CN110845472B - Preparation method of pyrazole amide compound - Google Patents
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Abstract
The invention provides a pyrazole amide compoundThe preparation method. The method comprises the following steps: carrying out hydrolysis reaction on the pyrazole amide nitrile compound shown as a general formula II to obtain a pyrazole amide compound; wherein R is 1 Selected from F, Cl, Br or I; r 2 Selected from F, Cl, Br or I; r 3 Selected from Cl or Br; r 4 Selected from Cl or H. As the reaction process has less byproducts, the purification and separation procedures of the reaction product are greatly simplified, and the pyrazole amide compound with high yield and high purity is obtained. Correspondingly, the reaction raw material utilization rate is high, the preparation process is simplified, and the preparation method provided by the invention is low in cost due to two reasons, and is very suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the field of pesticides, and particularly relates to a preparation method of a pyrazole amide compound.
Background
Since insecticides are resistant to pests over time, there is a continuing need for new and improved compounds and compositions having insecticidal activity. Meanwhile, with the increasing demand of people for agricultural and livestock products and the increasing emphasis on environmental protection, there is a continuing need for new pesticides that are less costly to use and environmentally friendly.
CN104447688 reports a pyrazole amide compound, which has excellent insecticidal activity and has a structure shown in general formula I:
however, the preparation method of the pyrazole amide compound has more byproducts and more complicated purification procedures. Meanwhile, the yield and purity of the target product are low, so that a large amount of corresponding medicaments are wasted, and the preparation cost is increased.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a pyrazole amide compound, which aims to solve the problems of more by-products, lower yield and purity of target products and the like in the prior art when the compound is prepared.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a process for preparing pyrazole amide compounds represented by the general formula i, which comprises the steps of: carrying out hydrolysis reaction on the pyrazole amide nitrile compound shown as a general formula II to obtain a pyrazole amide compound; the reaction formula of the hydrolysis reaction is as follows:
wherein R is 1 Selected from F, Cl, Br or I; r 2 Selected from F, Cl, Br or I; r 3 Selected from Cl or Br; r is 4 Selected from Cl or H.
Further, R 1 Selected from Cl or Br; r 2 Selected from Cl or Br.
Further, the hydrolysis reaction is carried out in an acidic solution, preferably a sulfuric acid solution or a concentrated hydrochloric acid solution with the concentration of 30-40 wt%.
Furthermore, the reaction temperature of the hydrolysis reaction is 35-40 ℃, and preferably 36-38 ℃.
Further, after the hydrolysis reaction is finished, the preparation method further comprises the following steps: and cooling and precipitating the reaction solution of the hydrolysis reaction to obtain the pyrazole amide compound.
Further, the temperature for cooling and precipitation is 0-10 ℃.
Further, the preparation method further comprises a step of synthesizing a pyrazolylamidonitrile compound before the hydrolysis reaction, wherein the compound III and the compound IV are synthesized into the pyrazolylamidonitrile compound according to the following reaction formula:
further, the synthesis reaction is carried out in an organic solvent, preferably one of acetonitrile, benzene, toluene, hexane and DMF.
Further, the step of synthesizing the pyrazolylamidonitrile compound includes: mixing a compound III, a compound IV and an organic solvent to obtain a mixture; and carrying out substitution reaction on the mixture to generate the pyrazole amido nitrile compound.
Further, the mixing temperature in the mixing step is 0-25 ℃, and the reaction temperature in the substitution reaction process is the reflux temperature of the mixture; preferably, after the step of substitution reaction, the reaction solution of substitution reaction is added to an alkaline solution, preferably a saturated sodium carbonate solution and/or a saturated sodium bicarbonate solution, to obtain the pyrazolylamidonitrile compound.
