CN106397282A - Oxidation process for 2-nitro-p-methylsulfonylbenzoic acid - Google Patents

Oxidation process for 2-nitro-p-methylsulfonylbenzoic acid Download PDF

Info

Publication number
CN106397282A
CN106397282A CN201610776924.XA CN201610776924A CN106397282A CN 106397282 A CN106397282 A CN 106397282A CN 201610776924 A CN201610776924 A CN 201610776924A CN 106397282 A CN106397282 A CN 106397282A
Authority
CN
China
Prior art keywords
nitro
oxidation
benzoic acid
thiamphenicol benzoic
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610776924.XA
Other languages
Chinese (zh)
Inventor
李仁峰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jujube Guipu Material Ltd Company
Original Assignee
Jujube Guipu Material Ltd Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jujube Guipu Material Ltd Company filed Critical Jujube Guipu Material Ltd Company
Priority to CN201610776924.XA priority Critical patent/CN106397282A/en
Publication of CN106397282A publication Critical patent/CN106397282A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00Preparation of sulfones; Preparation of sulfoxides
    • C07C315/04Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00Preparation of sulfones; Preparation of sulfoxides
    • C07C315/06Separation; Purification; Stabilisation; Use of additives

Abstract

The invention discloses an oxidation process for 2-nitro-p-methylsulfonylbenzoic acid. Raw materials for oxidation of 2-nitro-p-methylsulfonylbenzoic acid are composed of a nitration material, a mother liquor for an oxidation sleeve, a catalyst, nitric acid with a concentration of 68% and common water. An oxidation apparatus for 2-nitro-p-methylsulfonylbenzoic acid comprises an enamel reaction vessel, a stirring device and a tail gas absorbing device. According to the invention, tail gas produced in the process of oxidation can be absorbed and treated through arrangement of the tail gas absorbing device, so pollution is reduced; through oxidation via nitric acid under the catalysis of vanadic anhydride, product purity and yield are improved; water is used for replacing solvents like fatty acid and methanol, so production cost is substantially lowered, corrosion to equipment is reduced, discharge of waste acid is decreased, requirements of clean production are met, and security in the process of production is enhanced.

