CN109081809A - A kind of triangle ligand containing 3,5- dimethyl pyrazole and its synthetic method and application - Google Patents

A kind of triangle ligand containing 3,5- dimethyl pyrazole and its synthetic method and application Download PDF

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Publication number
CN109081809A
CN109081809A CN201810801858.6A CN201810801858A CN109081809A CN 109081809 A CN109081809 A CN 109081809A CN 201810801858 A CN201810801858 A CN 201810801858A CN 109081809 A CN109081809 A CN 109081809A
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China
Prior art keywords
triangle
dimethyl pyrazole
ligand
trimethylbenzenes
fertilizer
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CN201810801858.6A
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Chinese (zh)
Inventor
郭放
段文龙
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Liaoning University
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Liaoning University
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
    • Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures

Abstract

The present invention relates to a kind of the triangle ligand containing 3,5- dimethyl pyrazole and its synthetic method and application.The technical solution adopted is that: with anhydrous ZnCl2, paraformaldehyde, concentrated hydrochloric acid and 1,3,5- trimethylbenzenes are raw material, first prepare intermediate product 1,3,5- tri- (chloromethyl) -2,4,6- trimethylbenzenes, then under conditions of acetonitrile as solvents, intermediate product, Anhydrous potassium carbonate and 3 obtain target product after 5- dimethyl pyrazole is stirred to react.It is prepared by the present invention to contain 3, the triangle ligand of 5- dimethyl pyrazole can be used as nitrification inhibitor, the nitrifying process of ammonium fertilizer in the soil can effectively be adjusted, ammonium ion in soil is set to keep higher content, this new inhibitor has that dosage is low, inhibiting rate is high, long half time, small toxicity, effect on environment are small, therefore can be applied in fertilizer.

