CN1284406A - Catalyst for catalytic carboxylation to synthesize phenylacetic acid - Google Patents
Catalyst for catalytic carboxylation to synthesize phenylacetic acid Download PDFInfo
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- CN1284406A CN1284406A CN 00114646 CN00114646A CN1284406A CN 1284406 A CN1284406 A CN 1284406A CN 00114646 CN00114646 CN 00114646 CN 00114646 A CN00114646 A CN 00114646A CN 1284406 A CN1284406 A CN 1284406A
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- phenylacetic acid
- pyridine
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Abstract
The present invention relates to a new catalyst, pyridine-2-carboxylic cobalt and substituted pyridine-2-carboxylic cobalt, for the direct catalytic carboxylation of CO and benzyl halide to synthesize phenylacetic acid. The synthesis of phenylacetic acid is performed in the conditions of 0.1-3.0 MPa pressure, 40-100 deg.C temperature and catalyst concentration of 0.01-5.0 molarity. The synthesized product is first neutralized in the reactor to produce organic carboxylate, which is then separated and acidified to obtain phenylacetic acid. The catalyst of the present invention has high activity. and is easy to prepare and store, oxygen and water resistant, and reusable.
Description
The present invention is a kind of new catalyst-pyridine-2-carboxylic acids cobalt and substituent pyridine-2-carboxylic acids cobalt that is used for carbon monoxide and the direct catalytic carboxylation to synthesize phenylacetic acid technology of halogen benzyl.
The carbonylation method synthesize phenylacetic acid is a kind of new technology of developing since the sixties.This technology is in the presence of catalyst, by benzyl chloride and reaction of carbon monoxide synthetic benzene acetate, obtains phenylacetic acid through acidifying again, and the characteristics of this technology are the reaction condition gentlenesses, raw material low toxicity, cheap.Its reaction equation is as follows:
Up to now, above-mentioned according to the literature catalyst for reaction mainly is the complex compound of cobalt octacarbonyl, carbonyl cobalt salt and palladium, rhodium.L.Cassar (US 4128572,1978) is a catalyst with cobalt tetracarbonyl sodium, in water/organic facies two-phase system, and halogen benzyl carboxylation to synthesize phenylacetic acid, the productive rate of phenylacetic acid can reach 87%.(J.Organometallic Chem., 1990,382:419～421) such as Sang Chul Shim are found at Co
2(CO)
8/ KOH/C
6H
6In the system, be phase transfer catalyst with the benzyltriethylammoinium chloride, CO pressure 0.1MPa, under the room temperature, bromobenzyl carboxylation to synthesize phenylacetic acid, productive rate 93%.L.Cassar (J.Organometallic Chem., 1976,134:15) studied (PPh at Pd
3)
4/ t-Bu
4NX/PhCH
3/ H
2In the O/NaOH system, the technology that halogen benzyl oxonation has synthesized phenylacetic acid obtains the productive rate 84% of phenylacetic acid.1988, (J.Mol.Catal., 1988,44:179～181) such as Taqui Khan were catalyst with water miscible Ru (III)-EDTA complex compound, also can be with the halobenzene carboxylation to synthesize phenylacetic acid.
Domestic, primary track Asia, gold woods (Liaoning chemical industry, 1990,6:22) having studied with the carbonyl cobalt sodium is catalyst, and under alkali condition, benzyl chloride and carbon monoxide oxonation generate sodium phenylacetate, obtain the technology of phenylacetic acid again through acidifying, the productive rate of phenylacetic acid can reach 80%, selectivity 99%.Li Guangxing, Liu Yong [applied chemistry, 1998,15 (1): 116] has prepared cobalt tetracarbonyl sodium with the former cobalt method of lacquer, and the activity of its carboxylation to synthesize phenylacetic acid is studied, and under optimum reaction condition, the productive rate of phenylacetic acid is 90%, and selectivity is more than 99%.Li Hongbing etc. (fine chemistry industry, 1996,13:45～48) utilize industrial waste gas (tail gas of the ammoniacal copper solution scrubbing generated gas of chemical fertilizer factory and yellow phosphorus factory), under normal pressure, and Co
2(CO)
8The catalytic carbonylation benzyl chloride prepares phenylacetic acid, and productive rate can reach 90%, and product purity is more than 99%.