Description

A kind of 2- nitro-to thiamphenicol benzoic acid oxidation technology
Technical field
The present invention relates to chemical products manufacture field, specially a kind of 2- nitro-to thiamphenicol benzoic acid oxidation 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 normal 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 agricultural chemicals.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 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-and in thiamphenicol benzoic acid oxidation technology, quality cannot be protected with efficiency, exist simultaneously Substantial amounts of tail gas can be produced after oxidation, pollute environment, and using fat acid and methyl alcohol equal solvent, improve production cost, right The corrosion of 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 oxidation technology, to solve above-mentioned background The problem proposing in technology.
For achieving the above object, the present invention provides following technical scheme:A kind of 2- nitro-work is aoxidized to thiamphenicol benzoic acid Skill, described 2- nitro-thiamphenicol benzoic acid oxidationization raw material is included nitrifying material, aoxidizes and apply mechanically mother liquor, catalyst, 68% nitre Acid, ordinary water, described 2- nitro-to thiamphenicol benzoic acid oxidation unit includes enamel reaction still, agitating device, tail gas absorption dress Put,
Described 2- nitro-be to thiamphenicol benzoic acid oxidation step:
(1) in enamel reaction still, put into nitrification material, add oxidation to apply mechanically mother liquor 1400-1600kg, add catalyst 1.5-2.5kg, is stirred;
(2) when stirring intensification is dewatered to 135-145 DEG C, drip 68% nitric acid 350-450kg;
(3) when dripping 68% nitric acid, open device for absorbing tail gas, process nitrogen oxide, and after dripping off, enamel is reacted Kettle carries out insulation reaction 1-1.5 hour;
(4) carry out sample analysis after insulation reaction 1-1.5 hour, stop reaction after raw material is less than 0.5%;
(5) in enamel reaction still, temperature is cooled to addition ordinary water when 100-120 DEG C;
(6) when temperature is cooled to 20-30 DEG C in enamel reaction still, filter out product, disposing mother liquor dehydration is applied mechanically, filter cake Washing, obtains crude product.
Further, the capacity of described enamel reaction still is 3000L.
Further, described nitrification material for 2- nitro-to after thiamphenicol benzoic acid nitration processes produce raw material.
Further, described catalyst is vanadic anhydride.
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 oxidation technology, it is provided by exhaust gas processing device, permissible Absorb and process the tail gas producing in oxidizing process, reduce pollution, use nitric acid oxidation using under vanadic anhydride catalysis, can improve The purity of product and yield, replace aliphatic acid and methyl alcohol 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 this The scope of bright protection.
Embodiment 1
A kind of 2- nitro-to thiamphenicol benzoic acid oxidation technology, described 2- nitro-to thiamphenicol benzoic acid oxidationization raw material Apply mechanically mother liquor, catalyst, 68% nitric acid, ordinary water, described 2- nitro-dress is aoxidized to thiamphenicol benzoic acid including nitrification material, oxidation Put including enamel reaction still, agitating device, device for absorbing tail gas,
Described 2- nitro-be to thiamphenicol benzoic acid oxidation step:
(1) in enamel reaction still, put into nitrification material, add oxidation to apply mechanically mother liquor 1400kg, add catalyst 1.5kg, It is stirred;
(2) when stirring intensification is dewatered to 135 DEG C, drip 68% nitric acid 350kg;
(3) when dripping 68% nitric acid, open device for absorbing tail gas, process nitrogen oxide, and after dripping off, enamel is reacted Kettle carries out insulation reaction 1 hour;
(4) insulation reaction carried out sample analysis after 1 hour, stopped reaction after raw material is less than 0.5%;
(5) in enamel reaction still, temperature is cooled to addition ordinary water when 100 DEG C;
(6) when temperature is cooled to 20 DEG C in enamel reaction still, filter out product, disposing mother liquor dehydration is applied mechanically, filter cake water Wash, obtain crude product.
Further, the capacity of described enamel reaction still is 3000L.
Further, described nitrification material for 2- nitro-to after thiamphenicol benzoic acid nitration processes produce raw material.
Further, described catalyst is vanadic anhydride.
Embodiment 2
A kind of 2- nitro-to thiamphenicol benzoic acid oxidation technology, described 2- nitro-to thiamphenicol benzoic acid oxidationization raw material Apply mechanically mother liquor, catalyst, 68% nitric acid, ordinary water, described 2- nitro-dress is aoxidized to thiamphenicol benzoic acid including nitrification material, oxidation Put including enamel reaction still, agitating device, device for absorbing tail gas,
Described 2- nitro-be to thiamphenicol benzoic acid oxidation step:
(1) in enamel reaction still, put into nitrification material, add oxidation to apply mechanically mother liquor 1500kg, add catalyst 2kg, enter Row stirring;
(2) when stirring intensification is dewatered to 140 DEG C, drip 68% nitric acid 400kg;
(3) when dripping 68% nitric acid, open device for absorbing tail gas, process nitrogen oxide, and after dripping off, enamel is reacted Kettle carries out insulation reaction 1.2 hours;
(4) insulation reaction carried out sample analysis after 1.2 hours, stopped reaction after raw material is less than 0.5%;
(5) in enamel reaction still, temperature is cooled to addition ordinary water when 110 DEG C;
(6) when temperature is cooled to 25 DEG C in enamel reaction still, filter out product, disposing mother liquor dehydration is applied mechanically, filter cake water Wash, obtain crude product.
Further, the capacity of described enamel reaction still is 3000L.
Further, described nitrification material for 2- nitro-to after thiamphenicol benzoic acid nitration processes produce raw material.
Further, described catalyst is vanadic anhydride.
Embodiment 3
A kind of 2- nitro-to thiamphenicol benzoic acid oxidation technology, described 2- nitro-to thiamphenicol benzoic acid oxidationization raw material Apply mechanically mother liquor, catalyst, 68% nitric acid, ordinary water, described 2- nitro-dress is aoxidized to thiamphenicol benzoic acid including nitrification material, oxidation Put including enamel reaction still, agitating device, device for absorbing tail gas,
Described 2- nitro-be to thiamphenicol benzoic acid oxidation step:
(1) in enamel reaction still, put into nitrification material, add oxidation to apply mechanically mother liquor 1600kg, add catalyst 2.5kg, It is stirred;
(2) when stirring intensification is dewatered to 145 DEG C, drip 68% nitric acid 450kg;
(3) when dripping 68% nitric acid, open device for absorbing tail gas, process nitrogen oxide, and after dripping off, enamel is reacted Kettle carries out insulation reaction 1.5 hours;
(4) insulation reaction carried out sample analysis after 1.5 hours, stopped reaction after raw material is less than 0.5%;
(5) in enamel reaction still, temperature is cooled to addition ordinary water when 120 DEG C;
(6) when temperature is cooled to 30 DEG C in enamel reaction still, filter out product, disposing mother liquor dehydration is applied mechanically, filter cake water Wash, obtain crude product.
Further, the capacity of described enamel reaction still is 3000L.
Further, described nitrification material for 2- nitro-to after thiamphenicol benzoic acid nitration processes produce raw material.
Further, described catalyst is vanadic anhydride.
In sum, the present invention is provided by exhaust gas processing device, can absorb and process the tail producing in oxidizing process Gas, reduces pollution, using vanadic anhydride catalysis under use nitric acid oxidation, purity and the yield of product can be improve, simultaneously with Water replaces aliphatic acid and methyl alcohol equal solvent, not only greatly reduces production cost, reduces the corrosion to equipment, and also reduces The discharge of spent acid, meets cleanly production, also improves the security 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 oxidation technology it is characterised in that:Described 2- nitro-to thiamphenicol benzoic acid Oxidationization raw material includes nitrification material, mother liquor, catalyst, 68% nitric acid, ordinary water are applied mechanically in oxidation, and described 2- nitro-to methylsulfonyl benzene Oxidation of Formic Acid device includes enamel reaction still, agitating device, device for absorbing tail gas,
Described 2- nitro-be to thiamphenicol benzoic acid oxidation step:
(1) in enamel reaction still, put into nitrification material, add oxidation to apply mechanically mother liquor 1400-1600kg, add catalyst 1.5- 2.5kg, is stirred;
(2) when stirring intensification is dewatered to 135-145 DEG C, drip 68% nitric acid 350-450kg;
(3) when dripping 68% nitric acid, open device for absorbing tail gas, process nitrogen oxide, and after dripping off, enamel reaction still is entered Row insulation reaction 1-1.5 hour;
(4) carry out sample analysis after insulation reaction 1-1.5 hour, stop reaction after raw material is less than 0.5%;
(5) in enamel reaction still, temperature is cooled to addition ordinary water when 100-120 DEG C;
(6) when temperature is cooled to 20-30 DEG C in enamel reaction still, filter out product, disposing mother liquor dehydration is applied mechanically, filter cake water Wash, obtain crude product.
2. a kind of 2- nitro according to claim 1-to thiamphenicol benzoic acid oxidation technology it is characterised in that:Described ward off The capacity of porcelain reactor is 3000L.
3. a kind of 2- nitro according to claim 1-to thiamphenicol benzoic acid oxidation technology it is characterised in that:Described nitre Material be 2- nitro-to after thiamphenicol benzoic acid nitration processes produce raw material.
4. a kind of 2- nitro according to claim 1-to thiamphenicol benzoic acid oxidation technology it is characterised in that:Described urge Agent is vanadic anhydride.
CN201610776924.XA 2016-08-30 2016-08-30 Oxidation process for 2-nitro-p-methylsulfonylbenzoic acid Pending CN106397282A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610776924.XA CN106397282A (en) 2016-08-30 2016-08-30 Oxidation process for 2-nitro-p-methylsulfonylbenzoic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610776924.XA CN106397282A (en) 2016-08-30 2016-08-30 Oxidation process for 2-nitro-p-methylsulfonylbenzoic acid