The invention provides a preparation method of pyrazole amide compounds, which directly hydrolyzes pyrazole amide nitrile compounds to prepare compounds with a structure shown in a general formula I. As the reaction process has less byproducts, the purification and separation procedures of the reaction product are greatly simplified, and the pyrazole amide compound with high yield and high purity is obtained. Correspondingly, the reaction raw material utilization rate is high, the preparation process is simplified, and the preparation method provided by the invention is low in cost due to two reasons, and is very suitable for large-scale industrial production.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the preparation method of pyrazole amide compounds in the prior art has the problems of more by-products, lower yield and purity of target products and the like when the compounds are prepared. In order to solve the problems, the invention provides a preparation method of pyrazole amide compounds, which comprises the following steps of carrying out hydrolysis reaction on pyrazole amide nitrile compounds shown in a general formula II to obtain the pyrazole amide compounds, wherein the pyrazole amide nitrile compounds are shown in a general formula I, and the reaction formula of the hydrolysis reaction is as follows:
wherein R is 1 Selected from F, Cl, Br or I; r 2 Selected from F, Cl, Br or I; r 3 Selected from Cl or Br; r is 4 Selected from Cl or H.
According to the preparation method of the pyrazole amide compounds, the pyrazole amide nitrile compounds are directly hydrolyzed to prepare the compounds with the structures shown in the general formula I. As the reaction process has less byproducts, the purification and separation procedures of the reaction product are greatly simplified, and the pyrazole amide compound with high yield and high purity is obtained. Correspondingly, the reaction raw material utilization rate is high, the preparation process is simplified, and the preparation method provided by the invention has low cost due to two reasons, and is very suitable for large-scale industrial production.
In particular, when the above-mentioned hydrolysis reaction forms
Due to
Exist, stabilize
The electron cloud avoids the dehydration and cyclization formation in the hydrolysis environment
Thereby reducing the occurrence of side reactions, improving the yield and purity of the target product and simultaneously reducing the purification difficulty.
In order to further increase the yield of the reaction, in a preferred embodiment, R 1 Selected from Cl or Br; r 2 Selected from Cl or Br.
In a preferred embodiment, the hydrolysis reaction is carried out in an acidic solution, preferably a sulfuric acid solution or a concentrated hydrochloric acid solution with a concentration of 30-40 wt%. The acidic solution can be used as a catalyst for hydrolyzing organic matters, so that the hydrolysis reaction is promoted, the conversion rate of the reaction is further improved, and the formation of byproducts is reduced.
In order to promote the reaction in the forward direction toward the formation of the pyrazole amide compound, in a preferred embodiment, the hydrolysis reaction is maintained at a reaction temperature of 35 to 40 ℃, preferably 36 to 38 ℃.
After the hydrolysis reaction, in order to separate the pyrazole amide compound from the hydrolysis reaction system, in a preferred embodiment, after the hydrolysis reaction is finished, the method further comprises the step of cooling the reaction solution of the hydrolysis reaction to separate out, and filtering and separating out a solid precipitate to obtain the pyrazole amide compound. The temperature for cooling and precipitation is 0-10 ℃. For example, the reaction solution of the hydrolysis reaction may be poured into ice water to be cooled and precipitated, or another cooling method may be employed.
In a preferred embodiment, prior to the hydrolysis reaction, further comprising the step of synthesizing the pyrazolylamidonitrile compound, the compound III and the compound IV are synthesized into the pyrazolylamidonitrile compound according to the following reaction formula:
it should be noted here that since the present invention first utilizes the reaction of compound III and compound IV to prepare compound II, compound III and compound IV do not carry themselves
The intermediate compound II formed is also not carried
Further prevent due to
The dehydration ring of (2) is generated as a by-product. Therefore, the compound II is prepared by the step, the occurrence of side reactions is further reduced, and the yield and the purity of the target product are improved. Meanwhile, the compound II prepared by the reaction has the advantages of simple process, high stability and high conversion rate.
In order to improve the reaction stability of compound iii and compound iv, in a preferred embodiment, the synthesis reaction is carried out in an organic solvent, preferably one of acetonitrile, benzene, toluene, hexane and DMF.
In a preferred embodiment, the step of synthesizing the pyrazole amido nitrile compound comprises: mixing the compound III, the compound IV and an organic solvent to obtain a mixture; and carrying out substitution reaction on the mixture to generate the pyrazole amide nitrile compound. The compound III, the compound IV and the organic solvent are mixed, so that the two compounds can be better mixed and contacted, and then substitution reaction is carried out, and the pyrazole amide nitrile compound is obtained.
In a preferred embodiment, the mixing temperature in the mixing step is 0-25 ℃; while maintaining the reaction temperature during the substitution reaction at the reflux temperature of the mixture. Controlling the mixing temperature to fully mix and contact the compound III and the compound IV before reaction; maintaining the temperature of the substitution reaction at reflux temperature allows for a more complete reaction.
