CN100579948C - Halogen compound carbonylation reaction method - Google Patents
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Abstract
The present invention discloses a method of the halide carbonylation reaction. The key point of the technology is that the reaction uses a novel phase transfer catalyst 2-alkyl-1- 2 (2- hydroxyethyl)-2-chlorine imidazoline; the catalyst has the good catalytic performance for the carbonylation of the benzyl halogen, alpha-alkyl benzyl halogen and so on through the NaCo(CO)<SUB>4</SUB>; the phase transfer catalyst has the advantages of the good water-soluble performance, the good biodegradable performance, the low toxicity, the high efficiency of being recycled and reused, and so on.
Description
Technical field
The present invention relates to halogen compound oxo reaction method, use a kind of novel phase-transfer catalyst in halogen compound carbonylation reaction, this class phase-transfer catalyst can be used for producing from halides the carbonylation reaction of corresponding carboxylic acid effectively, belongs to technical field of organic chemistry.
Background technology
Carbon monoxide is air pollutant main in the atmosphere, and the carbon monoxide of vehicle exhaust and coke(oven)gas discharges in a large number, and serious threat is to natural harmony.Utilize carbonylation reaction that carbon monoxide is introduced in the organic compound molecule, it is the focus of chemical industry application research, also be the most effectively to substitute natural force in the Synthetic Organic Chemistry to change inorganics one of into organic method, the synthetic product can be respectively broad-spectrum aldehyde, ketone, ester, acid, acid amides and derivative thereof, simultaneously to effective utilization of carbon monoxide, can produce very significant environmental benefit, economic benefit and social benefit.In recent years, what carbonylation research was concentrated the most is to be suitable for big industrial halides biphasic catalysis carbonylation reaction, its core work be the design of catalyst system with preferred, phase-transfer catalyst is one of them important field of research.The intervention reaction system that phase-transfer catalyst is appropriate speed of reaction increase, product specificity are increased, and energy consumption is lower, and generation is reacted required negatively charged ion and used mineral alkali (as NaOH) price more cheap.Halides is synthesized carboxylic acid through the CO carbonylation, the new way of having opened up oxo process, and effective use of phase-transfer catalyst makes the reaction conditions of original harshness become gentle, is the very potential synthetic method of a class.
A type reaction in the halogen compound carbonylation reaction is to generate toluylic acid with the benzyl chloride carbonyl compound.Toluylic acid (Phenylacetic acid, benzeneacetic acid) has another name called benzene acetic acid, is a kind of sheet white crystal that has plant flavour.Owing to have a plurality of reactive behavior points such as carboxyl, methylene radical hydrogen and phenyl ring on the toluylic acid structure, make it that a plurality of type reactions can take place, therefore become a kind of important organic chemical industry's intermediate.Toluylic acid is widely used in industry such as medicine, agricultural chemicals, spices, and wherein main consumer field is to be used for penicillin G production, accounts for 85% of aggregate demand.In recent years, along with the development of penicillin and other derived product industries, the demand of toluylic acid presents the trend that enlarges day by day.
Nearly tens kinds of the production methods of toluylic acid, but owing to multiple reasons such as raw materials cost and energy consumption do not realize industrialization mostly.The main industrial process of China's toluylic acid is benzyl chloro-sodium cyanide method and benzyl chlorocarbonylation method, and wherein benzyl chloro-sodium cyanide method is owing to the reaction conditions gentleness, and technology simply becomes the main method that China's toluylic acid is produced.But the raw material sodium cyanide and the intermediate benzyl cyanide that use in this method are Poisons, not only environment are polluted, and also become the obstacle that improves the quality of products simultaneously.Therefore, accelerate to promote development benzyl chlorocarbonylation method and produce toluylic acid, replacing benzyl chloro-sodium cyanide method becomes industrial urgent task of China's toluylic acid and development trend, helps forming and increases economic efficiency and eco-friendly win-win situation.