Publications (1)

Publication Number Publication Date
CN106397282A true CN106397282A (en) 2017-02-15

Family

ID=58003232

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610776924.XA Pending CN106397282A (en) 2016-08-30 2016-08-30 Oxidation process for 2-nitro-p-methylsulfonylbenzoic acid

Country Status (1)

Country Link
CN (1) CN106397282A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
来虎钦 等: "2-硝基-4-甲磺酰基苯甲酸的绿色合成研究", 《浙江工业大学学报》 *
杨剑波 等: "硝磺酮的合成与除草效果", 《农药》 *
高学彦 等: "2-硝基-4-甲磺酰基苯甲酸的合成研究", 《化学试剂》 *

Similar Documents

Publication Publication Date Title
KR970000136B1 (en) Process for producing highly purified benzenedicarboxylic acid isomers
US6153790A (en) Method to produce aromatic dicarboxylic acids using cobalt and zirconium catalysts
JP2006528682A (en) Method for heating crude carboxylic acid slurry in post-oxidation zone by adding steam
CN101648866B (en) Preparation technology of p-tert-butyl benzoic acid
CN103771353B (en) A kind of renovation process of waste sulfuric acid from alkylation
JPS59106435A (en) Production of high-purity terephthalic acid
CN106966884B (en) Method for preparing anthraquinone by oxidizing anthracene
CN103638956A (en) Catalyst for synthesizing methyl acrylate by trioxymethylene or paraformaldehyde and acetic acid and acetic acid aqueous solution, its preparation and its application method
CN102020555B (en) Method for preparing hindered phenol antioxygens by ester exchange process
CN105688985B (en) A kind of preparation method of solid-carrying type ionic-liquid catalyst
CN103570493A (en) Method for synthesizing 1,2-orthodiol through immobilized type heteropolyacid phase-transfer catalytic oxidation
CN100543012C (en) Preparation 1,4-diamino-2, the method for 3-dicyan anthraquinone
CN102134331A (en) Recycling method of waste silicone rubber
CN106925349A (en) A kind of solid supported type metal porphyrin catalyst and its application in terms of maleic acid is prepared
CN104774165A (en) Green and industrial preparation method of rubber peptizer DBD
CN108794321B (en) Method for synthesizing aromatic carboxylic acid compounds in continuous flow microchannel reactor
CN1843938A (en) Method for preparing vanadium pentoxide
CN106278953B (en) A kind of production method for improving Metformin hydrochloride purity
CN103937616B (en) Method for extracting high-purity unsaturated fatty acid from soybean oil
CN104945250A (en) Method for synthesizing n-butyl acetate
CN104649911A (en) Preparation method of p-nitrophenol
CN106431930A (en) Method for preparing nitrobenzene from benzene
CN101121657A (en) Method for catalyzing acetylization reaction
CN105921161B (en) A kind of catalyst and preparation method thereof preparing 2,5- chlorophenesic acids for paracide hydroxylating
CN109912413B (en) Method for synthesizing butyl oleate by catalyzing oleic acid-based ionic liquid microemulsion

Legal Events

Date Code Title Description
PB01 Publication
C06 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20170215

RJ01 Rejection of invention patent application after publication