CN107056633A - A kind of method of diformazan Aminobenzoic Acid between production - Google Patents
A kind of method of diformazan Aminobenzoic Acid between production Download PDFInfo
- Publication number
- CN107056633A CN107056633A CN201610809652.9A CN201610809652A CN107056633A CN 107056633 A CN107056633 A CN 107056633A CN 201610809652 A CN201610809652 A CN 201610809652A CN 107056633 A CN107056633 A CN 107056633A
- Authority
- CN
- China
- Prior art keywords
- diformazan
- product
- acid
- catalyst
- aminobenzoic 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
Abstract
The present invention relates to a kind of method of diformazan Aminobenzoic Acid between production, this method uses m-Nitrobenzoic Acid raw material, catalyst is made of palladium carbon, methanol and ether mixture make solvent, 30 60oC temperature, normal pressure（30 centimetres to 50 centimeter water columns）Stirring hydrogenation produces gavaculine, after the completion of the hydrogen-sucking amount for treating the reduction of first step nitro, adds formalin, continues to stir hydrogenation in same temperature and pressure.After the completion of the hydrogen-sucking amount for treating second step hydrogenation, stop reaction, catalyst is recovered by filtration and is used for next time, filtrate concentration steams solvent, product is collected by filtration, after product is washed with a small amount, 100oC is dried, and produces product m-dimethyl amino benzoic acid, and yield is 90 93%, and fusing point is 151oC。
Description
Technical field
The present invention relates to a kind of method of diformazan Aminobenzoic Acid between production.
Background technology
M-dimethyl amino benzoic acid is a kind of important synthesis for having intermediate, mainly using pressure sensitive dye and heat sensitive dye, also
It can be used for the synthesis of liquid crystal material and paint pigment.The technology of existing synthesis m-dimethyl amino benzoic acid mainly has：1）Between
Nitrophthalic acid is raw material, obtains a diformazan Aminobenzoic Acid through reducing the steps such as decarboxylation that methylate, the shortcoming of this method is anti-
Answer accessory substance many, gross production rate is low；2）Using m-bromoaniline as raw material, through methylating and the step such as carboxylated obtains a diformazan phenalgin first
Acid, it is many that this method equally exists byproduct of reaction, the low shortcoming of gross production rate；3）Raw material is made with gavaculine, through methylating
A diformazan Aminobenzoic Acid is obtained, conventional methylating reagent has dimethyl suflfate and alkyl halide etc., and this method has the disadvantage an amino
Benzoic acid source is not wide, and easily oxidation, and also methylating reagent is poisonous, harmful to workman's body.Therefore, document US
4233458 report m-Nitrobenzoic Acids make raw material, and with methanol as solvent, catalyst is made with palladium carbon, adds a small amount of acetic acid to protect
Palladium-carbon catalyst is protected, gavaculine is generated through catalytic hydrogenating reduction, formaldehyde is then added and continues to be hydrogenated with, two between finally obtaining
First Aminobenzoic Acid；This method well just fortunately yield it is high, and there is no the accessory substance of influence environment；But autoclave pressure is used,
The Hydrogen Vapor Pressure of the first step is 0.28MPa, and the Hydrogen Vapor Pressure of second step is 0.68 MPa.This shortcoming will except in industrial production
Use outside autoclave pressure, the hydrogen residue amount of steel cylinder is larger, is unfavorable for reducing cost..
The content of the invention
The problem to be solved in the present invention is, without using autoclave pressure, to allow reaction to carry out at ambient pressure, has so both saved disposable
The cost of autoclave is bought in investment, and remaining hydrogen in steel cylinder has been saved again.
By the methods describeds of US 4233458, starting hydrogenation m-Nitrobenzoic Acid at low temperature, to produce a kind of solubility very low
Intermediate, catalyst is covered, the intermediate is exactly the poisonous substance of catalyst, makes hydrogenation be difficult to proceed down, when serious
Airway tube can even be blocked, prevent hydrogenation from going on.The present invention is that a small amount of ether solvent, such as fourth are added in solvent
Ether or tetrahydrofuran, dissolve the poisonous substance being initially generated, and no longer add acetic acid, and ether solvent consumption is 2% to 100%.
Reaction equation such as Fig. 1.
It is an advantage of the invention that reaction does not need autoclave pressure, first time cost of investment is reduced；Save hydrogen.