Description

One kind containing triangle ligand and its synthetic method and the application of 3,5- dimethyl pyrazole
Technical field
The present invention relates to fertilizer additive fields, specifically, ammonium fertilizer can effectively be adjusted in soil by being related to one kind In nitrifying process, so that ammonium ion is kept higher content, delay NH4 +- N is to NO3 -The conversion of-N, makes nitrogen with soil Earth is easier to the NH of absorption4 +The form long period of-N retains in the soil.
Background technique
China is fertilizer amount big country, and excessive fertilization will lead to soil hardening, underground water pollution, the eutrophy of water body in lake Change, the NH in nitrogenous fertilizer can be alleviated by adding nitrification inhibitor into fertilizer4 +- N is to NO3 -The conversion of-N reduces the leaching of nitrate Molten and nitrogen oxides discharge reduces the usage amount of fertilizer so that fertilizer efficiency period extends, and improves utilization rate of nitrogen fertilizer.Therefore it studies new The nitrification inhibitor of type has the significance for reducing environmental pollution and protecting environment.
Summary of the invention
An object of the present invention is to select nitrification inhibitor 3,5- dimethyl pyrazole and tri- (chloromethane of intermediate 1,3,5- Base) -2,4,6- trimethylbenzenes obtain the good nitrification inhibitor of novel stable by the method for organic synthesis, overcome nitrification The shortcomings that inhibitor 3,5- dimethyl pyrazole decomposition rate is fast, half-life period section, the effective utilization rate for improving nitrogenous fertilizer.
It, can be with the second object of the present invention is to contain the triangle ligand material of 3,5- dimethyl pyrazole as nitrification inhibitor The activity for inhibiting Nitromonas, delays NH4 +- N is to NO3 -The conversion of-N, nitrogen are easier to the NH of absorption with soil4 +The shape of-N The formula long period retains supply crop in the soil and absorbs.
The technical solution adopted by the invention is as follows: one kind contains the triangle ligand of 3,5- dimethyl pyrazole, preparation method packet Include following steps: with anhydrous ZnCl2, paraformaldehyde, concentrated hydrochloric acid and 1,3,5- trimethylbenzenes be raw material, be warming up to 90-100 DEG C, It is passed through dry hydrogen chloride gas, is stirred to react, 1,3,5- tri- (chloromethyl) -2 of intermediate product, 4,6- trimethylbenzenes are prepared；It takes Intermediate product 1,3,5- tri- is added with acetonitrile as solvents in Anhydrous potassium carbonate and 3,5- dimethyl pyrazole after being warming up to 40-50 DEG C (chloromethyl) -2,4,6- trimethylbenzenes are stirred to react 10-15h at 80-90 DEG C, are cooled to room temperature, filter to obtain crude product, ethyl alcohol Recrystallization, it is dry, obtain the triangle ligand that target product contains 3,5- dimethyl pyrazole.
Preferably, in molar ratio, 1,3,5- tri- (chloromethyl) -2,4,6- trimethylbenzenes: 3,5- dimethyl pyrazoles=1:3.
Preferably, the triangle ligand for containing 3,5- dimethyl pyrazole, crystal form belong to anorthic system, and space group is P-1。
Contain application of the triangle ligand of 3,5- dimethyl pyrazole as nitrification inhibitor in fertilizer.The fertilizer is Nitrogenous fertilizer.The nitrogenous fertilizer is urea.
The beneficial effects of the present invention are: the triangle ligand prepared by the present invention containing 3,5- dimethyl pyrazole has relatively The preferable activity for inhibiting Nitromonas, delays NH4 +- N is to NO3 -The conversion of-N makes nitrogen be easier to the NH of absorption with soil4 +The form long period of-N retains in the soil, can effectively adjust the nitrifying process of ammonium fertilizer in the soil, make in soil Ammonium ion keeps higher content, inhibitor of the invention have dosage is low, inhibiting rate is high, long half time, small toxicity, to ring Border influence is small, therefore can be applied in fertilizer.
Detailed description of the invention
Fig. 1 is the hot ellipsoid figure of monocrystalline of target product prepared by embodiment 1.
Fig. 2 is that target product x-ray diffractogram of powder made from embodiment 1 and single crystal data simulation drawing compare.
Specific embodiment
Triangle ligand containing 3,5- dimethyl pyrazole the preparation method is as follows:
1, the preparation of intermediate product 1,3,5- tri- (chloromethyl) -2,4,6- trimethylbenzene
Into 250mL three-necked flask, anhydrous ZnCl is sequentially added2, paraformaldehyde, 1,3,5- trimethylbenzenes and concentrated hydrochloric acid, 95 DEG C are warming up to, the dry hydrogen chloride gas of the concentrated sulfuric acid is passed through.Stop reaction after stirring 12h, after being cooled to room temperature, filters slightly Product, twice with ethyl alcohol recrystallization, dry 2h, obtains 1,3,5- tri- (chloromethyl) -2 of intermediate product, 4,6- front threes under the conditions of 80 DEG C Base benzene.
2, the preparation of the triangle ligand containing 3,5- dimethyl pyrazole
Into 250mL three-necked flask, Anhydrous potassium carbonate, 3,5- dimethyl pyrazole and acetonitrile are sequentially added, is warming up to 45 DEG C Afterwards, 1,3,5- tri- (chloromethyl) -2 are added, 4,6- trimethylbenzenes then heat to 85 DEG C, after being stirred to react 12h, stop anti- It answers, is cooled to room temperature to temperature, filter to obtain crude product, twice with ethyl alcohol recrystallization, 2h after drying, obtains white solid under the conditions of 80 DEG C Body is recrystallized with methylene chloride and methyl alcohol mixed liquor, obtains colourless transparent crystal, as contain the triangle of 3,5- dimethyl pyrazole Ligand.
