CN111454157A - Preparation method of 3-nitrophenyl alkyne - Google Patents
Preparation method of 3-nitrophenyl alkyne Download PDFInfo
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- CN111454157A CN111454157A CN202010409119.XA CN202010409119A CN111454157A CN 111454157 A CN111454157 A CN 111454157A CN 202010409119 A CN202010409119 A CN 202010409119A CN 111454157 A CN111454157 A CN 111454157A
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Abstract
The invention discloses a preparation method of 3-nitrophenyl alkyne, which comprises the following steps: in the presence of a complexing agent and a solvent, carrying out oxidation reaction on 2-amino-6-nitrobenzoic acid and an oxidant, and after the reaction is finished, distilling to remove the solvent to obtain a crude product of the 3-nitrophenyl alkyne; and recrystallizing the 3-nitrophenyl alkyne crude product by isopropyl ether to obtain the 3-nitrophenyl alkyne. The method adopts a one-step method to prepare the 3-nitrophenyl alkyne, simplifies the reaction operation, improves the yield of the reaction and the purity of the product, ensures that the obtained product is stable, and effectively reduces the production cost.
Description
Technical Field
The invention belongs to the technical field of pesticide preparation, and particularly relates to a preparation method of 3-nitrophenylyne.
Background
Benzovindiflupyr, a succinate dehydrogenase inhibitor, is a pyrazole amide bactericide. The benzovindiflupyr has excellent prevention effect on diseases of cereal crops such as wheat, corn, special crops and the like, can well prevent and control wheat leaf blight, peanut black spot, wheat take-all and wheat basal rot, particularly has special effect on wheat powdery mildew, corn small spot and gray mold, and has excellent prevention effect on Asian soybean rust. Moreover, the benzovindiflupyr, the strobilurin and the triazole bactericide have no cross resistance, and can be compounded with various bactericides for use. Therefore, the benzovindiflupyr is an important crop fungicide, and the 3-nitrophenyl alkyne is particularly important as an intermediate for preparing the benzovindiflupyr.
Patent numbers WO2010049228a1 and cn201180019764.x both adopt a one-pot method for preparing 3-nitrophenylyne, which is then directly put into the next reaction without purification. These existing methods have the disadvantages of low yield and purity of the product, and are not suitable for industrial production. Therefore, there is an urgent need for improvement of the existing preparation method.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the invention provides a preparation method of 3-nitrophenyl alkyne, which is economical, efficient and stable and solves the defects of low yield and low purity in the prior art.
The solution of the invention for solving the technical problem is as follows:
a preparation method of 3-nitrobenzeneyne comprises the following specific experimental route:
the preparation method comprises the following steps: in the presence of a complexing agent and a solvent, carrying out oxidation reaction on 2-amino-6-nitrobenzoic acid and an oxidant, and after the reaction is finished, distilling to remove the solvent to obtain a crude product of the 3-nitrophenyl alkyne; and recrystallizing the 3-nitrophenyl alkyne crude product by isopropyl ether to obtain the 3-nitrophenyl alkyne.
Further, the temperature of the oxidation reaction is 40 to 60 ℃, preferably 50 to 60 ℃, and more preferably 55 to 60 ℃.
Further, the time of the oxidation reaction is 1 to 4 hours, preferably 1 to 2 hours.
Further, the solvent is at least one of acetone, absolute ethyl alcohol, toluene, dioxane, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, diphenyl ether, N-butanol and cyclohexanol, and preferably acetone.
Further, the molar ratio of the 2-amino-6-nitrobenzoic acid to the oxidant to the complexing agent is 1.0 (1.0-3.0): (1.0-2.0), preferably 1.0 (1.0-2.0): (1.0-1.5), more preferably 1.0 (1.0-1.5): 1.0.
further, the oxidant is at least one of hydrogen peroxide, nitrous acid, isoamyl nitrite, potassium permanganate and potassium perchlorate, and is preferably isoamyl nitrite.
Further, the complexing agent is at least one of ruthenium trichloride, copper chloride, ferric chloride and zinc chloride, and is preferably copper chloride.
