CN101870678B - Pyrazole compound and preparation method thereof - Google Patents
Pyrazole compound and preparation method thereof Download PDFInfo
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- CN101870678B CN101870678B CN2010102130567A CN201010213056A CN101870678B CN 101870678 B CN101870678 B CN 101870678B CN 2010102130567 A CN2010102130567 A CN 2010102130567A CN 201010213056 A CN201010213056 A CN 201010213056A CN 101870678 B CN101870678 B CN 101870678B
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- amino
- pyrazol
- pyrazole
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- pyrazole compound
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Abstract
The invention discloses a pyrazole compound and a preparation method thereof. The compound is a pyrazole heterocyclic compound a pyrazole ring of which is connected with (2-ethoxycarbonyl-2-cyanoethylene) amino. The preparation method comprises the following steps of: taking amino pyrazole derivative, ethyl cyanoacetate and triethyl orthoformate as raw materials, dissolving the amino pyrazole derivative into anhydrous acetonitrile and mixing the solution uniformly, then adding the ethyl cyanoacetate and the triethyl orthoformate into the solution in turn, and obtaining a high-purity product through the operations of heating reflux polymerization, cooling crystallization, filter and crystal collection, crystal washing with anhydrous ethanol and the like. The pyrazole compound has pesticidal activity and is suitable to be used as pesticide. The preparation method has the advantages of few synthetic reaction step, simple purification method, simple and convenient experimental operation and high product purity.
Description
Technical field
The present invention relates to the pyrazoles heterogeneous ring compound.
Background technology
Studies show that, in many natural compoundss with physiology and pharmacologically active, all contain the pyrazole heterocycle structural unit.And intensive physiology and pharmacologically actives such as that the pyrazoles heterogeneous ring compound has really is antibiotic, spasmolytic, anti-inflammatory, coordinate plant growth and anti-platelet aggregation can be widely used in weeding, desinsection, sterilization, kill in plant protection product such as mite and heat and the photosensitive recording material.Therefore, the research to pyrazoles heterogeneous ring compound and synthetic just has crucial meaning.Yet in the pyrazoles heterocyclic compound compounds of existing synthetic, determined by its different constitutional features: the step of most of building-up reactionss is all many, and is difficult for purifying.
Summary of the invention
First purpose of the present invention is, a kind of general character that itself possesses the pyrazoles heterogeneous ring compound is provided, and the higher pyrazole compound of its purity.
Second purpose of the present invention is, provides a kind of building-up reactions step few, and purification process simply obtains the preparation method of the pyrazole compound of realizing first goal of the invention.
For realizing first goal of the invention, a kind of like this pyrazole compound is provided, on the pyrazoles ring of this pyrazole compound, be connected with (2-ethoxycarbonyl-2-acrylonitrile base) amino, and following I, two general formulas of II are arranged respectively:
In this I, two general formulas of II, R all selects for use-COOCH
3,-COOCH
2CH
3,-H.
For realizing second goal of the invention, a kind of like this preparation method of pyrazole compound is provided, this compound of this method preparation is a pyrazole compound of realizing first goal of the invention, it is that feedstock production forms by amino-pyrazol analog derivative, ethyl cyanoacetate and triethyl orthoformate, wherein, the amino-pyrazol analog derivative has following III, two general formulas of IV:
In III, two general formulas of IV, R all selects for use-COOCH
3,-COOCH
2CH
3,-H;
This method comprises the steps:
1. dissolve amino pyrazole derivatives with anhydrous acetonitrile; Wherein, anhydrous acetonitrile: amino-pyrazol analog derivative=40 milliliter: 0.05 mole;
2. add ethyl cyanoacetate and triethyl orthoformate successively, again the shaking by swirling mixing; Wherein, the amount of substance of ethyl cyanoacetate and triethyl orthoformate is 1～1.2 times of amino-pyrazol analog derivative amount of substance;
3. slow reflux 3.5～4.5 hours;
4. be cooled to crystal and separate out, filter and collect crystallization,
5. use absolute ethanol washing crystallization at least 3 times, treat promptly to get the described pyrazole compound of claim 1 after the ethanol volatilization fully.
