CN102093224A - Method for synthesizing nitrobenzoic acid by using microwaves - Google Patents

Method for synthesizing nitrobenzoic acid by using microwaves Download PDF

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CN102093224A
CN102093224A CN2011100280263A CN201110028026A CN102093224A CN 102093224 A CN102093224 A CN 102093224A CN 2011100280263 A CN2011100280263 A CN 2011100280263A CN 201110028026 A CN201110028026 A CN 201110028026A CN 102093224 A CN102093224 A CN 102093224A
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佘远斌
李静
孙志成
刘燃
钟儒刚
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Beijing University of Technology
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Beijing University of Technology
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Abstract

The invention relates to a method for synthesizing nitrobenzoic acid by using microwaves. The method comprises the following steps of: introducing 0 to 0.8 MPa of oxygen into 0.3 to 2 mol/L of sodium hydroxide solution by taking ortho-methylnitrobenzene as a raw material, acetonitrile, dimethyl formamide (DMF), ethanol or ethanol aqueous solution comprising 10 to 95 volume percent of ethanol as a solvent and 1 to 230 ppm of metalloporphyrin as a catalyst under the microwave promotion condition; and reacting at the microwave reaction temperature of between 60 and 170 DEG C and the microwave synthesis power of between 0 and 85 W for 2 to 60 minutes to obtain the nitrobenzoic acid. In the method, the conventional heating reaction is replaced by a microwave heating way, so that a target product is synthesized with high selectivity and high yield, reaction pressure is remarkably lowered, the amount of alkali used in the reaction is reduced, and reaction time is shortened, so that reaction energy consumption and operating cost are effectively lowered, reaction safety is enhanced, an aftertreatment process is simper and reaction efficiency is remarkably improved.

Description

The method of the synthetic o-Carboxynitrobenzene of microwave
Technical field
The present invention relates to a kind of method of synthetic aroma acid, specifically, relate to the method for the synthetic o-Carboxynitrobenzene of a kind of microwave.
Background technology
What at present, synthetic o-Carboxynitrobenzene research was more is by the bionically catalyzing and oxidizing method in alkaline medium.People such as She Yuanbin have successively reported in alkaline medium with anhydrous methanol (fine chemistry industry, 1998,45～47) and methyl alcohol-benzene (fine chemistry industry 1 (15):, 2004,21 (6): 474～478) selecting metal phthalocyanine for use for solvent is bionic catalyst, the method of the synthetic o-Carboxynitrobenzene of oxygen catalytic oxidation Ortho Nitro Toluene, this method have solved in acidic medium problems such as the serious and environmental pollution of the existing equipment corrosion of preparation o-Carboxynitrobenzene.Report the aqueous ethanolic solution that uses environmental protection after the people such as She Yuanbin again as solvent, adopted the green synthetic o-Carboxynitrobenzene (chemical industry journal, 2007, (58) 12:3055～3057) of iron porphyrin oxygen catalytic oxidation Ortho Nitro Toluene.Yet this method reaction pressure higher (2MPa), alkali concn higher (3.75mol/L), long reaction time (12h) causes the very big wasting of resources.
Chinese patent CN1944396A (open day: on April 11st, 2007) disclose a kind of synthetic method of o-Carboxynitrobenzene.This method is to be raw material with the Ortho Nitro Toluene, with the metalloporphyrin is catalyzer, to contain ethanol 50～95% volume of ethanol aqueous solution is solvent, in 1～6mol/L strong basicity (sodium hydroxide) aqueous ethanolic solution, feed the oxygen of 0.8～3MPa, control reaction temperature is 35～55 ℃, and reaction 2～14h obtains o-Carboxynitrobenzene.
Mainly there is following problem in the method for above-mentioned synthetic o-Carboxynitrobenzene:
(1) reaction pressure higher (0.8～3MPa), make the building-up reactions energy consumption also high accordingly, poor stability.
(2) sodium hydroxide concentration big (1～6mol/L), make that accordingly to be used for neutral acid amount in the last handling process also bigger, cause brine waste also many.Both waste ample resources, and caused serious environmental to pollute again.
