CN109651252A - The method for preparing 3,4- dimethyl pyrazole and its phosphate and metal organic complex - Google Patents
The method for preparing 3,4- dimethyl pyrazole and its phosphate and metal organic complex Download PDFInfo
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- CN109651252A CN109651252A CN201910027935.1A CN201910027935A CN109651252A CN 109651252 A CN109651252 A CN 109651252A CN 201910027935 A CN201910027935 A CN 201910027935A CN 109651252 A CN109651252 A CN 109651252A
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- dimethyl pyrazole
- isopropyl ketone
- iodide
- methyl isopropyl
- dimethyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/90—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting the nitrification of ammonium compounds or urea in the soil
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic System without C-Metal linkages
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Abstract
The invention discloses the methods for preparing 3,4- dimethyl pyrazole and its phosphate and metal organic complex.Wherein, prepare 3,4- dimethyl pyrazole method include: (1) under the effect of the catalyst, contact isoprene with water, obtain methyl isopropyl Ketone；(2) it contacts the methyl isopropyl Ketone under the action of sulfuric acid and iodide with hydrazine hydrate, obtains 3,4- dimethyl pyrazole.Using isoprene as raw material, preparation method is simple, the yield and purity is high of product.
Description
Technical field
The present invention relates to fertilizer additive technical fields, specifically, the present invention relates to preparation 3,4- dimethyl pyrazole and
The method of its phosphate and metal organic complex.
Background technique
3,4- dimethyl pyrazole phosphate (DMPP) is a kind of efficient, safe and nontoxic and cheap nitrogenous fertilizer that BASF is developed
Nitrification inhibitor DMPP is added in nitrification inhibitor in fertilizer, can control ammonium nitrogen and converts to nitrate nitrogen, to realize nitrogen
Stablize supply, reduce the discharge of the leaching loss, nitrogen oxide of nitrate nitrogen, with reach improve chemical fertilizer utilization rate, protection environment, promote
The purpose of agricultural development.For example, En Taike compound fertilizer can utilize the reinfocing effect of plant absorption ammonium nitrogen and nitrate nitrogen, assisted
The yield increase effect of same-action, crop also improves yield while reducing nitrogen consumption.But in alkaline fertilizer, DMPP's contains
Amount can decline rapidly with the extension of time, therefore, the DMPP preparation method of developing low-cost and be modified tool to DMPP
There is very wide development and application prospect.
In the prior art, DMPP is generally prepared by 3,4- dimethyl pyrazole.Preparation for 3,4- dimethyl pyrazole,
It is raw material that patent US5569769, which discloses 2- methyl-2-butene aldehyde, first generates to obtain dimethyl -3 3,4- with hydration hydrazine reaction,
4- dihydro-1 h-pyrazole, then the method that 3,4- dimethyl pyrazole is made in high temperature under the catalytic action of sodium iodide in concentrated sulfuric acid,
But the raw material 2- methyl-2-butene aldehyde of the method is expensive, and is easy to happen polymerization reaction.Patent CN102311388A
It needs to prepare 3- methylol-butanone in disclosed method, is easy to generate methyl during distillation separates 3- methylol-butanone
Isopropenyl ketone and polymerization reaction occurs, influence yield, can also generate a large amount of SO in reaction process2Equal gases, post-processing
A large amount of strongly acid wastewater can be generated in the process, and operating procedure is complicated, can not carry out continuous production.Patent
2- butanone is used in CN102911119A and paraformaldehyde is starting material, and 3- methyl -3- fourth is generated under the catalytic action of acid
Alkene -2- ketone, with prepare 3,4- dimethyl pyrazole with hydrogen peroxide oxidation dehydrogenation in alkaline environment again after hydration hydrazine reaction, then with phosphorus
Acid reaction preparation DMPP.3- methyl-3- butene-2 -one in this method is easy polymerization, not easy to maintain, and operating procedure is multiple
It is miscellaneous, need to use the equipment such as a large amount of reaction kettle, it is most important that can not continuous production, production efficiency is low.
Thus, existing preparation 3,4- dimethyl pyrazole, DMPP and still have much room for improvement to the means that DMPP is modified.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose is the method for proposing 3,4- dimethyl pyrazole and its phosphate and metal organic complex.Wherein, 3,4- are prepared
For the method for dimethyl pyrazole using isoprene as raw material, preparation method is simple, the yield and purity is high of product.
In one aspect of the invention, the invention proposes a kind of methods for preparing 3,4- dimethyl pyrazole.According to this hair
Bright embodiment contacts isoprene with water this method comprises: (1) is under the effect of the catalyst, obtains isopropyl methyl
Ketone；(2) it contacts the methyl isopropyl Ketone under the action of sulfuric acid and iodide with hydrazine hydrate, obtains 3,4- dimethyl pyrazole
Azoles.
The method of preparation 3,4- dimethyl pyrazole according to an embodiment of the present invention is greatly reduced using isoprene as raw material
Cost of material improves reaction efficiency while reducing reaction step, ensure that the yield and purity of product, while operating letter
It is single, it is low for equipment requirements, there is great industrial application value.
In addition, the method for preparation 3,4- dimethyl pyrazole according to the above embodiment of the present invention can also have following add
Technical characteristic:
In some embodiments of the invention, the catalyst includes active constituent and carrier, and the active constituent includes
Phosphoric acid and boron, the carrier are diatomite.It can further improve the yield of methyl isopropyl Ketone as a result,.
In some embodiments of the invention, in the catalyst, the content of the phosphoric acid is the catalyst gross mass
50~80%, the content of the boron is the 4~9% of the catalyst gross mass.It can further improve isopropyl methyl as a result,
The yield of ketone.
In some embodiments of the invention, in step (1), the molar ratio of the isoprene and the water is 1.0:
(1.0~10.0), the contact is at 180~300 DEG C of temperature and the pressure of 0.09~0.5MPa with 0.1~2.0h-1Sky
Speed carries out.It can further improve the yield of 3,4- dimethyl pyrazole as a result,.
