CN109020822B - Production process for producing methyl anthranilate by one-step method - Google Patents

Production process for producing methyl anthranilate by one-step method Download PDF

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Publication number
CN109020822B
CN109020822B CN201810813480.1A CN201810813480A CN109020822B CN 109020822 B CN109020822 B CN 109020822B CN 201810813480 A CN201810813480 A CN 201810813480A CN 109020822 B CN109020822 B CN 109020822B
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production
methyl anthranilate
chlorophthalimide
methanol
reaction
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CN109020822A (en
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叶华天
王涛
张朋朋
王林
隋兵
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Shandong Juqiang oasis Biotechnology Co., Ltd
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Shandong Juqiang Oasis Biotechnology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/22Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from lactams, cyclic ketones or cyclic oximes, e.g. by reactions involving Beckmann rearrangement

Abstract

The invention relates to a production process for producing methyl anthranilate by a one-step method. The technical scheme comprises the following steps: (1) adding N-chlorophthalimide, methanol and water into a reaction container at the temperature of below 0 ℃, wherein the molar ratio of the N-chlorophthalimide to the methanol is 1: 2-1: 20; (2) according to the molar ratio of liquid alkali to N-chlorophthalimide of 1.2: 1-3: 1, dropwise adding liquid caustic soda, and stirring for 20 minutes; (3) and (3) heating to 50-80 ℃ for reaction for one hour, naturally cooling, standing for ten hours for layering, and obtaining a product methyl anthranilate at the lower layer. The beneficial effects are that: the method has the advantages of high yield, less equipment required for production, low cost, little waste water generated in the production process, greatly reduced COD and ammonia nitrogen indexes, little environmental pollution, simple and safe production and suitability for industrial production, and the synthesis process of methyl anthranilate is completed in one reaction container.