(3) synthesising reacting time oversize (2～12h), synthetic cost is significantly increased.And in the short reaction times, be difficult to obtain high feed stock conversion, especially be difficult to obtain higher product selectivity and yield.
Microwave radiation is a kind of new heater means, and is different with common heating.Common heating is from outward appearance to inner essence to heat by radiation, convection current and conduction, and process is slower, and is excessive for avoiding thermograde, and rate of heating can not be too fast, can not carry out the selectivity heating to the blending ingredients that is in the same reaction unit.And microwave heating is its surface and inner a kind of system heating of carrying out simultaneously, does not need the conduction and the convection current of heat, does not rely on the promotion of thermograde, and system is heated evenly, and heats up rapidly.Because the ability of material absorbing microwave is relevant with its specific inductivity, microwave can carry out the selectivity heating to blending ingredients, helps improving the selectivity of reaction.Microwave heating does not have lag-effect in addition, does not have the thermal radiation loss, after closing microwave source, does not then have micro-wave energy and passes to material, and is highly beneficial to the reaction that temperature control requirement is high.
At present, microwave method is used for synthesizing of o-Carboxynitrobenzene do not see bibliographical information as yet.
Summary of the invention
Problem such as the objective of the invention is to overcome that the reaction pressure that exists in the existing synthetic method is higher, alkali large usage quantity, reaction times are long, selectivity of product and yield are not high provides the method for the synthetic o-Carboxynitrobenzene of a kind of microwave.Characteristics such as this method has that reaction pressure is low, the alkali consumption is few, the reaction times is short, selectivity of product and yield height.But this method not only efficent use of resources, reduce the synthetic cost and the energy consumption of o-Carboxynitrobenzene significantly, and the security that can significantly improve building-up reactions significantly reduces environmental pollution.
The method of the synthetic o-Carboxynitrobenzene of a kind of microwave provided by the present invention may further comprise the steps:
With the Ortho Nitro Toluene is raw material, with acetonitrile, DMF, ethanol or to contain ethanol 10～95% volume of ethanol aqueous solution be solvent, select for use 1～230ppm to have the metalloporphyrin of formula (I), formula (II) or formula (III) structure as catalyzer, in 0.3～2mol/L sodium hydroxide solution, feed the oxygen of 0～0.8MPa, be 60～170 ℃ in the microwave reaction temperature, the synthetic power of microwave is under the condition of 0～85W, reaction 2～60min, products therefrom detects through high performance liquid chromatography
Figure BDA0000045317440000021
Formula (I) formula (II)
Figure BDA0000045317440000022
Formula (III)
Wherein, M 1Represent iron, manganese, cobalt, copper or zinc, M 2Represent iron, manganese or cobalt, M 3And M 4Identical or different, identical Shi Jun represents iron, manganese or cobalt, not simultaneously, and M 3Represent iron, M 4Represent manganese, M 3Represent iron, M 4Represent cobalt or M 3Represent manganese, M 4Represent cobalt, R 11, R 12, R 13, R 21, R 22, R 23, R 31, R 32, R 33Represent hydrogen, nitro, halogen, hydroxyl, C 1-3Alkyl, C 1-3Alkoxyl group or hydroxyl; X represents halogen.
Above-mentioned M 1, M 2, M 3Or M 4Preferred iron, manganese or cobalt, M 3And M 4Identical.
The preferred chlorine of above-mentioned X.
Preferred 0.5～the 0.8MPa of above-mentioned reaction pressure.
Sodium hydroxide concentration is preferably 1～1.5mol/L.
Reaction times is preferably 40～60min.
Preferred 80～100 ℃ of temperature of reaction.
Microwave synthesizes the preferred 0～10W of power.
Preferred 10～the 20ppm of catalyst levels.
The reaction solvent preferred alcohol.
The inventive method is compared with existing method, has following beneficial effect:
(1) the present invention makes reaction pressure be reduced to 0～0.8MPa from existing 0.8～3MPa owing to adopt the synthetic o-Carboxynitrobenzene of microwave method, has not only reduced the required energy consumption of reaction, and has increased reaction safety greatly.