In some embodiments of the invention, the concentration of the sulfuric acid is 20~98wt%, and the concentration of the hydrazine hydrate is
40~80wt%, the iodide include selected from least one of sodium iodide, potassium iodide, silver iodide, iodine and hydrogen iodide.By
This, can further improve the yield of 3,4- dimethyl pyrazole.
In some embodiments of the invention, in step (2), the molar ratio of the methyl isopropyl Ketone and the sulfuric acid is
1.0:(1.0~3.0), the molar ratio of the methyl isopropyl Ketone and the hydrazine hydrate is 1.0:(1.0~3.0), the iodate
The quality of object is the 1.0~10.0% of the methyl isopropyl Ketone quality, and it is complete that the contact carries out 4~10h at 50~150 DEG C
At.It can further improve the yield of 3,4- dimethyl pyrazole as a result,.
In some embodiments of the invention, step (2) further comprises:
(2-1) contacts the methyl isopropyl Ketone under the action of sulfuric acid and iodide with hydrazine hydrate；
(2-2) is successively neutralized step (2-1) products therefrom, extraction processing and distillation are handled, and obtains described
3,4- dimethyl pyrazole.It can further improve the yield and purity of 3,4- dimethyl pyrazole as a result,.
In some embodiments of the invention, in the neutralisation treatment, using selected from sodium carbonate liquor, solution of potassium carbonate,
Calcium carbonate soln, carbonic acid magnesium solution, sodium hydroxide solution, potassium hydroxide solution, magnesium hydroxide solution, calcium hydroxide solution and three
At least one of ethamine is used as neutralizer.It can further improve the yield and purity of 3,4- dimethyl pyrazole as a result,.
In some embodiments of the invention, in the extraction processing, using selected from toluene, petroleum ether, methylene chloride, three
The conduct of at least one of chloromethanes, ethyl acetate, n-butanol, isobutanol, the tert-butyl alcohol, n-hexane, hexamethylene and butyl acetate
Extractant.It can further improve the yield and purity of 3,4- dimethyl pyrazole as a result,.
In some embodiments of the invention, in the neutralisation treatment, temperature is 30~100 DEG C, and pH value is 8~14；Institute
It states in extraction processing, the dosage of the extractant is 1.0~3.0 times of the methyl isopropyl Ketone quality.It as a result, can be further
Improve the yield and purity of 3,4- dimethyl pyrazole.
In some embodiments of the invention, in distillation processing, temperature is 30~150 DEG C, pressure is -0.09~
0.11MPa.It can further improve the yield and purity of 3,4- dimethyl pyrazole as a result,.
In another aspect of this invention, of the invention propose a kind of prepares the phosphatic method of 3,4- dimethyl pyrazole.
According to an embodiment of the invention, this method comprises: the preparation 3 of (a) according to above-described embodiment, the method preparation of 4- dimethyl pyrazole
Obtain 3,4- dimethyl pyrazole；(b) it in the first organic solvent, contacts 3, the 4- dimethyl pyrazole with phosphoric acid, obtains 3,
4- dimethyl pyrazole phosphate.
First, in accordance with the preparation 3 of above-described embodiment, the method for 4- dimethyl pyrazole simply and efficiently prepared this method as a result,
Obtained 3,4- dimethyl pyrazole, and then 3, the 4- dimethyl pyrazole being prepared using 3,4- dimethyl pyrazole and phosphatase reaction
Phosphate (DMPP).This method process flow is short, the yield and purity is high of product.
In addition, the phosphatic method of preparation 3,4- dimethyl pyrazole according to the above embodiment of the present invention can also have as
Under additional technical characteristic:
In some embodiments of the invention, first organic solvent include selected from methanol, ethyl alcohol, propyl alcohol, isopropanol,
At least one of n-butanol, isobutanol and tert-butyl alcohol.It can further improve the phosphatic receipts of 3,4- dimethyl pyrazole as a result,
Rate.
In some embodiments of the invention, the dosage of first organic solvent is 3, the 4- dimethyl pyrazole quality
0.5~2.0 times, the molar ratio of 3, the 4- dimethyl pyrazole and the phosphoric acid is 1.0:(1.0~1.5).It as a result, can be into one
Step improves the phosphatic yield of 3,4- dimethyl pyrazole.
In some embodiments of the invention, it is described contact under conditions of pH value is 1~3, temperature is 40~50 DEG C into
3~10h of row is completed.It can further improve the phosphatic yield of 3,4- dimethyl pyrazole as a result,.
In another aspect of the invention, of the invention propose a kind of prepares 3,4- dimethyl pyrazole metal organic complex
Method.According to an embodiment of the invention, this method comprises: (c) according to the preparation of above-described embodiment 3,4- dimethyl pyrazole
3,4- dimethyl pyrazole is prepared in method；(d) in a second organic solvent, 3, the 4- dimethyl pyrazole is connect with metal salt
Touching, obtains 3,4- dimethyl pyrazole metal organic complex.
First, in accordance with the preparation 3 of above-described embodiment, the method for 4- dimethyl pyrazole simply and efficiently prepared this method as a result,
Obtained 3,4- dimethyl pyrazole, and then 3, the 4- dimethyl pyrazole being prepared using 3,4- dimethyl pyrazole and reacting metal salt
Azoles metal organic complex.This method process flow is short, the yield and purity is high of product.Product is with 3,4- dimethyl pyrazole
While active, it is not easy to lose in alkaline fertilizer.
In addition, the method for preparation 3,4- dimethyl pyrazole metal organic complex according to the above embodiment of the present invention may be used also
To have following additional technical characteristic:
In some embodiments of the invention, second organic solvent include selected from methanol, ethyl alcohol, propyl alcohol, isopropanol,
At least one of butanol, isobutanol, the tert-butyl alcohol, acetone, butanone, ether, ethyl methyl ether, benzene, toluene and chloroform.As a result,
It can further improve the yield of 3,4- dimethyl pyrazole metal organic complex.
In some embodiments of the invention, the metal salt is chloride, bromide, sulfate or the nitre of metallic element
Hydrochlorate, the metallic element are Fe, Co, Ni, Cu, Ca, Mg, Zn or Mn.It can further improve 3,4- dimethyl pyrazole gold as a result,
Belong to stability of the organic coordination compound in alkaline fertilizer.
