CN111320573B - Preparation method of pyridylamine compounds - Google Patents
Preparation method of pyridylamine compounds Download PDFInfo
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- CN111320573B CN111320573B CN201811526892.3A CN201811526892A CN111320573B CN 111320573 B CN111320573 B CN 111320573B CN 201811526892 A CN201811526892 A CN 201811526892A CN 111320573 B CN111320573 B CN 111320573B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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Abstract
The invention relates to a preparation method of a pyridine amine compound, which obviously improves the product yield and purity by adding a specific catalyst, greatly shortens the reaction time and has obvious economic and environmental benefits.
Description
Technical Field
The invention belongs to the field of preparation methods of pyridinamines compounds, and relates to a preparation method of a pyridinamine compound serving as a pesticide.
Background
The compound with the molecular formula shown above (namely the compound shown in the formula III in the application) is a class of pyridylamine insecticides developed by Nippon mingzhi, has good activity on aphids and rice planthoppers and is environment-friendly.
CN103781764A, CN105980360A, CN106117132A, DE3639877A1, TW201613866A and the like report many synthetic methods of pyridylamine compounds, which can obtain the above compounds, but have the disadvantages of high raw material cost, difficult reaction operation, long reaction time, low yield, environmental unfriendliness and the like.
Therefore, the development of a novel method for preparing the pyridylamine compounds has practical significance.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of a novel pyridine amine compound. The method unexpectedly obtains the compound with high yield and high purity by adding the catalyst, and simultaneously greatly shortens the reaction time; the method has simple steps and little three wastes, and is suitable for large-scale production; in addition, no literature reports on methods for improving the reaction by adding a catalyst.
In order to realize the purpose of the invention, the invention provides the following technical scheme:
a method for producing a pyridylamine compound, which comprises a step of reacting a compound of formula (I) with a compound of formula (II) as starting materials in the presence of a catalyst to obtain a compound of formula (III);
in the reaction formula: m represents at least one selected from K, na, mg, al and Ga; x represents F, cl, br, I, CH3SO3、p-CH3C6H4SO3A leaving group;
the catalyst is selected from KI, naI, KBr, naBr and GaI2At least one of (a).
In another practical embodiment, the catalyst is selected from KI or NaI.
In another possible implementation of the above preparation method, the molar ratio of the compound of formula (I) to the catalyst is from 1, from 0.0001 to 1, further optionally from 1, from 0.001 to 1; still further alternatively 1.
In another practical implementation mode of the preparation method, X represents Cl or Br.
In another practical implementation mode of the preparation method, M represents K or Na.
In another practical implementation mode of the preparation method, the reaction temperature is-20 ℃ to 150 ℃, and the reaction time is 0.1 to 72 hours; optionally, the reaction temperature is 20-80 ℃, and the reaction time is 2-10 hours; further optionally, the reaction temperature is 50 ℃ to 55 ℃, and the reaction time is 2 to 10 hours.
In another practical implementation of the above preparation method, the reaction solvent is selected from: at least one of N, N-dimethylformamide, N-dimethylacetamide, acetonitrile, benzonitrile, methanol, isopropanol, N-propanol, N-butanol, diethyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, ethyl propionate, toluene, xylene, chlorobenzene, pyridine, 2-chloropyridine, 3-methylpyridine, dichloromethane, dichloroethane, methylcyclohexane, dimethyl sulfoxide, sulfolane, acetone, dimethyl carbonate, methyl isobutyl ketone, or a mixed solvent thereof with water; optionally at least one of acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran or a mixed solvent thereof with water.
In another practical implementation mode of the preparation method, the molar ratio of the compound of the formula (I) to the compound of the formula (II) is 1.2-10; alternatively 1.
In another practical implementation of the preparation method, the reaction is carried out under a nitrogen atmosphere.
In another practical implementation manner, the reaction can be carried out under normal pressure, high pressure and negative pressure, and optionally under normal pressure.
Compared with the prior art, the embodiment of the invention has the following beneficial effects:
according to the embodiment of the invention, the compound of the formula III with high yield and high purity is obtained unexpectedly by adding the specific catalyst, and meanwhile, the reaction time is greatly shortened; and the method has simple steps and small three wastes, and is suitable for large-scale production.
And by further selecting the type, the using amount and the reaction conditions of the catalyst, the reaction yield and the purity can be further improved, and the reaction time can be further shortened.
Detailed Description
The compound of formula (I) can be prepared by the method reported in patent TW201613866A, the compound of formula (II), the catalyst are all commercially available.