After the substitution reaction is completed, in order to separate the pyrazolylamidonitrile compound from the hydrolysis reaction system, in a preferred embodiment, after the substitution reaction step, the reaction solution of the substitution reaction is added to an alkaline solution (impurity removal step), and a solid precipitate, that is, the target compound of the substitution reaction, the pyrazolylamidonitrile compound, is precipitated.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
Preparation of Compound 5 (see Table below)
2-amino-3, 5-dichloro-N- (2-cyano-2-propyl) benzamide (25g,90mmol) and acetonitrile solution (200mL) were added sequentially to a reaction flask, stirred at room temperature (25. + -. 5 ℃) until the starting material was completely dissolved, then 60mL of acetonitrile solution containing 29.5g of 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carbonyl chloride (90mmol, see WO03/015519 for its preparation) was added with stirring, and after stirring for 20min, the reaction flask was slowly heated to reflux. After refluxing for 2h, the reaction solution was poured into saturated sodium carbonate solution, the solid was continuously washed out, the solid was filtered out after stirring for 30min, and after drying, 45.6g of off-white solid was obtained, and High Performance Liquid Chromatography (HPLC) analysis showed that the content of the amido nitrile generated by the reaction was 95%, and the yield was 86.5%.
Adding 100mL of concentrated hydrochloric acid with the concentration of 36% into a reaction bottle, heating to 36-38 ℃, adding the acylaminonitrile obtained in the previous step into the reaction bottle in batches, and ensuring that the reaction temperature does not exceed 40 ℃. After the addition, the reaction is carried out for 30min under the condition of heat preservation. The reaction was poured into ice water and a large amount of solid precipitated, and the temperature was maintained below 10 ℃ and stirred for 30 min. Filtering and drying to obtain 40g of white solid, and obtaining the 2-amino-N- (1-amino-2-methyl-1-oxoprop-2-yl) -3, 5-dichlorobenzamide with the content of 95 percent and the yield of 85 percent through High Performance Liquid Chromatography (HPLC). White solid, melting point: 164 ℃ and 168 ℃. 1 H NMR(300MHz,DMSO-d 6 ):10.35-11.45(m,2H),8.58(d,1H),8.51(d,1H),7.95(d,1H),7.72(d,1H),7.37(s,1H),1.12(s,6H)。
The yield of the compound synthesized in two steps was 73.5% based on 2-amino-N- (1-amino-2-methyl-1-oxoprop-2-yl) -3, 5-dichlorobenzamide.
The reaction formula of the above reaction is as follows:
example 2
Preparation of Compound 6 (see Table below)
In contrast to example 1, R in the compound IV 3 As Cl, the mixing temperature was 0 ℃. High Performance Liquid Chromatography (HPLC) analysis shows that the content of the amido nitrile generated by the substitution reaction is 95%, and the yield is 88%. The hydrolysis reaction produced 2-amino-N- (1-amino-2-methyl-1-oxoprop-2-yl) -3,5 dichlorobenzamide, the content of which was 93%, the yield was 90%. White solid, melting point: 158 ℃ and 162 ℃. 1 H NMR(300MHz,DMSO-d6):10.44(s,1H),8.44(dd,1H),8.23(s,1H),8.05(dd,1H),7.69(d,1H),7.65(d,1H),7.55(dd,1H),7.33(s,1H),7.03(s,1H),6.67(s,1H),1.30(s,6H)。
The yield of the two-step synthesized compound was 79.2% based on 2-amino-N- (1-amino-2-methyl-1-oxoprop-2-yl) -3, 5-dichlorobenzamide.
The benzamide compound shown in the general formula (I) can be prepared by the method provided by the invention, and the structures of part of the compounds shown in the general formula (I) are listed in Table 1.
TABLE 1 Structure of part of the compounds of the general formula (I)
The nuclear magnetic data and yields of some of the compounds were as follows:
compounds 5:10.44(s,1H),8.44(dd,1H),8.23(s,1H),8.05(dd,1H),7.69(d,1H),7.65(d,1H),7.55(dd,1H),7.33(s,1H),7.03(s,1H),6.67(s,1H),1.30(s, 6H). The total yield was 73.5%.