The reaction of benzyl chlorocarbonylation can be represented by the formula:
PhCH
2Cl+CO+2NaOH→PhCH
2COONa+NaCl+H
2O
PhCH
2COONa+HCl→PhCH
2COOH+NaCl
Side reaction in this reaction can be represented by the formula:
PhCH
2Cl+NaOH→PhCH
2OH+NaCl
To use appropriate catalyst in the reaction of benzyl chlorocarbonylation.The Primary Catalysts of comparative maturity is rhodium, palladium and cobalt complex catalyzer at present.Comparatively speaking, less to the research of applied phase-transfer catalyst in the reaction both at home and abroad, still adopt ancient quaternary ammonium salt (being mainly benzyltriethylammoinium chloride, octadecyl trimethyl ammonium chloride, dodecyl triethyl ammonium chloride, tetrabutylammonium chloride) as phase-transfer catalyst in the industrial production, mechanism of catalytic reaction is phase-transfer catalyst and aqueous phase OH
-In conjunction with, the benzyl chlorine adducts in itself and the organic phase is fully reacted, obtain the better conversion rate.The amount ratio of these phase-transfer catalysts and halides is generally about 1: 20, and recycling use efficient is at 1～2 time, and temperature of reaction focuses mostly on about 55 ℃, and reaction usually need be carried out under certain pressure.Use these phase-transfer catalysts to exist consumption big, the recycle and reuse rate is low, causes the loss of Primary Catalysts big, these quaternary ammonium salts have toxicity in various degree simultaneously, the environmental protection treatment difficulty, some long chain alkyl ammonium salt poorly water-solubles, easy deficiency such as decomposition failure in the strong basicity reaction system.Therefore, seeking the good and environment amenable phase-transfer catalyst of a kind of catalytic performance extremely needs industrial production.
Summary of the invention
The objective of the invention is to produce in the reaction process of carboxylic acid at halogen compound carbonylation, provide a kind of stable performance, safe in utilization, nontoxic, consumption is few and catalytic performance is high, can be recycled, environment amenable phase-transfer catalyst 2-alkyl-1-two (2-hydroxyethyl)-2-tetrahydroglyoxaline muriate, overcomes the main deficiency of prior art.
The contriver is through a large amount of experiment screenings, 2-alkyl-1-two (2-the hydroxyethyl)-2-tetrahydroglyoxaline muriate that is surprised to find that utilization structure formula (I) expression as the halogen compound carbonylation reaction phase-transfer catalyst often
Wherein R is C
7～C
11Alkyl
The halogen compound carbonylation of depressing the effective following structure of catalysis of energy obtains corresponding carboxylic acid, and can obtain productive rate preferably.
R
1Be H, CH
3Or CH
3CH
2R
2=H, CH
3Or Cl X=Br or Cl.
Above-mentioned carbonylation reaction uses cobalt carbonyl catalyst, described cobalt carbonyl catalyst can be cobalt tetracarbonyl negative ion sodium salt or cobalt octacarbonyl, 2-alkyl-1-two (2-hydroxyethyl)-2-tetrahydroglyoxaline muriate is as phase-transfer catalyst, and reaction back acidifying can obtain carboxide.
The mol ratio of 2-alkyl-1-two (2-hydroxyethyl)-2-tetrahydroglyoxaline muriate phase-transfer catalyst and halides is 1: 30～1: 40, after carbonylation reaction is finished, inorganicly separate, directly carry out acidifying mutually, go out corresponding carboxylic acid with ether or chloroform extraction to inorganic with organic phase.
Advantage of the present invention:
1,2-alkyl-1-two (2-hydroxyethyl)-2-tetrahydroglyoxaline muriate is as the halogen compound carbonylation reaction phase-transfer catalyst, good water solubility, anti-hard water, and biological degradability is good, and is nontoxic, environmentally friendlyly do not pollute, easy and simple to handle, safe in utilization;
2, carbonylation reaction mild condition, temperature of reaction are 45～50 ℃, do not need high pressure reflow, products obtained therefrom purity height;
3, use 2-alkyl-1-two (2-hydroxyethyl)-2-tetrahydroglyoxaline muriates as the halogen compound carbonylation reaction phase-transfer catalyst, its preparation technology is simple, cost is inexpensive, the amount of carbonylation phase-transfer catalyst consumption and halides is than little (being 1: 30～1: 40), and can be recycled, help big industrial production.
4,2-alkyl-1-two (2-hydroxyethyl)-2-tetrahydroglyoxaline muriate phase-transfer catalyst uses in this carbonylation acid-base reaction system, has corrosion inhibition to the hardware excellence, and has a sterilizing ability, to industrial sewage, add the static sterilization of 120mg/L 10～24 hours, sterilizing rate all can reach more than 86%.
5, in this phase-transfer catalyst structure, because the existence of two hydroxyethyls, increase greatly not only that it is water-soluble, and absorption property is improved, the phase-transfer catalysis over-all properties is promoted greatly, can play the purpose of catalyzed reaction well.
