CN101948400B - Preparation method of methyl anthranilate - Google Patents
Preparation method of methyl anthranilate Download PDFInfo
- Publication number
- CN101948400B CN101948400B CN201010265474.0A CN201010265474A CN101948400B CN 101948400 B CN101948400 B CN 101948400B CN 201010265474 A CN201010265474 A CN 201010265474A CN 101948400 B CN101948400 B CN 101948400B
- Authority
- CN
- China
- Prior art keywords
- solution
- reaction
- ammoniacal liquor
- methyl
- esterification
- 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.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the synthesis method of an organic compound, in particular to a preparation method of methyl anthranilate. The preparation method comprises the following steps: firstly using phthalic anhydride and ammonia water as raw materials to perform an amidation reaction and generate ammonium phthalamate; secondly adding sodium hydroxide solution to perform a displacement reaction and generate sodium phthalamate, removing ammonia molecules in the reaction solution, then adding methanol solution and sodium hypochlorite solution in the reaction solution to react and obtain paste methyl anthranilate, heating the paste methyl anthranilate to dissolve in water; and finally distilling the mixed liquid of methyl anthranilate and water to obtain methyl anthranilate. The methyl anthranilate prepared by the method of the invention has high content which is up to 98.4%; the appearance is good, the light transmittance of the product is 58.6%; the yield is high, which is increased by 0.4%-0.5% compared with the original technology; and the technology is advanced, the secondary recovery of ammonia water and methanol can be performed, and three wastes are not discharged in the production process.
Description
Technical field
The present invention relates to the preparation method of a kind of synthetic method of organic compound, particularly methyl o-aminobenzoate.
Background technology
Methyl o-aminobenzoate is one of flavouring agent, and do joined perfume material more, be extensively present in the spice berry of natural product, especially with jasmin oil, petitgrain oil, to plant in the grape of cold zone content richer.Along with the increase of the mankind to flavouring agent demand, seeking industrial synthetic perfume becomes one of main development direction of Modern Fine Chemical Industry industry.At present the method for the synthetic methyl o-aminobenzoate of industry has o-Carboxynitrobenzene reduction esterification process and take o-Carboxynitrobenzene as raw material, synthesize o-Carboxynitrobenzene methyl esters through esterification, then under Raney's nickel exists, shortening makes methyl o-aminobenzoate, the methyl o-aminobenzoate content that these two kinds of methods obtain is low, yield is low, and in production process, there is waste water to produce, contaminate environment.
Summary of the invention
It is high that technical problem to be solved by this invention is to provide a kind of methyl o-aminobenzoate content, yield is high, in production process without the preparation method of the methyl o-aminobenzoate of " three wastes " discharge.
Technical scheme of the present invention is:
The preparation method of methyl o-aminobenzoate, first generate adjacent formamide benzene ammonium formate take phthalic anhydride and ammoniacal liquor as raw material through amidate action, then directly add sodium hydroxide solution to generate adjacent formamide benzene sodium formiate through replacement(metathesis)reaction, amino molecule in reaction soln is removed, in reaction soln, add methanol solution and chlorine bleach liquor again, reaction generates the methyl o-aminobenzoate of paste, by rear the methyl o-aminobenzoate heating of paste and water dissolution, the mixed solution that finally distills methyl o-aminobenzoate and water obtains methyl o-aminobenzoate.
The preparation method of methyl o-aminobenzoate comprises the following steps:
(1) 25% the ammoniacal liquor of 10 ℃ is put into amidate action still, phthalic anhydride is put in amidate action still, in ammoniacal liquor and the phthalic anhydride environment below 30 ℃, reaction generates adjacent formamide benzene ammonium formate;
(2) in amidate action still, put into 30% sodium hydroxide solution, adjacent formamide benzene ammonium formate and sodium hydroxide generation replacement(metathesis)reaction generate adjacent formamide benzene sodium formiate, then the temperature in amidate action still is risen to 50 ℃, by the amino molecule evaporation in mixing solutions;
(3) solution in amidate action still is squeezed in reaction kettle of the esterification, to putting into 75% methanol solution and 14% chlorine bleach liquor in reaction kettle of the esterification, keeping the temperature in reaction kettle of the esterification is 10 ℃, reaction generates the methyl o-aminobenzoate of paste, after end, the temperature in reaction kettle of the esterification is risen to 50 ℃, methyl o-aminobenzoate and the water dissolution of last paste;
(4) solution in reaction kettle of the esterification is sent into stratification in formicester slurry tank, by the solution on upper strata with being pumped into Methanol Recovery operation, the solution of lower floor obtains filtrate through liquid-jet vacuum pump suction filtration, filtrate is through secondary stratification, by the solution on upper strata, with being pumped into Methanol Recovery operation, lower floor's filtrate is squeezed in still kettle, is 2.00Kpa at pressure, temperature is to distill in the environment of 135.5 ℃, both finished product.