Description

Production process for producing methyl anthranilate by one-step method
Technical Field
The invention relates to a preparation method of methyl anthranilate, in particular to a production process for producing methyl anthranilate by a one-step method.
Background
Methyl anthranilate, also known as methyl anthranilate, of the formula C8H9NO2Molecular weight 151.16, colorless crystalline or pale yellow liquid. Slightly soluble in water and insoluble in glycerol. The boiling point is 273 ℃, and the melting point is 24-25 ℃. The natural aromatic plant perfume is a monomer perfume with strong and lasting fragrance, is one of edible perfumes, is mostly used as an aromatic raw material, and is widely present in natural aromatic plants, particularly jasmine oil, orange leaf oil and grapes planted in cold regions with high content. The method is mainly used for preparing grape, orange, sweet strawberry, watermelon and other types of essence, and is also an essential raw material for preparing the artificial orange oil. Methyl anthranilate can also produce over 60 flavors, which is a flavor for human beingsThe increase of the demand, the search for industrial synthetic perfume becomes one of the main development directions of the modern fine chemical industry, and meanwhile, the methyl anthranilate is also the main raw material for producing saccharin sodium, so the market demand is extremely high.
The current production route for synthesizing methyl anthranilate mainly comprises two routes: the amidation degradation of phthalic anhydride, and the reduction and esterification of o-nitrobenzoic acid. The method comprises the steps of firstly carrying out amidation reaction on phthalic anhydride and ammonia water serving as raw materials to generate anthranilic acid amide, then adding a sodium hydroxide solution to generate sodium anthranilate through displacement reaction, removing ammonia molecules in a reaction solution, then adding a methanol solution and a sodium hypochlorite solution to the reaction solution to generate pasty methyl anthranilate, heating the pasty methyl anthranilate, dissolving the pasty methyl anthranilate with water, and finally distilling a mixed solution of the methyl anthranilate and the water to obtain the methyl anthranilate. The o-nitrobenzoic acid reduction and esterification method not only uses the expensive raw material o-nitrobenzoic acid, the price of which is ten times of the current o-nitrobenzoic acid price, but also adopts the sodium sulfide or iron powder reduction method firstly, and then directly esterifies to generate a large amount of waste water, and the o-nitrobenzoic acid forms inner salt, uses a large amount of acid catalysts, and the esterification yield is very low.
Therefore, how to find an environment-friendly and economical method for producing methyl anthranilate is a problem that needs to be improved in the current production.
Disclosure of Invention
The invention aims to provide a production process for producing methyl anthranilate by a one-step method aiming at the defects in the prior art, the methyl anthranilate produced by the production process has very high yield and few production equipment, the methyl anthranilate synthesis process is completed in a reaction kettle, the produced waste water is less, the COD and ammonia nitrogen indexes are greatly reduced, the environmental pollution is low, the production is simple and safe, and the production process is suitable for industrial production.
The invention provides a production process for producing methyl anthranilate by a one-step method, which has the technical scheme that the production process comprises the following steps:
(1) adding N-chlorophthalimide, methanol and water into a reaction container at the temperature of below 0 ℃, wherein the molar ratio of the N-chlorophthalimide to the methanol is 1: 2-1: 20;
(2) according to the molar ratio of liquid alkali to N-chlorophthalimide of 1.2: 1-3: 1, dropwise adding liquid caustic soda, and stirring for 20 minutes;
(3) and (3) heating to 50-80 ℃ for reaction for one hour, naturally cooling, standing for ten hours for layering, and obtaining a product methyl anthranilate at the lower layer.
Preferably, the liquid alkali is an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide.
Preferably, the liquid alkali is a 30% by weight aqueous solution of sodium hydroxide or a 30% by weight aqueous solution of potassium hydroxide.
Preferably, the reaction equation for N-chlorophthalimide, methanol and liquid base is:
the invention has the beneficial effects that: the method takes N-chlorophthalimide, methanol and liquid caustic soda as raw materials, can synthesize methyl anthranilate by one-step reaction simply and conveniently, has the advantages of high yield, less equipment required for production and low cost, completes the synthesis process of methyl anthranilate in one reaction container, generates less waste water in the production process, greatly reduces COD and ammonia nitrogen indexes, has little pollution to the environment, is simple and safe to produce, and is suitable for industrial production.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Example 1: the invention provides a production process for producing methyl anthranilate by a one-step method, which specifically comprises the following steps:
(1) 18.2g of N-chlorophthalimide, 6.4g of methanol and 40g of water are added into a three-neck flask, then the temperature is reduced to below 0 ℃, and stirring and pulping are carried out.
(2) Dropwise adding 16.2g of 30% sodium hydroxide aqueous solution, and stirring for 20 minutes at the temperature below 0 ℃ after dropwise adding;
(3) and heating to 50-80 ℃ for reaction for one hour, naturally cooling, standing for ten hours for layering, and obtaining a product 13.8g of methyl anthranilate on the lower layer. The product purity was 99.8% and the yield was 91.4%.
Example 2: the invention provides a production process for producing methyl anthranilate by a one-step method, which specifically comprises the following steps:
(1) 18.2g of N-chlorophthalimide, 64g of methanol and 40g of water are added into a three-neck flask, then the temperature is reduced to below 0 ℃, and stirring and pulping are carried out.
(2) 40g of 30% sodium hydroxide aqueous solution is dripped, and the temperature is maintained below 0 ℃ and stirred for 20 minutes after dripping;
(3) heating to 50-80 ℃ for reaction for one hour, then decompressing and steaming to remove methanol, then naturally cooling, standing for ten hours for layering, and obtaining a product of 14.0g of methyl anthranilate on the lower layer. The product purity was 99.5% and the yield was 92.7%.
Example 3: the invention provides a production process for producing methyl anthranilate by a one-step method, which specifically comprises the following steps:
(1) 91g of N-chlorophthalimide, 80g of methanol and 200g of water are added into a three-neck flask, then the temperature is reduced to below 0 ℃, and stirring and pulping are carried out.
(2) Dropping 200g of 30% sodium hydroxide aqueous solution, and stirring for 20 minutes at the temperature below 0 ℃ after dropping;
(3) and heating to 50-80 ℃ for reaction for one hour, naturally cooling, standing for ten hours for layering, and obtaining 70g of methyl anthranilate at the lower layer. The product purity was 99.8% and the yield was 92.7%.
Example 4: the invention provides a production process for producing methyl anthranilate by a one-step method, which specifically comprises the following steps:
(1) 18.2g of N-chlorophthalimide, 16g of methanol and 50g of water are added into a three-neck flask, then the temperature is reduced to below 0 ℃, and stirring and pulping are carried out.
(2) Dropwise adding 34g of 30% potassium hydroxide aqueous solution, and stirring for 20 minutes at the temperature below 0 ℃ after dropwise adding;
(3) heating to 50-80 ℃ for reaction for one hour, naturally cooling, standing for ten hours for layering, and obtaining a product 13.6g of methyl anthranilate on the lower layer. The product purity was 99.6% and the yield was 90%.
Compared with the prior art, the method is compared with the following table:
in the process using o-nitrobenzoic acid as a raw material, although the sewage quantity and COD index are not high, the production cost is very high, and the process is not suitable for large-scale production of the product. The method for producing methyl anthranilate has the advantages of high yield compared with other processes, less equipment required by production, low cost, capability of completing the synthesis process of methyl anthranilate in one reaction container, less waste water generated in the production process, greatly reduced COD (chemical oxygen demand) and ammonia nitrogen indexes, little environmental pollution, simple production, safety and suitability for industrial production.
The above description is only a few of the preferred embodiments of the present invention, and any person skilled in the art may modify the above-described embodiments or modify them into equivalent ones. Therefore, any simple modifications or equivalent substitutions made in accordance with the technical solution of the present invention are within the scope of the claims of the present invention.

