CN102558054A - Process for preparing 3,4-dimethylpyrazole phosphate - Google Patents
Process for preparing 3,4-dimethylpyrazole phosphate Download PDFInfo
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- CN102558054A CN102558054A CN2011104360604A CN201110436060A CN102558054A CN 102558054 A CN102558054 A CN 102558054A CN 2011104360604 A CN2011104360604 A CN 2011104360604A CN 201110436060 A CN201110436060 A CN 201110436060A CN 102558054 A CN102558054 A CN 102558054A
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Abstract
The invention provides a process for preparing 3,4-dimethylpyrazole phosphate, which includes the steps: (1) reacting metallic sodium with 2-butanone and ethyl formate to produce 2-methyl-3-oxobutanoic acid sodium salt; (2) reacting hydrazine hydrate with the 2-methyl-3-oxobutanoic acid sodium salt to produce 3,4-dimethyl pyrazole; and (3) reacting the 3,4-dimethyl pyrazole with phosphoric acid to produce the 3,4-dimethylpyrazole phosphate. The process for preparing the 3,4-dimethylpyrazole phosphate has the advantages that raw materials are easy to obtain, reaction conditions are mild, the reaction time is short and by-products are few.
Description
Technical field
The present invention relates to a kind ofly 3, the 4-methylpyrazole method for production of phosphate salt particularly a kind ofly can synthesize 3,4-dimethyl pyrazole method for production of phosphate salt efficiently
Background technology
In various agriculture prodn activities, people use chemical fertilizer unreasonably in a large number for the output of pursuing crop, and according to investigations, it is 200kg/ha that pure nitrogen level is executed in China's annual at present.In the developed area such as execute pure nitrogen level Taihu Lake basin year and reach more than the 600kg/ha; In many regional purity nitrogen usage quantitys even up to 5001300kg/ha; Very easily run off behind the nitrogen application, rural activity scope in addition is huge, and the pollution of area source of generation is much bigger more than industrial point-source pollution influence.Have investigation to show that the total nitrogen turnover rate in farmland, basin accounts for 20% of whole nitrogenous fertilizer usage quantitys, wherein, the restricted factor phosphorus of body eutrophication 87%, nitrogen 70% all derive from widespread pollution from the overuse of fertilizers and pesticides in rural area.
Current, cause the body eutrophication aggravation, the agricultural area source environmental pollution of alga eruption has become a serious global problem.A large amount of losses of agricultural land soil nitrogen cause surface water and phreatic pollution serious day by day.
Simultaneously, the seepage of nitrate salt can cause groundwater pollution in the widespread pollution from the overuse of fertilizers and pesticides in rural area, and tap water and Nitrate Content in Food content roll up, thereby causes the infant to suffer from Va content decline disease or the like in methemoglobinemia, respiratory system disease, the liver.According to the underground water sample survey result demonstration of the Chinese Academy of Agricultural Sciences to provinces and cities such as Beijing, Tianjin, Shandong, 45% water sample has surpassed WHO standard (11.3mg/L N).The exceeding standard rate of nitric nitrogen also reaches 38% in China's TAI HU AREA tap water.The Groundwater Nitrate-nitrogen content in suburb of Beijing district is more up to 61.6120.4mg L 1.
How to reduce the migration of nitrogen in water body and become one of focus of water environment protection field people concern.
3, and 4-dimethyl pyrazole phosphoric acid salt (3,4-dimethyl phrazole phosphate; DMPP) be a kind of staple of new nitrification; DMPP reduces the loss of ammonium nitrogen to improving utilization rate of nitrogen fertilizer, improves crop yield and has great importance; So synthesize 3 effectively, 4-dimethyl pyrazole phosphoric acid salt is significant in agricultural and environmental protection field.
