CN106986783A - A kind of preparation method of 3 aminophthalic acid - Google Patents
A kind of preparation method of 3 aminophthalic acid Download PDFInfo
- Publication number
- CN106986783A CN106986783A CN201710206049.6A CN201710206049A CN106986783A CN 106986783 A CN106986783 A CN 106986783A CN 201710206049 A CN201710206049 A CN 201710206049A CN 106986783 A CN106986783 A CN 106986783A
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- CN
- China
- Prior art keywords
- acids
- nitrophthalic
- aminophthalic
- added
- hydrogenation
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Classifications
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- 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
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- 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
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
Abstract
The invention discloses a kind of method that nitrophthalic acid of hydro-reduction in aqueous 3 prepares 3 aminophthalic acids, it is to generate 3 nitrophthalic acids and sodium hydroxide solution effect after its sodium salt solution, it is that reducing agent reduces nitro as amino using hydrogen under palladium carbon catalytic action.It is 95%, purity that yield, which can be obtained,>98% 3 aminophthalic acids.Operation is simple for this method, and technological process is short, and production cost is low, and good product purity, high income, environmental pollution is small.
Description
Technical field
3- aminophthalic acids are prepared the present invention relates to a kind of hydro-reduction 3- nitrophthalic acids in aqueous
Method.
Background technology
3- aminophthalic acids are widely used, are medicine, agricultural chemicals, pigment, the important intermediate of the industry such as dyestuff.The production
The preparation method document report of product seldom, there is the report of palladium carbon catalytic hydrogenating reduction, but raw material is is converted into sodium salt form, used
Solvent is organic solvent（Such as：Ethanol）, dangerous big, technological operation is more, and cost is high.There is the report using hydrazine hydrate reduction, make
It is dangerous big with hydrazine hydrate as reducing agent, it is unfavorable for industrialized production, and also cost is higher.Also have in addition using iron powder also
The report of former preparation-aminophthalic acid, its environmental pollution is big, and yield is low.
The content of the invention
The present invention provides a kind of method for preparing 3- aminophthalic acids, it using 3- nitrophthalic acids as raw material,
Under palladium carbon catalytic action, by reducing agent of hydrogen, reduction prepares 3- aminophthalic acids.It is short using this method technological process,
Production cost is low, good product purity, high income.
The method that what the present invention was provided prepare 3- aminophthalic acids, its chemical reaction process is as follows：
Including following preparation process：
（1）3- nitrophthalic acids and sodium hydrate aqueous solution effect are generated into its sodium salt solution, the wherein adjacent benzene two of 3- nitros
The mol ratio of formic acid and sodium hydroxide is 1:2.05~1:3.0；
（2）To step（1）Catalyst palladium carbon is added in the solution generated, catalyst amount is 3- nitrophthalic acid consumptions
0.1% ~ 30%；
（3）Foregoing mixed solution is added in hydriding reactor, carried out after gas displacement, insulation hydrogenation, hydrogenation temperature is 5 ~ 95 DEG C,
Hydrogenation pressure is 0.05 ~ 10Mpa；
（4）After the completion of hydrogenation, palladium carbon is filtered out, concentrated hydrochloric acid is added into filtrate to pH<1, after crystallisation by cooling, filtration drying 3- ammonia
Base phthalic acid.
In the present invention, the mol ratio of 3- nitrophthalic acids and sodium hydroxide is 1:2.05~1:3.0；Catalyst is used
Measure as the 0.1% ~ 30% of 3- nitrophthalic acid consumptions.
Using the method for the present invention, after 3- nitrophthalic acids are made into sodium salt solution through sodium hydrate aqueous solution,
Under catalyst action, hydro-reduction amino is nitro, can obtain yield ＞ 95%, purity>98% 3- aminophthalic acids.
This method, production cost is low, and good product purity, high income, environmental pollution is small.
Embodiment
Embodiment one
（1）65g purified waters are added into 200mL beakers, 3.79gNaOH stirring and dissolvings is added, is cooled to after room temperature（25-35℃）,
Add 3- nitrophthalic acids (10g), stirring and dissolving；
（2）Above-mentioned 3- nitrophthalic acids solution is added in 2L hydriding reactors, 0.5g palladium charcoals is added, opens stirring, use nitrogen
Displaced air, then nitrogen is replaced with hydrogen, Hydrogen Vapor Pressure is maintained at 0.7-0.9Mpa, keeps reacting liquid temperature to enter at 55-65 DEG C
Row hydrogenation.Reaction about needs 12h；
（3）After reaction terminates, nitrogen displacement hydrogen is used, palladium carbon is filtered out；
（4）Filtrate is poured into 2L flasks, and reduction temperature is added dropwise about 18.8mL concentrated hydrochloric acids, maintains the temperature at -5-5 to -5-0 DEG C
DEG C, about 30min is dripped off, after being added dropwise to complete, insulated and stirred 0.5h；
（5）Suction filtration, and with ethyl acetate rinsing twice.Solid is transferred in vacuum drying chamber, in 20-45 DEG C of dry 24h（Vacuum
Degree≤- 0.095Mpa）, obtain 3- aminophthalic acid finished products.
