CN1279128A - Process of preparing halobenzoic acid and its special composite catalyst - Google Patents
Process of preparing halobenzoic acid and its special composite catalyst Download PDFInfo
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- CN1279128A CN1279128A CN 99116532 CN99116532A CN1279128A CN 1279128 A CN1279128 A CN 1279128A CN 99116532 CN99116532 CN 99116532 CN 99116532 A CN99116532 A CN 99116532A CN 1279128 A CN1279128 A CN 1279128A
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- catalyst
- composite catalyst
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Abstract
A process for preparing halobenzoic acid by oxidizing halotoluene with a composite catalyst is disclosed. Said composite catalyst contains primary catalyst and cocatalyst. The halotoluene, under the existance of solvent which is not raw material and does not take part in oxidation reaction or not, and using air as oxidant by composite catalyst takes part in reaction at 80-200 deg.C to obtain halobenzoic acid with output rate higher than 98% and purity higher than 99%.
Description
The present invention relates to a kind ofly prepare the preparation method and the special-purpose composite catalyst thereof of halogen benzoic acid with benzyl halide, it is a kind ofly to have under solvent or the condition of no solvent, by the benzoic method of liquid-phase catalysis air oxidation benzyl halide synthesizing halogen.
Halogen benzoic acid is the important medicine of a class, dyestuff and pesticide intermediate.For example, parachlorobenzoic-acid is synthetic broad-spectrum de-worming medicine mebendazole (medical industry, 1977, (2), 12) and Flubendazole (medical industry, 1983, (11) 1), the raw material of synthetic analgesia anti-inflammation medicine indocin, acemetacin and Oxametacin etc. (Xiang Tan chemical industry, the 24th volume first phase); 0-chloro-benzoic acid is that synthetic antipsychotic drug is put forth energy still quiet, chlorpromazine, the adrenergic pro-banthine and breathe heavily logical, Clofenamic Acid, the raw material of antifungal clotrimazole etc. also can be used for making dyestuff and color film (Xiang Tan chemical industry, the 24th volume first phase; The fine chemicals handbook, the first volume, P454, Science Press, Beijing in 1992); 2, the 4-dichlorobenzoic acid is the raw material (fine chemicals handbook, the first volume, P643, Science Press, Beijing in 1992) of synthetic antimalarial quinacrine hydrochloride and non-mercurial diuretic furosemide etc.; 2, the 6-dichlorobenzoic acid is the raw material that the synthetic acidic media floats blue B; Parafluorobenzoic acid is the raw material (US4,605,757) of synthetic anthelmintic; O-bromobenzoic acid is raw material (US4,605,757) of synthetic sweetener or the like.The preparation of above halogen benzoic acid mainly is to be raw material with the benzyl halide, adopts method for oxidation to make.Oxidant commonly used mainly contains two classes, and a class is a chemical oxidizing agent, as potassium bichromate, potassium permanganate and nitric acid (CN1104626) etc.Owing to make the oxidant cost height with potassium bichromate and potassium permanganate, discharging contains the waste water of heavy metal ion in a large number, and is at present industrial more with the nitric acid application, although the nitric acid oxidation method cost is low, but contains NO in a large number because of discharging
xWaste gas and waste water, serious environment pollution, its application has been subjected to the strictness restriction of national environmental protection department, and some adopts the producer of this technology to be stopped production by time limit or changes other production technologies.Another kind of is with air oxidant, makes catalyst with the salt of cobalt, iron, nickel, copper, molybdenum or manganese, is solvent with the lower aliphatic carboxylic acid of 2～3 carbon, under pressure with one-step oxidation process synthetic (US4,605,757; Khim-Farm.Zh.1991,25 (1), 68-9; Zh.Prikl.Khim. (Leningrad) 1977,50 (1), 133-6; Jp58-32843).The shortcoming of this technology is that mother liquor can not directly recycle, and acetic acid corrosivity is extremely strong, needs to make consersion unit with titanium steel, cause production cost very high, environmental pollution is serious, and factory's labour health condition is poor, also causes the producer of this explained hereafter halogen benzoic acid of many employings to stop production or change the line of production.