In some embodiments of the invention, the contact carries out 1~48h completion at 0~100 DEG C.It as a result, can be into one
Step improves the yield of 3,4- dimethyl pyrazole metal organic complex.
As previously mentioned, preparation 3,4- dimethyl pyrazole according to an embodiment of the present invention and its phosphate and metal organic complexes
The method of object, is prepared methyl isopropyl Ketone by raw material of isoprene first, and in the step, the conversion ratio of isoprene can
Up to 93.4%, the yield of methyl isopropyl Ketone is up to 89.4%.It is subsequent, 3,4- dimethyl pyrazole is prepared using methyl isopropyl Ketone
Azoles, product purity is up to 99.5%, and yield is up to 75.45%.Further, with 3,4- dimethyl pyrazole prepare its phosphate and
Metal organic complex, the yield of 3,4- dimethyl pyrazoles is up to 95.4%, 3,4- dimethyl pyrazole metal organic complex
Yield is up to 88.1%.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Above-mentioned and/or additional aspect of the invention and advantage will become from the description of the embodiment in conjunction with the following figures
Obviously and it is readily appreciated that, in which:
Fig. 1 is the method flow schematic diagram according to an embodiment of the invention for preparing 3,4- dimethyl pyrazole；
Fig. 2 is the method flow schematic diagram for preparing 3,4- dimethyl pyrazole of further embodiment according to the present invention；
Fig. 3 is the phosphatic method flow schematic diagram of preparation 3,4- dimethyl pyrazole according to an embodiment of the invention；
Fig. 4 is the method flow according to an embodiment of the invention for preparing 3,4- dimethyl pyrazole metal organic complex
Schematic diagram；
Specific embodiment
The embodiment of the present invention is described below in detail.The embodiments described below is exemplary, and is only used for explaining this hair
It is bright, and be not considered as limiting the invention.Particular technique or condition are not specified in embodiment, according to text in the art
It offers described technology or conditions or is carried out according to product description.Reagents or instruments used without specified manufacturer,
For can be with conventional products that are commercially available.
In addition, term " first ", " second " are used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance
Or implicitly indicate the quantity of indicated technical characteristic.Define " first " as a result, the feature of " second " can be expressed or
Implicitly include at least one this feature.In the description of the present invention, the meaning of " plurality " is at least two, such as two, three
It is a etc., unless otherwise specifically defined.
In one aspect of the invention, the invention proposes a kind of methods for preparing 3,4- dimethyl pyrazole.According to this hair
Bright embodiment contacts isoprene with water this method comprises: (1) is under the effect of the catalyst, obtains isopropyl methyl
Ketone；(2) it contacts methyl isopropyl Ketone under the action of sulfuric acid and iodide with hydrazine hydrate, obtains 3,4- dimethyl pyrazole.
The method of preparation 3,4- dimethyl pyrazole according to an embodiment of the present invention is greatly reduced using isoprene as raw material
Cost of material improves reaction efficiency while reducing reaction step, ensure that the yield and purity of product, while operating letter
It is single, it is low for equipment requirements, there is great industrial application value.
It is carried out below with reference to Fig. 1~2 pair method according to an embodiment of the present invention for preparing 3,4- dimethyl pyrazole further
Detailed description.According to an embodiment of the invention, this method comprises:
S100: methyl isopropyl Ketone is prepared
In the step, isoprene is contacted with water under the effect of the catalyst with reference to formula (I), obtains isopropyl methyl
Ketone.Inventor has found in the research to 3,4- dimethyl pyrazole preparation method, generally uses 2- methyl -2- fourth in the prior art
The raw materials such as olefine aldehydr, 3- methylol-butanone, 3- methyl-3- butene-2 -one or intermediate product prepare 3,4- dimethyl pyrazole, exist
Cost of material height, is difficult to the problems such as continuous production at complex process.In turn, inventor is had found by lot of experiments, can be with
Methyl isopropyl Ketone is used to prepare 3,4- dimethyl pyrazole for raw material.The preparation method of methyl isopropyl Ketone is simple and high income,
It is easy to large-scale continuous production, and the isoprene for being used to prepare methyl isopropyl Ketone is at low cost, and then different using methyl
Propyl ketone is that raw material prepares 3,4- dimethyl pyrazole, can substantially reduce the cost of material of 3,4- dimethyl pyrazole,
According to an embodiment of the invention, can be common in this field with the reaction that isoprene and water prepare methyl isopropyl Ketone
Catalytic reactor in carry out.Specifically, the isoprene of gasification and water can be preheated first, some realities according to the present invention
Example is applied, the isoprene and water of gasification can be preheated to 180 DEG C.Gasification isoprene and water preheating after can from reactor head into
The catalyst bed for entering to be disposed with catalyst is reacted, and methyl isopropyl Ketone is obtained.
According to an embodiment of the invention, above-mentioned catalyst includes active constituent and carrier, wherein active component includes phosphoric acid
And boron, carrier are diatomite.Inventors have found that being reacted by the way that phosphoric acid and boron to be carried on diatomite as isoprene and water
The catalyst for preparing methyl isopropyl Ketone can be further improved the conversion ratio and product methyl isopropyl Ketone of isoprene
Yield and purity.Wherein, using boron as one of catalyst active component, the conversion ratio and selectivity of isoprene can be improved.
According to an embodiment of the invention, in above-mentioned catalyst, the content of phosphoric acid can for catalyst gross mass 50~
80%, the content of boron can be the 4~9% of catalyst gross mass.If the phosphorus acid content in catalyst is too low, can not play
Effectively catalytic effect；And if phosphorus acid content is excessively high, catalyst cost increases, and can cause side reaction.If catalyst
In boron content it is too low, then can not play effectively catalytic effect；And if boron content is excessively high, catalyst higher cost, and
It is also possible to cause side reaction.Comprehensively consider the cost and yield yield of catalyst, it is preferred that the content of phosphoric acid is the total matter of catalyst
55~75%, more preferably the 60~70% of amount；Preferably, the content of boron is 5~8%, more preferably the 6 of catalyst gross mass
~7%.
