CN106366023A - Production process for 2-nitro-methyl sulfone benzoic acid - Google Patents
Production process for 2-nitro-methyl sulfone benzoic acid Download PDFInfo
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- CN106366023A CN106366023A CN201610776958.9A CN201610776958A CN106366023A CN 106366023 A CN106366023 A CN 106366023A CN 201610776958 A CN201610776958 A CN 201610776958A CN 106366023 A CN106366023 A CN 106366023A
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- nitro
- benzoic acid
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- thiamphenicol benzoic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
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Abstract
The invention discloses a production process for 2-nitro-4-methylsulfonylbenzoic acid. Production materials of the 2-nitro-4-methylsulfonylbenzoic acid include 4-methylsulfonyl toluene, nitric acid, sulfuric acid, vanadium pentoxide, sodium hydroxide and hydrochloric acid. The production process for the 2-nitro-4-methylsulfonylbenzoic acid includes the steps: nitrating; oxidizing; purifying. According to the production process, production efficiency can be improved by the aid of nitrating, oxidizing and purifying steps, the 2-nitro-4-methylsulfonylbenzoic acid is oxidized by the nitric acid under catalysis of the vanadium pentoxide, purity and yield of products can be improved, solvents such as fatty acid and methyl alcohol are replaced by water, production cost is greatly reduced, device corrosion is decreased, emission of waste acid is reduced, clean production is met, and safety in the production process is improved.
Description
Technical field
The present invention relates to chemical productss manufacture field, specially a kind of 2- nitro-to thiamphenicol benzoic acid production technology.
Background technology
2- nitryl-4-thiamphenicol benzoic acid, also known as adjacent nitro is to thiamphenicol benzoic acid, cas no. is 110964-79-9；
English name is 2-nitro-4-methylsulfonylbenzoic acid or o-nitro-p-methylsulfonyl
Benzoic acid (referred to as nmsba)；Molecular formula is c8h7no6s, and molecular weight is 245.21, is white or yellowish under room temperature
Color crystalline powder.2- nitryl-4-thiamphenicol benzoic acid is important organic synthesis intermediate, be widely used in dyestuff, medicine and
The production of pesticide.2- nitro is a kind of important medicinal intermediate to thiamphenicol benzoic acid.The benzene of 2- nitro -4- methylsulfonyltoluene
Two strong electron-withdrawing groups group is had on ring so that methyl oxidation is relatively difficult for carboxyl, and to the control of degree of oxidation also very
Difficult.At present, existing report is mainly divided by the method that 2- nitro -4- methylsulfonyltoluene prepares 2- nitryl-4-thiamphenicol benzoic acid
For chemical oxidization method and liquid phase oxygen (air) oxidizing process.Prepare this kind of benzoic acid containing multiple electron-withdrawing groups, generally will use
The toluene of the corresponding substituent group of strong oxidizer nitric acid oxidation and obtain, because the difficult oxidation of the toluene containing electron-withdrawing group is still needed in five oxidations
Just can carry out under two vanadium catalysis.
But existing 2- nitro-in thiamphenicol benzoic acid production technology, purity and poor yields, and using fat acid and first
Alcohol equal solvent, improves production cost, and the corrosion to equipment is big, is unfavorable for our popularization and use.
Content of the invention
It is an object of the invention to provide a kind of 2- nitro-to thiamphenicol benzoic acid production technology, to solve above-mentioned background
The problem proposing in technology.
For achieving the above object, the present invention provides a kind of following technical scheme: 2- nitro-produce work to thiamphenicol benzoic acid
Skill, is to methylsulfonyltoluene, nitric acid, sulphuric acid, vanadic anhydride, hydrogen-oxygen including 2- nitro-to thiamphenicol benzoic acid production material
Change sodium, hydrochloric acid, described 2- nitro-be to thiamphenicol benzoic acid production manufacturing technique method step: nitrification, oxidation, purification.