Embodiment 1
(1) preparation method
1, the preparation of intermediate product 1,3,5- tri- (chloromethyl) -2,4,6- trimethylbenzene
Into 250mL three-necked flask, anhydrous ZnCl is sequentially added2(22.5g, 100mmol), paraformaldehyde (30g, 1mol), 1,3,5- trimethylbenzenes (15mL, 100mmol), 60mL concentrated hydrochloric acid is warming up to 95 DEG C, is passed through the dry chlorination of the concentrated sulfuric acid Hydrogen.Stop reaction after stirring 12h, after being cooled to room temperature, filters to obtain crude product, twice with ethyl alcohol recrystallization, 80 DEG C of conditions Lower dry 2h obtains 1,3,5- tri- (chloromethyl) -2 of intermediate product, 4,6- trimethylbenzenes (16.8g, 60%).
Structural characterization is as follows: m.p.:173.5-174.4 DEG C.
2, the preparation of the triangle ligand containing 3,5- dimethyl pyrazole
Into 250mL three-necked flask, Anhydrous potassium carbonate (4.23g, 30.59mmol), 3,5- dimethyl pyrazole are sequentially added (2.71g, 28.24mmol) and 30mL acetonitrile after being warming up to 45 DEG C, adds 1,3,5- tri- (chloromethyl) -2,4,6- trimethyls Benzene (2.50g, 9.41mmol) then heats to 85 DEG C, after being stirred to react 12h, stops reaction, is cooled to room temperature to temperature, mistake Filter crude product and with ethyl alcohol recrystallization twice, it is dry under the conditions of 80 DEG C after 2h, obtain white solid (3.78g, 90%), use dichloro Methane and methyl alcohol mixed liquor are recrystallized to give colourless transparent crystal.
(2) it detects
Graphite monochromatised Mo K α is used on Bruker D8- x ray diffractometer xRadiation is used as diffraction Light source collects the diffracted intensity data of monocrystalline.The triangle ligand for containing 3,5- dimethyl pyrazole for taking preparation, obtains through SC-XRD Data, and further obtain structure as shown in Figure 1.Its crystal form belongs to anorthic system, space group P-1, α=119.756 (1) ° β=99.166 (2) °, γ=91.012 (1) °, V= 1245.2, Z=2, R=0.044, wR=0.130, T=296K.
Powder diffraction experiment is carried out to crystal using Bruker D8Advance X-ray powder diffraction instrument.Stone is used Black monochromatization CuK α radiation, wavelengthSolid-state detector, 0.01 ° of step-length, 0.3sec when step, 5 ° of scanning range ≤2θ≤45°.Triangle ligand x-ray diffractogram of powder obtained containing 3,5- dimethyl pyrazole and single crystal data simulation drawing phase It matches (Fig. 2).
Triangle ligand crystallographic data of the table 1 containing 3,5- dimethyl pyrazole
Embodiment 2
Into 250mL three-necked flask, 3,5- dimethyl pyrazole, the Carbon Dioxide of (5.42g 56.48mmol) are sequentially added After being warming up to 45 DEG C, 1,3, the 5- tri- (chlorine of (5.00g 18.82mmol) are added in potassium (8.49g, 61.18mmol) and 30mL acetonitrile Methyl) -2,4,6- trimethylbenzenes then heat to 85 DEG C, after being stirred to react 12h, and stop reaction, is cooled to room temperature to temperature, Filter crude product and with ethyl alcohol recrystallization twice, it is dry under the conditions of 80 DEG C after 2h, obtain white solid (7.22g, 86.36%).
Embodiment 3
It is sequentially added into 250mL three-necked flask by 3,5- dimethyl pyrazole (10.84g 0.113mol), Anhydrous potassium carbonate After being warming up to 45 DEG C, 1,3, the 5- tri- (chlorine of (10.00g 0.0376mol) are added in (16.98g, 0.122mol) and 30mL acetonitrile Methyl) -2,4,6- trimethylbenzenes then heat to 85 DEG C, after being stirred to react 12h, and stop reaction, is cooled to room temperature to temperature, Filter crude product and with ethyl alcohol recrystallization twice, it is dry under the conditions of 80 DEG C after 2h, obtain white solid (13.21g, 87.36%).
Embodiment 4
1, method: weighing the triangle ligand 0g (control sample) for containing 3,5- dimethyl pyrazole of the preparation of embodiment 1 respectively, 0.03g, 0.05g, 0.07g, 0.10g are respectively placed in 250mL conical flask, in every bottle be added 10.00g wind desiceted soil, 1g urea, Conical flask is put into constant temperature culture oscillator (180 revs/min) after oscillation 48h simultaneously, filters, respectively by 100mL phosphate buffer Measure nitrate nitrogen (including nitrite nitrogen) the mass fraction ω in sample and control sample solution1。
2, the triangle ligand for containing 3,5- dimethyl pyrazole of Different adding amount is calculated in the calculating of Nitrifying inhibition rate Nitrifying inhibition rate, as a result such as table 2.
Wherein, dN: Nitrifying inhibition rate (%)；
ω1Nitrate nitrogen (including nitrite nitrogen) mass fraction of-sample；
ω2Nitrate nitrogen (including nitrite nitrogen) mass fraction of-control sample, ω2=900.50.
Nitrate nitrogen mass fraction ω in 2 sample of table and control sample solution1With Nitrifying inhibition rate dN
As can be seen from Table 2, Nitrifying inhibition rate is all larger than to contain the triangle ligand of 3,5- dimethyl pyrazole for nitrification inhibitor 6%.When additive amount is gradually increased, Nitrifying inhibition rate is although incrementally increasing, it is contemplated that cost factor adds 5 ‰ to be most suitable Dosage.So it may be concluded that: the triangle ligand of the invention containing 3,5- dimethyl pyrazole can be used as nitrification inhibitor and exist Carried out in fertilizer urea using.