In order to overcome above shortcoming, many people have carried out deep research to the preparation method of halogen benzoic acid.For example, containing 1 of NaOH, in the 2-dimethoxy-ethane solvent, making catalyst with crown ether, use the dioxygen oxidation benzyl halide, can synthesizing halogen benzoic acid (Tetrahedron Letter, Vol.25, No.43,4989-4992), but reaction rate is very slow, reacts yield only about 20% 5 hours; And crown ether costs an arm and a leg, and a large amount of NaOH are difficult to reclaim, and environmental pollution is big, consider from the production cost of halogen benzoic acid and the present market price, this technology be impossible realize industrialized; Make catalyst with cobalt salt and 17-58 carbon quaternary ammonium salt, without solvent, also can synthesizing halogen benzoic acid (US 4,990,659), but the quaternary ammonium salt consumption is big, and long chain quaternary costs an arm and a leg, and causes production cost very high, also is unsuitable for the production of halogen benzoic acid.
The object of the present invention is to provide a kind of method that is exclusively used in the composite catalyst of preparation halogen benzoic acid and prepares halogen benzoic acid with this composite catalyst.Adopt this Preparation of Catalyst halogen benzoic acid, its reaction condition should more gentle, safety, essentially no environmental pollution and equipment corrosion, catalyst amount is few, cost is not higher than prior art, sets up once the cover process units and can produce serial halogen benzoic acid product.
As follows for realizing the technical scheme that above-mentioned purpose of the present invention adopts:
The present invention includes a kind of composite catalyst and general formula is oxidized to the method for general formula for the halogen benzoic acid of (II) for the benzyl halide of (I) with this catalyst.
X in the formula
1And X
2Represent hydrogen or halogen (fluorine, chlorine or bromine etc.) respectively, but wherein have at least one to represent halogen.
Specify as follows:
One, composite catalyst,
It is made up of by 0.01: 1～2.5: 1 mol ratio major catalyst and co-catalyst, and best mol ratio is 0.15: 1～2: 1.Major catalyst is the inorganic acid salt or the acylate of variable valency metal, or its mixture; Co-catalyst is made up of simple substance bromine or bromide and not brominated polar compound.Both ratios are 0.01: 1～1.5: 1, are preferably 0.05: 1～1: 1.Major catalyst in simple substance bromine or bromide in metallic atom molal quantity, the co-catalyst by the bromine atoms molal quantity, not brominated polar compound molal quantity meter.
Described variable valency metal is iron, cobalt, nickel, copper, vanadium, chromium or manganese etc.The inorganic acid salt of variable valency metal is fluoride, chloride, bromide or nitrate etc.The acylate of variable valency metal is acetate, oxalates, benzoate, naphthenate, stearate or oleate etc.
Bromide as co-catalyst is Br
2, NaBr, KBr, NH
4Br, MnBr
24H
2O, CoBr
26H
2O, CBr
4, CHBr
2CHBr
2Or HBr etc.Not brominated polar compound as co-catalyst is pyridine, acetylacetone,2,4-pentanedione or water (comprising the crystallization water).After adding the small amount of polar compound, can promote the dissolving and the dispersion of catalyst, shorten oxidation reaction induction period.In general, water can reduce liquid-phase catalysis air oxidation reaction speed, but in the used system of the present invention, the water of trace but can play catalytic action.
Two, the method for preparing halogen benzoic acid with above-mentioned composite catalyst:
It is to be raw material with the benzyl halide, solvent-free or have in the presence of the non-raw material solvent of the oxidation reaction of not participating in, the composite catalyst that in every mole of raw material, adds 0.0001～0.05 mole, feed the air of 0.25～2.5MPa, reacted about 4 hours cooling back separated and collected product halogen benzoic acid down at 80～200 ℃.