Further, described 2- nitro-to thiamphenicol benzoic acid produce nitration method step be: (1) first to enamel react
Put into methylsulfonyltoluene in kettle, put into sulphuric acid in enamel reaction still, be then stirred；(2) after the completion of stirring and then right
Chilled brine is added to be lowered the temperature in enamel reaction still, until temperature stops to less than 15 DEG C；(3) slow in enamel reaction still
Slow addition 68% nitric acid, is then stirred reacting 1 hour, is being sampled analyzing；(4) when content terminates instead more than 99%
Should, then add ordinary water, and by temperature control at 15 DEG C -20 DEG C, itrated compound is all separated out, filter, solid product is treated down
Step reaction is used, and after mother liquor concentrations dehydration, next time feeds intake and applies mechanically, and continues to apply mechanically during abjection water reaction treatment product, second when feeding intake
Add moderate amount of sulfuric acid.
Further, described 2- nitro-to thiamphenicol benzoic acid produce oxidation process steps be: (1) in enamel still, throw
Enter upper step nitrification material, add oxidation to apply mechanically mother solution, add catalyst, stirring intensification is dewatered to 140 DEG C；(2) and then anti-to enamel
Answer kettle to start Deca 68% nitric acid, open device for absorbing tail gas simultaneously, process nitrogen oxide, drip off insulation reaction sampling point in 1 hour
Analysis, raw material be less than 0.5% after stopped reaction, (3) are when in enamel reaction still, temperature is cooled to below 120 DEG C, plus recovery water
In right amount, when in enamel reaction still temperature be cooled to less than 30 DEG C, filter out product, disposing mother liquor dehydration is applied mechanically, and filter cake is washed, and obtains
Crude product.
Further, described 2- nitro-to thiamphenicol benzoic acid produce method of purification step be: (1) will aoxidize after thick
Product put in enamel reaction still, plus appropriate ordinary water, Deca 15% alkali liquor when stirring is below 40 DEG C, control ph solid in 7-8, kettle
After material is substantially entirely molten, in another reactor, filter cake returns to upper rinse reaction to vacuum filter, and filtrate is neutralized with hydrochloric acid
Ph2-3, stirring surveys that ph value is constant to be dried it is ensured that product all separates out with centrifuge for 1 hour, washes filter cake, wet feed send drying room dry
Dry, drying and packaging enters storehouse, and filtrate and washing water enter sewage plant, process up to standard time circulatory pool, make Municipal Sewage for Circulating.
Compared with prior art, the invention has the beneficial effects as follows:
A kind of 2- nitro of the present invention-and to thiamphenicol benzoic acid production technology, by nitrification, oxidation, the process purifying, can
Improve the efficiency of production, adjacent nitro is used nitric acid oxidation to thiamphenicol benzoic acid under vanadic anhydride catalysis, can improve
The purity of product and yield, replace fatty acid and methanol equal solvent with water simultaneously, not only greatly reduce production cost, reduce
Corrosion to equipment, and also reduce the discharge of spent acid, meet cleanly production, also improve the peace in production process simultaneously
Quan Xing.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described it is clear that being retouched
The embodiment stated is only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, this
The every other embodiment that field those of ordinary skill is obtained under the premise of not making creative work, broadly falls into the present invention
The scope of protection.
The present invention provides a kind of technical scheme: a kind of 2- nitro-to thiamphenicol benzoic acid production technology, including 2- nitro-
It is to methylsulfonyltoluene, nitric acid, sulphuric acid, vanadic anhydride, sodium hydroxide, hydrochloric acid to thiamphenicol benzoic acid production material, described
2- nitro-be to thiamphenicol benzoic acid production manufacturing technique method step: nitrification, oxidation, purification.
Described 2- nitro-be to thiamphenicol benzoic acid production nitration method step: (1) first puts into first in enamel reaction still
Sulfuryl toluene, puts into sulphuric acid in enamel reaction still, is then stirred；(2) after the completion of stirring and then to enamel reaction still
Middle addition chilled brine is lowered the temperature, until temperature stops to less than 15 DEG C；(3) it is slowly added into 68% in enamel reaction still
Nitric acid, is then stirred reacting 1 hour, is being sampled analyzing；(4) when content terminates to react more than 99%, Ran Houzai
Add ordinary water, and by temperature control at 15 DEG C -20 DEG C, itrated compound all separated out, filter, solid product treats that the next step is used,
After mother liquor concentrations dehydration, next time feeds intake and applies mechanically, and continues to apply mechanically during abjection water reaction treatment product, adds appropriate when feeding intake for the second time
Sulphuric acid.