The invention has the beneficial effects that: the method adopts a one-step method to prepare the 3-nitrophenyl alkyne, and is simple to operate. Because metal ions in the complexing agent and alkynyl can form a tetradentate bond complex, an alkynyl triple bond structure can be fixed, the reactivity of alkynyl is reduced, and the stability of alkynyl is improved, so that the decomposition of a product is inhibited, the reaction yield and the product purity are improved, and the production cost is effectively reduced by the efficient preparation method.
Drawings
FIG. 1 is a graph of HP L C of the product obtained in example 1;
FIG. 2 is a graph of HP L C of the product obtained in example 4;
FIG. 3 is a graph of HP L C of the product obtained in example 9;
FIG. 4 is a graph of HP L C of the product obtained in example 11.
Detailed Description
The conception, specific structure, and technical effects of the present application will be described clearly and completely with reference to the following embodiments, so that the purpose, features, and effects of the present application can be fully understood. Obviously, the described embodiments are only a part of the embodiments of the present application, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts based on the embodiments of the present application belong to the protection scope of the present application.
Example 1
2-amino-6-nitrobenzoic acid (1.00g, 5.50mmol), isoamyl nitrite (1.93g, 16.5mmol) and acetone (10 ml) are added into a 50ml three-neck flask, the temperature is raised to 55 ℃, copper chloride (1.48g, 11.0mmol) is slowly added in batches, after stirring and reacting for 2 hours, the solvent is removed by reduced pressure rotary evaporation to obtain 0.40g of a brownish black solid crude product, the yield is 60.0%, and after recrystallization by isopropyl ether, 0.35g of brown solid is obtained, the yield is 54.6%, and the content is 96.1%.
Example 2
2-amino-6-nitrobenzoic acid (1.00g, 5.50mmol), isoamyl nitrite (1.29g, 11.0mmol) and acetone (10 ml) were added to a 50ml three-necked flask, the temperature was raised to 60 ℃, copper chloride (1.48g, 11.0mmol) was added in portions and slowly, after stirring for reaction for 2 hours, the solvent was removed by rotary evaporation under reduced pressure to obtain 0.46g of a brown-black crude solid product with a yield of 69.1%, and after recrystallization from isopropyl ether, 0.41g of a brown solid was obtained with a yield of 61.2% and a content of 97.2%.
Example 3
2-amino-6-nitrobenzoic acid (1.00g, 5.50mmol), isoamyl nitrite (0.97g, 8.25mmol) and acetone (10 ml) are added into a 50ml three-neck flask, the temperature is raised to 58 ℃, copper chloride (1.48g, 11.0mmol) is slowly added in batches, after stirring and reacting for 2 hours, the solvent is removed by reduced pressure rotary evaporation to obtain 0.48g of a brownish black solid crude product, the yield is 72.1%, and after recrystallization by isopropyl ether, 0.43g of brown solid is obtained, the yield is 64.6%, and the content is 96.5%.
Example 4
2-amino-6-nitrobenzoic acid (1.00g, 5.50mmol), isoamyl nitrite (0.65g, 5.50mmol) and acetone (10 ml) are added into a 50ml three-neck flask, the temperature is raised to 60 ℃, copper chloride (1.11g, 8.25mmol) is slowly added in batches, after stirring and reacting for 2 hours, the solvent is removed by reduced pressure rotary evaporation to obtain 0.46g of a brownish black solid crude product, the yield is 69.0%, and after recrystallization by isopropyl ether, 0.40g of brown solid is obtained, the yield is 60.0%, and the content is 95.7%.
Example 5
2-amino-6-nitrobenzoic acid (1.00g, 5.50mmol), isoamyl nitrite (0.97g, 8.25mmol) and acetone (10 ml) were added to a 50ml three-necked flask, the temperature was raised to 57 ℃, copper chloride (0.74g, 5.50mmol) was added in portions and slowly, after stirring for reaction for 2 hours, the solvent was removed by rotary evaporation under reduced pressure to obtain 0.56g of a crude product as a brownish black solid in a yield of 84.1%, and after recrystallization from isopropyl ether, 0.52g of a brown solid was obtained in a yield of 78.0% and a content of 97.7%.