From present bibliographical information as can be seen, the synthetic employed catalyst of phenylacetic acid of halogen benzyl carbonylation is the complex compound of cobalt octacarbonyl, carbonyl cobalt salt and palladium, rhodium.Above-mentioned activity of such catalysts is higher, but the preparation difficulty of cobalt carbonyl catalyst, and stability is very poor, store and transportation all very difficult, the separation of reaction back cobalt and reclaim and all be difficult to solve, and palladium, using rhodium complex catalysts costliness lack using value, are unfavorable for industrialization.Therefore, the suitable oxonation catalyst of development is the key that realizes the carbonyl process synthesize phenylacetic acid.
The present invention provides a kind of new catalyst-pyridine-2-carboxylic acids cobalt and substituent pyridine-2-carboxylic acids cobalt that is used for the technology of catalysis halogen benzyl and carbon monoxide carbonylation synthesize phenylacetic acid, uses this catalyst efficient, inexpensive, also recyclable.
The chemical equation of the process that catalyst of the present invention is related is as follows:
X=Cl, Br, IR=H, alkyl, NO
2, F, Cl, Br, I, NR
2, CN alkali=NaOH, KOH, LiOH, Ca (OH)
2M=K
+, Na
+, Li
+, Ca
2+.n=1,2
The related concrete catalytic process of catalyst of the present invention is as follows:
[α of the pyridine ring of pyridine-2-carboxylic acids, β, γ position are by F, Cl, Br, I, NO with catalyst-pyridine-2-carboxylic acids cobalt or substituent pyridine-2-carboxylic acids cobalt in autoclave
2, CN, H, RO-, N (CH
3)
2, CH
3, COOR replaces, as nitro substituted pyridines-2-carboxylic acid cobalt, methoxyl group substituted pyridines-2-carboxylic acid cobalt] be dissolved in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, dimethyl sulfoxide (DMSO), N as organic solvent, in the dinethylformamide, and feeding carbon monoxide, antalkali NaOH, potassium hydroxide, lithium hydroxide, calcium hydroxide and reactant halogen benzyl are added in the autoclave by the mode that drips, product is neutralized into phenylacetate, organic salt is made phenylacetic acid through acidifying after separating.The oxonation condition is pressure 0.1～3.0 MPa, 40～140 ℃ of temperature, catalyst concn 0.01～5.0 mol.
New catalyst among the present invention has overcome traditional carbonyl process synthesize phenylacetic acid catalyst and met oxygen, the labile shortcoming of water, and preparation is simple, active high, be easy to reclaim, the catalyst after the recovery can directly use, after applying mechanically 10 times, activity still can reach more than 95% of fresh catalyst.
Embodiments of the invention are as follows:
Example 1. is 80ml methyl alcohol, and 2.0 gram pyridine-2-carboxylic acids cobalts join in the autoclave, stirs and makes catalyst dissolution in 5 minutes, replaces in the still air 3 times with CO, is warming up to 60 ℃, and pressure rises to 2.5MPa.In 1 hour, simultaneously 16.5 gram benzyl chlorides and 20ml, 20%NaOH solution are dropwise added in the reactor.React after 8 hours, stop to stir and heating, be cooled to room temperature, emit residual gas.Take out reaction mixture, thin up is removed wherein methyl alcohol with Rotary Evaporators, regulates about pH value to 2 with concentrated hydrochloric acid, use extracted with diethyl ether then, extract adds anhydrous magnesium sulfate drying, and suction filtration is removed magnesium sulfate, boils off ether with Rotary Evaporators again, promptly get phenylacetic acid, productive rate is 90%, and measuring its fusing point with the fusing point instrument is 75～76 ℃, and the infrared spectrogram of products benzene acetate is consistent with the standard spectrogram of phenylacetic acid.
Example 2. is with the 80ml isopropyl alcohol, and 2.0 gram 4-chloro-pyridine-2-carboxylic acids cobalts join in the autoclave, stir and make catalyst dissolution in 5 minutes.Remaining operation and reaction condition are with example 1.The solid product that obtains is a phenylacetic acid, and productive rate is 85%, and the analysis of product is with example 1.
Example 3. is 80ml methyl alcohol, 25ml water, and 2.0 gram pyridine-2-carboxylic acids cobalts, 5.6 gram solid oxidation calcium and 16.5 gram benzyl chlorides join in the autoclave, with air in the CO displacement still 3 times, start to stir also and are warming up to 100 ℃, and pressure rises to 2.5MPa.Remaining operation is with example 1.The solid product that obtains is a phenylacetic acid, and productive rate is 95%, and the analysis of product is with example 1.