Technical key point：
Using methanol and the mixed solvent of ethers, ethers can be also butyl ether, cyclic ethers, such as tetrahydrofuran.It can also be pure ethers
Solvent.
Hydrogenate at ambient pressure, the consumption of ether can be also 2 % -100%.
Reaction temperature is 30oC is to system boiling point.
Brief description of the drawings
Fig. 1 is the synthetic route chart of this production method.
Fig. 2 is reaction unit schematic diagram.
Embodiment
【Example 1】
In 250mL glass there-necked flask, 95mL methanol and 3mL tetrahydrofurans, 16.7g m-Nitrobenzoic Acids, 0.2g 5% are added
Palladium carbon, in constant pressure funnel add 15.2mL 37% formalin.Air in reaction system is taken out with water pump
Walk, then pass to atmospheric hydrogen.Temperature is risen to 64oC, stirring reaction is to no longer inhaling hydrogen.Formalin is added from dropping funel,
Continue to stir to be hydrogenated at this temperature no longer to inhale hydrogen.Stop stirring, catalyst is recovered by filtration, filtrate concentration, product is to separate out.
Product is collected by filtration, product is washed with a small amount, then again 100oC is dried, and obtains product m-dimethyl amino benzoic acid 15.3g, is produced
Rate is 93%.After catalyst is reclaimed, lower secondary response is used further to after being washed with reaction dissolvent.
【Example 2】
In 250mL glass there-necked flask, addition 100mL tetrahydrofurans, 16.7g m-Nitrobenzoic Acids, 0.2g 5% palladium carbon,
15.2mL 37% formalin is added in constant pressure funnel.Air in reaction system is taken away with water pump, Ran Houtong
Enter atmospheric hydrogen.Temperature is risen to 66oC, stirring reaction is to no longer inhaling hydrogen.Formalin is added from dropping funel, is continued herein
At a temperature of stirring be hydrogenated to and no longer inhale hydrogen.Stop stirring, catalyst is recovered by filtration, filtrate concentration, product is to separate out.It is collected by filtration
Product, is washed with a small amount product, and then again 100oC is dried, and obtains product m-dimethyl amino benzoic acid 15.2g, yield is 92%.
After catalyst is reclaimed, lower secondary response is used further to after being washed with reaction dissolvent.
【Example 3】
In 250mL glass there-necked flask, 98mL methanol and 2mL butyl ether, 16.7g m-Nitrobenzoic Acids, 0.2g 5% are added
Palladium carbon, in constant pressure funnel add 15.2mL 37% formalin.Air in reaction system is taken out with water pump
Walk, then pass to atmospheric hydrogen.Temperature is risen to 65oC, stirring reaction is to no longer inhaling hydrogen.Formalin is added from dropping funel,
Continue to stir to be hydrogenated at this temperature no longer to inhale hydrogen.Stop stirring, catalyst is recovered by filtration, filtrate concentration, product is to separate out.
Product is collected by filtration, product is washed with a small amount, then again 100oC is dried, and obtains product m-dimethyl amino benzoic acid 14.9g, is produced
Rate is 90%.After catalyst is reclaimed, lower secondary response is used further to after being washed with reaction dissolvent.
Claims (5)
1. a kind of method of diformazan Aminobenzoic Acid between production, using m-Nitrobenzoic Acid as raw material, is mixed with methanol and ether solvent
Thing is solvent, using palladium carbon as catalyst, at ambient pressure, 30oC is at a temperature of boiling point, and hydrogenation obtains intermediate product m-aminophenyl
Formic acid, then adds formalin and continues after normal pressure hydrogenation, separating catalyst, concentration obtains diformazan phenalgin first between product after filtering
Acid.
2. the method for diformazan Aminobenzoic Acid between production according to claim 1, it is characterised in that methanol and ether solvent are mixed
Compound is solvent, such as ether solvent butyl ether, cyclic ethers, tetrahydrofuran.
3. the ratio of ether solvent can be 2% to 100%.
4. the method for diformazan Aminobenzoic Acid between production according to claim 1, it is characterised in that reaction temperature is 35oC is to body
It is boiling point.
