CN114478417A - Synthesis method of 5-p-tolyl-1, 2, 4-triazine-3 (2H) -ketone - Google Patents
Synthesis method of 5-p-tolyl-1, 2, 4-triazine-3 (2H) -ketone Download PDFInfo
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- CN114478417A CN114478417A CN202210150369.5A CN202210150369A CN114478417A CN 114478417 A CN114478417 A CN 114478417A CN 202210150369 A CN202210150369 A CN 202210150369A CN 114478417 A CN114478417 A CN 114478417A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
- C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
- C07D253/06—1,2,4-Triazines
- C07D253/065—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members
- C07D253/07—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members 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
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Abstract
The invention discloses a method for synthesizing 5-p-tolyl-1, 2, 4-triazine-3 (2H) -ketone, and relates to the technical field of organic synthesis. The method takes 4-methylacetophenone as a starting material, and the 5-p-tolyl-1, 2, 4-triazine-3 (2H) -ketone is synthesized through stepwise reaction.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing 5-p-tolyl-1, 2, 4-triazine-3 (2H) -ketone.
Background
5-p-tolyl-1, 2, 4-triazin-3 (2H) -one is an important intermediate for some pharmaceutical products.
Therefore, it is necessary to provide a method for synthesizing 5-p-tolyl-1, 2, 4-triazine-3 (2H) -ketone with high efficiency and low cost.
Disclosure of Invention
The invention aims to provide a method for synthesizing 5-p-tolyl-1, 2, 4-triazine-3 (2H) -ketone, which has high efficiency, low cost and simple and convenient synthesis operation.
In order to achieve the purpose, the invention is realized by the following technical scheme: 1. the synthesis process of 5-p-tolyl-1, 2, 4-triazine-3 (2H) -ketone includes the following steps:
which comprises the following steps:
s1, preparing a compound II: mixing an oxidant, water, an organic solvent a and a compound I, and uniformly stirring until the reaction is finished, wherein the reaction temperature is 20-60 ℃;
s2, preparing a compound III: dissolving a compound II in an organic solvent b, adding water and semicarbazide hydrochloride, uniformly stirring until the reaction is finished, wherein the reaction temperature is 0-60 ℃, and the molar ratio of the compound II to the semicarbazide hydrochloride is 1: 1.0-3.0;
s2, preparing a compound IV: dissolving the compound III in water, adding alkali, and uniformly stirring until the reaction is finished, wherein the reaction temperature is 60-120 ℃.
2. The method of synthesis according to claim 1, characterized in that: the oxidant in the step S1 is sulfuric acid and nitric acid, and the molar ratio of the compound I to the sulfuric acid to the nitric acid is 1: 3.0-10: (3.0-10).
Preferably, the oxidant in step S1 is one or more of selenium dioxide, manganese dioxide, ozone, and IBX.
Preferably, the organic solvent a in step S1 is one or more of dichloromethane, chloroform, carbon tetrachloride and dioxane.
Preferably, the organic solvent b in step S2 is one or more selected from methanol, ethanol, acetonitrile, tetrahydrofuran, dioxane and N, N-dimethylformamide.
Preferably, the alkali in step S3 is one or more of sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, and lithium hydroxide.
Advantageous effects
Compared with the prior art, the invention provides a method for synthesizing 5-p-tolyl-1, 2, 4-triazine-3 (2H) -ketone, which has the following beneficial effects:
the synthesis method of the 5-p-tolyl-1, 2, 4-triazine-3 (2H) -ketone adopts 4-methylacetophenone as a starting material to be synthesized in three steps, so that the synthesis efficiency is higher, the cost is lower, and the synthesis operation is simpler and more convenient.
Drawings
FIG. 1 is a H-NMR spectrum of 5-p-tolyl-1, 2, 4-triazin-3 (2H) -one synthesized in the present invention;
FIG. 2 is a schematic diagram of the synthetic route of the present invention.
Detailed Description
For the sake of understanding, the present invention will be described in detail below by way of specific examples. It is specifically intended that the examples be given solely for the purpose of illustration and that all modifications that would be apparent to one skilled in the art from this disclosure are within the scope of the invention.
The synthetic route of the 5-p-tolyl-1, 2, 4-triazine-3 (2H) -ketone provided by the invention is shown in figure 2.
EXAMPLE 1 Synthesis of Compound II
80g of selenium dioxide and 10g of water were put in a 1L flask, 400mL of methylene chloride was added to the flask, and heated under reflux to dissolve the selenium dioxide, and 53.7g of 4-methylacetophenone was added to the flask to react for 6 hours.
And (3) treatment: the reaction product was filtered, washed with ethyl acetate, the filtrate was collected, the organic solvent of the filtrate was removed by rotary evaporation, and the concentrate was recrystallized in hot water to give 58.8g of compound ii as a white solid with a yield of 88%.
1H NMR (400 MHz,CDCl3) δ: 9.66 (s, 1H), 8.10-8.12 (d, 2H), 8.02-8.04 (d, 2H), 2.45 (S, 3H, CH3)。
EXAMPLE 2 Synthesis of Compound III
To a suspension of 148g of compound II in 1L of methanol at room temperature was added 200mL of water, to which 112g of semicarbazide hydrochloride was slowly added over 15 minutes. The resulting reaction mixture was stirred at room temperature for 12 hours.
And (3) treatment: the resulting precipitate was isolated by filtration to give 133g of compound III in 65% yield.
EXAMPLE 3 Synthesis of Compound IV
A2L flask was charged with 1L of water, 100g of Compound III and 104g of sodium carbonate were added, and the mixture was refluxed for 1 hour.
And (3) treatment: water was evaporated under reduced pressure, the resulting solution was dissolved in methanol, insoluble matter was filtered off, and methanol was evaporated under reduced pressure to dryness to give 77g of Compound IV with a yield of 84%.
1H NMR (400 MHz,DMSO-d6) δ: 10.97 (s, 1H),7.90-7.92 (d, 2H), 7.76 (s,1H),7.33-7.35(d, 2H), 2.38 (S, 3H, CH3)。
Claims (6)
1. The synthesis process of 5-p-tolyl-1, 2, 4-triazine-3 (2H) -ketone includes the following steps:
which comprises the following steps:
s1, preparing a compound II: mixing an oxidant, water, an organic solvent a and a compound I, and uniformly stirring until the reaction is finished, wherein the reaction temperature is 20-60 ℃;
s2, preparing a compound III: dissolving a compound II in an organic solvent b, adding water and semicarbazide hydrochloride, uniformly stirring until the reaction is finished, wherein the reaction temperature is 0-60 ℃, and the molar ratio of the compound II to the semicarbazide hydrochloride is 1: 1.0-3.0;
s2, preparing a compound IV: dissolving the compound III in water, adding alkali, and uniformly stirring until the reaction is finished, wherein the reaction temperature is 60-120 ℃.
2. The method of synthesis according to claim 1, characterized in that: the oxidant in the step S1 is sulfuric acid and nitric acid, and the molar ratio of the compound I to the sulfuric acid to the nitric acid is 1: 3.0-10: (3.0-10).
3. The method of synthesis according to claim 1, characterized in that: the oxidant in step S1 is one or more of selenium dioxide, manganese dioxide, ozone, and IBX.
4. The method of synthesis according to claim 1, characterized in that: the organic solvent a in the step S1 is one or more of dichloromethane, chloroform, carbon tetrachloride and dioxane.
5. The method of synthesis according to claim 1, characterized in that: the organic solvent b in step S2 is one or more of methanol, ethanol, acetonitrile, tetrahydrofuran, dioxane, and N, N-dimethylformamide.
6. The method of synthesis according to claim 1, characterized in that: the alkali in step S3 is one or more of sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, and lithium hydroxide.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210150369.5A CN114478417A (en) | 2022-02-18 | 2022-02-18 | Synthesis method of 5-p-tolyl-1, 2, 4-triazine-3 (2H) -ketone |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210150369.5A CN114478417A (en) | 2022-02-18 | 2022-02-18 | Synthesis method of 5-p-tolyl-1, 2, 4-triazine-3 (2H) -ketone |
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| CN202210150369.5A Pending CN114478417A (en) | 2022-02-18 | 2022-02-18 | Synthesis method of 5-p-tolyl-1, 2, 4-triazine-3 (2H) -ketone |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1349514A (en) * | 1999-05-04 | 2002-05-15 | 辛根塔参与股份公司 | Pesticidal triazine derivatives |
| WO2018101312A1 (en) * | 2016-11-30 | 2018-06-07 | 田辺三菱製薬株式会社 | Method for producing triazine compound |
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- 2022-02-18 CN CN202210150369.5A patent/CN114478417A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1349514A (en) * | 1999-05-04 | 2002-05-15 | 辛根塔参与股份公司 | Pesticidal triazine derivatives |
| WO2018101312A1 (en) * | 2016-11-30 | 2018-06-07 | 田辺三菱製薬株式会社 | Method for producing triazine compound |
Non-Patent Citations (1)
| Title |
|---|
| 王月梅等: "杀菌剂氰霜唑的合成新方法", 《农药》, vol. 54, no. 5, pages 325 * |
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