In above-mentioned preparation method, the usage quantity of 25% ammoniacal liquor is that reaction is required 105%, and described reaction is required refers to 25% the ammoniacal liquor that amidate action is required.
The massfraction that " 25% ammoniacal liquor " described in technical solution of the present invention is solvent is 25% ammoniacal liquor.The massfraction that " 30% sodium hydroxide solution " described in technical solution of the present invention is solvent is 30% sodium hydroxide solution.The massfraction that " 75% methanol solution " described in technical solution of the present invention is solvent is 75% methanol solution.The massfraction that " 14% chlorine bleach liquor " described in technical solution of the present invention is solvent is 14% chlorine bleach liquor.
Send into the solution of Methanol Recovery operation by being pumped in methanol rectifying tower, utilize the boiling point difference of a component in solution, first the methyl alcohol in solution is evaporated, methanol steam obtains methanol solution through condensation, surplus solution is sent into whizzer after crystallisation by cooling, can be used as Industrial Salt and sell after centrifugation.
The invention has the beneficial effects as follows, gained methyl o-aminobenzoate content of the present invention is high, can reach 98.4%; Outward appearance is good, and product transmittance is 58.6%; Yield is high, and more originally technique has improved 0.4%-0.5%; Technology advanced person, ammoniacal liquor, methyl alcohol can secondary recovery utilizations, in production process without " three wastes " discharge.
Embodiment
The preparation method of methyl o-aminobenzoate comprises the following steps:
(1) 25% the ammoniacal liquor of 937kg10 ℃ is put into amidate action still, 1000kg phthalic anhydride is put in amidate action still, in ammoniacal liquor and the phthalic anhydride environment below 30 ℃, reaction generates adjacent formamide benzene ammonium formate, reaction times 2.5h.Actual 25% the ammoniacal liquor of participating in amidate action is 892.3kg, the ammoniacal liquor that adds 937kg25% for amidate action more fully completely.
(2) after amidate action, to the sodium hydroxide solution of putting into 879kg30% in amidate action still, adjacent formamide benzene ammonium formate and sodium hydroxide generation replacement(metathesis)reaction generate adjacent formamide benzene sodium formiate, then the temperature in amidate action still is risen to 50 ℃, by the amino molecule evaporation in mixing solutions, the ammonia of evaporation causes the water absorption of two-stage tandem water absorption tower through induced draft fan and obtains ammoniacal liquor, ammoniacal liquor is delivered in ammoniacal liquor storage tank, in ammoniacal liquor storage tank, add liquefied ammonia, be made into 25% ammoniacal liquor recycling.
(3) solution in amidate action still is squeezed in reaction kettle of the esterification, to the chlorine bleach liquor who puts into methanol solution and the 3451kg14% of 1561kg75% in reactor, keeping the temperature in reaction kettle of the esterification is 10 ℃, reaction generates the methyl o-aminobenzoate of paste, reaction times 3h, reaction finishes rear temperature in reaction kettle of the esterification to be risen to 50 ℃.The methyl o-aminobenzoate of paste dissolves and in backward reaction kettle of the esterification, adds 1000kg hot water.
(4) solution in reaction kettle of the esterification is sent in formicester slurry tank and left standstill and be divided into, by the solution on upper strata with being pumped into Methanol Recovery operation, the solution of lower floor obtains filtrate through liquid-jet vacuum pump suction filtration, filtrate leaves standstill and is divided into through secondary, by the solution on upper strata, with being pumped into Methanol Recovery operation, lower floor's filtrate is squeezed in still kettle, is 2.00Kpa at pressure, temperature is to distill in the environment of 135.5 ℃, both finished product.
Send into the solution of Methanol Recovery operation by being pumped in methanol rectifying tower, utilize the boiling point difference of a component in solution, first the methyl alcohol in solution is evaporated, methanol steam obtains methanol solution through condensation, surplus solution is sent into whizzer after crystallisation by cooling, can be used as Industrial Salt and sell after centrifugation.
In above-mentioned preparation method, the usage quantity of 25% ammoniacal liquor is that reaction is required 105%, and described reaction is required refers to 25% the ammoniacal liquor that amidate action is required.
The massfraction that " 25% ammoniacal liquor " described in technical solution of the present invention is solvent is 25% ammoniacal liquor.The massfraction that " 30% sodium hydroxide solution " described in technical solution of the present invention is solvent is 30% sodium hydroxide solution.The massfraction that " 75% methanol solution " described in technical solution of the present invention is solvent is 75% methanol solution.The massfraction that " 14% chlorine bleach liquor " described in technical solution of the present invention is solvent is 14% chlorine bleach liquor.