From the structural formula of the scheme that realizes first goal of the invention, as can be seen, the invention provides a kind of pyrazole compound of the new general character that possesses similar compound.Checking shows that this is connected with (2-ethoxycarbonyl-2-acrylonitrile base) amino its purity height of pyrazole compound, and especially has parasiticidal activity, is suitable for doing the usefulness of sterilant.
As can be seen, preparation method's of the present invention building-up reactions step is few from the scheme that realizes second goal of the invention, and purification process is simple; Checking shows that its experiment is easy and simple to handle, and product purity reaches more than 93%.
Below in conjunction with embodiment, the present invention is described further.
Embodiment
(1) a kind of pyrazole compound on the pyrazoles ring of this pyrazole compound, is connected with (2-ethoxycarbonyl-2-acrylonitrile base) amino, and following I, two general formulas of II are arranged respectively:
In this I, two general formulas of II, R all selects for use-COOCH
3,-COOCH
2CH
3,-H.
(2) a kind of preparation method of pyrazole compound, the compound of this method preparation is embodiment (one's) a pyrazole compound, it is that feedstock production forms by amino-pyrazol analog derivative, ethyl cyanoacetate and triethyl orthoformate, wherein, the amino-pyrazol analog derivative has following III, two general formulas of IV:
In III, two general formulas of IV, R all selects for use-COOCH
3,-COOCH
2CH
3,-H;
This method comprises the steps:
1. dissolve amino pyrazole derivatives with anhydrous acetonitrile; Wherein, anhydrous acetonitrile: amino-pyrazol analog derivative=40 milliliter: 0.05 mole;
2. add ethyl cyanoacetate and triethyl orthoformate successively, again the shaking by swirling mixing; Wherein, the amount of substance of ethyl cyanoacetate and triethyl orthoformate is 1～1.2 times of amino-pyrazol analog derivative amount of substance;
3. slow reflux 3.5～4.5 hours;
4. be cooled to crystal and separate out, filter and collect crystallization,
5. use absolute ethanol washing crystallization at least 3 times, treat promptly to get the described pyrazole compound of claim 1 after the ethanol volatilization fully.
Further, above-mentioned the 2. in the step, the amount of substance of ethyl cyanoacetate and triethyl orthoformate is 1.2 times of amino-pyrazol analog derivative amount of substance.Theoretically, when the above two amount of substance is 1 times (amount of substance that is them all equates) of latter's amount of substance, just satisfied the synthetic reacting weight.The above two amount of substance is 1.2 times of latter's amount of substance, is " excessive " for the latter, and this " excessive " can make latter's's (being the amino-pyrazol analog derivative) conversion more approaching fully.Therefore, in following each example, all come for example and checking with excessive ethyl cyanoacetate and triethyl orthoformate.
The present invention has passed through at breadboard verification experimental verification.In proof procedure, at first prepare the various concrete pyrazole compound of embodiment () according to the step of above-mentioned embodiment (two).1. all use 100 ml flasks in step in, in this flask, dissolve each concrete amino-pyrazol analog derivative of 0.05 mole with 40 milliliters of anhydrous acetonitriles; In the slow reflux time of step in 3., though all grasp between 3.5～4.5 hours, but still with the amino-pyrazol analog derivative degree of being converted into fully of can trying one's best, so average out to is about 4 hours.All the other are identical with previous embodiment, do not give unnecessary details.Each checking for example down.
Checking example 1:
By the 3-amino-pyrazol in the amino-pyrazol analog derivative is raw material, and the gained pyrazole compound is 3-(2-ethoxycarbonyl-2-acrylonitrile base) amino-pyrazol.Reaction formula is as follows:
Infrared spectroscopy:
IR(cm
-1，KBr)：3238.3，3049.5，2982.9，2939.4，2220.1，1678.5，1570.4，1531.0，1492.8，1471.1，1239.1。
Nuclear magnetic resonance spectroscopy:
The chemical displacement value of each hydrogen atom and carbon atom in 3-(2-ethoxycarbonyl-2-acrylonitrile base) the amino-pyrazol structural formula (δ/ppm) as shown below:
Mass spectroscopy: M
+(molecular ion peak) 206.