Described 2- nitro-be to thiamphenicol benzoic acid production oxidation process steps: (1), in enamel still, input walks nitre
Material, adds oxidation to apply mechanically mother solution, adds catalyst, and stirring intensification is dewatered to 140 DEG C；(2) and then to enamel reaction still start
Deca 68% nitric acid, opens device for absorbing tail gas simultaneously, processes nitrogen oxide, drips off 1 hour sample analysis of insulation reaction, raw material is low
Stopped reaction after 0.5%, (3) are when in enamel reaction still, temperature is cooled to below 120 DEG C, plus recovery appropriate amount of water, when warding off
Porcelain reactor temperature is cooled to less than 30 DEG C, filters out product, and disposing mother liquor dehydration is applied mechanically, and filter cake is washed, and obtains crude product.
Described 2- nitro-be to thiamphenicol benzoic acid production method of purification step: the crude product input after (1) will aoxidize is warded off
In porcelain reactor, plus appropriate ordinary water, Deca 15% alkali liquor when stirring is below 40 DEG C, control ph solid material in 7-8, kettle substantially complete
After molten, in another reactor, filter cake returns to upper rinse reaction to vacuum filter, and filtrate is neutralized with hydrochloric acid ph2-3, stirring
1 hour survey ph value constant it is ensured that product all separates out, with centrifuge dry, wash filter cake, wet feed send drying room be dried, dry wrap
Put into storehouse, filtrate and washing water enter sewage plant, process up to standard time circulatory pool, make Municipal Sewage for Circulating.
In sum, the present invention passes through nitrification, oxidation, the process of purification, can improve the efficiency of production, by adjacent nitro pair
Thiamphenicol benzoic acid uses nitric acid oxidation under vanadic anhydride catalysis, can improve purity and the yield of product, simultaneously with water generation
For fatty acid and methanol equal solvent, not only greatly reduce production cost, reduce the corrosion to equipment, and also reduce spent acid
Discharge, meet cleanly production, also improve the safety in production process simultaneously.
Although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, permissible
Understand and can carry out multiple changes, modification, replacement to these embodiments without departing from the principles and spirit of the present invention
And modification, the scope of the present invention be defined by the appended.
Claims (4)
1. a kind of 2- nitro-to thiamphenicol benzoic acid production technology it is characterised in that: include 2- nitro-to thiamphenicol benzoic acid
Production material is to methylsulfonyltoluene, nitric acid, sulphuric acid, vanadic anhydride, sodium hydroxide, hydrochloric acid, described 2- nitro-to methylsulfonyl
Benzoic acid produces manufacturing technique method step: nitrification, oxidation, purification.
2. a kind of 2- nitro according to claim 1-to thiamphenicol benzoic acid production technology it is characterised in that: described 2-
Nitro-be to thiamphenicol benzoic acid production nitration method step: (1) first puts into methylsulfonyltoluene in enamel reaction still, right
Put into sulphuric acid in enamel reaction still, be then stirred；(2) after the completion of stirring and then to addition chilled brine in enamel reaction still
Lowered the temperature, until temperature stops to less than 15 DEG C；(3) it is slowly added into 68% nitric acid in enamel reaction still, then carry out
Stirring reaction 1 hour, is being sampled analyzing；(4) when content terminates to react more than 99%, then add ordinary water, and will
Temperature control, at 15 DEG C -20 DEG C, itrated compound is all separated out, and filters, and solid product treats that the next step is used, after mother liquor concentrations dehydration
Feed intake next time and apply mechanically, continue to apply mechanically during abjection water reaction treatment product, when feeding intake, add moderate amount of sulfuric acid for the second time.