It in the vitriol oil is that catalyzer is synthetic 3 with NaI that a kind of 3-of utilization methyl-2-butanone and Hydrazine Hydrate 80 are arranged in the prior art, and the method for 4-dimethyl pyrazole also has a kind of utilizations instead-2; 3-tiglic aldehyde and Hydrazine Hydrate 80 reaction generate an intermediate product, and in the vitriol oil, NaI catalysis cyclization generates 3 to this intermediate product again; The method of 4-dimethyl pyrazole, more than the implementation process of two kinds of schemes all need to use the vitriol oil more in large quantities, and temperature of reaction all surpasses 110 degrees centigrade; Therefore higher to equipment requirements, in addition, heat release is remarkable when neutralizing a large amount of vitriol oil; Complicated operation has potential safety hazard, simultaneously; React required starting material 3-methyl-2-butanone and anti--2 price and compare higherly, be unfavorable for suitability for industrialized production.In other a kind of known technology, utilize 2-butanone and methyl-formiate under base catalysis, to generate intermediate product 2-methyl-3-oxo butyraldehyde sodium, this product generates 3, the 4-dimethyl pyrazole with the Hydrazine Hydrate 80 cyclization under acidic conditions.Though this scheme two-step reaction all at room temperature carries out, reaction conditions is relatively gentleer, and the reaction times is long, needs 16-24 hour, and has the isomer generation in the highly basic catalysis generation intermediate product process, finally has by product 3-ethyl pyrazoles and generates.
Therefore, be necessary to send out the problem that exists in the above-mentioned prior art is improved.
Summary of the invention
To technical problem of the prior art, the present invention provides a kind of efficient, high yield, cheapness and the lower high purity 3 of working condition requirement, the phosphatic novel method of 4-dimethyl pyrazole.
It is a kind of 3 that the present invention provides, and 4-dimethyl pyrazole method for production of phosphate salt comprises: step S1, utilize sodium Metal 99.5 and 2-butanone and ethyl formate to generate 2-methyl-3-oxo butyraldehyde sodium; Step S2 utilizes Hydrazine Hydrate 80 and 2-methyl-3-oxo butyraldehyde sodium to generate 3, the 4-dimethyl pyrazole; Step S3 utilizes 3, and 4-dimethyl pyrazole and phosphatase reaction generate 3,4-dimethyl pyrazole phosphoric acid salt.
According to a preferred embodiment of the invention, in said step S1, earlier said sodium Metal 99.5 is placed organic solvent, and add said 2-butanone therein, generation 2-methyl-3-oxo butyraldehyde sodium with ethyl formate reacts.
According to a preferred embodiment of the invention, said organic solvent is any one or the multiple combination in ether, sherwood oil, hexanaphthene, hexane, THF, the benzene,toluene,xylene, and the quality of solvent be sodium quality 1-20 doubly.
According to a preferred embodiment of the invention, in said step S2, under the katalysis of catalyzer, the aqueous solution of said Hydrazine Hydrate 80 and said 2-methyl-3-oxo butyraldehyde sodium is reacted, obtain 3 through extraction, the 4-dimethyl pyrazole.
According to a preferred embodiment of the invention, said catalyzer is organic acid or mineral acid.
According to a preferred embodiment of the invention; Said organic acid is any one or the multiple combination in sulfuric acid, phosphoric acid, nitric acid, the hydrochloric acid; Said organic acid is any one or the multiple combination in formic acid, acetate, propionic acid, butyric acid, the trifluoroacetic acid, and the pH value of acid solution is 1-5.
According to a preferred embodiment of the invention; In said step S2; After the aqueous solution of said Hydrazine Hydrate 80 and said 2-methyl-3-oxo butyraldehyde sodium reacts; Comprise that also utilizing the antacid step of alkali, said alkali is any one or multiple combination in sodium hydroxide, Pottasium Hydroxide, the ammonia, and to make the pH value of solution value after the neutralization be 8-10.
According to a preferred embodiment of the invention, the extraction agent of extraction employing is one or more combinations in chloroform, methylene dichloride, ethylene dichloride, ETHYLE ACETATE, the propyl carbinol.