Example 1
Under the atmosphere of nitrogen, 0.05mol of pyridine-2-yl (trifluoroacetyl) sodium amide, 0.05mol of 2-chloro-5-chloromethylpyridine, 0.0006mol of KI and 15ml of acetonitrile are added into a 250ml four-neck flask, the temperature is raised to 50-55 ℃, the heat preservation reaction is carried out for 8 hours, the HPLC tracking analysis reaction is finished, the temperature is reduced to the room temperature, 75 g of water is added, and a large amount of solid is separated out. Filtering and drying the obtained solid to obtain an off-white solid, wherein the molar yield is 95%, the product purity is 98.5%, the melting point is 153-155 ℃,1HNMR (400 MHz, internal standard TMS, solvent DMSO-d)6) The following were used: Δ ppm 8.70 (1H, dd), 8.51 (1H, d), 8.30 (1H, dd), 8.07 (1H, m), 7.86 (1H, dd), 7.52 (1H, d), 7.20 (1H,m), 5.60 (2H, s). The compound of formula III was confirmed to be obtained from both melting point and nuclear magnetic data.
Example 2
Under the nitrogen atmosphere, 0.05mol of pyridine-2-yl (trifluoroacetyl) sodium amide, 0.05mol of 2-chloro-5-chloromethylpyridine, 0.0007mol of NaI and 15ml of acetonitrile are added into a 250ml four-neck flask, the temperature is increased to 50-55 ℃, the reaction is kept for 7 hours, HPLC (high performance liquid chromatography) tracking analysis is carried out, the reaction is finished, the temperature is reduced to the room temperature, 75 g of water is added, and a large amount of solid is separated out. And (3) carrying out suction filtration and drying on the obtained solid to obtain an off-white solid, wherein the molar yield is 93%, the product purity is 98.2%, the melting point is 152-153 ℃, and the compound shown in the formula III is obtained.
Example 3
Under the atmosphere of nitrogen, 0.05mol of pyridine-2-yl (trifluoroacetyl) sodium amide, 0.05mol of 2-chloro-5-chloromethylpyridine, 0.0018mol of KI and 15ml of acetonitrile are added into a 250ml four-neck flask, the temperature is increased to 50-55 ℃, the reaction is kept for 4 hours, HPLC (high performance liquid chromatography) tracking analysis is carried out, the temperature is reduced to room temperature after the reaction is finished, 75 g of water is added, and a large amount of solid is separated out. And (3) carrying out suction filtration and drying on the obtained solid to obtain an off-white solid, wherein the molar yield is 96.8%, the product purity is 98.8%, and the melting point is 154-156 ℃, thus confirming that the compound shown in the formula III is obtained.
Example 4
Under the atmosphere of nitrogen, 0.05mol of pyridine-2-yl (trifluoroacetyl) sodium amide, 0.05mol of 2-chloro-5-bromomethylpyridine, 0.0006mol of KI and 15ml of acetonitrile are added into a 250ml four-neck flask, the temperature is increased to 50-55 ℃, the reaction is kept for 6 hours, HPLC (high performance liquid chromatography) tracking analysis is carried out, the temperature is reduced to room temperature after the reaction is finished, 75 g of water is added, and a large amount of solid is separated out. And (3) carrying out suction filtration and drying on the obtained solid to obtain an off-white solid, wherein the molar yield is 93.7%, the product purity is 98.1%, the melting point is 152-154 ℃, and the compound shown in the formula III is confirmed to be obtained.
Example 5
Under the atmosphere of nitrogen, 0.05mol of pyridine-2-yl (trifluoroacetyl) potassium amide, 0.05mol of 2-chloro-5-chloromethylpyridine, 0.0006mol of KI and 15ml of tetrahydrofuran are added into a 250ml four-neck flask, the temperature is raised to 50-55 ℃, the reaction is kept for 8 hours, HPLC (high performance liquid chromatography) tracking analysis is carried out, the temperature is reduced to room temperature after the reaction is finished, 75 g of water is added, and a large amount of solid is separated out. And (3) carrying out suction filtration and drying on the obtained solid to obtain an off-white solid, wherein the molar yield is 94.3%, the product purity is 98.2%, and the melting point is 153-155 ℃, so that the compound shown in the formula III is obtained.