Compounds 6:10.34(d,1H),8.45(d,1H),7.84(dd,1H),7.33(dd,1H),7.23(s,1H),7.18(d,1H),7.12(d,1H),6.89(s,1H),6.33(s,1H),5.58(s,1H),1.55(s, 6H). The total yield is 79.2%.
Compounds 7:10.45(s,1H),8.44(d,1H),8.20(s,1H),8.06(d,1H),7.80(d,1H),7.73(d,1H),7.56(dd,1H),7.33(s,1H),7.03(s,1H),6.67(s,1H),1.29(s, 6H). The total yield was 79.7%.
Compounds 8:10.44(s,1H),8.45(dd,1H),8.22(s,1H),8.09(d,1H),7.83(d,1H),7.76(d,1H),7.56(dd,1H),7.40(s,1H),7.05(s,1H),6.70(s,1H),1.28(s, 6H). The total yield is 77.1%.
Compounds 9:10.38(s,1H),8.44(dd,1H),8.13(s,1H),8.05(d,1H),7.55(dd,1H),7.49(s,1H),7.46(s,1H),7.33(s,1H),7.00(s,1H),6.67(s,1H),1.33(s, 6H). The total yield was 79.0%.
Compounds 10:10.37(s,1H),8.44(d,1H),8.14(s,1H),8.06(d,1H),7.56(dd,1H),7.51(s,1H),7.48(s,1H),7.39(s,1H),7.01(s,1H),6.68(s,1H),1.25(s, 6H). The total yield was 78.4%.
Compounds 11:10.42(s,1H),8.43(d,1H),8.16(s,1H),8.03(d,1H),7.89(d,1H),7.82(d,1H),7.54(dd,1H),7.34(s,1H),6.98(s,1H),6.60(s,1H),1.26(s, 6H). The total yield is 75.8%.
Compounds 12:10.48(s,1H),8.84(s,1H),8.43(dd,1H),8.03(dd,1H),7.94(d,1H),7.61(d,1H),7.54(dd,1H),7.34(s,1H),6.98(s,1H),6.60(s,1H),1.26(s, 6H). The total yield is 80.2%.
Compounds 17:10.53(s,1H),8.59(d,1H),8.51(d,1H),8.36(s,1H),7.82(dd,1H),7.43(s,1H),7.17(s,1H),6.83(s,1H),1.26(s, 6H). The total yield was 79.9%.
Comparative example 1
(1) Synthesis of 2-amino-N- (1-amino-2-methyl-1-oxoprop-2-yl) -3, 5-dichlorobenzamide
2-amino-3, 5-dichloro-N- (2-cyano-2-propyl) benzamide (68g, 250mmol), potassium hydroxide (16.8g, 280mmol), and ethanol (200mL) were added to a reaction flask, hydrogen peroxide (144g, 1.27mol, 30%) was slowly added dropwise in an ice-water bath, and reacted at room temperature for 24 hours, the solvent was evaporated under reduced pressure to obtain a reddish brown oil, ethyl acetate (1L) was added to the residue, water (500mL) was separated and extracted, the organic phase was washed with saturated brine (500mL), dried over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure, and the residue was purified by column chromatography (eluent: ethyl acetate: petroleum ether ═ 1:1) to obtain 20.9g of a yellow solid with weak polarity, yield: 30%, melting point: 170 ℃ and 173 ℃.
(2) Synthesis of N- [2- [ [ (2-amino-1, 1-dimethyl-2-oxoethyl) amino ] carbonyl ] -4, 6-dichlorophenyl ] -3-bromo-1- (3-chloro-2-pyridinyl) -pyrazolecarboxamide
To a reaction flask was added 2-amino-N- (1-amino-2-methyl-1-oxoprop-2-yl) -3, 5-dichlorobenzamide (25g86.3mmol), acetonitrile (100mL), and a solution of 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carbonyl chloride (33.3g, 103.5mmol, for its preparation see WO03/015519) in acetonitrile (50mL) was added dropwise. After 12 hours of reaction at room temperature, the solvent was evaporated, ethyl acetate (500mL) was added, and the mixture was washed twice with saturated sodium bicarbonate (100mL), twice with saturated brine (100mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 46g of a yellow solid. Content 52%, yield: 46.5 percent.