Ultimate analysis:
C%:52.02, N%:27.37, O%:15.46 (theoretical value: C%:52.43, N%:27.18, O%:15.53).
Purity: 96.58%.
Conclusion: checking example 1 prepared compound really is 3-(2-ethoxycarbonyl-2-acrylonitrile base) amino-pyrazol.
Checking example 2:
By the 5-amino-pyrazol in the amino-pyrazol analog derivative is raw material, and the gained pyrazole compound is 5-(2-ethoxycarbonyl-2-acrylonitrile base) amino-pyrazol.Reaction formula is as follows:
Infrared spectroscopy:
IR(cm
-1，KBr)：3238.3，3049.5，2982.9，2939.4，2220.1，1678.5，1570.4，1531.0，1492.8，1471.1，1239.1。
Nuclear magnetic resonance spectroscopy:
The chemical displacement value of each hydrogen atom and carbon atom in 5-(2-ethoxycarbonyl-2-acrylonitrile base) the amino-pyrazol structural formula (δ/ppm) as shown below:
Mass spectroscopy: M
+(molecular ion peak) 206.
Ultimate analysis:
C%:52.02, N%:27.37, O%:15.46 (theoretical value: C%:52.43, N%:27.18, O%:15.53).
Purity: 96.58%.
Conclusion: checking example 2 prepared compounds really are 5-(2-ethoxycarbonyl-2-acrylonitrile base) amino-pyrazol.
Specify: 5-(2-ethoxycarbonyl-2-acrylonitrile base) amino-pyrazol and 3-(2-ethoxycarbonyl-2-acrylonitrile base) are although amino-pyrazol exists pro forma difference on structural formula is write, but the two has identical physico-chemical property, so, must not distinguish under their situation need especially having, those skilled in the art completely are not expressed as 3 (5)-(2-ethoxycarbonyl-2-acrylonitrile base) amino-pyrazols to them with making any distinction between often yet.In the checking example of back, promptly adopt this form of presentation.
Checking example 3:
By 3 (5)-amino-pyrazols in the amino-pyrazol analog derivative-4-methyl-formiate is raw material, and the gained pyrazole compound is 3 (5)-(2-ethoxycarbonyl-2-acrylonitrile base) amino-pyrazols-4-methyl-formiate.Reaction formula is as follows respectively:
Infrared spectroscopy:
IR(cm
-1，KBr)：3221.4，3049.3，2979.5，2219.1，1676.2，1611.8，1497.8，1511.0，1490.8，1393.5。
Nuclear magnetic resonance spectroscopy:
The chemical displacement value of each hydrogen atom and carbon atom in 3 (5)-(2-ethoxycarbonyl-2-acrylonitrile base) amino-pyrazol-4-methyl-formiate structural formulas (δ/ppm) as shown below:
Mass spectroscopy: M
+(molecular ion peak) 264.
Ultimate analysis:
C%:50.13, N%:20.97, O%:24.75 (theoretical value: C%:50.00, N%:21.21, O%:24.24).
Purity: 93.66%.
Conclusion: checking example 4 prepared compounds really are 3 (5)-(2-ethoxycarbonyl-2-acrylonitrile base) amino-pyrazols-4-methyl-formiate.