According to a preferred embodiment of the invention, in said step S3, with 3; The 4-dimethyl pyrazole is dissolved in the alcoholic solvent, and adds phosphoric acid therein, thereby generates 3; The phosphatic throw out of 4-dimethyl pyrazole; To 3, the phosphatic throw out of 4-dimethyl pyrazole obtains solid 3,4-dimethyl pyrazole phosphoric acid salt after filtering, drying.
According to a preferred embodiment of the invention, said alcoholic solvent is one or more the combination in methyl alcohol, ethanol, Virahol, butanols, the trimethyl carbinol, terepthaloyl moietie, USP Kosher, the butyleneglycol.
Compared to prior art, the present invention 3, in the 4-dimethyl pyrazole method for production of phosphate salt; Replace other highly basic with sodium Metal 99.5, thereby made 2-butanone more be prone to generate carbanion, and optionally generated the secondary ion of thermodynamically stable enol; Avoid generating the end by product that carbanion brought, both shortened the reaction times, also make reaction have excellent selectivity; Thereby synthetic product, and institute expeditiously responds and all is under the room temperature environment, and its reaction conditions is gentle; Requirement to production unit is lower, and has higher security.Simultaneously, in above-mentioned preparing method's process, the by product of generation is less, and 3, the phosphatic production rate of 4-dimethyl pyrazole is higher, and above-mentioned preparing method's reaction times is short, helps the mass production of product.
Description of drawings
Fig. 1 is the present invention 3, the schema of 4-dimethyl pyrazole method for production of phosphate salt.
Fig. 2 be that step S2 generates among the preparation method shown in Figure 13, the chemical formula structure figure of 4-dimethyl pyrazole.
Fig. 3 be among the preparation method shown in Figure 1 final generate 3, the phosphatic chemical formula structure figure of 4-dimethyl pyrazole.
Embodiment
Below in conjunction with accompanying drawing preferred embodiment of the present invention is set forth in detail, thereby protection scope of the present invention is made more explicit defining so that advantage of the present invention and characteristic can be easier to it will be appreciated by those skilled in the art that.
It is a kind of 3 that the present invention provides, and 4-dimethyl pyrazole method for production of phosphate salt is in present method; Adopt the organic solvent of sodium Metal 99.5 to replace highly basic; Make 2-butanone and ethyl formate generation condensation reaction generate 2-methyl-3-oxo butyraldehyde sodium, thereby highly selective synthesize 3, the 4-dimethyl pyrazole.3,4-dimethyl pyrazole and phosphatase reaction obtain 3,4-dimethyl pyrazole phosphoric acid salt.
The present invention provides a kind of raw material to be easy to get, and reaction conditions is gentle, and the reaction times is short, and what by product was few effectively synthesizes 3, the phosphatic method of 4-dimethyl pyrazole.
See also Fig. 1; Fig. 1 is the present invention 3, the schema of 4-dimethyl pyrazole method for production of phosphate salt, 3; 4-dimethyl pyrazole method for production of phosphate salt comprises: step S1, with mixed solution generation 2-methyl-3-oxo butyraldehyde sodium of sodium Metal 99.5 and 2-butanone and ethyl formate; Step S2 stirs the acid and the aqueous solution of Hydrazine Hydrate 80 and 2-methyl-3-oxo butyraldehyde sodium, adds alkali and neutralizes, thereby isolate 3, the 4-dimethyl pyrazole; Step S3, with 3,4-dimethyl pyrazole and phosphatase reaction generate 3,4-dimethyl pyrazole phosphoric acid salt.Concrete:
In step S1, at first sodium Metal 99.5 is added and be equipped with in the reaction vessel of machine solvent, through stirring; In the mixed solution of sodium Metal 99.5 machine solvent, drip the mixed solution of 2-butanone and ethyl formate; Behind the room temperature reaction 1 hour, the volume throw out that reaction is generated filters, and gets white solid 2-methyl-3-oxo butyraldehyde sodium; Then that solid 2-methyl-3-oxo butyraldehyde sodium is soluble in water, the aqueous solution that generates solid 2-methyl-3-oxo butyraldehyde sodium is for use.
