controlled at 90-110 ℃, pH＞7.0 of filtrate (reaction solution), preferably 9-14 helps the hydrolysis of ester like this.The yield of alcohol is more than 80%.
After treating that alcohol steams, solution is chilled to room temperature, with hydrochloric acid or sulfuric acid acidation, endpoint pH is controlled between the 1-2, promptly gets the crude benzol acetic acid product shown in the formula II, and centrifugation gets the technical grade toluylic acid, the concentration of used acid is trapped among 10-40% during acidification, is preferably in 20-30%.
Be with substituent toluylic acid with method production of the present invention, yield can reach 85-95%, and purity is about 98%.
Isolate the waste water of product, the pure and mild cobalt of recovery, reusable, the yield of product there is not obvious influence.
The present invention has following advantage compared to existing technology:
1, whole process of production only need be reacted, and reclaims cobalt, four steps of hydrolysis distillation and acidifying, and also the industrial chemicals that uses is cheap and easy to get, production technique unit, and easy to operate, with short production cycle.
2, CO unstripped gas can use the industrial tail gas that is rich in CO, phosphorus production tail gas for example, and cuprammonium resurgent gases or silicon carbide are produced tail gas, have so both utilized industrial tail gas, have reduced cost again.
3, neutralizing agent NaON can be directly and alcoholic solution be made into reaction medium, perhaps add synchronously with reaction mass, reaction solution only requires it is that alkalescence get final product, makes to operate to become simple and easy to do.
4, air oxidation process is adopted in the recovery of catalyzer cobalt-carbonyl, and it is easy to reclaim technology, does not need to add chemical in addition, with low cost.
5, reaction pressure is a normal pressure.
6, the cobalt of Hui Shouing, methyl alcohol, ethanol, Virahol, propyl alcohol etc. can use repeatedly, to not influence of productive rate.
To be further described under the present invention:
Example 1: 1 liter three-necked bottle of stirring is housed, adds 205 milliliters of industrial methanols, feed small fertilizer plant's cuprammonium resurgent gases, (CO 85.6%, H
27.7%, N
24.5%, through acid-alkali washing and deoxidation treatment) replaced 20 minutes, add 6 gram Co
2(CO)
8, and be heated to＞600 rev/mins of 55 ℃ of stirring velocitys maintenances, drip the solution that 95 industrial benzyl chlorides of gram and 60 gram NaON and 125 ml waters are made into respectively with two dropping funnels.Dripped off in about 2 hours, and continued reaction 2 hours, do not absorb up to CO, reaction terminating, leaches the cobalt slag at bubbling air oxidation half an hour, methyl alcohol is reclaimed in distillation, steams to 100 ℃ always and by product is taken out of cooling with steam, with 20% hcl acidifying, filter washing, get 96% gram phenylethyl alcohol, yield 94.1%, purity 98.66%, fusing point 75.5-76.6 ℃.
Example 2: be similar to aforesaid operations, make source of the gas with pure CO, Co
2(CO)
82 grams, 60 milliliters of methyl alcohol, adjacent chlorobenzyl chloride 31.7 grams and NaOH20 gram are dissolved in the solution of 40 ml waters, get 32.2 gram o-chlorobenzene acetic acid, and yield is 95.8%.
Example 3: be similar to example 1 operation, make source of the gas with pure CO, Co
2(CO)
82 restrain, and in (95%) 80 milliliter of ethanol, dropping restrains in 32 ml water solution methoxyl group benzyl chloride 25 grams and NaON 16, under 50 ℃, drips off in 5 hours, continues reaction 2 hours, gets 24 and restrains yield 90.5%.
Example 4: with the operational condition of example 2, also same just 2.60 ml methanol of catalyzer and reaction raw materials and 5 ml waters are made into solvent, and 15.7 gram NaOH are dissolved in 28 ml waters, react 5 hours, and the productive rate of o-chlorobenzene acetic acid is 74.4%.
Example 5, working method and condition are with example 3, and 12.5,8 gram NaOH are dissolved in 16 ml waters to the methoxyl group benzyl chloride, and 95% ethanol is made solvent for 50 milliliters, drips off in 4 hours, reacts product yield 86.4% again 2 hours.
Example 6, working method and condition are with example 3, and to methoxyl group benzyl chloride 12.5 grams, 8 gram NaOH are dissolved in 13 ml waters, 1.5 gram Co
2(CO)
8Catalyzer, the water of 40 ml methanol and 3 milliliters is made into solvent, drips off in following 3 hours at 60 ℃, continues reaction 2 hours, product yield 64.1%.
Example 7, reaction conditions are with example 6, with Co
2(CO)
8Increase to 2 grams, the reaction times becomes 3.5 hours, yield 60.4%.