According to an embodiment of the invention, in S100, the molar ratio of isoprene and water can for 1.0:(1.0~
10.0), contact of the isoprene with water can at 180~300 DEG C of temperature and the pressure of 0.09~0.5MPa with 0.1~
2.0h-1Air speed carry out.Under the above reaction condition, isoprene can obtain methyl isopropyl Ketone in high conversion rate.The step
In rapid, if the proportion of water is too low, it not can guarantee isoprene and react completely and be converted into methyl isopropyl Ketone, if water is matched
Than excessively high, then reaction efficiency declines.If reaction temperature or hypotony, it not can guarantee isoprene and react completely and be converted into
Methyl isopropyl Ketone.If reaction temperature or hypertonia, reaction selectivity are poor.If air speed is too low, reaction efficiency
It is lower, and reaction selectivity is lower.If air speed is excessively high, it not can guarantee reactant and come into full contact with catalyst, lead to isoamyl
The conversion ratio of diene reduces.Comprehensively consider reaction yield and reaction efficiency, it is preferred that the molar ratio of isoprene and water is 1.0:
(3.0~8.0), more preferably 1.0:(5.0~7.0)；Preferably, reaction temperature be 200~280 DEG C, more preferably 200~
250℃；Preferably, reaction pressure is normal pressure~0.3MPa, more preferably normal pressure~0.2MPa；Preferably, air speed be 0.1~
1.0h-1；More preferably 0.1~0.5h-1.In addition, it is necessary to which explanation, in the present invention, is such as not particularly illustrated, air speed is
Refer to liquid hourly space velocity (LHSV) (LHSV).
S200: 3,4- dimethyl pyrazole is obtained
In the step, with reference to formula (II), contact methyl isopropyl Ketone under the action of sulfuric acid and iodide with hydrazine hydrate,
Obtain 3,4- dimethyl pyrazole.The carbonyl in amino attack methyl isopropyl Ketone under the action of sulfuric acid and iodide, in hydrazine
Carbon, dehydration generates hydrazone, and then hydrazone cyclization under acid and heating condition obtains 3,4- dimethyl pyrazole.As a result, in the step, first
Base nezukone and hydrazine hydrate can obtain 3,4- dimethyl pyrazole in high conversion rate, be suitable for large-scale continuous production.
According to an embodiment of the invention, the concentration of above-mentioned sulfuric acid can be 20~98wt%, the concentration of above-mentioned hydrazine hydrate can
Think 40~80wt%, above-mentioned iodide may include in sodium iodide, potassium iodide, silver iodide, iodine and hydrogen iodide at least
One of.If sulfuric acid concentration is too low, enough acid and/or oxidative conditions possibly can not be provided for reaction；If hydrazine hydrate
Concentration it is too low, then isopropyl methyl reactive ketone is incomplete, influence 3,4- dimethyl pyrazole yield；If the concentration of hydrazine hydrate
Excessively high, then risk is higher, and higher cost.Preferably, the concentration of sulfuric acid be 30~80wt%, more preferably 40~
60wt%；Preferably, the concentration of hydrazine hydrate is 60~80wt%, more preferably 70~80wt%.
According to an embodiment of the invention, in s 200, the molar ratio of methyl isopropyl Ketone and sulfuric acid can be 1.0:(1.0
~3.0), the molar ratio of methyl isopropyl Ketone and hydrazine hydrate can be 1.0:(1.0~3.0), the quality of iodide can be first
The 1.0~10.0% of base nezukone quality, contact of the methyl isopropyl Ketone with hydrazine hydrate can carry out 4 at 50~150 DEG C
~10h is completed.Under the above reaction condition, methyl isopropyl Ketone can obtain 3,4- dimethyl pyrazole in high conversion rate.The step
In rapid, if the proportion of sulfuric acid is too low, enough acid and/or oxidative conditions possibly can not be provided for reaction, if sulfuric acid
Proportion it is excessively high, then the later period neutralizes, the dosage of alkali in alkalinization will increase, and processing is difficult and increased costs.If hydration
The proportion of hydrazine is too low, then isopropyl methyl reactive ketone is incomplete, influences the yield of 3,4- dimethyl pyrazole；If hydrazine hydrate is matched
Than excessively high, then cause hydrazine hydrate superfluous, will increase production cost.If the proportion of iodide is too low, intermediate 3,4- diformazan
Base pyrazoline oxidative dehydrogenation is incomplete, influences the yield of 3,4- dimethyl pyrazole；If the proportion of iodide is excessively high, iodine
Surplus influences the economy of production.If reaction temperature it is too low or carry out time it is too short, not can guarantee methyl isopropyl Ketone
Reaction is converted into 3,4- dimethyl pyrazole completely；If reaction temperature it is excessively high or carry out overlong time, influence conventional efficient,
And there may be side reactions.Preferably, the molar ratio of methyl isopropyl Ketone and sulfuric acid is 1.0:(1.2~2.5), more preferably
1.0:(1.5~2.0)；Preferably, the molar ratio of methyl isopropyl Ketone and hydrazine hydrate is 1.0:(1.2~2.5), more preferably
1.0:(1.5~2.0)；Preferably, the quality of iodide is 2.0~8.0%, more preferably the 4.0 of methyl isopropyl Ketone quality
~6.0%.Preferably, reaction temperature is 60~140 DEG C, more preferably 70~130 DEG C；Preferably, reaction carry out the time be 5~
9h, more preferably 6~8h.
According to an embodiment of the invention, S200 can further include with reference to Fig. 2:
S210: contact methyl isopropyl Ketone under the action of sulfuric acid and iodide with hydrazine hydrate；S210: to obtained by S200
Product is successively neutralized, extraction processing and distillation are handled, and obtains 3,4- dimethyl pyrazole.It as a result, can be by simple
Post-processing effectively separates 3,4- dimethyl pyrazole from reaction system, 3,4- dimethyl pyrazole yields and purity is high,
And post-processing approach is suitable for large-scale continuous production.