Total consumption excursion broad of catalyst, common every moles of halogenated toluene is preferably 0.0015～0.025 mole with 0.0001～0.05 mole catalyst.
The oxidant that the present invention uses is air, and its pressure size is 0.25～2.5MPa, is preferably 0.6～1.5MPa.Use air oxidant, both cheap, convenient than using purity oxygen, also than purity oxygen safety.
The liquid-phase catalysis air oxidation is a heterogeneous reaction, can be dispersed in the reactor in order to make air, should air sparger be set at reactor bottom, and dispose suitable agitator.
Oxidation reaction is a strong exothermal reaction, and the size of air mass flow should be complementary with the heat-sinking capability of reactor, also should make the oxygen content in the tail gas be lower than 5% simultaneously, carries out to guarantee oxidation reaction safety.
When enforcement was of the present invention, reaction temperature can change between 80 ℃ to 200 ℃, is preferably 100 ℃～160 ℃.
The method of isolating halogen benzoic acid from the reactant mixture of using the present invention's preparation can adopt conventional basic technology operation to carry out according to material properties.For example: again filter cake is made with extra care after distillation, the filtration etc.Usually the solubility of halogen benzoic acid in raw material or solvent is less, adopt filter operation get final product the halogen benzoic acid crude product.Mother liquor and the wherein contained catalyst that has can directly recycle, and the little amount of catalyst of carrying under one's arms in the product also can reclaim again and use.
Compared with the prior art, adopt catalyst provided by the invention and method to prepare halogen benzoic acid, oxidant is an air, not only convenient, safety, but also greatly reduce corrosion and the environmental pollution degree of reaction system to equipment, solvent for use and catalyst reclaim easily and recycle, the yield of products obtained therefrom is greater than 98%, therefore purity be particularly suitable for substituting existing manufacturing technique greater than 99%, has important promotional value.
Below in conjunction with specific embodiment technical scheme of the present invention is further described:
Embodiment 1
The preparation of parachlorobenzoic-acid
With 189.75g (1.5mol) parachlorotoluene, 0.3g (0.96mmol) cobalt naphthenate, 0.1g (0.51mmol) MnCl
24H
2O, 0.2g (1.68mmol) KBr mixes in the back adding 300ml stainless steel autoclave, the control mixing speed is 500 rev/mins, bubbling air when temperature is elevated to 80 ℃, the stainless steel needle valve control that air mass flow is installed with the autoclave exit, tail gas enters and measures and discharge through spinner flowmeter again after tail gas condenser reclaims a small amount of raw material, the flow size is advisable less than 5% with oxygen content remaining in the tail gas, generally be controlled to be 200ml/min, reaction pressure 0.8MPa, reaction temperature 125-130 ℃, after reaction is carried out about 4 hours, reaction mixture is separated, washing, be drying to obtain parachlorobenzoic-acid, calculate according to the parachlorotoluene that has reacted, yield 98.7%, purity 99.1%.
Embodiment 2
The preparation of 0-chloro-benzoic acid
With 189.75g (1.5mol) ortho-chlorotolu'ene, 0.35g (1.12mmol) cobalt naphthenate, 0.2g (0.7mmol) MnBr
24H
2O mixes the back and adds in the 300ml stainless steel autoclave, and operating procedure is with embodiment 1, with example 1 difference be that reaction temperature is controlled at 130～135 ℃.React after 4 hours, reaction mixture, separation, washing, the dry 0-chloro-benzoic acid that gets calculate yield 98.1%, purity 99.5% according to the ortho-chlorotolu'ene that has reacted.
Embodiment 3
2, the preparation of 4-dichlorobenzoic acid
With 193.2g (1.2mol) 2,4-dichlorotoleune, 0.25g (1.05mmol) CoCl
26H
2O, 0.35g (1.43mmol) Mn (C
2H
3O
2)
24H
2O, 0.4g (3.36mmol) KBr mixes the back and adds in the 300ml stainless steel autoclave, and operating procedure is controlled air mass flow 250ml/min with embodiment 1,135 ℃～140 ℃ of temperature, air pressure 0.8MPa reacts after 4 hours reaction mixture, separation, washing, drying, get 2, the 4-dichlorobenzoic acid, according to reacted 2, the 4-dichlorotoleune calculates, yield 98.5%, purity 99.3%.