(2) sodium hydroxide concentration is reduced to 0.3～2.0mol/L from existing 1～6mol/L, makes that to be used for neutral acid amount in the corresponding last handling process also less, and it is also less to produce saliniferous waste water, has both saved ample resources, has reduced environmental pollution again.
(3) reaction times of the present invention is reduced to 2～60min from existing 2～12h, and the reaction times shortens greatly, has reduced synthetic cost and energy consumption significantly.And identical at other reaction conditionss, and reaction times when being 2～60min, this method is compared with existing method, and its conversion of raw material also has product selectivity and yield all to be significantly improved.Concrete correlation data sees Table 1.
Embodiment
Embodiment 1
In the 10ml glass reaction tube, add the metalloporphyrin (R wherein that 5ppm has formula (I) structure successively 11Be H, R 12Be H, R 13Be CH 3, M 1Be Fe), 0.2g sodium hydroxide, the 0.173g Ortho Nitro Toluene, the 2.5ml acetonitrile feeds 0.8MPa oxygen, reacts 30min under the synthetic power of the microwave of 80 ℃ temperature of reaction and 0～0.5W.After reaction was finished, reaction mixture detected through high performance liquid chromatography.The transformation efficiency of Ortho Nitro Toluene is 32.3%, and the selectivity of o-Carboxynitrobenzene is 49.4%, and yield is 16.2%.
Embodiment 2
In the 10ml glass reaction tube, add the metalloporphyrin (R wherein that 10ppm has formula (I) structure successively 11Be H, R 12Be H, R 13Be OH, M 1Be Mn), 0.03g sodium hydroxide, the 0.173g Ortho Nitro Toluene, 2.5mlDMF feeds 0.8MPa oxygen, reacts 30min under the synthetic power of the microwave of 80 ℃ temperature of reaction and 3～6W.After reaction was finished, reaction mixture detected through high performance liquid chromatography, and the transformation efficiency of Ortho Nitro Toluene is 94.4%, and the selectivity of o-Carboxynitrobenzene is 40.5%, and yield is 38.2%.
Embodiment 3
In the 10ml glass reaction tube, add the metalloporphyrin (R wherein that 15ppm has formula (I) structure successively 11Be Cl, R 12Be H, R 13Be H, M 1Be Zn), 0.185g sodium hydroxide, the 0.173g Ortho Nitro Toluene, 2.5ml ethanol feeds 0.8MPa oxygen, reacts 60min under the synthetic power of the microwave of 60 ℃ temperature of reaction and 0～1W.After reaction was finished, reaction mixture detected through high performance liquid chromatography, and the transformation efficiency of Ortho Nitro Toluene is 19.8%, and the selectivity of o-Carboxynitrobenzene is 90%, and yield is 17.8%.
Embodiment 4
In the 10ml glass reaction tube, add the metalloporphyrin (R wherein that 15ppm has formula (II) structure successively 21Be H, R 22Be CH 3, R 23Be H, M 2Be Co, X is Br), 0.185g sodium hydroxide, the 0.173g Ortho Nitro Toluene, 2.5ml ethanol feeds 0.8MPa oxygen, reacts 60min under the synthetic power of the microwave of 120 ℃ temperature of reaction and 2～6W.After reaction was finished, reaction mixture detected through high performance liquid chromatography, and the transformation efficiency of Ortho Nitro Toluene is 98.5%, and the selectivity of o-Carboxynitrobenzene is 40.7%, and yield is 40%.
Embodiment 5
In the 10ml glass reaction tube, add the metalloporphyrin (R wherein that 100ppm has formula (I) structure successively 11Be CH 3, R 12Be H, R 13Be H, M 1Be Cu), 0.185g sodium hydroxide, the 0.173g Ortho Nitro Toluene, 2.5ml ethanol feeds 0.8MPa oxygen, reacts 10min under the synthetic power of the microwave of 85 ℃ temperature of reaction and 1～2W.After reaction was finished, reaction mixture detected through high performance liquid chromatography, and the transformation efficiency of Ortho Nitro Toluene is 45.3%, and the selectivity of o-Carboxynitrobenzene is 63.1%, and yield is 28.6%.