Claims (3)

1. A production process for producing methyl anthranilate by a one-step method is characterized by comprising the following steps:
(1) adding N-chlorophthalimide, methanol and water into a reaction container at the temperature of below 0 ℃, wherein the molar ratio of the N-chlorophthalimide to the methanol is 1: 2-1: 20;
(2) according to the molar ratio of liquid alkali to N-chlorophthalimide of 1.2: 1-3: 1, dropwise adding liquid caustic soda, and stirring for 20 minutes;
(3) heating to 50-80 ℃ for reaction for one hour, naturally cooling, standing for ten hours for layering, and obtaining a product methyl anthranilate at the lower layer;
the reaction equation of N-chlorophthalimide, methanol and liquid alkali is:
2. the one-step production process for producing methyl anthranilate according to claim 1, characterized by comprising the following steps: the liquid alkali adopts sodium hydroxide aqueous solution.
3. The one-step production process for producing methyl anthranilate according to claim 2, characterized by comprising the following steps: the liquid alkali adopts 30 percent sodium hydroxide aqueous solution by mass percentage concentration.
CN201810813480.1A 2018-07-23 2018-07-23 Production process for producing methyl anthranilate by one-step method Active CN109020822B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989000203A1 (en) * 1987-07-06 1989-01-12 Basf K & F Corp. A method for the preparation of "natural" methyl anthranilate
CN101948400A (en) * 2010-08-30 2011-01-19 濮阳市佳华化工有限公司 Preparation method of methyl anthranilate
CN104844469A (en) * 2015-04-08 2015-08-19 尹罡煜 Clean production technology of methyl anthranilate
CN108101800A (en) * 2018-01-12 2018-06-01 山东聚强化学有限公司 A kind of synthetic method of ortho-aminobenzoic acid

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989000203A1 (en) * 1987-07-06 1989-01-12 Basf K & F Corp. A method for the preparation of "natural" methyl anthranilate
CN101948400A (en) * 2010-08-30 2011-01-19 濮阳市佳华化工有限公司 Preparation method of methyl anthranilate
CN104844469A (en) * 2015-04-08 2015-08-19 尹罡煜 Clean production technology of methyl anthranilate
CN108101800A (en) * 2018-01-12 2018-06-01 山东聚强化学有限公司 A kind of synthetic method of ortho-aminobenzoic acid

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
邻氨基苯甲酸甲酯合成新工艺研究;金欣,等;《香料香精化妆品》;20070630;第5-6页 *

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