According to an embodiment of the invention, in above-mentioned neutralisation treatment, can using selected from sodium carbonate liquor, solution of potassium carbonate,
Calcium carbonate soln, carbonic acid magnesium solution, sodium hydroxide solution, potassium hydroxide solution, magnesium hydroxide solution, calcium hydroxide solution and three
At least one of ethamine is used as neutralizer.Above-mentioned neutralizer it is from a wealth of sources, low in cost, and will not be to 3,4- in system
Dimethyl pyrazole causes the adverse effect such as to decompose, go bad.In addition, it is necessary to which explanation, is such as not particularly illustrated, above-mentioned solution is equal
Concentration for aqueous solution, above-mentioned solution can need a large amount of neutralizer if neutralizer concentration is too low for 10~40wt%
Neutralisation treatment could be completed, if neutralizer excessive concentration, the terminal that will lead to neutralisation treatment is difficult to control.Preferably, on
The concentration for stating solution is 15~30wt%, more preferably 20~25wt%.
According to an embodiment of the invention, in above-mentioned neutralisation treatment, temperature can be 30~100 DEG C, pH value can for 8~
14.Thus, it is possible to avoid reacting in neutralisation treatment excessively acutely, the loss of 3,4- dimethyl pyrazole is avoided.Preferably, temperature is
40~90 DEG C, more preferably 50~80 DEG C；Preferably, pH value is 9~13, more preferably 9~10.
According to an embodiment of the invention, in above-mentioned extraction processing, it can be using selected from toluene, petroleum ether, methylene chloride, three
The conduct of at least one of chloromethanes, ethyl acetate, n-butanol, isobutanol, the tert-butyl alcohol, n-hexane, hexamethylene and butyl acetate
Extractant.Dissolubility of 3, the 4- dimethyl pyrazoles in above-mentioned extractant is good, by using above-mentioned extractant to neutralisation treatment
Product carries out extraction processing, and the yield of 3,4- dimethyl pyrazoles is higher.
According to an embodiment of the invention, the dosage of extractant can be methyl isopropyl Ketone quality in above-mentioned extraction processing
1.0~3.0 times.If the capacity of extractant is too low, excessive concentration of 3, the 4- dimethyl pyrazole in extractant will lead to,
It is easy to cause 3,4- dimethyl pyrazole to lose in extraction processing excessive, if the dosage of extractant is excessively high, influences later period steaming
Evaporate efficiency.Preferably, the dosage of extractant is 1.1~2.5 times, more preferably 1.5~2.0 times of methyl isopropyl Ketone quality.
In some embodiments, extractant can be repeated as many times for the extraction to neutralisation treatment product.
According to an embodiment of the invention, temperature can be 30~150 DEG C in above-mentioned distillation processing, pressure can be -0.09
~0.11MPa, such as -0.09MPa~normal pressure.Thus, it is possible to the yield of 3, the 4- dimethyl pyrazole further increased and
Purity.In the step, if vapo(u)rizing temperature is too low or hypertonia, it can not steam；If vapo(u)rizing temperature is excessively high or pressure mistake
It is low, then yield is influenced phenomena such as reaction system meeting coking, carbonization in distillation process.In some embodiments, after the completion of distillation processing
Rectifying further can be carried out to 3, the 4- dimethyl pyrazole that collection obtains, so that 3 are further increased, 4- dimethyl pyrazole product
Purity.
In another aspect of this invention, of the invention propose a kind of prepares the phosphatic method of 3,4- dimethyl pyrazole.
According to an embodiment of the invention, this method comprises: the preparation 3 of (a) according to above-described embodiment, the method preparation of 4- dimethyl pyrazole
Obtain 3,4- dimethyl pyrazole；(b) it in the first organic solvent, contacts 3,4- dimethyl pyrazole with phosphoric acid, obtains 3,4- bis-
Methylpyrazole phosphate.
First, in accordance with the preparation 3 of above-described embodiment, the method for 4- dimethyl pyrazole simply and efficiently prepared this method as a result,
Obtained 3,4- dimethyl pyrazole, and then 3, the 4- dimethyl pyrazole being prepared using 3,4- dimethyl pyrazole and phosphatase reaction
Phosphate (DMPP).This method process flow is short, the yield and purity is high of product.
The phosphatic method of preparation 3,4- dimethyl pyrazole according to an embodiment of the present invention is carried out into one below with reference to Fig. 3
The detailed description of step.According to an embodiment of the invention, this method comprises:
S100: methyl isopropyl Ketone is prepared；
S200: 3,4- dimethyl pyrazole is obtained；
Firstly, 3,4- dimethyl pyrazole is prepared in the method for 4- dimethyl pyrazole according to the preparation 3 of above-described embodiment,
Details are not described herein.
S300: 3,4- dimethyl pyrazole phosphate is obtained
In the step, with reference to formula (III), in the first organic solvent, contacts 3,4- dimethyl pyrazole with phosphoric acid, obtain
3,4- dimethyl pyrazole phosphate,
According to an embodiment of the invention, above-mentioned first organic solvent may include selected from methanol, ethyl alcohol, propyl alcohol, isopropanol,
At least one of n-butanol, isobutanol and tert-butyl alcohol.Above-mentioned organic solvent can provide for 3,4- dimethyl pyrazole and phosphoric acid
Good dissolubility, and dissolubility of the product DMPP in above-mentioned organic solvent is low, it can be from reactant by simply filtering
Isolated DMPP product in system.
According to an embodiment of the invention, the dosage of the first organic solvent can for 3,4- dimethyl pyrazole quality 0.5~
2.0 times, the molar ratio of 3,4- dimethyl pyrazoles and phosphoric acid can be 1.0:(1.0~1.5).If the dosage of the first organic solvent
It is too low, then it reacts insufficient, yield is caused to be lower；If the dosage of the first organic solvent is excessively high, DMPP may be made certain
It is dissolved in degree in the first organic solvent, the yield of DMPP is caused to reduce.If the dosage of phosphoric acid is too low, 3,4- dimethyl pyrazoles
Azoles cannot react completely, and DMPP yield is caused to be lower；If the dosage of phosphoric acid is excessively high, the DMPP for reacting generation can be dissolved in
In the phosphoric acid of amount, lead to the reduction of DMPP yield.Preferably, the dosage of the first organic solvent is 3,4- dimethyl pyrazole quality
0.8~1.5 times, more preferably 1.0~1.2 times.Preferably, the molar ratio of 3,4- dimethyl pyrazole and phosphoric acid be 1.0:(1.1~
1.4), more preferably 1.0:(1.2~1.3).