Claims (5)
1. catalyst that is used for synthesize phenylacetic acid technology, its synthesize phenylacetic acid process is in autoclave catalyst to be dissolved in the organic solvent, and feeding carbon monoxide, antalkali and reactant halogen benzyl are added in the autoclave by the mode that drips, product is neutralized into phenylacetate, after organic salt separates, make phenylacetic acid through acidifying, the oxonation condition is pressure 0.1～3.0MPa, 40～140 ℃ of temperature, it is characterized in that employed catalyst is the pyridine-2-carboxylic acids cobalt in this technology, catalyst concn is 0.01～5.0 mol.
2. catalyst according to claim 1 is characterized in that, said organic solvent is: methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, dimethyl sulfoxide (DMSO) or N, dinethylformamide.
3. catalyst that is used for synthesize phenylacetic acid technology, its synthesize phenylacetic acid process is in autoclave catalyst to be dissolved in the organic solvent, and feeding carbon monoxide, antalkali and reactant halogen benzyl are added in the autoclave by the mode that drips, product is neutralized into phenylacetate, after organic salt separates, make phenylacetic acid through acidifying, the oxonation condition is pressure 0.1～3.0MPa, 40～140 ℃ of temperature, it is characterized in that employed catalyst is substituent pyridine-2-carboxylic acids cobalt in this technology, catalyst concn is 0.01～5.0 mol.
4. catalyst according to claim 3 is characterized in that, said organic solvent is: methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, dimethyl sulfoxide (DMSO) or N, dinethylformamide.
5. catalyst according to claim 3 is characterized in that, said substituting group is meant that α, β, the γ position of the pyridine ring of pyridine-2-carboxylic acids are by F, Cl, Br, I, NO
2, CN, H, RO-, N (CH
3)
2, CH
3, COOR replaces.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001146467A CN1133501C (en) | 2000-06-21 | 2000-06-21 | Catalyst for catalytic carboxylation to synthesize phenylacetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001146467A CN1133501C (en) | 2000-06-21 | 2000-06-21 | Catalyst for catalytic carboxylation to synthesize phenylacetic acid |
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| Publication Number | Publication Date |
|---|---|
| CN1284406A true CN1284406A (en) | 2001-02-21 |
| CN1133501C CN1133501C (en) | 2004-01-07 |
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ID=4584295
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001146467A Expired - Fee Related CN1133501C (en) | 2000-06-21 | 2000-06-21 | Catalyst for catalytic carboxylation to synthesize phenylacetic acid |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1901737B (en) * | 2005-07-21 | 2010-06-16 | 智捷科技股份有限公司 | Switching and data access method for radio communication device base station |
| 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 |
| CN109320413A (en) * | 2017-08-01 | 2019-02-12 | 江苏联化科技有限公司 | A kind of preparation method of phenylacetic acid class compound |
| CN114394895A (en) * | 2022-01-21 | 2022-04-26 | 西安凯立新材料股份有限公司 | Preparation method of 2,4, 6-trimethylphenylacetic acid |
| CN114774973A (en) * | 2022-04-22 | 2022-07-22 | 河北师范大学 | Nanometer flower-like cobalt molybdenum sulfide supported catalyst and preparation method and application thereof |
-
2000
- 2000-06-21 CN CNB001146467A patent/CN1133501C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1901737B (en) * | 2005-07-21 | 2010-06-16 | 智捷科技股份有限公司 | Switching and data access method for radio communication device base station |
| 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 |
| CN109320413A (en) * | 2017-08-01 | 2019-02-12 | 江苏联化科技有限公司 | A kind of preparation method of phenylacetic acid class compound |
| CN109320413B (en) * | 2017-08-01 | 2021-07-30 | 江苏联化科技有限公司 | Preparation method of phenylacetic acid compound |
| CN114394895A (en) * | 2022-01-21 | 2022-04-26 | 西安凯立新材料股份有限公司 | Preparation method of 2,4, 6-trimethylphenylacetic acid |
| CN114394895B (en) * | 2022-01-21 | 2023-09-15 | 西安凯立新材料股份有限公司 | Preparation method of 2,4, 6-trimethylphenylacetic acid |
| CN114774973A (en) * | 2022-04-22 | 2022-07-22 | 河北师范大学 | Nanometer flower-like cobalt molybdenum sulfide supported catalyst and preparation method and application thereof |
| CN114774973B (en) * | 2022-04-22 | 2024-03-08 | 河北师范大学 | Nanometer flower-like cobalt-molybdenum sulfide supported catalyst and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1133501C (en) | 2004-01-07 |
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