Comparative example 1
Under the nitrogen atmosphere, 0.05mol of pyridine-2-yl (trifluoroacetyl) sodium amide, 0.05mol of 2-chloro-5-chloromethylpyridine, 0.0009mol of tetrabutylammonium bromide and 15ml of acetonitrile are added into a 250ml four-neck flask, the temperature is increased to 50-55 ℃, the reaction is kept for 16 hours, HPLC (high performance liquid chromatography) tracking analysis is carried out, the reaction is finished, the temperature is reduced to the room temperature, 75 g of water is added, and a large amount of solid is separated out. The obtained solid is filtered and dried to obtain an off-white solid, the molar yield is 87.4 percent, the product purity is 95.8 percent, and the melting point is 152-154 ℃.
Comparative example 2
Under the atmosphere of nitrogen, 0.05mol of pyridine-2-yl (trifluoroacetyl) sodium amide, 0.05mol of 2-chloro-5-chloromethylpyridine, 0.0025mol of 4-dimethylaminopyridine and 15ml of acetonitrile are added into a 250ml four-neck flask, the temperature is increased to 50-55 ℃, the reaction is kept for 17 hours, HPLC (high performance liquid chromatography) tracking analysis is carried out, the reaction is finished, the temperature is reduced to room temperature, 75 g of water is added, and a large amount of solid is separated out. Filtering and drying the obtained solid to obtain an off-white solid, wherein the molar yield is 85.9%, the product purity is 95.0%, and the melting point is 150-152 ℃.
TABLE 1 comparison of the novel synthesis process of the invention of this patent with the process of the patent TW201613866A and other catalysts
| Catalyst and process for producing the same | Reaction time (h) | Yield (%) | Purity (%) | |
| Example 1 | KI | 8 | 95 | 98.5 |
| Example 2 | NaI | 7 | 93 | 98.2 |
| Example 3 | KI | 4 | 96.8 | 98.8 |
| Example 4 | KI | 6 | 93.7 | 98.1 |
| Example 5 | KI | 8 | 94.3 | 98.2 |
| Comparative example 1 | Tetrabutylammonium bromide | 16 | 87.4 | 95.8 |
| Comparative example 2 | 4-dimethylaminopyridine | 17 | 85.9 | 95.0 |
| TW201613866A | Is composed of | 18 | 88.5 | 97.9 |
As can be seen from Table 1, after the catalyst KI or NaI is added, the reaction time is greatly shortened, the reaction time is reduced by more than 10 hours, the reaction yield is obviously improved, the reaction yield is improved from 88.5 percent to more than 93 percent, and the highest reaction yield can reach more than 96 percent, which indicates that the addition of the catalyst KI or NaI is beneficial to the reaction. In addition, the effect is not achieved by the conventional catalyst, for example, when the catalyst is tetrabutylammonium bromide or 4-dimethylaminopyridine, the technical effect of the application is not achieved.
Claims (16)
1. A method for producing a pyridylamine compound, characterized by comprising a step of reacting a compound of formula (I) with a compound of formula (II) as starting materials in the presence of a catalyst to obtain a compound of formula (III);
in the reaction formula: m represents K or Na; x represents F, cl, br, I, CH3SO3、p-CH3C6H4SO3A leaving group of at least one;
the catalyst is at least one selected from KI, naI, KBr and NaBr.
2. The process for producing a pyridylamine compound according to claim 1, wherein the catalyst is KI or NaI.
3. The process for producing a pyridylamine compound according to claim 1 or 2, wherein the molar ratio of the compound of formula (I) to the catalyst is from 1.
4. The process for producing a pyridylamine compound according to claim 1 or 2, wherein the molar ratio of the compound of formula (I) to the catalyst is from 1.
5. The process for producing a pyridylamine compound according to claim 1 or 2, wherein the molar ratio of the compound of formula (I) to the catalyst is 1.
6. The process for producing a pyridylamine compound according to claim 1 or 2, wherein X represents a group selected from Cl or Br.
7. The process for producing a pyridylamine compound according to claim 1 or 2, wherein the reaction temperature is-20 ℃ to 150 ℃ and the reaction time is 0.1 to 72 hours.
8. The process for producing a pyridylamine compound according to claim 1 or 2, wherein the reaction temperature is 20 ℃ to 80 ℃ and the reaction time is 2 to 10 hours.
9. The process for producing a pyridylamine compound according to claim 1 or 2, wherein the reaction temperature is 50 ℃ to 55 ℃ and the reaction time is 2 to 10 hours.
10. The process for producing a pyridylamine compound according to claim 1 or 2, wherein the reaction solvent is selected from the group consisting of: at least one of N, N-dimethylformamide, N-dimethylacetamide, acetonitrile, benzonitrile, methanol, isopropanol, N-propanol, N-butanol, diethyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, ethyl propionate, toluene, xylene, chlorobenzene, pyridine, 2-chloropyridine, 3-methylpyridine, dichloromethane, dichloroethane, methylcyclohexane, dimethyl sulfoxide, sulfolane, acetone, dimethyl carbonate, methyl isobutyl ketone, or a mixed solvent thereof with water.