Embodiment 6
In the 10ml glass reaction tube, add the metalloporphyrin (R wherein that 15ppm has formula (II) structure successively 21Be H, R 22Be H, R 23Be Cl, M 2Be Fe, X is Cl), 0.185g sodium hydroxide, the 0.173g Ortho Nitro Toluene, 2.5ml ethanol feeds 0.8MPa oxygen, reacts 40min under the synthetic power of the microwave of 85 ℃ temperature of reaction and 1～2W.After reaction was finished, reaction mixture detected through high performance liquid chromatography, and the transformation efficiency of Ortho Nitro Toluene is 56.8%, and the selectivity of o-Carboxynitrobenzene is 89.4%, and yield is 50.8%.
Embodiment 7
In the 10ml glass reaction tube, add the metalloporphyrin (R wherein that 15ppm has formula (II) structure successively 21Be OCH 3, R 22Be H, R 23Be H, M 2Be Mn, X is Cl), 0.185g sodium hydroxide, the 0.173g Ortho Nitro Toluene, 2.5ml ethanol feeds 0.8MPa oxygen, reacts 2min under the synthetic power of the microwave of 170 ℃ temperature of reaction and 80W.After reaction was finished, reaction mixture detected through high performance liquid chromatography, and the transformation efficiency of Ortho Nitro Toluene is 95.9%, and the selectivity of o-Carboxynitrobenzene is 20.3%, and yield is 19.5%.
Embodiment 8
In the 10ml glass reaction tube, add the metalloporphyrin (R wherein that 15ppm has formula (II) structure successively 21Be Cl, R 22Be H, R 23Be H, M 2Be Fe, X is Cl), 0.15g sodium hydroxide, the 0.173g Ortho Nitro Toluene, 2.5ml ethanol feeds 0.8MPa oxygen, reacts 60min under the synthetic power of the microwave of 85 ℃ temperature of reaction and 1～2W.After reaction was finished, reaction mixture detected through high performance liquid chromatography, and the transformation efficiency of Ortho Nitro Toluene is 63.8%, and the selectivity of o-Carboxynitrobenzene is 95.9%, and yield is 61.2%.
Embodiment 9
In the 10ml glass reaction tube, add the metalloporphyrin (R wherein that 15ppm has formula (II) structure successively 21Be H, R 22Be H, R 23Be Cl, M 2Be Fe, X is Cl), 0.185g sodium hydroxide, the 0.173g Ortho Nitro Toluene, 2.5ml ethanol, normal pressure aerating oxygen (0MPa) reacts 60min under the synthetic power of the microwave of 85 ℃ temperature of reaction and 1～2W.After reaction was finished, reaction mixture detected through high performance liquid chromatography, and the transformation efficiency of Ortho Nitro Toluene is 23.2%, and the selectivity of o-Carboxynitrobenzene is 67.7%, and yield is 15.7%.
Embodiment 10
In the 10ml glass reaction tube, add the metalloporphyrin (R wherein that 15ppm has formula (II) structure successively 21Be Cl, R 22Be H, R 23Be H, M 2Be Mn, X is Cl), 0.185g sodium hydroxide, the 0.173g Ortho Nitro Toluene, 0.5ml ethanol, 2ml water feed 0.8MPa oxygen, react 60min under the synthetic power of the microwave of 85 ℃ temperature of reaction and 1～2W.After reaction was finished, reaction mixture detected through high performance liquid chromatography, and the transformation efficiency of Ortho Nitro Toluene is 35.3%, and the selectivity of o-Carboxynitrobenzene is 92.4%, and yield is 32.6%.