Claims (3)
1. the preparation method of methyl o-aminobenzoate, is characterized in that, comprises the following steps:
(1) 25% the ammoniacal liquor of 10 ℃ is put into amidate action still, phthalic anhydride is put in amidate action still, in ammoniacal liquor and the phthalic anhydride environment below 30 ℃, reaction generates adjacent carbamyl ammonium benzoate;
(2) in amidate action still, put into 30% sodium hydroxide solution, adjacent carbamyl ammonium benzoate and sodium hydroxide generation replacement(metathesis)reaction generate adjacent carbamyl Sodium Benzoate, then the temperature in amidate action still is risen to 50 ℃, by the amino molecule evaporation in mixing solutions;
(3) solution in amidate action still is squeezed in reaction kettle of the esterification, to putting into 75% methanol solution and 14% chlorine bleach liquor in reaction kettle of the esterification, keeping the temperature in reaction kettle of the esterification is 10 ℃, reaction generates the methyl o-aminobenzoate of paste, after end, the temperature in reaction kettle of the esterification is risen to 50 ℃, methyl o-aminobenzoate and the water dissolution of last paste;
(4) solution in reaction kettle of the esterification is sent into stratification in methyl esters slurry tank, by the solution on upper strata with being pumped into Methanol Recovery operation, the solution of lower floor obtains filtrate through liquid-jet vacuum pump suction filtration, filtrate is through secondary stratification, by the solution on upper strata, with being pumped into Methanol Recovery operation, lower floor's filtrate is squeezed in still kettle, is 2.00kPa at pressure, temperature is to distill in the environment of 135.5 ℃, both finished product.
2. the preparation method of methyl o-aminobenzoate according to claim 1, is characterized in that, the usage quantity of 25% ammoniacal liquor be reaction required 105%, described reaction is required refers to 25% the ammoniacal liquor that amidate action is required.
3. the preparation method of methyl o-aminobenzoate according to claim 1, is characterized in that, comprises the following steps:
(1) 25% the ammoniacal liquor of 937kg10 ℃ is put into amidate action still, 1000kg phthalic anhydride is put in amidate action still, in ammoniacal liquor and the phthalic anhydride environment below 30 ℃, reaction generates adjacent carbamyl ammonium benzoate, reaction times 2.5h;
(2) after amidate action, to the sodium hydroxide solution of putting into 879kg30% in amidate action still, adjacent carbamyl ammonium benzoate and sodium hydroxide generation replacement(metathesis)reaction generate adjacent carbamyl Sodium Benzoate, then the temperature in amidate action still is risen to 50 ℃, by the amino molecule evaporation in mixing solutions, the ammonia of evaporation causes the water absorption of two-stage tandem water absorption tower through induced draft fan and obtains ammoniacal liquor, ammoniacal liquor is delivered in ammoniacal liquor storage tank, in ammoniacal liquor storage tank, add liquefied ammonia, be made into 25% ammoniacal liquor recycling;
(3) solution in amidate action still is squeezed in reaction kettle of the esterification, to the chlorine bleach liquor who puts into methanol solution and the 3451kg14% of 1561kg75% in reaction kettle of the esterification, keeping the temperature in reaction kettle of the esterification is 10 ℃, reaction generates the methyl o-aminobenzoate of paste, after end, the temperature in reaction kettle of the esterification is risen to 50 ℃, methyl o-aminobenzoate and the 1000kg water dissolution of last paste;
(4) solution in reaction kettle of the esterification is sent in methyl esters slurry tank and left standstill and be divided into, by the solution on upper strata with being pumped into Methanol Recovery operation, the solution of lower floor obtains filtrate through liquid-jet vacuum pump suction filtration, filtrate leaves standstill and is divided into through secondary, by the solution on upper strata, with being pumped into Methanol Recovery operation, lower floor's filtrate is squeezed in still kettle, is 2.00kPa at pressure, temperature is to distill in the environment of 135.5 ℃, both finished product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010265474.0A CN101948400B (en) | 2010-08-30 | 2010-08-30 | Preparation method of methyl anthranilate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010265474.0A CN101948400B (en) | 2010-08-30 | 2010-08-30 | Preparation method of methyl anthranilate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101948400A CN101948400A (en) | 2011-01-19 |
| CN101948400B true CN101948400B (en) | 2014-06-18 |
Family