The yield of the compound synthesized in two steps was 14% based on 2-amino-N- (1-amino-2-methyl-1-oxoprop-2-yl) -3, 5-dichlorobenzamide.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: by applying the technical scheme of the invention, the compound with the structure of the general formula I is prepared by directly hydrolyzing the pyrazole amide nitrile compound. As the reaction process has less byproducts, the purification and separation procedures of the reaction product are greatly simplified, and the pyrazole amide compound with high yield and high purity is obtained. Correspondingly, the reaction raw material utilization rate is high, the preparation process is simplified, and the preparation method provided by the invention has low cost due to two reasons, and is very suitable for large-scale industrial production.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. A preparation method of pyrazole amide compounds is disclosed, wherein the pyrazole amide compounds are shown as a general formula I, and is characterized by comprising the following steps: carrying out hydrolysis reaction on pyrazole amide nitrile compounds shown in a general formula II to obtain pyrazole amide compounds; the reaction formula of the hydrolysis reaction is as follows:
Ⅱ Ⅰ
wherein R is 1 Selected from F, Cl, Br or I; r is 2 Selected from F, Cl, Br or I; r 3 Selected from Cl or Br; r is 4 Selected from Cl or H;
the hydrolysis reaction is carried out in an acid solution, the acid solution is a concentrated hydrochloric acid solution with the concentration of 30-40 wt%, and the temperature of the hydrolysis reaction is 36-38 ℃.
2. The method of claim 1, wherein R is 1 Selected from Cl or Br; the R is 2 Selected from Cl or Br.
3. The method according to claim 1, wherein after the hydrolysis reaction is completed, the method further comprises: and cooling and precipitating the reaction solution of the hydrolysis reaction to obtain the pyrazole amide compound.
4. The production method according to claim 3, wherein the temperature of the cooled precipitation is 0 to 10 ℃.
5. The production method according to any one of claims 1 to 4, characterized in that, prior to the hydrolysis reaction, the production method further comprises a step of synthesizing the pyrazole amido nitrile compound by reacting compound III and compound IV according to the following reaction formula:
Ⅲ Ⅳ Ⅱ。
6. the method according to claim 5, wherein the synthesis reaction is carried out in an organic solvent.
7. The method of claim 6, wherein the organic solvent is one of acetonitrile, benzene, toluene, hexane, and DMF.
8. The production method according to claim 6, characterized in that the step of synthesizing the pyrazole amido nitrile compound comprises:
mixing the compound III, the compound IV and the organic solvent to obtain a mixture;
and carrying out substitution reaction on the mixture to generate the pyrazole amido nitrile compound.
9. The method according to claim 8, wherein the mixing temperature in the mixing step is 0 to 25 ℃, and the reaction temperature during the substitution reaction is a reflux temperature of the mixture.
10. The production method according to claim 9, wherein the step of the substitution reaction is followed by adding a reaction solution of the substitution reaction to an alkaline solution to obtain the pyrazolylamidonitrile compound.
11. The method according to claim 10, wherein the alkaline solution is a saturated sodium carbonate solution and/or a saturated sodium bicarbonate solution.
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| CN102020633A (en) * | 2009-09-21 | 2011-04-20 | 中国中化股份有限公司 | Method for preparing 1-(3,5- dichloropyridine-2-yl)-pyrazolecarboxamide compounds |
| CN104447688A (en) * | 2013-11-25 | 2015-03-25 | 中国中化股份有限公司 | Pyrazole amide compound and application thereof |
| CN105367548A (en) * | 2015-10-21 | 2016-03-02 | 邓方坤 | Cyan dihalogenation pyrazol amide series compound and preparation method and application thereof |
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| CN102020633A (en) * | 2009-09-21 | 2011-04-20 | 中国中化股份有限公司 | Method for preparing 1-(3,5- dichloropyridine-2-yl)-pyrazolecarboxamide compounds |
| CN104447688A (en) * | 2013-11-25 | 2015-03-25 | 中国中化股份有限公司 | Pyrazole amide compound and application thereof |
| CN105367548A (en) * | 2015-10-21 | 2016-03-02 | 邓方坤 | Cyan dihalogenation pyrazol amide series compound and preparation method and application thereof |
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