Embodiment
For a more clear understanding of the present invention, the present invention is described in further detail for the embodiment that provides by the contriver below.
Embodiment 1:
2-undecyl-1-two (2-hydroxyethyl)-2-tetrahydroglyoxaline muriate is made phase-transfer catalyst, (phase-transfer catalyst synthetic method reference literature: history is true for benzyl chlorocarbonylation reaction synthesize phenylacetic acid, Yang Weiguo. synthesizing of dihydroxy ethyl tetrahydroglyoxaline cats product. chemistry world, 1994,1:14-15).
Catalyzer carbonyl cobalt salt Co (CO)
4 -Synthetic: in the 100mL there-necked flask, add 0.286g (0.0012mol) CoCl
26H
2O, the 15mL tetrahydrofuran (THF) feeds CO, adds 0.095g (0.0025mol) NaBH in batches
4, sustained reaction 2h under 0-5 ℃ of reaction conditions, this moment, reaction solution was blue settled solution (catalytic performance carbonyl cobalt salt preferably is green settled solution, no black precipitate).
Add 1.2mmol 2-undecyl-1-two (2-the hydroxyethyl)-2-tetrahydroglyoxaline muriate phase-transfer catalysts and the 10mL 30%NaOH aqueous solution in the carbonyl cobalt salt of preparation, normal temperature is reaction 5min down.Drip tetrahydrofuran (THF) (30mL) solution of 40mmol benzyl chlorine, about 15min drips off, and temperature of reaction is controlled at about 50 ℃, stirs down reaction 3h.Termination reaction, this moment, reaction solution divided two-phase, and upper organic phase is yellow settled solution, and lower floor's water is the bluish voilet turbid solution.Remove organic phase, water is regulated pH=3～4 with 10% hydrochloric acid soln, and solution becomes pink clear liquor.With ether or chloroform extraction (15mL * 3), merge the organic phase extraction liquid, anhydrous MgSO
4Drying, and the phase-transfer catalyst of recovery aqueous phase.Filter concentrating under reduced pressure and promptly separate out toluylic acid, product is the white plates crystal, productive rate 55%, purity 99%, nuclear-magnetism, mass spectrum, infrared and the ultimate analysis data are consistent with bibliographical information.
Embodiment 2:
2-nonyl-1-two (2-hydroxyethyl)-2-tetrahydroglyoxaline muriate is made phase-transfer catalyst, benzyl chlorocarbonylation reaction synthesize phenylacetic acid:
Add 1.2mmol 2-nonyl-1-two (2-the hydroxyethyl)-2-tetrahydroglyoxaline muriate phase-transfer catalysts and the 10mL 30%NaOH aqueous solution in the carbonyl cobalt salt of preparation, normal temperature is reaction 5min down.Drip tetrahydrofuran (THF) (30mL) solution of 40mmol benzyl chlorine, about 15min drips off, at 50 ℃, and reaction 2.5h.Remove organic phase, water is adjusted to acidity with 10% hydrochloric acid soln, and solution becomes pink settled solution.With extracted with diethyl ether (15mL * 3), merge ether extraction liquid, anhydrous MgSO
4Drying, and the phase-transfer catalysis agent solution of recovery aqueous phase.Filter concentrating under reduced pressure and promptly separate out toluylic acid, product is the white plates crystal, productive rate 63%, purity 99%, nuclear-magnetism, mass spectrum, infrared and the ultimate analysis data are consistent with bibliographical information.
Embodiment 3:
2-nonyl-1-two (2-hydroxyethyl)-2-tetrahydroglyoxaline muriate is made phase-transfer catalyst, benzyl chlorocarbonylation reaction synthesize phenylacetic acid:
Similar to Example 2, difference is: what add in the carbonyl cobalt salt of preparation that embodiment 2 reclaims uses 3 times the phase-transfer catalysis agent solution and the 5mL 30%NaOH aqueous solution, and the remaining reaction condition is identical.Toluylic acid productive rate 52%, purity 99%, nuclear-magnetism, mass spectrum, infrared and the ultimate analysis data are consistent with bibliographical information.