Embodiment 11
In the 10ml glass reaction tube, add the metalloporphyrin (R wherein that 15ppm has formula (I) structure successively 11Be CH 3, R 12Be H, R 13Be H, M 1Be Fe), 0.185g sodium hydroxide, the 0.173g Ortho Nitro Toluene, 2.5ml ethanol feeds 0.8MPa oxygen, reacts 30min under the synthetic power of the microwave of 85 ℃ temperature of reaction and 1～2W.After reaction was finished, reaction mixture detected through high performance liquid chromatography, and the transformation efficiency of Ortho Nitro Toluene is 51.9%, and the selectivity of o-Carboxynitrobenzene is 90.6%, and yield is 47.0%.
Following Comparative Examples is to adopt the common heating method, and other reactions steps is with corresponding embodiment.
The comparative example A
In the 100ml autoclave, add the metalloporphyrin (R wherein that 15ppm has formula (II) structure successively 21Be OCH 3, R 22Be H, R 23Be H, M 2Be Mn, X is Cl), 1.85g sodium hydroxide, the 1.73g Ortho Nitro Toluene, 25ml ethanol feeds 0.8MPa oxygen, reacts 2min under 170 ℃ oil bath temperature.After reaction was finished, reaction mixture detected through high performance liquid chromatography, and the transformation efficiency of Ortho Nitro Toluene is 0%, and the selectivity of o-Carboxynitrobenzene is 0%, and yield is 0%.
Comparative Examples B
In the 100ml autoclave, add the metalloporphyrin (R wherein that 100ppm has formula (I) structure successively 11Be CH 3, R 12Be H, R 13Be H, M 1Be Cu), 1.85g sodium hydroxide, the 1.73g Ortho Nitro Toluene, 25ml ethanol feeds 0.8MPa oxygen, reacts 10min under 85 ℃ bath temperature.After reaction was finished, reaction mixture detected through high performance liquid chromatography, and the transformation efficiency of Ortho Nitro Toluene is 0%, and the selectivity of o-Carboxynitrobenzene is 0%, and yield is 0%.
Comparative Examples C
In the 100ml autoclave, add the metalloporphyrin (R wherein that 15ppm has formula (I) structure successively 11Be CH 3, R 12Be H, R 13Be H, M 1Be Fe), 1.85g sodium hydroxide, the 1.73g Ortho Nitro Toluene, 25ml ethanol feeds 0.8MPa oxygen, reacts 30min under 85 ℃ bath temperature.After reaction was finished, reaction mixture detected through high performance liquid chromatography, and the transformation efficiency of Ortho Nitro Toluene is 18.2%, and the selectivity of o-Carboxynitrobenzene is 4.6%, and yield is 0.8%.
Comparative Examples D
In the 100ml autoclave, add the metalloporphyrin (R wherein that 15ppm has formula (II) structure successively 21Be H, R 22Be H, R 23Be Cl, M 2Be Fe, X is Cl), 1.85g sodium hydroxide 1.73g Ortho Nitro Toluene, 25ml ethanol feeds 0.8MPa oxygen, reacts 40min under 85 ℃ bath temperature.After reaction was finished, reaction mixture detected through high performance liquid chromatography, and the transformation efficiency of Ortho Nitro Toluene is 38.2%, and the selectivity of o-Carboxynitrobenzene is 40.8%, and yield is 15.6%.
Comparative Examples E
In the 100ml autoclave, add the metalloporphyrin (R wherein that 15ppm has formula (II) structure successively 21Be Cl, R 22Be H, R 23Be H, M 2Be Fe, X is Cl), 1.5g sodium hydroxide, the 1.73g Ortho Nitro Toluene, 25ml ethanol feeds 0.8MPa oxygen, reacts 60min under 85 ℃ bath temperature.After reaction was finished, reaction mixture detected through high performance liquid chromatography, and the transformation efficiency of Ortho Nitro Toluene is 52.2%, and the selectivity of o-Carboxynitrobenzene is 53.6%, and yield is 28.0%.