Example 8, reaction conditions are with example 3, and 12.5,8 gram NaOH are dissolved in 16 ml waters Co to the methoxyl group benzyl chloride
2(CO)
82 grams are made solvent with 60 milliliters of pure methyl alcohol, react 4.5 hours down in 60 ℃, and productive rate is 49%.
The present invention compares with external patent family
Claims (7)
1, a kind of by general formula (I) compound carbonylation prepare can formula (II) method of compound,
Wherein R is respectively N, Ne, NeO, Cl, C
2H
5, comprising:
1) Co
2(CO)
8Be catalyzer, alkali is neutralizing agent, and CO is a unstripped gas, and the mixed solution of alkali, alcohol and water is a reaction medium;
2) alcohol is reclaimed in air distillation;
3) chemical precipitation method reclaims cobalt;
4) the reaction solution acidifying is made general formula I (II) compound,
It is characterized in that:
(1) alcohol, perhaps the mixed solution of alcohol and water is a reaction solvent;
(2) neutralizing agent alkaline solution and general formula (I) compound joins in the reaction solvent in reaction process synchronously;
(3) the CO unstripped gas is selected from the industrial tail gas that is rich in CO;
(4) oxidation Co
2(CO)
8Reclaim cobalt;
(5) the hydrolysis distillation end point is at 90-110 ℃.
2, the method for claim 1 is characterized in that: in the pure water mixed solvent, alcohol accounts for 85-100%, and water accounts for 0-15%, and ratio is preferably, pure 90-100%, water 0-10%;
3, method as claimed in claim 1 or 2 is characterized in that: when reactant for to the methoxyl group benzyl chloride time, reaction solvent is the alcohol of 90-98%, is preferably ethanol.
4, method as claimed in claim 1 or 2 is characterized in that: when reactant was adjacent chlorobenzyl chloride, reaction solvent was an absolute alcohol, is preferably anhydrous methanol.
5, the method for claim 1 is characterized in that: the pH of reaction medium＞7.0 are preferably 9-14.
6, the method for claim 1 is characterized in that: as CO during from industrial tail gas, the unstripped gas compositing range is:
(1) phosphorus production tail gas: CO 85-97%, CO
22-5%, O
20.10-0.15%;
(2) cuprammonium resurgent gases: CO 80-90%;
(3) silicon carbide is produced tail gas: CO 90-97%.
7, the method for claim 1 is characterized in that: oxidation CO
2(CO)
8Reclaiming the used oxygenant of cobalt is air or oxygen, is preferably oxygen, and most economical is air.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90110384 CN1030192C (en) | 1990-12-31 | 1990-12-31 | Method for prepn. of phenylacetic acid by chloride benzyl carbonylation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90110384 CN1030192C (en) | 1990-12-31 | 1990-12-31 | Method for prepn. of phenylacetic acid by chloride benzyl carbonylation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1054584A true CN1054584A (en) | 1991-09-18 |
| CN1030192C CN1030192C (en) | 1995-11-01 |
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ID=4881886
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90110384 Expired - Fee Related CN1030192C (en) | 1990-12-31 | 1990-12-31 | Method for prepn. of phenylacetic acid by chloride benzyl carbonylation |
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|---|---|
| CN (1) | CN1030192C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070433A (en) * | 2010-12-27 | 2011-05-25 | 桂林师范高等专科学校 | Preparation method for aryl acetic acid derivative |
| DE102012224021A1 (en) | 2012-05-09 | 2013-11-14 | Lanzhou Institute Of Chemical Physics, Chinese Academy Of Sciences | A process for the synthesis of phenylacetic acid by carbonylation of toluene |
| CN109438215A (en) * | 2018-11-12 | 2019-03-08 | 西南化工研究设计院有限公司 | A kind of method of carbonylation synthesis phenylacetic acid |
-
1990
- 1990-12-31 CN CN 90110384 patent/CN1030192C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070433A (en) * | 2010-12-27 | 2011-05-25 | 桂林师范高等专科学校 | Preparation method for aryl acetic acid derivative |
| CN102070433B (en) * | 2010-12-27 | 2013-03-27 | 桂林师范高等专科学校 | Preparation method for aryl acetic acid derivative |
| DE102012224021A1 (en) | 2012-05-09 | 2013-11-14 | Lanzhou Institute Of Chemical Physics, Chinese Academy Of Sciences | A process for the synthesis of phenylacetic acid by carbonylation of toluene |
| US8921591B2 (en) | 2012-05-09 | 2014-12-30 | Lanzhou Institute Of Chemical Physics, Chinese Academy Of Sciences | Process for synthesizing phenylacetic acid by carbonylation of toluene |
| CN109438215A (en) * | 2018-11-12 | 2019-03-08 | 西南化工研究设计院有限公司 | A kind of method of carbonylation synthesis phenylacetic acid |
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| Publication number | Publication date |
|---|---|
| CN1030192C (en) | 1995-11-01 |
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