Embodiment 4
2, the preparation of 6-dichlorobenzoic acid
With 193.2g (1.2mol) 2,6-dichlorotoleune, 0.5g (1.53mmol) CoBr
26H
2O, 0.4g (2.02mmol) MnCl
24H
2O, 0.4g (3.88mmol) add in the 300ml autoclave behind the NaBr mixing, operating procedure is with embodiment 1,140 ℃ of control reaction temperatures, air pressure 0.8MPa reacts reaction mixture, separation, washing, drying after 4 hours, get 2, the 6-dichlorobenzoic acid, yield 97.6%, purity 99.0%.
Embodiment 5
The preparation of parafluorobenzoic acid
With 198.2g (1.8mol) p-fluorotoluene, 0.3g (0.96mmol) Co (Ac) 2,0.2g (0.82mmol) Mn (NO
3)
24H
2O, 0.2g (1.68mmol) KBr, mix the back and add in the 300ml stainless steel autoclave, operating procedure is controlled 140 ℃ of reaction temperatures with embodiment 1, air pressure 0.8MPa, react reaction mixture after 4 hours, separate, wash, be drying to obtain parafluorobenzoic acid, calculate according to the p-fluorotoluene that has reacted, yield 99.1%, purity 99.3%.
Embodiment 6
The preparation of parabromobenzoic acid
With 188.14g (1.1mol) parabromotoluene, 0.4g (1.68mmol) CoCl
26H
2O, 0.35g (1.43mmol) Mn (C
2H
3O
2)
24H
2O, 0.4g (3.36mmol) KBr mixes in the back adding 300ml stainless steel autoclave, method of operating is with embodiment 1,140 ℃ of control reaction temperatures, reaction pressure 0.8MPa reacts reaction mixture after 4 hours, separate, wash, be drying to obtain parabromobenzoic acid, calculate yield 96.5%, purity 99.1% according to the parabromotoluene that has reacted.
Embodiment 7
The preparation of parachlorobenzoic-acid
With 126.5g (1mol) parachlorotoluene, 0.3g (0.96mmol) cobalt naphthenate, 0.35g (1.43mmol) Mn (C
2H
3O
2)
24H
2O, 0.2g (1.68mmol) KBr and 78g (1mol) benzene mixes in the back adding 300ml autoclave, operating procedure is with embodiment 1,130 ℃～135 ℃ of control reaction temperatures, after treating that oxygen content rises to 16%～17% (need react approximately 4 hours) gradually in the tail gas, reaction mixture, separation, washing, drying get parachlorobenzoic-acid.Yield 98.8%, purity 99.1%.
Claims (12)
1. composite catalyst that is used to prepare halogen benzoic acid, it is characterized in that it is made up of by 0.02: 1～2.5: 1 mol ratio major catalyst and helping agent, major catalyst is one or more the mixture in variable valency metal inorganic acid salt or the acylate; Co-catalyst is simple substance bromine or bromide and not brominated polar compound.
2. by the described composite catalyst of claim 1, it is characterized in that described variable valency metal is iron, cobalt, nickel, copper, vanadium, chromium or manganese.
3. by the described composite catalyst of claim 1, the inorganic acid salt that it is characterized in that described variable valency metal is fluoride, chloride, bromide or nitrate.
4. by the described composite catalyst of claim 1, the acylate that it is characterized in that described variable valency metal is acetate, oxalates, benzoate, naphthenate, stearate or oleate.
5. by the described composite catalyst of claim 1, it is characterized in that the bromide as co-catalyst is Br
2, NaBr, KBr, NH
4Br, MnBr
24H
2O, CoBr
26H
2O, CBr
4, CHBr
2CHBr
2Or HBr.