Checking example 4:
By 3 (5)-amino-pyrazols in the amino-pyrazol analog derivative-4-ethyl formate is raw material, and the gained pyrazole compound is 3 (5)-(2-ethoxycarbonyl-2-acrylonitrile base) amino-pyrazols-4-ethyl formate.Reaction formula is as follows respectively:
Infrared spectroscopy:
IR(cm
-1，KBr)：3229.1，3050.2，2982.7，2220.4，1679.9，1618.8，1492.6，1531.0，1472.7，1239.2。
Nuclear magnetic resonance spectroscopy:
The chemical displacement value of each hydrogen atom and carbon atom in 3 (5)-(2-ethoxycarbonyl-2-acrylonitrile base) amino-pyrazol-4-ethyl formate structural formulas (δ/ppm) as shown below:
Mass spectroscopy: M
+(molecular ion peak) 278.
Ultimate analysis:
C%:51.72, N%:20.25, O%:23.03 (theoretical value: C%:51.80, N%:20.14, O%:23.02).
Purity: 96.03%.
Conclusion: checking example 4 prepared compounds really are 3 (5)-(2-ethoxycarbonyl-2-acrylonitrile base) amino-pyrazols-4-ethyl formate.
Each concrete pyrazole compound in above-mentioned each example by the insecticidal toxicity determination test, proves that they have the higher activity of killing (seeing Table 1) to small cabbage moth, are particularly suitable for killing the usefulness of small cabbage moth (Plutella xylostella L.).
The toxicity test testing sequence:
1. each compound is mixed with desired concn, every kind of compound is provided with 6 concentration gradients, and each concentration gradient is provided with 3 repetitions;
2. the Plantula Brassicae chinensis leaf was soaked for 5 seconds in each compound solution respectively, after taking-up is dried, put into the culture dish that is covered with filter paper of 9 centimetres of diameters;
3. in culture dish, put into 15 small cabbage moth 3 instar larvaes;
4. check the death condition of small cabbage moth after 24 hours,, then be considered as death if health is motionless with writing brush point touching examination worm.
Table 1 pyrazole compound is to the activity of killing of small cabbage moth
| Pyrazole compound | Median lethal concentration (100 μ g/mL) |
| 3 (5)-(2-ethoxycarbonyl-2-acrylonitrile base) amino-pyrazols | ?93.74 |
| 3 (5)-(2-ethoxycarbonyl-2-acrylonitrile base) amino-pyrazols-4-methyl-formiate | ?54.62 |
| 3 (5)-(2-ethoxycarbonyl-2-acrylonitrile base) amino-pyrazols-4-ethyl formate | ?72.55 |
Claims (3)
1. a pyrazole compound is characterized in that, on the pyrazoles ring of this pyrazole compound, is connected with (2-ethoxycarbonyl-2-acrylonitrile base) amino, and two general formulas of following I, II are arranged respectively:
In two general formulas of this I, II, R all selects for use-COOCH
3Or-COOCH
2CH
3
2. the preparation method of a pyrazole compound, it is characterized in that, this compound is the described pyrazole compound of claim 1, it is that feedstock production forms by amino-pyrazol analog derivative, ethyl cyanoacetate and triethyl orthoformate, wherein, described amino-pyrazol analog derivative has two general formulas of following III, IV:
In two general formulas of III, IV, R all selects for use-COOCH
3Or-COOCH
2CH
3
This method comprises the steps:
1. dissolve amino pyrazole derivatives with anhydrous acetonitrile; Wherein, anhydrous acetonitrile: amino-pyrazol analog derivative=40 milliliter: 0.05 mole;
2. add ethyl cyanoacetate and triethyl orthoformate successively, again the shaking by swirling mixing; Wherein, the amount of substance of ethyl cyanoacetate and triethyl orthoformate is 1～1.2 times of amino-pyrazol analog derivative amount of substance;
3. slow reflux 3.5～4.5 hours;
4. be cooled to crystal and separate out, filter and collect crystallization,
5. use absolute ethanol washing crystallization at least 3 times, treat promptly to get the described pyrazole compound of claim 1 after the ethanol volatilization fully.
3. as the preparation method of pyrazole compound as described in the claim 2, it is characterized in that the 2. in the step, the amount of substance of described ethyl cyanoacetate and triethyl orthoformate is 1.2 times of amino-pyrazol analog derivative amount of substance.
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