5. the method for diformazan Aminobenzoic Acid between production according to claim 1, it is characterised in that reaction hydrogen pressure is normal pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610809652.9A CN107056633A (en) | 2016-09-08 | 2016-09-08 | A kind of method of diformazan Aminobenzoic Acid between production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610809652.9A CN107056633A (en) | 2016-09-08 | 2016-09-08 | A kind of method of diformazan Aminobenzoic Acid between production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107056633A true CN107056633A (en) | 2017-08-18 |
Family
ID=59617082
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610809652.9A Pending CN107056633A (en) | 2016-09-08 | 2016-09-08 | A kind of method of diformazan Aminobenzoic Acid between production |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107056633A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4233458A (en) * | 1978-07-28 | 1980-11-11 | American Cyanamid Company | Process for preparing N,N-dimethylaminobenzoic acids |
| JP2000256291A (en) * | 1999-03-09 | 2000-09-19 | Mitsui Chemicals Inc | Production of n-alkyl-substituted aromatic amino compound |
| CN1418863A (en) * | 2001-11-14 | 2003-05-21 | 中国石油化工股份有限公司 | Process for producing m-dimethylamine benzoic acid |
| CN104098485A (en) * | 2014-05-26 | 2014-10-15 | 张家港威胜生物医药有限公司 | Preparation method of o-aminophenyl hydroxylamine |
-
2016
- 2016-09-08 CN CN201610809652.9A patent/CN107056633A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4233458A (en) * | 1978-07-28 | 1980-11-11 | American Cyanamid Company | Process for preparing N,N-dimethylaminobenzoic acids |
| JP2000256291A (en) * | 1999-03-09 | 2000-09-19 | Mitsui Chemicals Inc | Production of n-alkyl-substituted aromatic amino compound |
| CN1418863A (en) * | 2001-11-14 | 2003-05-21 | 中国石油化工股份有限公司 | Process for producing m-dimethylamine benzoic acid |
| CN104098485A (en) * | 2014-05-26 | 2014-10-15 | 张家港威胜生物医药有限公司 | Preparation method of o-aminophenyl hydroxylamine |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cabrero-Antonino et al. | A general protocol for the reductive N-methylation of amines using dimethyl carbonate and molecular hydrogen: mechanistic insights and kinetic studies | |
| CN102285891B (en) | Method for preparing arylamine by catalytic hydrogenation of aromatic nitro compound | |
| Sajiki et al. | Highly chemoselective hydrogenation with retention of the epoxide function using a heterogeneous Pd/C‐ethylenediamine catalyst and THF | |
| JPH01146831A (en) | Production of fluorinated c4-c6 hydrocarbon | |
| CN104507904B (en) | Method for producing amino propyl methyl monoethanolamine | |
| CN106518755B (en) | A kind of method synthesizing 2,3- dichloropyridine | |
| CN107056633A (en) | A kind of method of diformazan Aminobenzoic Acid between production | |
| CN108698989B (en) | Process for the preparation of 1-methylpyrrolidin-3-ol | |
| CN103880617A (en) | Method for preparing acetylenic ketone through oxidizing propargyl alcohol | |
| CN105859574A (en) | Synthesis method of 2-amino-5-chloro-N,3-dimethylbenzamide | |
| CN104292113A (en) | Preparation method of 3-chloro-4-fluoroaniline | |
| JP5277665B2 (en) | Method for producing cycloaliphatic diamine | |
| CN107488118A (en) | A kind of method that one kettle way prepares tertiary amino alcoholic compound | |
| Kende et al. | Synthesis of 1-hydroxyoxindoles | |
| CN101538212A (en) | Method for preparing 4-hydroxy-3-methoxybenzylamine hydrochloride | |
| CN105152884B (en) | Preparation method of 4-methoxycyclohexanon | |
| CN104086452A (en) | Method for preparing high-purity (3,4-diaminophenyl)(4-fluorophenyl) ketone by virtue of catalytic hydrogenation | |
| JP2006249036A (en) | Method for producing 2, 3, 5-trimethylhydroquinone | |
| KR100723562B1 (en) | Method for Producing 2-Benzylaniline | |
| CN104230690B (en) | A kind of solid catalysis efficiently prepares the method for 9-Fluorenone | |
| CN106380439A (en) | A Pd/C reduction method adopting water as a solvent for preparing indole-2-carboxylic acid | |
| CN103804350B (en) | A kind of preparation method of high purity pool horse degree amine | |
| JP2012001471A (en) | Production step control method of sulfolane | |
| CN107383076A (en) | A kind of synthetic method of the chlorophenylboronic acid pinacol ester of 3 amino 4 | |
| CN105294568A (en) | Novel preparation method of benzimidazolone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | 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: 20170818 |
|
| RJ01 | Rejection of invention patent application after publication |