6. by the described composite catalyst of claim 1, it is characterized in that the not brominated polar compound as co-catalyst is pyridine, acetylacetone,2,4-pentanedione or water.
7. by the described composite catalyst of claim 1, the mol ratio that it is characterized in that described major catalyst and co-catalyst is 0.15: 1～2: 1.
8. by the described composite catalyst of claim 1, it is characterized in that the bromide in the co-catalyst and the mol ratio of not brominated polar compound are 0.05: 1～1: 1.
9. one kind prepares the method for halogen benzoic acid with any described composite catalyst in the claim 1～8, and it is that general formula is oxidized to the halogen benzoic acid of general formula for (II) for the benzyl halide of (I),
X in the formula
1And X
2Represent hydrogen or halogen (fluorine, chlorine or bromine etc.) respectively, but wherein have at least one to represent halogen, with the benzyl halide is raw material, it is characterized in that: solvent-free or have in the presence of the non-raw material solvent of the oxidation reaction of not participating in, the composite catalyst that in every mole of raw material, adds 0.0001～0.05 mole, feed the air of 0.25～2.5Mpa, reacted about 4 hours down, cooling back separated and collected product halogen benzoic acid at 80～200 ℃.
10. by the described method of claim 9, the mol ratio that it is characterized in that raw material and composite catalyst is 1: 0.0015～1: 0.02.
11. by the described method of claim 9, it is characterized in that a kind of or wherein several mixture in carbon tetrachloride, benzene, nitrobenzene, fluorobenzene or the phenyl polyfluoride of described non-raw material solvent.
12., it is characterized in that preferred reaction temperature is 100～160 ℃ by the described method of claim 9.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102126996A (en) * | 2010-01-18 | 2011-07-20 | 中国中化股份有限公司 | Preparation method of 2-chlorin-4-mesyl benzoic acid |
| CN103601639A (en) * | 2013-11-20 | 2014-02-26 | 南通波涛化工有限公司 | O-chlorobenzoic acid synthesis process |
| CN108558636A (en) * | 2018-05-11 | 2018-09-21 | 黄石市利福达医药化工有限公司 | A kind of preparation method of 4- bromobenzoic acids |
| CN108558637A (en) * | 2018-05-11 | 2018-09-21 | 浙江阿尔法化工科技有限公司 | 0-chloro-benzoic acid production equipment and synthetic method |
| CN116099574A (en) * | 2023-01-29 | 2023-05-12 | 山东尚舜化工有限公司 | Compound catalyst and method for producing 2,2' -disulfide diphenylamine by using same |
-
1999
- 1999-06-30 CN CN 99116532 patent/CN1279128A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102126996A (en) * | 2010-01-18 | 2011-07-20 | 中国中化股份有限公司 | Preparation method of 2-chlorin-4-mesyl benzoic acid |
| CN102126996B (en) * | 2010-01-18 | 2013-10-23 | 中国中化股份有限公司 | Preparation method of 2-chlorin-4-mesyl benzoic acid |
| CN103601639A (en) * | 2013-11-20 | 2014-02-26 | 南通波涛化工有限公司 | O-chlorobenzoic acid synthesis process |
| CN108558636A (en) * | 2018-05-11 | 2018-09-21 | 黄石市利福达医药化工有限公司 | A kind of preparation method of 4- bromobenzoic acids |
| CN108558637A (en) * | 2018-05-11 | 2018-09-21 | 浙江阿尔法化工科技有限公司 | 0-chloro-benzoic acid production equipment and synthetic method |
| CN113563174A (en) * | 2018-05-11 | 2021-10-29 | 浙江阿尔法化工科技有限公司 | Production equipment and synthesis method of o-chlorobenzoic acid |
| CN116099574A (en) * | 2023-01-29 | 2023-05-12 | 山东尚舜化工有限公司 | Compound catalyst and method for producing 2,2' -disulfide diphenylamine by using same |
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