Embodiment 4:
2-undecyl-1-two (2-hydroxyethyl)-2-tetrahydroglyoxaline muriate is made phase-transfer catalyst, benzyl bromine carbonylation reaction synthesize phenylacetic acid:
Add 1.2mmol 2-undecyl-1-two (2-the hydroxyethyl)-2-tetrahydroglyoxaline muriate phase-transfer catalysts and the 10mL 30%NaOH aqueous solution in the carbonyl cobalt salt of preparation, normal temperature is reaction 5min down.Drip tetrahydrofuran (THF) (30mL) solution of 40mmol benzyl bromine, about 15min drips off, 45 ℃ of temperature of reaction, reaction times 2.5h.Remove organic phase, water is regulated pH=3～4 with 10% hydrochloric acid soln.Gained solution merges ether extraction liquid, anhydrous MgSO with extracted with diethyl ether (15mL * 3)
4Drying, and the phase-transfer catalyst of recovery aqueous phase.Filter concentrating under reduced pressure and promptly separate out toluylic acid, product is the white plates crystal, productive rate 68%, purity 99%, nuclear-magnetism, mass spectrum, infrared and the ultimate analysis data are consistent with bibliographical information.
Embodiment 5:
2-nonyl-1-two (2-hydroxyethyl)-2-tetrahydroglyoxaline muriate is made phase-transfer catalyst, benzyl bromine carbonylation reaction synthesize phenylacetic acid:
Add 1.2mmol 2-nonyl-1-two (2-the hydroxyethyl)-2-tetrahydroglyoxaline muriate phase-transfer catalysts and the 10mL 30%NaOH aqueous solution in the carbonyl cobalt salt of preparation, normal temperature is reaction 5min down.Drip tetrahydrofuran (THF) (30mL) solution of 42mmol benzyl bromine, about 12min drips off, at 45 ℃, and reaction 2.5h.Remove organic phase, water is regulated pH=3～4 with 10% hydrochloric acid soln.The gained settled solution merges ether extraction liquid, anhydrous MgSO with extracted with diethyl ether (15mL * 3)
4Drying, and the phase-transfer catalyst of recovery aqueous phase.Filter concentrating under reduced pressure and promptly separate out toluylic acid, product is the white plates crystal, productive rate 72%, purity 99%, nuclear-magnetism, mass spectrum, infrared and the ultimate analysis data are consistent with bibliographical information.
Embodiment 6:
2-heptane base-1-two (2-hydroxyethyl)-2-tetrahydroglyoxaline muriate is made phase-transfer catalyst, benzyl bromine carbonylation reaction synthesize phenylacetic acid:
Add 1.2mmol 2-heptane base-1-two (2-the hydroxyethyl)-2-tetrahydroglyoxaline muriate phase-transfer catalysts and the 10mL 30%NaOH aqueous solution in the carbonyl cobalt salt of preparation, normal temperature is reaction 5min down.Drip tetrahydrofuran (THF) (30mL) solution of 45mmol benzyl chlorine, about 15min drips off, and under 50 ℃ of temperature, continues stirring reaction 2.5h.Remove organic phase, water is regulated pH=3～4 with 10% hydrochloric acid soln, and gained solution merges ether extraction liquid, anhydrous MgSO with extracted with diethyl ether (15mL * 3)
4Drying, and the phase-transfer catalyst of recovery aqueous phase.Filter concentrating under reduced pressure and promptly separate out toluylic acid, product is the white plates crystal, productive rate 62%, purity 99%, nuclear-magnetism, mass spectrum, infrared and the ultimate analysis data are consistent with bibliographical information.
Embodiment 7:
Similar to Example 6, difference is to use octadecyl trimethyl ammonium chloride to replace 2-undecyl-1-two (2-hydroxyethyl)-2-tetrahydroglyoxaline muriate phase-transfer catalysts, and the toluylic acid productive rate that obtains only is 46%.
Embodiment 8:
2-nonyl-1-two (2-hydroxyethyl)-2-tetrahydroglyoxaline muriate is made phase-transfer catalyst, and the bromine chloride carbonylation reaction is synthesized 4-Chlorophenylacetic acid:
Add 1.2mmol 2-nonyl-1-two (2-the hydroxyethyl)-2-tetrahydroglyoxaline muriate phase-transfer catalysts and the 10mL 30%NaOH aqueous solution in the carbonyl cobalt salt of preparation, normal temperature is reaction 5min down.Drip tetrahydrofuran (THF) (30mL) solution of 45mmol to bromine chloride, about 15min drips off.Under 45 ℃ of temperature, continue stirring reaction 2.5h.Remove organic phase, water is regulated pH=3～4 with 10% hydrochloric acid soln.Gained solution chloroform extraction (15mL * 3), combined chloroform extraction liquid, anhydrous MgSO
4Drying, and the phase-transfer catalyst of recovery aqueous phase.Filter concentrating under reduced pressure and promptly separate out 4-Chlorophenylacetic acid, product is the white plates crystal, productive rate 76%, purity 99%, nuclear-magnetism, mass spectrum, infrared and the ultimate analysis data are consistent with bibliographical information.
Embodiment 9:
2-undecyl-1-two (2-hydroxyethyl)-2-tetrahydroglyoxaline muriate is made phase-transfer catalyst, and is synthetic to methylphenyl acetic acid to methyl benzyl bromine carbonylation reaction:
Add 1.2mmol 2-undecyl-1-two (2-the hydroxyethyl)-2-tetrahydroglyoxaline muriate phase-transfer catalysts and the 10mL 30%NaOH aqueous solution in the carbonyl cobalt salt of preparation, normal temperature is reaction 5min down.Drip tetrahydrofuran (THF) (30mL) solution of 45mmol to methyl benzyl bromine, about 15min drips off.Under 45 ℃ of temperature, continue stirring reaction 2.5h.Remove organic phase, water is regulated pH=3～4 with 10% hydrochloric acid soln.Gained solution merges ether extraction liquid, anhydrous MgSO with extracted with diethyl ether (15mL * 3)
4Drying, and the phase-transfer catalyst of recovery aqueous phase.Filter concentrating under reduced pressure and promptly separate out methylphenyl acetic acid, product is the white plates crystal, productive rate 58%, purity 99%, nuclear-magnetism, mass spectrum, infrared and the ultimate analysis data are consistent with bibliographical information.
Embodiment 10:
Similar to Example 9, difference is to use benzyltriethylammoinium chloride to replace 2-undecyl-1-two (2-hydroxyethyl)-2-tetrahydroglyoxaline muriate phase-transfer catalysts, and what obtain only is 41% to the methylphenyl acetic acid productive rate.
Claims (4)
1, halogen compound oxo reaction method is characterized in that: use cobalt tetracarbonyl negative ion sodium salt as catalyzer, 2-alkyl-1-two (2-the hydroxyethyl)-2-tetrahydroglyoxaline muriate of utilization structure formula (I) expression is as the halogen compound carbonylation reaction phase-transfer catalyst,
Wherein R is C
7～C
11Alkyl,
Described halides structural formula is:
R
1Be H, CH
3Or CH
3CH
2R
2=H, CH
3Or Cl X=Br or Cl.
2, according to the described halogen compound oxo reaction method of claim 1, it is characterized in that: 2-alkyl-1-two (2-the hydroxyethyl)-2-tetrahydroglyoxaline muriate of described structural formula (I) expression is as phase-transfer catalyst, and reaction back acidifying can obtain carboxide.
3, according to the described halogen compound oxo reaction method of claim 2, it is characterized in that: the mol ratio of 2-alkyl-1-two (2-hydroxyethyl)-2-tetrahydroglyoxaline muriate phase-transfer catalyst and halides is 1: 30～1: 40.
4, according to the described halogen compound oxo reaction method of claim 3, it is characterized in that: after carbonylation reaction is finished, inorganicly separate, directly carry out acidifying mutually, go out carboxylic acid with ether or chloroform extraction to inorganic with organic phase.
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Non-Patent Citations (6)
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| 二羟乙基咪唑啉阳离子表面活性剂的合成. 史真，杨卫国.化学世界，第1期. 1994 |
| 二羟乙基咪唑啉阳离子表面活性剂的合成. 史真，杨卫国.化学世界，第1期. 1994 * |
| 相转移催化苯乙酸新合成方法的研究. 李敏谊等.广东医药学院学报，第10卷第1期. 1994 |
| 相转移催化苯乙酸新合成方法的研究. 李敏谊等.广东医药学院学报，第10卷第1期. 1994 * |
| 苯乙酸合成研究进展. 刘府芳等.江西科学，第19卷第2期. 2001 |
| 苯乙酸合成研究进展. 刘府芳等.江西科学，第19卷第2期. 2001 * |
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Effective date of registration: 20160825 Address after: 710000, No. 2, No. 1, No. 38, No. 3, No. 201, West Avenue, new industrial park, hi tech Zone, Shaanxi, Xi'an Patentee after: Shaanxi high green biological chemical Co. Ltd. Address before: 710075 Shaanxi city of Yanan province Chang Tai Road No. 88 Chang Taiyuan Patentee before: Yan'an Changtai Pharmaceutical Co., Ltd. |