Table 1 general heating method and microwave heating method are in result's contrast of same reaction synthetic o-Carboxynitrobenzene under the time
Figure BDA0000045317440000061

Claims (10)

1. the method for the synthetic o-Carboxynitrobenzene of a microwave may further comprise the steps:
With the Ortho Nitro Toluene is raw material, with acetonitrile, DMF, ethanol or to contain ethanol 10～95% volume of ethanol aqueous solution be solvent, select for use 1～230ppm to have the metalloporphyrin of formula (I), formula (II) or formula (III) structure as catalyzer, in 0.3～2mol/L sodium hydroxide solution, feed the oxygen of 0～0.8MPa, be 60～170 ℃ in the microwave reaction temperature, the synthetic power of microwave is under the condition of 0～85W, reaction 2～60min, products therefrom detects through high performance liquid chromatography
Figure FDA0000045317430000011
Formula (I) formula (II)
Figure FDA0000045317430000012
Formula (III)
Wherein, M 1Represent iron, manganese, cobalt, copper or zinc, M 2Represent iron, manganese or cobalt, M 3And M 4Identical or different, identical Shi Jun represents iron, manganese or cobalt, not simultaneously, and M 3Represent iron, M 4Represent manganese, M 3Represent iron, M 4Represent cobalt or M 3Represent manganese, M 4Represent cobalt, R 11, R 12, R 13, R 21, R 22, R 23, R 31, R 32, R 33Represent hydrogen, nitro, halogen, hydroxyl, C 1-3Alkyl, C 1-3Alkoxyl group or hydroxyl; X represents halogen.
2. according to the method for claim 1, it is characterized in that M 1, M 2, M 3Or M 4Represent iron, manganese or cobalt, M 3And M 4Identical.
3. according to the method for claim 1, it is characterized in that X represents chlorine.
4. according to the method for claim 1, it is characterized in that reaction pressure is 0.5～0.8MPa.
5. according to the method for claim 1, it is characterized in that sodium hydroxide concentration is 1～1.5mol/L.
6. according to the method for claim 1, it is characterized in that the reaction times is 40～60min.
7. according to the method for claim 1, it is characterized in that temperature of reaction is 80～100 ℃.
8. according to the method for claim 1, it is characterized in that the synthetic power of microwave is 0～10W.
9. according to the method for claim 1, it is characterized in that catalyst levels is 10～20ppm.
10. according to the method for claim 1, it is characterized in that described solvent is an ethanol.
CN2011100280263A 2011-01-26 2011-01-26 Method for synthesizing nitrobenzoic acid by using microwaves Pending CN102093224A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5291837A (en) * 1976-01-24 1977-08-02 Nippon Kayaku Co Ltd Preparation of p-nitrobenzoic acid
JPS5821650A (en) * 1981-07-30 1983-02-08 Toray Ind Inc Preparation of m-nitrobenzoic acid
JPS58183646A (en) * 1982-04-21 1983-10-26 Toray Ind Inc Preparation of p-nitrobenzoic acid
CN1944396A (en) * 2006-10-27 2007-04-11 北京工业大学 Process for preparing ortho-nitro benzoic acid by bionically catalystic ally oxidizing ortho-nitro toluene with oyxgen
US7488843B1 (en) * 2007-10-31 2009-02-10 Hong Kong Baptist University Oxidation process for aromatic compound

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5291837A (en) * 1976-01-24 1977-08-02 Nippon Kayaku Co Ltd Preparation of p-nitrobenzoic acid
JPS5821650A (en) * 1981-07-30 1983-02-08 Toray Ind Inc Preparation of m-nitrobenzoic acid
JPS58183646A (en) * 1982-04-21 1983-10-26 Toray Ind Inc Preparation of p-nitrobenzoic acid
CN1944396A (en) * 2006-10-27 2007-04-11 北京工业大学 Process for preparing ortho-nitro benzoic acid by bionically catalystic ally oxidizing ortho-nitro toluene with oyxgen
US7488843B1 (en) * 2007-10-31 2009-02-10 Hong Kong Baptist University Oxidation process for aromatic compound

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
佘远斌等: "取代铁卟啉催化氧化邻硝基甲苯绿色合成邻硝基苯甲酸", 《化工学报》 *

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Application publication date: 20110615