Wherein, the consumption of ethyl formate and sodium is 1-5 times (pressing amount of substance calculates) of 2-butanone consumption.
Wherein, organic solvent can be any one or multiple combination wherein such as ether, sherwood oil, hexanaphthene, hexane, THF, benzene,toluene,xylene, and the consumption of solvent generally is that the 1-20 of the consumption of sodium doubly measures (by Mass Calculation).
In this step; Utilize sodium to replace the highly basic in its traditional method; For example sodium methylate, sodium ethylate, Pottasium Hydroxide, sodium hydroxide etc. make the reaction of 2-butanone and ethyl formate generate 2-methyl-3-oxo butyraldehyde sodium, thereby have avoided the restriction of the use of strong basicity raw material to working condition.
In step S2, acid (as catalyzer) and Hydrazine Hydrate 80 are added in the aqueous solution of 2-methyl-3-oxo butyraldehyde sodium simultaneously, stirring at room 10 hours until the reaction completion; Utilize condensation ring-closure reaction synthetic 3; 4-dimethyl pyrazole, the pH value of solution value of the resultant of reaction of this moment reaction between 1-5, then the pH value between 1-5 3; Add alkali in the solution of 4-dimethyl pyrazole and carry out neutralization reaction, when the pH value that neutralizes is about 8-10, stop neutralization reaction.After selecting the extraction of suitable extraction agent then for use, carry out separatory and drying operation, and organic phase boils off solvent, thus 3, the 4-dimethyl pyrazole.3, the chemical formula structure of 4-dimethyl pyrazole is as shown in Figure 2.
Wherein, Acid as catalyzer can be mineral acid or organic acid; Wherein mineral acid can be any one or the multiple combination in sulfuric acid, phosphoric acid, nitric acid, the hydrochloric acid; Organic acid can be any one or the multiple combination in formic acid, acetate, propionic acid, butyric acid, the trifluoroacetic acid, and the pH value of acid solution is for best between the 1-5.
The used alkali of catalyst neutralisation acid can be any one or the multiple combination in sodium hydroxide, Pottasium Hydroxide and the ammonia, and alkali consumption standard is to make the pH value of neutralization solution for being the best between the 8-10.
Used extraction agent can be any one or the multiple combination in chloroform, methylene dichloride, ethylene dichloride, ETHYLE ACETATE, the propyl carbinol.
In step S3,3, the 4-dimethyl pyrazole is dissolved in alcoholic solvent (methyl alcohol, ethanol; Virahol, butanols, the trimethyl carbinol, terepthaloyl moietie; USP Kosher, butyleneglycol) in, in alcoholic solution, drip phosphoric acid, generate deposition; After separating out throw out,, be 3,4-dimethyl pyrazole phosphoric acid salt with obtaining white solid after throw out filtration, the oven dry.Wherein 3,4-dimethyl pyrazole phosphoric acid salt purity is higher than 98%.3, the phosphatic chemical formula structure of 4-dimethyl pyrazole is as shown in Figure 3
In above-mentioned steps S1-step S3, institute responds and all is in room temperature state, and concrete, room temperature is controlled between 15 ℃-35 ℃.
Compared to prior art, of the present invention 3, in the 4-dimethyl pyrazole processes for producing phosphates; Replace other highly basic with sodium Metal 99.5, thereby made 2-butanone more be prone to generate carbanion, and optionally generated the secondary ion of thermodynamically stable enol; Avoid generating the end by product that carbanion brought, both shortened the reaction times, also make reaction have excellent selectivity; Thereby synthetic product, and institute expeditiously responds and all is under the room temperature environment, and its reaction conditions is gentle; Requirement to production unit is lower, and has higher security.Simultaneously, in above-mentioned preparing method's process, the by product of generation is less, and 3, the phosphatic production rate of 4-dimethyl pyrazole is higher, and above-mentioned preparing method's reaction times is short, helps the mass production of product.