3. a kind of 2- nitro according to claim 1-to thiamphenicol benzoic acid production technology it is characterised in that: described 2-
Nitro-be to thiamphenicol benzoic acid production oxidation process steps: (1), in enamel still, in input, step nitrification material, adds and aoxidize set
With mother solution, add catalyst, stirring intensification is dewatered to 140 DEG C；(2) and then to enamel reaction still start Deca 68% nitric acid, with
Shi Kaiqi device for absorbing tail gas, processes nitrogen oxide, drips off 1 hour sample analysis of insulation reaction, and raw material stops anti-after being less than 0.5%
Should, (3) are when in enamel reaction still, temperature is cooled to below 120 DEG C, plus recovery appropriate amount of water, when in enamel reaction still, temperature is cold
But to less than 30 DEG C, filter out product, disposing mother liquor dehydration is applied mechanically, and filter cake is washed, and obtains crude product.
4. a kind of 2- nitro according to claim 1-to thiamphenicol benzoic acid production technology it is characterised in that: described 2-
Nitro-be to thiamphenicol benzoic acid production method of purification step: the crude product after (1) will aoxidize puts in enamel reaction still, plus often
Appropriate amount of water, Deca 15% alkali liquor when stirring is less than 40 DEG C, control ph in 7-8, kettle solid expect substantially entirely molten after, vacuum filter arrives
In another reactor, filter cake returns to upper rinse reaction, and filtrate is neutralized with hydrochloric acid ph2-3, and stirring surveys ph value not in 1 hour
Become it is ensured that product all separates out, dried with centrifuge, wash filter cake, wet feed send drying room to be dried, and drying and packaging enters storehouse, filtrate and
Washing water enters sewage plant, processes up to standard time circulatory pool, makees Municipal Sewage for Circulating.
Priority Applications (1)
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|---|---|---|---|
| CN201610776958.9A CN106366023A (en) | 2016-08-30 | 2016-08-30 | Production process for 2-nitro-methyl sulfone benzoic acid |
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| CN201610776958.9A CN106366023A (en) | 2016-08-30 | 2016-08-30 | Production process for 2-nitro-methyl sulfone benzoic acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503437A (en) * | 2019-01-16 | 2019-03-22 | 江苏新鑫隆医药科技股份有限公司 | The preparation method of 2- nitryl-4-thiamphenicol benzoic acid |
| CN111302984A (en) * | 2020-04-09 | 2020-06-19 | 利民化学有限责任公司 | Method for recycling acid in synthesis of 2-nitro-4-methylsulfonylbenzoic acid |
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| US4781750A (en) * | 1985-08-27 | 1988-11-01 | Rohm And Haas Company | Herbicidally active enols |
| CN1038584C (en) * | 1992-10-19 | 1998-06-03 | Basf公司 | Preparation of methylsulfonylbenzoic acids |
| CN101921215A (en) * | 2010-08-20 | 2010-12-22 | 安吉豪森药业有限公司 | Method for producing 2-nitro-p-methylsullfonyl benzoic acid |
| CN104803815A (en) * | 2015-03-25 | 2015-07-29 | 浙江嘉化能源化工股份有限公司 | Industrial production method of benzoic acid containing electron withdrawing groups on benzene rings |
| CN105669504A (en) * | 2016-03-07 | 2016-06-15 | 山东润博生物科技有限公司 | Preparation method of 2-nitro-4-methyl sulphonyl benzoic acid |
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| CN1038584C (en) * | 1992-10-19 | 1998-06-03 | Basf公司 | Preparation of methylsulfonylbenzoic acids |
| CN101921215A (en) * | 2010-08-20 | 2010-12-22 | 安吉豪森药业有限公司 | Method for producing 2-nitro-p-methylsullfonyl benzoic acid |
| CN104803815A (en) * | 2015-03-25 | 2015-07-29 | 浙江嘉化能源化工股份有限公司 | Industrial production method of benzoic acid containing electron withdrawing groups on benzene rings |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503437A (en) * | 2019-01-16 | 2019-03-22 | 江苏新鑫隆医药科技股份有限公司 | The preparation method of 2- nitryl-4-thiamphenicol benzoic acid |
| CN111302984A (en) * | 2020-04-09 | 2020-06-19 | 利民化学有限责任公司 | Method for recycling acid in synthesis of 2-nitro-4-methylsulfonylbenzoic acid |
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