Claims (6)

1. the triangle ligand that one kind contains 3,5- dimethyl pyrazole, which is characterized in that preparation method includes the following steps: with anhydrous ZnCl2, paraformaldehyde, concentrated hydrochloric acid and 1,3,5- trimethylbenzenes be raw material, be warming up to 90-100 DEG C, be passed through dry hydrogen chloride gas Body is stirred to react, and prepares 1,3,5- tri- (chloromethyl) -2 of intermediate product, 4,6- trimethylbenzenes；Take Anhydrous potassium carbonate and 3,5- bis- 1,3,5- tri- (chloromethyl) -2 of intermediate product, 4,6- front threes are added with acetonitrile as solvents in methylpyrazole after being warming up to 40-50 DEG C Base benzene is stirred to react 10-15h at 80-90 DEG C, is cooled to room temperature, and filters to obtain crude product, and ethyl alcohol recrystallization is dry, obtains target Product contains the triangle ligand of 3,5- dimethyl pyrazole.
2. the triangle ligand that one kind according to claim 1 contains 3,5- dimethyl pyrazole, which is characterized in that by mole Than, 1,3,5- tri- (chloromethyl) -2,4,6- trimethylbenzenes: 3,5- dimethyl pyrazoles=1:3.
3. the triangle ligand that one kind according to claim 1 contains 3,5- dimethyl pyrazole, which is characterized in that described contains There is the triangle ligand of 3,5- dimethyl pyrazole, crystal form belongs to anorthic system, space group P-1.
4. the triangle ligand described in claim 1,2 or 3 for containing 3,5- dimethyl pyrazole is as nitrification inhibitor in fertilizer Application.
5. application according to claim 4, it is characterised in that: the fertilizer is nitrogenous fertilizer.
6. application according to claim 5, it is characterised in that: the nitrogenous fertilizer is urea.
CN201810801858.6A 2018-07-20 2018-07-20 A kind of triangle ligand containing 3,5- dimethyl pyrazole and its synthetic method and application Pending CN109081809A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1592516A (en) * 1977-11-02 1981-07-08 Fahlberg List Magdeberg Chemis Method for inhibiting or regulating the nitrification of ammonium nitrogen in cultivated soils
CN1506339A (en) * 1996-08-06 2004-06-23 Basf Application of novel nitration inhibitor and polyacid in processing inorganic fertilizer containing nitration inhibitor
DE19822340B4 (en) * 1998-05-19 2008-02-28 Skw Stickstoffwerke Piesteritz Gmbh Thermostable low volatility alkyl-1H-1-pyrazolylmethanamine derivatives and their use as nitrification inhibitors
CN101134698A (en) * 2006-09-01 2008-03-05 中国科学院沈阳应用生态研究所 Application of 1-formamido-3,5-dimethylpyrazole as nitration inhibitor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1592516A (en) * 1977-11-02 1981-07-08 Fahlberg List Magdeberg Chemis Method for inhibiting or regulating the nitrification of ammonium nitrogen in cultivated soils
CN1506339A (en) * 1996-08-06 2004-06-23 Basf Application of novel nitration inhibitor and polyacid in processing inorganic fertilizer containing nitration inhibitor
DE19822340B4 (en) * 1998-05-19 2008-02-28 Skw Stickstoffwerke Piesteritz Gmbh Thermostable low volatility alkyl-1H-1-pyrazolylmethanamine derivatives and their use as nitrification inhibitors
CN101134698A (en) * 2006-09-01 2008-03-05 中国科学院沈阳应用生态研究所 Application of 1-formamido-3,5-dimethylpyrazole as nitration inhibitor

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
HONG-CUI YU等: "Insights into the formation of chiral second sphere coordination complexes with aromatic tris amines: combined single crystal X-ray crystallography and molecular modeling analyses", 《DALTON TRANSACTIONS》 *
JUN-NA LIU等: "Crystal structure of 1,3,5-tris[(3,5-dimethylpyrazol)-1-ylmethyl]-2,4,6- trimethylbenzene, C27H36N6", 《ZEITSCHRIFT FUER KRISTALLOGRAPHIE - NEW CRYSTAL STRUCTURES》 *
MATHIAS M. SCHULZE等: "Crystalline Ammonium Complexes of Trimethyl- and Triethylbenzene-Based Tripodal Compounds Bearing Pyrazole and Indazole Groups", 《EUROPEAN JOURNAL OF ORGANIC CHEMISTRY》 *
STEFAN N. L. ANDREE等: "Structural examination of halogen-bonded co-crystals of tritopic acceptors", 《MOLECULES》 *
史云峰等: "1-羟甲基-3,5-二甲基吡唑(DMHMP)的硝化抑制效应初探", 《土壤通报》 *
孙志梅: "3,5-二甲基吡唑的硝化抑制效果", 《中国科学院沈阳应用生态研究所博士学位论文》 *

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Application publication date: 20181225