For more effective explanation the present invention 3,4-dimethyl pyrazole processes for producing phosphates below is introduced the present invention through a specific embodiment, wherein:
Measure unit is:
Volume: milliliter (mL)
Amount of substance: mole (mol)
Quality: gram (g)
Time: hour (h)
Starting material are:
Dry ether: 100mL
Sodium Metal 99.5: 24g (1mol)
2-butanone: 36g (0.5mol)
Ethyl formate: 52g (0.7mol)
Hydrazine Hydrate 80: 0.2mol
The vitriol oil (98%): an amount of
Sodium hydroxide solution (20%): an amount of
Chloroform: 250mL
Methyl alcohol: 30mL
Phosphoric acid (85%): 36g
Concrete preparation process is:
Under whipped state, in the 100mL dry ether, add the sodium Metal 99.5 of 24g (1mol) chopping, the mixed solution with 36g (0.5mol) 2-butanone and 52g (0.7mol) ethyl formate joins in the above-mentioned system then; Stirring at room 1h; Filter, get white solid (being 2-methyl-3-oxo butyraldehyde sodium) 51.5g, yield 84%; And white solid (being 2-methyl-3-oxo butyraldehyde sodium) is dissolved in the 200mL water, generate stock solution.
Then, at room temperature, the 0.2mol Hydrazine Hydrate 80 (80% volume ratio) and the vitriol oil (98% volume ratio) are added drop-wise in the above-mentioned stock solution simultaneously, the dropping time is controlled at 0.5-1h, makes the pH value of solution be 1-5, continues under the room temperature to stir 10 hours.Then, the sodium hydroxide solution with 20% adjusts to 8.1 with the pH value, and residual solution is used the 250mL chloroform extraction, merges organic phase, and drying boils off solvent and gets product 3,4-dimethyl pyrazole 30g, yield 75%.
At last, with 30g 3, the 4-dimethyl pyrazole is dissolved in 30mL methyl alcohol, adds 36g phosphoric acid (85%), separates out deposition, filters, and drying obtains 63g 3, and 4-dimethyl pyrazole phosphoric acid salt, yield are 96%, and the entire reaction total recovery is 60%.
In the foregoing invention method, the room temperature of reaction is controlled at 15 ℃-35 ℃.
More than be merely preferred case study on implementation of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various changes and variation.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. one kind 3,4-dimethyl pyrazole method for production of phosphate salt comprises:
Step S1 utilizes sodium Metal 99.5 and 2-butanone and ethyl formate to generate 2-methyl-3-oxo butyraldehyde sodium;
Step S2 utilizes Hydrazine Hydrate 80 and 2-methyl-3-oxo butyraldehyde sodium to generate 3, the 4-dimethyl pyrazole;
Step S3 utilizes 3, and 4-dimethyl pyrazole and phosphatase reaction generate 3,4-dimethyl pyrazole phosphoric acid salt.
2. according to claim 13,4-dimethyl pyrazole method for production of phosphate salt is characterized in that; In said step S1; Earlier said sodium Metal 99.5 is placed organic solvent, and add said 2-butanone therein, generation 2-methyl-3-oxo butyraldehyde sodium with ethyl formate reacts.
3. according to claim 23; 4-dimethyl pyrazole method for production of phosphate salt; It is characterized in that; Said organic solvent is any one or the multiple combination in ether, sherwood oil, hexanaphthene, hexane, THF, the benzene,toluene,xylene, and the quality of solvent be sodium quality 1-20 doubly.
4. according to claim 13; 4-dimethyl pyrazole method for production of phosphate salt is characterized in that, in said step S2; Under the katalysis of catalyzer; The aqueous solution of said Hydrazine Hydrate 80 and said 2-methyl-3-oxo butyraldehyde sodium is reacted, obtain 3 through extraction, the 4-dimethyl pyrazole.
5. according to claim 43,4-dimethyl pyrazole method for production of phosphate salt is characterized in that, said catalyzer is organic acid or mineral acid.