According to an embodiment of the invention, 3,4- dimethyl pyrazoles with reacting for phosphoric acid can be 1~3 in pH value, temperature 40
3~10h is carried out under conditions of~50 DEG C to complete.If pH value is too low, the DMPP for reacting generation can be dissolved in phosphoric acid, be caused
DMPP yield reduces.If pH value is excessively high, reacts insufficient, yield is caused to be lower.If reaction temperature is too low or reacts
Between it is too short, then react insufficient, yield caused to be lower；If reaction temperature is excessively high or the reaction time is too long, DMPP may be made
It is dissolved in the first organic solvent to a certain extent, the yield of DMPP is caused to reduce.Preferably, the reaction time is 5~9h, more excellent
It is selected as 4~8h.
It should be noted that the preparation 3, the phosphatic method of 4- dimethyl pyrazole has described previously for preparation 3,4- diformazan
Whole feature and advantage described in the method for base pyrazoles, details are not described herein.
In another aspect of the invention, of the invention propose a kind of prepares 3,4- dimethyl pyrazole metal organic complex
Method.According to an embodiment of the invention, this method comprises: (c) according to the preparation of above-described embodiment 3,4- dimethyl pyrazole
3,4- dimethyl pyrazole is prepared in method；(d) in a second organic solvent, make 3,4- dimethyl pyrazole and metal salt contacts,
Obtain 3,4- dimethyl pyrazole metal organic complex.
First, in accordance with the preparation 3 of above-described embodiment, the method for 4- dimethyl pyrazole simply and efficiently prepared this method as a result,
Obtained 3,4- dimethyl pyrazole, and then 3, the 4- dimethyl pyrazole being prepared using 3,4- dimethyl pyrazole and reacting metal salt
Azoles metal organic complex.This method process flow is short, the yield and purity is high of product.Product is with 3,4- dimethyl pyrazole
While active, it is not easy to lose in alkaline fertilizer.
Below with reference to Fig. 4 to the method according to an embodiment of the present invention for preparing 3,4- dimethyl pyrazole metal organic complex
It is further described in detail.According to an embodiment of the invention, this method comprises:
S100: methyl isopropyl Ketone is prepared；
S200: 3,4- dimethyl pyrazole is obtained；
Firstly, 3,4- dimethyl pyrazole is prepared in the method for 4- dimethyl pyrazole according to the preparation 3 of above-described embodiment,
Details are not described herein.
S400: 3,4- dimethyl pyrazole metal organic complex is obtained
In the step, in a second organic solvent, makes 3,4- dimethyl pyrazole and metal salt contacts, obtain 3,4- dimethyl
Pyrazoles metal organic complex.A specific example according to the present invention can use 3,4- dimethyl pyrazole with reference to formula (IV)
Cooperate zinc with zinc chloride preparation 3,4- dimethyl pyrazole,
According to an embodiment of the invention, above-mentioned second organic solvent may include selected from methanol, ethyl alcohol, propyl alcohol, isopropanol,
At least one of butanol, isobutanol, the tert-butyl alcohol, acetone, butanone, ether, ethyl methyl ether, benzene, toluene and chloroform.Some
In embodiment, the second organic solvent includes at least one above-mentioned pure and mild acetone, butanone, ether, ethyl methyl ether, benzene, toluene or three
Chloromethanes.Above-mentioned organic solvent can provide good dissolubility for 3,4- dimethyl pyrazole and metal salt, and metal is organic matches
It is low to close dissolubility of the object product in above-mentioned organic solvent, by simply filter can from reaction system it is isolated.
According to an embodiment of the invention, above-mentioned metal salt can be chloride, bromide, sulfate or the nitre of metallic element
Hydrochlorate, metallic element can be Fe, Co, Ni, Cu, Ca, Mg, Zn or Mn.By utilizing above-mentioned metal salt and 3,4- dimethyl pyrazole
Azoles forms metal organic complex, can make product while retaining 3,4- dimethyl pyrazole activity, be not easy in alkaline fertilizer
Loss.
According to an embodiment of the invention, reacting for 3,4- dimethyl pyrazoles and metal salt can carry out 1 at 0~100 DEG C~
48h is completed.If reaction temperature is too low or the reaction time is too short, react insufficient；If reaction temperature is excessively high or reacts
Between it is too long, then reaction efficiency is too low or has side reaction.Preferably, reaction temperature is 20~80 DEG C, more preferably 30~50 DEG C；It is excellent
Choosing, the reaction time be 4~for 24 hours, more preferably 5~16h.
It should be noted that the preparation 3, the method for 4- dimethyl pyrazole metal organic complex has described previously for preparation
Whole feature and advantage described in the method for 3,4- dimethyl pyrazoles, details are not described herein.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, without limiting the invention in any way.
Embodiment 1
(1) synthesis of methyl isopropyl Ketone
After water and isoprene are vaporized mixing respectively, 180 DEG C are preheated to, into H3PO4- B/ diatomite catalyst bed
Carry out hydration reaction.Catalyst phosphorus acid content is 65wt%, and boron content 6wt%, reaction temperature is 250 DEG C, water and isoamyl two
Alkene molar ratio is 6.0, and air speed LHSV is 0.5h-1, reaction pressure 0.1MPa.The pressure that reaction pressure passes through reactor exit
Controller is adjusted.Isoprene conversion ratio is 93.4%, and selectivity is 95.7%, yield 89.4%, gas Chromatographic Determination
Product purity is 99.7%.
(2) synthesis of 3,4- dimethyl pyrazole
The hydrazine hydrate 150kg (3kmole) that mass fraction is 80% is added in reaction kettle, a small amount of water is then added, opens
Stirring is opened, is warming up to and the sulfuric acid 300kg (3kmole) that concentration is 98% is slowly added dropwise after 50 DEG C, iodate is added after being added dropwise
Methyl isopropyl Ketone 172.26kg (2kmole) is added dropwise after then heating to 120~125 DEG C in sodium 5kg, with 2.5h by methyl isopropyl
Base ketone is added drop-wise in reaction kettle, carries out a point water after being added dropwise, and temperature after water is divided to be increased to 130~135 DEG C, warm herein
Degree is lower the reaction was continued 3h, the sulfur dioxide gas generated in reaction process are absorbed with lye.