Embodiment two
（1）To 65kg purified waters are added in 200L enamel stills, 3.79kgNaOH stirring and dissolvings are added, are cooled to after room temperature（25-35
℃）, it is transferred to after adding 3- nitrophthalic acids (10kg), stirring and dissolving in turnover barrel；
（2）The above-mentioned solution of about 20L is taken, palladium charcoal (dry weight 0.5kg) is disperseed wherein, to be pumped into 200L hydriding reactors with vacuum, then
Remaining 3- nitrophthalic acids solution is pumped into 200L hydriding reactors with vacuum, stirring is opened, nitrogen displacement air is used, then use
Hydrogen replaces nitrogen, and Hydrogen Vapor Pressure is maintained at 0.7-0.9Mpa, keeps reacting liquid temperature to be hydrogenated at 55-65 DEG C.Reaction is about
Need 12h；
（3）After reaction terminates, nitrogen displacement hydrogen is used, palladium carbon is filtered to remove with sand stick filter, it is diatomaceous with adding
Filter is refiltered once, and filtrate is pumped into filtrate in 200L enamel stills with vacuum；
（4）Temperature is reduced to -5-0 DEG C, 22.3kg is added dropwise（About 18.75L）Concentrated hydrochloric acid, maintains the temperature at -5-5 DEG C, about 30min drops
It is complete, after being added dropwise to complete, insulated and stirred 0.5h；
（5）Centrifugal filtration, and with ethyl acetate rinsing twice, each 5kg.Solid is transferred in vacuum drying chamber, in 20-45 DEG C
Dry 24h（Vacuum≤- 0.095Mpa）, obtain 3- aminophthalic acid finished products.
Claims (4)
1. a kind of method that 3- nitrophthalic acids of hydro-reduction in aqueous prepare 3- aminophthalic acids, its feature
It is that it comprises the following steps：
3- nitrophthalic acids and sodium hydroxide solution effect are generated into its sodium salt solution,；
To step（1）Catalyst palladium carbon is added in the solution generated；
Foregoing mixed solution is added in hydriding reactor, carried out after gas displacement, insulation hydrogenation；
After the completion of hydrogenation, palladium carbon is filtered out, concentrated hydrochloric acid is added into filtrate to pH=1, after crystallisation by cooling, filtration drying obtains 3- ammonia
Base phthalic acid.
2. the method according to claim 1 that 3- aminophthalic acids are prepared with 3- nitrophthalic acids, its feature
The mol ratio for being 3- nitrophthalic acids and sodium hydroxide is 1:2.05~1:3.0.
3. the method according to claim 1 that 3- aminophthalic acids are prepared with 3- nitrophthalic acids, its feature
The consumption for being palladium carbon is the 0.1% ~ 30% of 3- nitrophthalic acid consumptions.
4. the method according to claim 1 that 3- aminophthalic acids are prepared with 3- nitrophthalic acids, its feature
It is 5 ~ 95 DEG C to be hydrogenation temperature, and hydrogenation pressure is 0.05 ~ 10MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710206049.6A CN106986783A (en) | 2017-03-31 | 2017-03-31 | A kind of preparation method of 3 aminophthalic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710206049.6A CN106986783A (en) | 2017-03-31 | 2017-03-31 | A kind of preparation method of 3 aminophthalic acid |
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| Publication Number | Publication Date |
|---|---|
| CN106986783A true CN106986783A (en) | 2017-07-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710206049.6A Pending CN106986783A (en) | 2017-03-31 | 2017-03-31 | A kind of preparation method of 3 aminophthalic acid |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012178A (en) * | 2007-02-12 | 2007-08-08 | 潘健 | Method of preparing 3-aminophthalic acid from 3-nitrophthalic acid |
| CN105330587A (en) * | 2015-11-27 | 2016-02-17 | 东华大学 | Preparation method of 3-acetyl aminophthalimide |
| WO2016174685A1 (en) * | 2015-04-27 | 2016-11-03 | Mylan Laboratories Limited | Process for the enantiomeric resolution of apremilast intermediates |
-
2017
- 2017-03-31 CN CN201710206049.6A patent/CN106986783A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012178A (en) * | 2007-02-12 | 2007-08-08 | 潘健 | Method of preparing 3-aminophthalic acid from 3-nitrophthalic acid |
| WO2016174685A1 (en) * | 2015-04-27 | 2016-11-03 | Mylan Laboratories Limited | Process for the enantiomeric resolution of apremilast intermediates |
| CN105330587A (en) * | 2015-11-27 | 2016-02-17 | 东华大学 | Preparation method of 3-acetyl aminophthalimide |
Non-Patent Citations (2)
| Title |
|---|
| STEWART H.MERRILL: "The Hydrogenation of Nitrophathalic Acids", 《JOURNAL OF ORGANIC CHEMISTRY》 * |
| 赵东江 等: "氟虫双酰胺的合成研究", 《精细化工中间体》 * |
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| PB01 | Publication | ||
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| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170728 |
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| RJ01 | Rejection of invention patent application after publication |