6. according to claim 53; 4-dimethyl pyrazole method for production of phosphate salt; It is characterized in that; Said organic acid is any one or the multiple combination in sulfuric acid, phosphoric acid, nitric acid, the hydrochloric acid, and said organic acid is any one or the multiple combination in formic acid, acetate, propionic acid, butyric acid, the trifluoroacetic acid, and the pH value of acid solution is 1-5.
7. according to claim 53; 4-dimethyl pyrazole method for production of phosphate salt is characterized in that, in said step S2; After the aqueous solution of said Hydrazine Hydrate 80 and said 2-methyl-3-oxo butyraldehyde sodium reacts; Comprise that also utilizing the antacid step of alkali, said alkali is any one or multiple combination in sodium hydroxide, Pottasium Hydroxide, the ammonia, and to make the pH value of solution value after the neutralization be 8-10.
8. according to claim 53,4-dimethyl pyrazole method for production of phosphate salt is characterized in that, the extraction agent that extraction is adopted is one or more combinations in chloroform, methylene dichloride, ethylene dichloride, ETHYLE ACETATE, the propyl carbinol.
9. according to claim 13,4-dimethyl pyrazole method for production of phosphate salt is characterized in that; In said step S3, with 3, the 4-dimethyl pyrazole is dissolved in the alcoholic solvent; And add phosphoric acid therein, thereby generate 3, the phosphatic throw out of 4-dimethyl pyrazole; To 3,4-dimethyl pyrazole phosphoric acid salt.
10. according to claim 10 3,4-dimethyl pyrazole method for production of phosphate salt is characterized in that, said alcoholic solvent is one or more the combination in methyl alcohol, ethanol, Virahol, butanols, the trimethyl carbinol, terepthaloyl moietie, USP Kosher, the butyleneglycol.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109651252A (en) * | 2019-01-11 | 2019-04-19 | 中化农业（临沂）研发中心有限公司 | The method for preparing 3,4- dimethyl pyrazole and its phosphate and metal organic complex |
| CN110218188A (en) * | 2019-05-21 | 2019-09-10 | 武威金仓生物科技有限公司 | A kind of 3,4- dimethyl pyrazole and 3,4- dimethyl pyrazole method for production of phosphate salt |
| CN110392675A (en) * | 2017-02-01 | 2019-10-29 | 欧洲化学农业有限公司 | Mixture and application thereof containing 3,4- dimethyl pyrazole |
| CN110997599A (en) * | 2017-08-18 | 2020-04-10 | 巴斯夫欧洲公司 | Process for preparing improved 3, 4-dimethyl-1H-pyrazole phosphate formulations |
| CN114181149A (en) * | 2021-12-30 | 2022-03-15 | 浙江本立科技股份有限公司 | Synthetic method of 3, 4-dimethylpyrazole |
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| CN1506339A (en) * | 1996-08-06 | 2004-06-23 | Basf | Application of novel nitration inhibitor and polyacid in processing inorganic fertilizer containing nitration inhibitor |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110392675A (en) * | 2017-02-01 | 2019-10-29 | 欧洲化学农业有限公司 | Mixture and application thereof containing 3,4- dimethyl pyrazole |
| CN110997599A (en) * | 2017-08-18 | 2020-04-10 | 巴斯夫欧洲公司 | Process for preparing improved 3, 4-dimethyl-1H-pyrazole phosphate formulations |
| CN109651252A (en) * | 2019-01-11 | 2019-04-19 | 中化农业（临沂）研发中心有限公司 | The method for preparing 3,4- dimethyl pyrazole and its phosphate and metal organic complex |
| CN110218188A (en) * | 2019-05-21 | 2019-09-10 | 武威金仓生物科技有限公司 | A kind of 3,4- dimethyl pyrazole and 3,4- dimethyl pyrazole method for production of phosphate salt |
| CN114181149A (en) * | 2021-12-30 | 2022-03-15 | 浙江本立科技股份有限公司 | Synthetic method of 3, 4-dimethylpyrazole |
| CN114181149B (en) * | 2021-12-30 | 2024-04-02 | 浙江本立科技股份有限公司 | Synthesis method of 3, 4-dimethylpyrazole |
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