It is cooled to after 50~60 DEG C and is neutralized to pH=9~10 with the sodium hydroxide solution of 25wt%, controlled in N-process
About 350kg isobutanol is added within 90 DEG C in temperature processed after being cooled to room temperature after neutralization, stratification obtains organic layer,
First vacuum distillation recycling isobutanol after obtain 3,4- dimethyl pyrazole crude product, by rectification under vacuum collect 105~107 DEG C/
11mmHg fraction obtains about 145.97kg 3,4- dimethyl pyrazole, and yield is about 75.45%, and gas Chromatographic Determination product is pure
Degree 99.5%.
Embodiment 2
The synthesis of 3,4- dimethyl pyrazole phosphate (DMPP)
145kg 3,4- dimethyl pyrazole is dissolved in the phosphoric acid that rear and 174kg mass fraction is 85% in 174kg ethyl alcohol
Carry out react, reaction temperature be 50 DEG C, reaction time 8h successively cools down after the reaction was completed, crystallize, filtering, be dried to obtain
About 279.5kg white powdery solids product, yield 95.4%, it is 99.3% that high performance liquid chromatography, which measures product purity,.
Embodiment 3
The synthesis of 3,4- dimethyl pyrazole cooperation zinc
Containing Zinc Chloride 34kg is added dropwise after 96kg (1kmole) 3,4- dimethyl pyrazole is dissolved in 200kg chloroform
The dehydrated alcohol 100kg of (250mole).8h is stirred under room temperature, is filtered after the reaction was completed, and filter cake is washed 1~2 time with methanol, is done
About 115kg white powdery solids product, yield about 88% are obtained after dry, high performance liquid chromatography measurement product purity is
95.4%, Nitrifying inhibition rate is 64%~67.7%.
Embodiment 4
3,4 dimethyl pyrazoles cooperate the Nitrifying inhibition rate test of zinc
1) test raw material
It is standard soil for examination soil, picks up from Henan yellow moist soil, soil pH=8.15, organic matter 13.2g/kg, full nitrogen
0.77g/kg, hydrolyzable nitrogen 76mg/kg, available phosphorus 23.3mg/kg, available potassium 0.29g/Kg, slowly available potassium 0.95g/kg.
It is that 3, the 4- dimethyl pyrazole being prepared in embodiment 3 cooperates zinc for examination nitrification inhibitor, makes white powder by oneself,
Purity is 95.4%.
It is ammonium sulfate (ASN), content 99.00%, white crystal for examination nitrogen source.
2) culture experiment
Design 3,4- dimethyl pyrazole cooperation zinc dosage be pure nitrogen level 0 (CK), 1.0%, 2.0%, 3.0%, 3.5%,
4.0%, 4.5%, 5.0%, 6.0% and 7.0% totally 10 levels, 3 repetitions of each level.It is sodium sulphate for examination nitrogen source
(ASN, nitrogen content 21.21%), dosage N0.5g/kg, standard soil.Ammonium sulfate and 3,4- dimethyl pyrazole cooperation zinc are pressed
Experimental design requires to be dissolved in the water, and mixes well, is put into PVC valve bag with 1kg standard soil, close to 1cm above soil
1 horizontally-arranged ventilation hole (totally 6) is pricked to create aerobic environment by place, is placed on constant temperature dark culturing in 25 DEG C of phjytotrons.Training
It is used weight method moisturizing 1 time daily during supporting, soil moisture content is made to be maintained at the 60~65% of field capacity.Start in culture
Afterwards 2,3,5,10,15,20d it is separately sampled, every sub-sampling 25g, sampling soil is extracted with the KCl solution of 2.0mol/L immediately, leaching
Mention solution be put into -20 DEG C of refrigerator save it is to be measured.
3) Nitrifying inhibition rate calculation formula
Inhibiting rate test method is digested referring to GB/T 35113-2017.
In formula, A is NO before and after the soil incubation that the cooperation zinc inhibitor processing of 3,4- dimethyl pyrazole is not added3 -The difference of N content
(mg/kg), B is NO before and after the soil incubation for adding the cooperation zinc inhibitor processing of 3,4- dimethyl pyrazole3 -Difference (the mg/ of N content
kg)。
Test result is shown in Table 1:
NO in 1 3,4- dimethyl pyrazole of table cooperation zinc Different adding amount, the soil of different disposal time3 -- N (mg/kg) contains
The data and Nitrifying inhibition rate of amount
Test result shows that the Nitrifying inhibition rate of 3,4- dimethyl pyrazole cooperation zinc is 64~67.7%.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of method for preparing 3,4- dimethyl pyrazole characterized by comprising
(1) under the effect of the catalyst, it contacts isoprene with water, obtains methyl isopropyl Ketone；
(2) it contacts the methyl isopropyl Ketone under the action of sulfuric acid and iodide with hydrazine hydrate, obtains 3,4- dimethyl pyrazole
Azoles.
2. the method according to claim 1, wherein the catalyst includes active constituent and carrier, the work
Property ingredient include phosphoric acid and boron, the carrier is diatomite；
Optionally, in the catalyst, the content of the phosphoric acid is the 50~80% of the catalyst gross mass, and the boron contains
Amount is the 4~9% of the catalyst gross mass.
3. the method according to claim 1, wherein in step (1), mole of the isoprene and the water
Than for 1.0:(1.0~10.0), the contact at 180~300 DEG C of temperature and the pressure of 0.09~0.5MPa with 0.1~
2.0h-1Air speed carry out.
4. the method according to claim 1, wherein the concentration of the sulfuric acid is 20~98wt%, the hydration
The concentration of hydrazine be 40~80wt%, the iodide include in sodium iodide, potassium iodide, silver iodide, iodine and hydrogen iodide extremely
It is one of few.
5. the method according to claim 1, wherein in step (2), the methyl isopropyl Ketone and the sulfuric acid
Molar ratio be 1.0:(1.0~3.0), the molar ratio of the methyl isopropyl Ketone and the hydrazine hydrate be 1.0:(1.0~
3.0), the quality of the iodide is the 1.0~10.0% of the methyl isopropyl Ketone quality, and the contact is at 50~150 DEG C
4~10h of lower progress is completed.