Example 6
2-amino-6-nitrobenzoic acid (1.00g, 5.50mmol), isoamyl nitrite (1.29g, 11.0mmol) and 10ml of N, N-dimethylacetamide are added into a 50ml three-neck flask, the temperature is raised to 55 ℃, copper chloride (0.74g, 5.50mmol) is slowly added in batches, after stirring for reaction for 2 hours, the solvent is removed by rotary evaporation under reduced pressure to obtain 0.30g of a brown-black crude solid with a yield of 45.0%, and after recrystallization with isopropyl ether, 0.26g of a brown solid with a yield of 39.0% and a content of 94.2% is obtained.
Example 7
2-amino-6-nitrobenzoic acid (1.00g, 5.50mmol), isoamyl nitrite (1.93g, 16.5mmol) and 10ml of N, N-dimethylformamide are added into a 50ml three-neck flask, the temperature is raised to 56 ℃, copper chloride (0.74g, 5.50mmol) is slowly added in batches, after stirring for reaction for 2 hours, the solvent is removed by rotary evaporation under reduced pressure to obtain 0.32g of a brownish black crude solid with the yield of 48.1%, and after recrystallization with isopropyl ether, 0.27g of a brown solid with the yield of 40.5% and the content of 93.2% is obtained.
Example 8
2-amino-6-nitrobenzoic acid (100.0g, 550mmol), isoamyl nitrite (97g, 825mmol) and acetone 1L were added to a three-necked flask of 1L, the mixture was heated to 60 ℃, copper chloride (74g, 550mmol) was added in portions and slowly, after stirring for 2 hours, the solvent was removed by rotary evaporation under reduced pressure to give 58g of crude brownish black solid in 87.1%, and the crude product was recrystallized from isopropyl ether to give 54g of brown solid in 81.1% yield and 97.9% content.
Example 9
2-amino-6-nitrobenzoic acid (1.00g, 5.50mmol), potassium perchlorate (1.52g, 11.0mmol), toluene (2 ml) and dioxane (8 ml) were added to a 50ml three-necked flask, the temperature was raised to 55 ℃, copper chloride (0.74g, 5.50mmol) was added slowly in portions, after stirring for 2 hours, the solvent was removed by rotary evaporation under reduced pressure to give 0.20g of a brown-black crude solid in a yield of 30.1%, and after recrystallization from isopropyl ether, 0.16g of a brown solid was obtained in a yield of 24.4% and a content of 58.0%.
Example 10
2-amino-6-nitrobenzoic acid (1.00g, 5.50mmol), potassium permanganate (1.29g, 8.25mmol), absolute ethyl alcohol (2 ml) and acetone (8 ml) are added into a 50ml three-neck flask, the temperature is raised to 56 ℃, zinc chloride (0.75g, 5.50mmol) is slowly added in batches, after stirring and reacting for 1.5h, the solvent is removed by reduced pressure rotary evaporation, 0.43g of brown black solid crude product is obtained, the yield is 64.5%, and after recrystallization by isopropyl ether, 0.34g of brown solid is obtained, the yield is 51.1% and the content is 49.6%.
Example 11
2-amino-6-nitrobenzoic acid (1.00g, 5.50mmol), nitrous acid (0.39g, 8.25mmol) and 10ml of N-methylpyrrolidone were added to a 50ml three-necked flask, heated to 56 ℃, ferric chloride (0.89g, 5.50mmol) was added slowly in portions, stirred for reaction for 1 hour, and after removal of the solvent by rotary evaporation under reduced pressure, 0.22g of a brown-black crude solid was obtained in a yield of 33.1%, and after recrystallization from isopropyl ether, 0.15g of a brown solid was obtained in a yield of 22.5% and a content of 59.7%.
Example 12
2-amino-6-nitrobenzoic acid (1.00g, 5.50mmol), hydrogen peroxide (0.28g, 8.25mmol), diphenyl ether (1 ml), n-butanol (2 ml) and cyclohexanol (7 ml) are added into a 50ml three-neck flask, the temperature is raised to 58 ℃, ruthenium trichloride (1.14g, 5.50mmol) is slowly added in batches, after stirring and reacting for 1.5h, the solvent is removed by reduced pressure rotary evaporation, 0.24g of brown black solid crude product is obtained, the yield is 36.0%, after recrystallization by isopropyl ether, 0.19g of brown solid is obtained, the yield is 28.5%, and the content is 93.2%.