11. The process for producing a pyridylamine compound according to claim 1 or 2, wherein the reaction solvent is at least one of acetonitrile, tetrahydrofuran and 2-methyltetrahydrofuran, or a mixed solvent of these solvents with water.
12. The process for producing a pyridylamine compound according to claim 1 or 2, wherein the molar ratio of the compound of formula (I) to the compound of formula (II) is 1.2 to 10.
13. The process for producing a pyridylamine compound according to claim 1 or 2, wherein the molar ratio of the compound of formula (I) to the compound of formula (II) is from 1.
14. The process for producing a pyridylamine compound according to claim 1 or 2, wherein the reaction is carried out in a nitrogen atmosphere.
15. The process for producing a pyridylamine compound according to claim 1 or 2, wherein the reaction is carried out under normal pressure, high pressure or negative pressure.
16. The process for producing a pyridylamine compound according to claim 1 or 2, wherein the reaction is carried out under normal pressure.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811526892.3A CN111320573B (en) | 2018-12-13 | 2018-12-13 | Preparation method of pyridylamine compounds |
| PCT/CN2019/123477 WO2020119583A1 (en) | 2018-12-13 | 2019-12-06 | Method for preparing pyridinamine compound |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811526892.3A CN111320573B (en) | 2018-12-13 | 2018-12-13 | Preparation method of pyridylamine compounds |
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| CN111320573B true CN111320573B (en) | 2022-11-01 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0268915A2 (en) * | 1986-11-21 | 1988-06-01 | Bayer Ag | Trifluoromethylcarbonyl derivatives |
| CN102892260A (en) * | 2011-03-23 | 2013-01-23 | 深圳市福智软件技术有限公司 | Clamp for media player |
| CN103781764A (en) * | 2011-08-26 | 2014-05-07 | 明治制果药业株式会社 | Method for producing pest controlling agent |
| CN104220424A (en) * | 2012-02-29 | 2014-12-17 | 明治制果药业株式会社 | Nitrogen-containing heterocyclic derivative having 2-imino group and pest control agent including the same |
| TW201613866A (en) * | 2014-07-07 | 2016-04-16 | Bayer Cropscience Ag | Process for preparing fluorinated iminopyridine compounds |
| CN105980360A (en) * | 2014-03-10 | 2016-09-28 | 明治制果药业株式会社 | Method for producing 2-acyliminopyridine derivative |
| WO2018052115A1 (en) * | 2016-09-16 | 2018-03-22 | Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 | Optimized production method for pest control agent |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AR085872A1 (en) * | 2011-04-08 | 2013-10-30 | Basf Se | HETEROBICICLIC DERIVATIVES N-SUBSTITUTES USEFUL TO COMBAT PARASITES IN PLANTS AND / OR ANIMALS, COMPOSITIONS THAT CONTAIN THEM AND METHODS TO COMBAT SUCH PESTS |
| JP5745704B2 (en) * | 2012-02-29 | 2015-07-08 | Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 | Pest control composition containing a novel iminopyridine derivative |
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- 2018-12-13 CN CN201811526892.3A patent/CN111320573B/en active Active
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- 2019-12-06 WO PCT/CN2019/123477 patent/WO2020119583A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0268915A2 (en) * | 1986-11-21 | 1988-06-01 | Bayer Ag | Trifluoromethylcarbonyl derivatives |
| CN102892260A (en) * | 2011-03-23 | 2013-01-23 | 深圳市福智软件技术有限公司 | Clamp for media player |
| CN103781764A (en) * | 2011-08-26 | 2014-05-07 | 明治制果药业株式会社 | Method for producing pest controlling agent |
| CN104220424A (en) * | 2012-02-29 | 2014-12-17 | 明治制果药业株式会社 | Nitrogen-containing heterocyclic derivative having 2-imino group and pest control agent including the same |
| CN105980360A (en) * | 2014-03-10 | 2016-09-28 | 明治制果药业株式会社 | Method for producing 2-acyliminopyridine derivative |
| TW201613866A (en) * | 2014-07-07 | 2016-04-16 | Bayer Cropscience Ag | Process for preparing fluorinated iminopyridine compounds |
| WO2018052115A1 (en) * | 2016-09-16 | 2018-03-22 | Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 | Optimized production method for pest control agent |
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| CN111320573A (en) | 2020-06-23 |
| WO2020119583A1 (en) | 2020-06-18 |
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