6. described in any item methods according to claim 1~5, which is characterized in that step (2) further comprises:
(2-1) contacts the methyl isopropyl Ketone under the action of sulfuric acid and iodide with hydrazine hydrate；
(2-2) is successively neutralized step (2-1) products therefrom, extraction processing and distillation are handled, and obtains described 3,4-
Dimethyl pyrazole；
Optionally, in the neutralisation treatment, using molten selected from sodium carbonate liquor, solution of potassium carbonate, calcium carbonate soln, magnesium carbonate
At least one of liquid, sodium hydroxide solution, potassium hydroxide solution, magnesium hydroxide solution, calcium hydroxide solution and triethylamine are made
For neutralizer；
Optionally, in the extraction processing, using selected from toluene, petroleum ether, methylene chloride, chloroform, ethyl acetate, positive fourth
At least one of alcohol, isobutanol, the tert-butyl alcohol, n-hexane, hexamethylene and butyl acetate are used as extractant；
Optionally, in the neutralisation treatment, temperature is 30~100 DEG C, and pH value is 8~14；In the extraction processing, the extraction
The dosage of agent is 1.0~3.0 times of the methyl isopropyl Ketone quality；
Optionally, in the distillation processing, temperature is 30~150 DEG C, and pressure is -0.09~0.11MPa.
7. a kind of prepare the phosphatic method of 3,4- dimethyl pyrazole characterized by comprising
(a) 3,4- dimethyl pyrazole is prepared according to the described in any item methods of claim 1~6；
(b) it in the first organic solvent, contacts 3, the 4- dimethyl pyrazole with phosphoric acid, obtains 3,4- dimethyl pyrazole phosphoric acid
Salt.
8. the method according to the description of claim 7 is characterized in that first organic solvent includes being selected from methanol, ethyl alcohol, third
At least one of alcohol, isopropanol, n-butanol, isobutanol and tert-butyl alcohol；
Optionally, the dosage of first organic solvent is 0.5~2.0 times of 3, the 4- dimethyl pyrazole quality, described 3,
The molar ratio of 4- dimethyl pyrazole and the phosphoric acid is 1.0:(1.0~1.5)；
Optionally, the contact carries out 3~10h completion under conditions of pH value is 1~3, temperature is 40~50 DEG C.
9. a kind of method for preparing 3,4- dimethyl pyrazole metal organic complex characterized by comprising
(c) 3,4- dimethyl pyrazole is prepared according to the described in any item methods of claim 1~6；
(d) in a second organic solvent, make 3, the 4- dimethyl pyrazole and metal salt contacts, obtain 3,4- dimethyl pyrazole gold
Belong to organic coordination compound.
10. according to the method described in claim 9, it is characterized in that, second organic solvent include selected from methanol, ethyl alcohol,
In propyl alcohol, isopropanol, butanol, isobutanol, the tert-butyl alcohol, acetone, butanone, ether, ethyl methyl ether, benzene, toluene and chloroform extremely
It is one of few；
Optionally, the metal salt is chloride, bromide, sulfate or the nitrate of metallic element, and the metallic element is
Fe, Co, Ni, Cu, Ca, Mg, Zn or Mn；
Optionally, the contact carries out 1~48h completion at 0~100 DEG C.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85104430A (en) * | 1984-06-25 | 1986-12-10 | 陶氏化学公司 | Handle the method and the mixture that can keep nitrogen in the soil of soil |
| US5637131A (en) * | 1992-04-08 | 1997-06-10 | Skw Stickstoffwerke Piesteritz Gmbh | Agent combinations to inhibit or control nitrification of ammonia nitrogen in cultivated soils and substrates |
| CN1261351A (en) * | 1997-06-23 | 2000-07-26 | 巴斯福股份公司 | Method for producing substituted pyrazoles |
| CN101168497A (en) * | 2006-10-24 | 2008-04-30 | 胡建国 | Method for producing methyl isopropyl ketone |
| CN102558054A (en) * | 2011-12-21 | 2012-07-11 | 深圳中航资源有限公司 | Process for preparing 3,4-dimethylpyrazole phosphate |
| CN102911119A (en) * | 2012-09-30 | 2013-02-06 | 浙江工业大学 | Preparation methods of 3,4-dimethyl pyrazole and 3,4-dimethyl pyrazole phosphate |
-
2019
- 2019-01-11 CN CN201910027935.1A patent/CN109651252A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85104430A (en) * | 1984-06-25 | 1986-12-10 | 陶氏化学公司 | Handle the method and the mixture that can keep nitrogen in the soil of soil |
| CN85104656A (en) * | 1984-06-25 | 1986-12-24 | 陶氏化学公司 | The treatment process of soil and the prescription that is used for keeping nitrogen at soil |
| US5637131A (en) * | 1992-04-08 | 1997-06-10 | Skw Stickstoffwerke Piesteritz Gmbh | Agent combinations to inhibit or control nitrification of ammonia nitrogen in cultivated soils and substrates |
| CN1261351A (en) * | 1997-06-23 | 2000-07-26 | 巴斯福股份公司 | Method for producing substituted pyrazoles |
| CN101168497A (en) * | 2006-10-24 | 2008-04-30 | 胡建国 | Method for producing methyl isopropyl ketone |
| CN102558054A (en) * | 2011-12-21 | 2012-07-11 | 深圳中航资源有限公司 | Process for preparing 3,4-dimethylpyrazole phosphate |
| CN102911119A (en) * | 2012-09-30 | 2013-02-06 | 浙江工业大学 | Preparation methods of 3,4-dimethyl pyrazole and 3,4-dimethyl pyrazole phosphate |
Non-Patent Citations (1)
| Title |
|---|
| 黄生建 等: "3,4-二甲基吡唑磷酸盐的合成", 《浙江化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112321507A (en) * | 2020-09-18 | 2021-02-05 | 武威金仓生物科技有限公司 | Preparation method of 3, 4-dimethylpyrazole and phosphate thereof |
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