As can be seen from the examples, the product obtained by the method of the present invention has high yield, high content and high purity, and the types and the amounts of the reagents, the oxidizing agents and the complexing agents used in each step and the experimental conditions have great influence on the experimental results.
While the preferred embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that the invention is not limited to the details of the embodiments, but is capable of various modifications and substitutions without departing from the spirit of the invention.
Claims (7)
1. A preparation method of 3-nitrobenzeneyne is characterized by comprising the following steps: in the presence of a complexing agent and a solvent, carrying out oxidation reaction on 2-amino-6-nitrobenzoic acid and an oxidant, and after the reaction is finished, distilling to remove the solvent to obtain a crude product of the 3-nitrophenyl alkyne; and recrystallizing the 3-nitrophenyl alkyne crude product by isopropyl ether to obtain the 3-nitrophenyl alkyne.
2. The process for the preparation of 3-nitrophenylyne according to claim 1, wherein the temperature of the oxidation reaction is between 40 ℃ and 60 ℃, preferably between 50 ℃ and 60 ℃, more preferably between 55 ℃ and 60 ℃.
3. The process for preparing 3-nitrophenylyne according to claim 1, wherein the oxidation reaction is carried out for a time ranging from 1 hour to 4 hours, preferably from 1 hour to 2 hours.
4. The process for producing 3-nitrophenylyne according to claim 1, wherein the solvent is at least one of acetone, absolute ethanol, toluene, dioxane, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, diphenyl ether, N-butanol and cyclohexanol, preferably acetone.
5. The preparation method of 3-nitrophenylyne according to claim 1, wherein the molar ratio of the 2-amino-6-nitrobenzoic acid to the oxidizing agent to the complexing agent is 1.0 (1.0-3.0): (1.0-2.0), preferably 1.0 (1.0-2.0): (1.0-1.5), more preferably 1.0 (1.0-1.5): 1.0.
6. the method for preparing 3-nitrophenylyne according to claim 5, wherein the oxidant is at least one of hydrogen peroxide, nitrous acid, isoamyl nitrite, potassium permanganate and potassium perchlorate, preferably isoamyl nitrite.
7. The method for preparing 3-nitrophenylyne according to claim 5, wherein the complexing agent is at least one of ruthenium trichloride, copper chloride, ferric chloride and zinc chloride, preferably copper chloride.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070185148A1 (en) * | 2004-03-17 | 2007-08-09 | Glaxo Group Limited | M3 muscarinic acetylchoine receptor antagonists |
| CN101277938A (en) * | 2005-09-16 | 2008-10-01 | 先正达参股股份有限公司 | Process for the production of amides |
| US20090306166A1 (en) * | 2006-04-07 | 2009-12-10 | Syngenta Crop Protection, Inc. | Method of Controlling Phytopathogenic Diseases on Turfgrass |
| AU2009309884A1 (en) * | 2008-10-27 | 2010-05-06 | Syngenta Participations Ag | Process for the preparation of benzonorbornenes |
| CN102282695A (en) * | 2009-01-19 | 2011-12-14 | 新日铁化学株式会社 | Organic electroluminescent element |
| WO2012166987A2 (en) * | 2011-05-31 | 2012-12-06 | California Institute Technology | Liphagal enantiomers and their derivatives and precursors, and enantioselective methods of making the same |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070185148A1 (en) * | 2004-03-17 | 2007-08-09 | Glaxo Group Limited | M3 muscarinic acetylchoine receptor antagonists |
| CN101277938A (en) * | 2005-09-16 | 2008-10-01 | 先正达参股股份有限公司 | Process for the production of amides |
| US20090306166A1 (en) * | 2006-04-07 | 2009-12-10 | Syngenta Crop Protection, Inc. | Method of Controlling Phytopathogenic Diseases on Turfgrass |
| AU2009309884A1 (en) * | 2008-10-27 | 2010-05-06 | Syngenta Participations Ag | Process for the preparation of benzonorbornenes |
| CN102282695A (en) * | 2009-01-19 | 2011-12-14 | 新日铁化学株式会社 | Organic electroluminescent element |
| WO2012166987A2 (en) * | 2011-05-31 | 2012-12-06 | California Institute Technology | Liphagal enantiomers and their derivatives and precursors, and enantioselective methods of making the same |
Non-Patent Citations (8)
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