ID=43452045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010265474.0A Active CN101948400B (en) | 2010-08-30 | 2010-08-30 | Preparation method of methyl anthranilate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101948400B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109020822B (en) * | 2018-07-23 | 2021-02-26 | 叶华天 | Production process for producing methyl anthranilate by one-step method |
| CN109111368A (en) * | 2018-10-24 | 2019-01-01 | 王红凯 | A kind of preparation method of ethyl o-aminobenzoate |
| CN110204432A (en) * | 2019-06-20 | 2019-09-06 | 深圳市仙迪化妆品有限公司 | A kind of application for the method and palmitoleic acid preparing palmitoleic acid using macadamia nut oil |
| CN110257175A (en) * | 2019-06-20 | 2019-09-20 | 深圳市仙迪化妆品有限公司 | It is a kind of to prepare linoleic method and linoleic application using rose hip oil |
| CN110156593A (en) * | 2019-06-20 | 2019-08-23 | 深圳市仙迪化妆品有限公司 | It is a kind of to prepare linolenic method and linolenic application using rose hip oil |
| CN112250590B (en) * | 2020-09-30 | 2022-04-08 | 广东石油化工学院 | Method for continuously preparing methyl anthranilate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1436810A (en) * | 1974-05-09 | 1976-05-26 | Ici Ltd | Preparation of iostoic anhydride and anthranilic acid |
| IN142232B (en) * | 1974-05-01 | 1977-06-11 | Council Scient Ind Res | |
| DE3909142A1 (en) * | 1989-03-21 | 1990-10-04 | Basf Ag | METHOD FOR PRODUCING AMINES |
| RU2187496C1 (en) * | 2001-06-05 | 2002-08-20 | Волгоградское открытое акционерное общество "Химпром" | Method of synthesis of anthranilic acid |
-
2010
- 2010-08-30 CN CN201010265474.0A patent/CN101948400B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IN142232B (en) * | 1974-05-01 | 1977-06-11 | Council Scient Ind Res | |
| GB1436810A (en) * | 1974-05-09 | 1976-05-26 | Ici Ltd | Preparation of iostoic anhydride and anthranilic acid |
| DE3909142A1 (en) * | 1989-03-21 | 1990-10-04 | Basf Ag | METHOD FOR PRODUCING AMINES |
| RU2187496C1 (en) * | 2001-06-05 | 2002-08-20 | Волгоградское открытое акционерное общество "Химпром" | Method of synthesis of anthranilic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101948400A (en) | 2011-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101948400B (en) | Preparation method of methyl anthranilate | |
| CN108840310B (en) | Device and process for producing hydrogen chloride by deep analysis from dilute hydrochloric acid | |
| CN103467245B (en) | Method for complexing and removing water contained in ethanol and water mixed solution by utilizing eutectic solvent | |
| CN104086362A (en) | Method for recycling organic solvents of wastewater generated in synthesis of hydrazine hydrate by ketazine method | |
| CN102757308A (en) | Method of preparing high-purity ethanol | |
| CN102442917A (en) | Energy-saving and environment-friendly method for producing glycin based on chloroacetic acid method | |
| CN101607890B (en) | Method for continuously neutralizing and extracting citric acid | |
| CN101117314B (en) | Production method of sodium citrate | |
| CN103880680B (en) | The method that a kind of efficient low-consume cleaning produces carbonic acid alkoxy ethyl methacrylate | |
| CN102206014A (en) | Sodium carboxymethylcellulose (CMC) production waste water treatment and valuable ingredient comprehensive use process | |
| CN104844469A (en) | Clean production technology of methyl anthranilate | |
| CN101519360B (en) | Method for preparing iminodiacetic acid | |
| CN101434539B (en) | Preparation of benzyl acetate | |
| CN204058303U (en) | A kind of purifying plant of sodium formiate | |
| CN110804018A (en) | Refining method and refining system of caprolactam | |
| CN105418536A (en) | Method for preparing 2,2'-dithiodibenzothiazole from waste residues generated during process of AE-active ester production | |
| CN102336685B (en) | Method for preparing cyanoacetic acid through continuous dehydration | |
| CN104910142A (en) | Method for preparing vitamin B1 intermediate (pyrimidine) | |
| CN103464178A (en) | AG-01 catalyst used for synthesis of dichloropropanol by hydrochlorination of glycerin | |
| CN103435070B (en) | A kind of from containing the method reclaiming product the waste residue of Sodium Fluoride | |
| CN104261629B (en) | The combination treatment method of addition waste water and cyclization waste water in production process of lipoic acid | |
| CN107032986A (en) | A kind of method that presence of acidic ionic liquid catalyst synthesizes the propanol ether acetate of 2 methoxyl group 1 | |
| CN103864632B (en) | Production method for glycine ethyl ester hydrochloride | |
| CN102491796B (en) | Continuous production device for composite trace element plant nutrient solution | |
| CN107285993A (en) | A kind of ketoside solid waste resource recovery processing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Wang Chuanming Inventor after: You Jianling Inventor after: Gao Lianjia Inventor before: Gao Lianjia |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: GAO LIANJIA TO: WANG CHUANMING YOU JIANLING GAO LIANJIA |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |