CA2208529A1 - Use of pyrazole derivatives containing hydrophobic radicals as nitrification inhibitors - Google Patents
Use of pyrazole derivatives containing hydrophobic radicals as nitrification inhibitorsInfo
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- CA2208529A1 CA2208529A1 CA002208529A CA2208529A CA2208529A1 CA 2208529 A1 CA2208529 A1 CA 2208529A1 CA 002208529 A CA002208529 A CA 002208529A CA 2208529 A CA2208529 A CA 2208529A CA 2208529 A1 CA2208529 A1 CA 2208529A1
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- halogen
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- pyrazole
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/243—Two or more independent types of crosslinking for one or more polymers
-
- 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
- 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
- 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
- C07D231/14—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/16—Halogen atoms or nitro radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2321/00—Characterised by the use of unspecified rubbers
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Disclosed is the use as nitrification inhibitors of pyrazole derivatives of formula (I), or salts thereof, in which the groups R1-R4 have the following meanings: R1, R2 and R3 represent C1-C20 alkyl, C3-C8 cycloalkyl, C5-C20 aryl or alkyl aryl (these four groups can be singly or doubly substituted by a halogen and/or hydroxyl), and halogen, nitro or hydrogen; and R4 represents either (a) C6-C20 alkyl, one or two hydrogen atoms being optionally substituted by a halogen; or (b) C1-C20 alkyl. In the latter case, 1-4 hydrogen atoms can be substituted by a group of formula (II), in which R5, R6, and R7 represent C1-C20 alkyl, C3-C8 cycloalkyl, C5-C20 aryl or alkyl aryl (these four groups can be singly or doubly substituted by a halogen and/or hydroxyl), as well as halogen, nitro or hydrogen; and 1 or two hydrogen atoms are optionally substituted by a halogen.
Description
CA 02208~29 1997-06-16 Use of pyrazole derivatives containing hydrophobic radicals as nitrification inhibitors 5 The present invention relates to the use of pyrazole derivatives of the formula I
;~ N
Rl'' N' ~ R4 or their salts, where the radicals Rl to R4 have the following meanings:
- Rl, R2 and R3 are Cl- to C20-alkyl, C3- to c8-cycloalkyl, C5-to C20-aryl or C6- to C20-alkylaryl, it being possible for these 4 radicals to be monosubstituted or disubstituted by halogen and/or hydroxyl; and halogen, nitro or hydrogen, and - R4 iS either a) C6- to C20-alkyl, in which 1 or 2 hydrogen atoms may be replaced by halogen, or b) Cl- to C20-alkyl, in which - 1 to 4 hydrogen atoms are replaced by a radical having the formula II
~ II
R5~N~ ~
where R5, R6 and R7 are Cl- to C20-alkyl, C3- to C8-cycloalkyl, C5-to C20-aryl or C6- to C20-alkylaryl, it being possible for these 4 radicals to be monosubstituted or disubstituted by halogen and/or hydroxyl; and halogen, nitro or hydrogen, and - 1 to 2 hydrogen atoms may be replaced by halogen, as nitrification inhibitors.
. 0050/45506 CA 02208~29 1997-06-16 ~. .
The invention furthermore relates to novel pyrazole derivatives which are suitable for this intended use, and processes for their preparation.
5 In order to make available to plants the nitrogen needed by them, they are fertilized, as is known, with ammonium compounds. Ammo-nium compounds, however, are microbially converted to nitrate in the soil in a relatively short time (nitrification).
10 Because nitrate is leached from the soil more easily than ammo-nium and the leached portion is no longer available for plant nutrition, however, rapid nitrification is undesirable. In order that the fertilizer is utilized better, it was therefore proposed to add nitrification inhibitors to the soil.
EPA-A 474 037 discloses 3-methylpyrazole derivatives in which one nitrogen atom of the pyrazole ring carries a methyl, cycloalkyl, aryl or aralkyl radical. It is proposed to use these compounds as intermediates for the preparation of pharmaceutical products or 20 crop protection agents.
US-A 3 635 690 discloses the employment of various pyrazole derivatives for the inhibition of nitrification. In the pyrazole derivatives proposed, the nitrogen atoms in the pyrazole ring do 25 not carry any substituents or one of the nitrogen atoms carries a saturated or unsaturated Cl- to C3-hydrocarbon radical. One or more carbon atoms in the pyrazole ring can be substituted by hydrocarbon radicals which may carry halogens as substituents.
Examples of these are 3-methylpyrazoles such as 4-chloro-30 3-methylpyrazole.
US-A-4 969 946 also describes the use of pyrazole derivatives as nitrification inhibitors. In these derivatives, the nitrogen atoms in the pyrazole ring are unsubstituted, and several of the 35 ring carbon atoms are substituted by halogen or methyl.
DE A 3 704 359 relates to compositions which inhibit nitrifica-tion. As active compound, they contain pyrazole derivatives which, on one nitrogen atom of the pyrazole ring, carry a radical 40 of the formula C C= O
OH R' 0050/45506 CA 02208~29 1997-06-16 ., .
R' being a substituted or unsubstituted organic radical or a hydroxy radical.
Further nitrification inhibitors are disclosed in EP-A 0 160 804.
5 They are pyrazole derivatives in which a nitrogen atom in the pyrazole ring carries a substituted oxycarbonyl, sulfinyl or sul-fonyl radical.
DE-A 4 018 395 mentions derivatives of 1-cyano-3-methylpyrazole 10 and its acid addition products or coordination compounds as nit-rification inhibitors.
SU-A 1 470 737 discloses N-hydroxymethyl derivatives of pyrazole.
These active compounds are still not entirely satisfactory as nitrification inhibitors as they have one or more of the follow-ing disadvantages:
20 - excessively low activity based on the application rate;
- excessively low stability against hydrolysis, whereby the duration of action in the soil and the stability on storage is reduced. This relates especially to pyrazole derivatives such as chloromethylpyrazole, N-glyoxylpyrazoles and N-hy-droxy-methylpyrazoles;
- excessively high toxicity or ecotoxicity;
30 - only accessible by complicated preparation processes;
- excessively low absorption of the compounds in the soil, whereby they are rapidly leached;
35 - excessively high volatility. This results in the compounds being easily given off from the soil into the atmosphere unless the compounds are introduced into the soil using tech-nically complicated processes (eg. by probe).
40 It is an object of the present invention to make available sub-stances which act as nitrification inhibitors and which do not have the disadvantages mentioned.
The object specifically applies to the discovery of known com-45 pounds having the desired properties, and the synthesis of novel compounds havinq properties of this type.
0050/45506 CA 02208~29 1997-06-16 We have now found that this object is achieved by the pyrazole derivatives of the formula I, which are suitable as nitrification inhibitors. The compounds of the formula Ia according to the invention R2 ~ R3 R7 R6 Ia Rl N'N " _~'N'N R5 are furthermore provided.
For use as nitrification inhibitors, those compounds are particu-larly suitable in which the substituents, Rl~ R2 and R3 are Cl- to 15 C5-alkyl or halogen. Suitable alkyl radicals are especially methyl and ethyl and suitable halogen radicals are Br, Cl and ~. The pyrazole derivatives of the formula I particularly preferably contain units which are derived from 4-halopyrazoles such as 4-bro ~pyLazole and 4-chloropyrazole, methylpyrazoles such as 20 4-methylpyrazole and 3-methylpyrazole, and 4-halo-3-methylpyra-zoles such as 4-bromo-3-methylpyrazole and 4-chloro-3-methylpyra-zole, and from 3,4-dimethylpyrazole.
Suitable R4 radicals are a) C6- to C20-, preferably C8- to C20-alkyl radicals, especially those having an even number of carbon atoms, in which 1 or 2 hydrogen atoms can possibly be replaced by halogen, or 30 b) Cl- to C20-alkyl radicals, in which 1 to 4, preferably 1 or 2, hydrogen atoms are replaced by a radical of the formula II
R6 ~ R7 II
R5J~N~N~
and 1 or 2 further hydrogen atoms of the Cl- to C20-alkyl radical are possibly replaced by halogen, preferably Cl or F.
Among the radicals R4 having the meaning indicated under (a) un-substituted branched and, especially, unbranched C8- to C20-alkyl radicals, in particular those having an even number of carbon atoms such as C8-, C10-, Cl2-, Cl4-, Cl6- or Cl8-radicals, are par-45 ticularly preferred.
' ' 0050/455~6 CA 02208~29 1997-06-16 .
Suitable R4 radicals having the meaning indicated under (b~ are in particular Cl- to C6-alkyl radicals in which 2, preferably one, hydrogen atom is substituted by a radical of the formula II, par-ticularly preferred compounds being those of the formula Ia.
AS R5, R6 and R7 substituents, those are preferred which are also preferred as Rl~ R2 or R3 substituents. Particularly simply accessible compounds are those in which each of Rl and R5, R2 and R6, and R3 and R7 in each case have the same meaning as those in 10 which each of Rl and R7, R2 and R6, and R3 and R5 in each case have the same meaning.
Among the compounds of the formula Ia, those are especially pre-ferred in which one or 2 of the radicals Rl, R2 or R3 and one or 2 15 of the radicals R5, R6 or R7 are halogen, preferably Cl or F, or methyl or ethyl, eg. the compound in which R3 and R5 are hydrogen, Rl and R7 are methyl and R2 and R6 are hydrogen, or in which R3 and R7 are hydrogen, Rl and R5 are methyl and R2 and R6 are hydrogen.
The pyrazole derivatives of the formula I can be used in free form or in the form of their salts, ie. as an acid addition or coordination compound. These salts are preferably derived from mineral acids such as hydrochloric acid, sulfuric acid, phospho-25 ric acid or nitric acid.
The compounds are accessible by generally known proce~ses, forexample as described in EP-A 0 474 037. In this process, a suit-able hydrazine derivative reacts with a suitable derivative of a 30 but-2-ene-1,4-diol, but-1-ene-3,4-diol or but-1-yn-3-ol to give the corresponding pyrazole derivatives.
The pyrazole derivatives of the formula I which carry a radical R4 having the meaning indicated under (a) can also be prepared in a 35 simple manner by reacting a pyrazole derivative of the formula III
RY ~ RZ III
~ RXJ~N~NH
where RX, RY and RZ radicals are the same radicals which are also suitable as Rl, R2, R3, R5, R6 or R7 radicals, with a C6- to 45 C20-haloalkane (haloalkane a), which carries at least one iodine, bromine or chlorine atom and possibly one or two further halogen atoms. In this reaction, an iodine, bromine or chlorine atom 0050/45506 CA 02208~29 1997-06-16 (substitutable halogen atom) is replaced by a unit derived from a pyrazole derivative of the formula III.
If it is desired that the substituent R4 in the pyrazole deriva-5 tive of the formula I should carry a number of substitutable halogen atoms as defined, a haloalkane (a) is employed which car-ries one substitutable halogen atom more than the desired number in the substituent R4. It is generally known in the technical world how to select the reaction conditions such that the sub-10 stitution of an iodine, bromine or chlorine atom in the halo-alkane (a) employed only takes place once. The desired result can be achieved, for example, by employing the haloalkanes (a) in a high molar excess based on the pyrazole derivatives of the for-mula III.
It furthermore has to be taken into account in the choice of a pyrazole derivative of the formula III that a radical Rx in a pyrazole derivative of the formula III corresponds to a radical Rl in a pyrazole derivative of the formula I, a radical RY to a radi-20 cal R2 and a radical R2 to a radical R3.
As the pyrazole derivatives of the formula III tautomerize underthe reaction conditions in which the reaction is customarily car-ried out RY~r=q~ RZ = RY~ RZ
RX ~ W' H RX ~ N~
it can generally not be avoided that, if the substituents Rx and RY are different, isomer mixtures of the pyrazole derivatives of the formula I are formed which also contain a structural isomer in which a radical RZ from the pyrazole derivative of the for-35 mula III corresponds to the radical Rl and a radical Rx corre-sponds to the radical R3.
The pyrazole derivatives of the formula I in which the radical R4 has the meaning indicated under (b) are obtained in a similar 40 manner to those in which the radical R4 has the meaning indicated under (a), from a pyrazole derivative of the formula III and a Cl-to C20-di-bis-tetrahaloalkane (haloalkane b), at least 2 of the halogen atoms being iodine, chlorine or bromine. Correspondingly, the pyrazole derivatives of the formula Ib can be obtained from a 45 pyrazole derivative of the formula III and dibromo-, diiodo- or dichloromethane.
0050/45506 CA 02208~29 1997-06-16 In the reaction of one of the dihalomethane derivatives indicated with a pyrazole derivative of the formula III in which the radi-cals Rx and RZ are different, because of the tautomerization of the pyrazole derivatives of the formula III, both pyrazole deri-5 vatives of the formula Ib in which each of Rl and R5, and R3 and R7, have the same meaning in each case and those in which each of Rl and R7, and R3 and R5, have the same meaning in each case are customarily obtained.
10 The number of iodine, chlorine or bromine atoms in the haloalkane (b), which can be substituted by a pyrazole derivative of the formula III, can be determined by the choice of the stoichiomet-ric ratios.
15 More conveniently, the reaction of the haloalkanes (a) or (b) with a pyrazole derivative of the formula III is performed at from 0 to 80~C under normal pressure in an inert solvent, eg. a polyglycol, acetonitrile or dimethyl sulfoxide, in the presence of, based on the starting material of the formula III, approxi-20 mately equimolar amounts of an organic or inorganic base, eg. ofan alkali metal hydroxide or of a tertiary amine, and catalytic amounts of a phase-transfer catalyst. Suitable phase-transfer catalysts are C2- to C30-alkylammonium hydroxides, eg. octyltri-ethylammonium hydroxide or polyether compounds, eg. of a crown 25 ether.
The use of the pyrazole derivatives of the formula I as nitrifi-cation inhibitors takes place by the generally customary pro-cesses.
They can thus be applied directly to the soil, for example in the form of a powder or in granulated form and also in the form of an aqueous suspension.
35 Advantageously, mixtures of the nitrification inhibitor with a mineral fertilizer, in particular a nitrogen fertilizer, are also employed. Such mixtures preferably contain from 500 to 10,000 ppm by weight of nitrification inhibitor, based on the mineral fer-tilizer. Those mixtures which are described in DE-A 4 128 828 40 have proven particularly suitable here. According to this pre-ferred procedure, granules of mineral fertilizers are impregnated with a nitrification inhibitor by spraying them with a solution or suspension of the nitrification inhibitor and drying again.
The sealing of the impregnated granules with a paraffin wax pro-45 posed in DE-A 4 128 828 is in general unnecessary on account of 0050/45506 CA 02208~29 1997-06-16 the substantially lower volatility of the nitrification inhibi-tors according to the invention.
Customarily, the nitrification inhibitors are applied to the soil 5 in amounts from 100 g/ha to 10 kg/ha.
The pyrazole derivatives of the formula I which can be prepared in a simple manner from cost-effective starting materials are es-pecially distinguished in their use as nitrification inhibitors 10 in that they effectively inhibit the nitrification of ammonium nitrogen in the soil for a long period of time.
In addition, these compounds are hardly toxic, have a low vapor pressure and are well absorbed in the soil. This has the con-15 sequence that they are neither released into the atmosphere to anoticeable extent by sublimation nor easily leached out by water.
As a result, on the one hand economic advantages result such as high economy as a result of the longer-lasting action of the ni-trification inhibitors and on tXe other hand ecological advant-20 ages such as reduction in the pollution of air and surface watersand ground water.
A. Preparation examples 25 Example 1 (No. 319 784) 6.8 g of pyrazole (0.1 mol), 5.6 g of KOH, 50 mg of octyltri-ethylammonium hydroxide and 26 g of hexadecyl bromide were dis-solved in 100 ml of acetonitrile and stirred overnight at room 30 temperature. The solution was evaporated, the residue was taken up in water and the solution was extracted several times with ether. After drying over Na2SO4 and removing the ether, 25.6 g (88% of theory) of N-hexadecylpyrazole were obtained from the ethereal solution in >99% purity (m.p. 39~C).
Example 2 (No. 319 785) 8.2 g of 3-methylpyrazole were treated as in Example 1. After removing the ether, a colorless oil remained which crystallized 40 on standing in the refrigerator. Yield 27.8 g of N-hexadecyl-3-methylpyrazole (91% of theory).
Example 3 (No. 320 564) 45 10.3 g of 4-chloropyrazole were treated as in Example 1. Yield 29.8 g (88.5% of theory) of N-hexadecyl-3-methyl-4-chloropyrazole of m.p. 15~C.
- 0050/45506 CA 02208~29 1997-06-16 . g Example 4 (No. 319 781) 11.6 g of 3-methyl-4-chloropyrazole were treated as in Example 1.
Yield 29.8 g (88.5% of theory) of N-hexadecyl-3-methyl-4-chloro-5 pyrazole of m.p. 15~C.
Example 5 (No. 300 340) 8.2 g (0.1 mol) of 3-methylpyrazole, 5.6 g of KOH and 50 mg of 10 octyltriethylammonium hydroxide were initially introduced into 50 ml of dimethyl sulfoxide. A solution of 8.7 g (95 mmol) of methylene bromide in 50 ml of dimethyl sulfoxide was added drop-wise at room temperature in the course of 3 h. After about 12 h, the reaction mixture was evaporated to dryness under reduced 15 pressure. The residue was taken up in water and the solution was extracted several times with ether. After drying the ethereal phase over Na2SO4, the ether and solvent residues were removed.
Yield of N,N~-methylenebis-3-methylpyrazole: 7 g (78% of theory) of colorless oil.
Example 6 (No. 320 565) 11.6 g of 4-chloro-3-methylpyrazole were processed as in Example 1. 10.5 g (86% of theory) of N,N'-methylene-25 bis-3-methyl-4-chloropyrazole were obtained as a colorless powder of m.p. 97~C.
B. Application tests 30 Volatility at room temperature Examples Vapor pressure lmbar]
Example 2 7.9 x 10-7 35 Example 4 8.2 x 10-8 Comparison examples Vapor pressure [mbar]
3-Methylpyrazole 7.0 x 10-2 40 4-Chloro-3-methylpyrazole 2.8 x 10-3 The measurement of the vapor pressure was carried out at 20 C
according to OECD Guideline 79/831JEEC V, updated version of February 1990, part A4.
;~ N
Rl'' N' ~ R4 or their salts, where the radicals Rl to R4 have the following meanings:
- Rl, R2 and R3 are Cl- to C20-alkyl, C3- to c8-cycloalkyl, C5-to C20-aryl or C6- to C20-alkylaryl, it being possible for these 4 radicals to be monosubstituted or disubstituted by halogen and/or hydroxyl; and halogen, nitro or hydrogen, and - R4 iS either a) C6- to C20-alkyl, in which 1 or 2 hydrogen atoms may be replaced by halogen, or b) Cl- to C20-alkyl, in which - 1 to 4 hydrogen atoms are replaced by a radical having the formula II
~ II
R5~N~ ~
where R5, R6 and R7 are Cl- to C20-alkyl, C3- to C8-cycloalkyl, C5-to C20-aryl or C6- to C20-alkylaryl, it being possible for these 4 radicals to be monosubstituted or disubstituted by halogen and/or hydroxyl; and halogen, nitro or hydrogen, and - 1 to 2 hydrogen atoms may be replaced by halogen, as nitrification inhibitors.
. 0050/45506 CA 02208~29 1997-06-16 ~. .
The invention furthermore relates to novel pyrazole derivatives which are suitable for this intended use, and processes for their preparation.
5 In order to make available to plants the nitrogen needed by them, they are fertilized, as is known, with ammonium compounds. Ammo-nium compounds, however, are microbially converted to nitrate in the soil in a relatively short time (nitrification).
10 Because nitrate is leached from the soil more easily than ammo-nium and the leached portion is no longer available for plant nutrition, however, rapid nitrification is undesirable. In order that the fertilizer is utilized better, it was therefore proposed to add nitrification inhibitors to the soil.
EPA-A 474 037 discloses 3-methylpyrazole derivatives in which one nitrogen atom of the pyrazole ring carries a methyl, cycloalkyl, aryl or aralkyl radical. It is proposed to use these compounds as intermediates for the preparation of pharmaceutical products or 20 crop protection agents.
US-A 3 635 690 discloses the employment of various pyrazole derivatives for the inhibition of nitrification. In the pyrazole derivatives proposed, the nitrogen atoms in the pyrazole ring do 25 not carry any substituents or one of the nitrogen atoms carries a saturated or unsaturated Cl- to C3-hydrocarbon radical. One or more carbon atoms in the pyrazole ring can be substituted by hydrocarbon radicals which may carry halogens as substituents.
Examples of these are 3-methylpyrazoles such as 4-chloro-30 3-methylpyrazole.
US-A-4 969 946 also describes the use of pyrazole derivatives as nitrification inhibitors. In these derivatives, the nitrogen atoms in the pyrazole ring are unsubstituted, and several of the 35 ring carbon atoms are substituted by halogen or methyl.
DE A 3 704 359 relates to compositions which inhibit nitrifica-tion. As active compound, they contain pyrazole derivatives which, on one nitrogen atom of the pyrazole ring, carry a radical 40 of the formula C C= O
OH R' 0050/45506 CA 02208~29 1997-06-16 ., .
R' being a substituted or unsubstituted organic radical or a hydroxy radical.
Further nitrification inhibitors are disclosed in EP-A 0 160 804.
5 They are pyrazole derivatives in which a nitrogen atom in the pyrazole ring carries a substituted oxycarbonyl, sulfinyl or sul-fonyl radical.
DE-A 4 018 395 mentions derivatives of 1-cyano-3-methylpyrazole 10 and its acid addition products or coordination compounds as nit-rification inhibitors.
SU-A 1 470 737 discloses N-hydroxymethyl derivatives of pyrazole.
These active compounds are still not entirely satisfactory as nitrification inhibitors as they have one or more of the follow-ing disadvantages:
20 - excessively low activity based on the application rate;
- excessively low stability against hydrolysis, whereby the duration of action in the soil and the stability on storage is reduced. This relates especially to pyrazole derivatives such as chloromethylpyrazole, N-glyoxylpyrazoles and N-hy-droxy-methylpyrazoles;
- excessively high toxicity or ecotoxicity;
30 - only accessible by complicated preparation processes;
- excessively low absorption of the compounds in the soil, whereby they are rapidly leached;
35 - excessively high volatility. This results in the compounds being easily given off from the soil into the atmosphere unless the compounds are introduced into the soil using tech-nically complicated processes (eg. by probe).
40 It is an object of the present invention to make available sub-stances which act as nitrification inhibitors and which do not have the disadvantages mentioned.
The object specifically applies to the discovery of known com-45 pounds having the desired properties, and the synthesis of novel compounds havinq properties of this type.
0050/45506 CA 02208~29 1997-06-16 We have now found that this object is achieved by the pyrazole derivatives of the formula I, which are suitable as nitrification inhibitors. The compounds of the formula Ia according to the invention R2 ~ R3 R7 R6 Ia Rl N'N " _~'N'N R5 are furthermore provided.
For use as nitrification inhibitors, those compounds are particu-larly suitable in which the substituents, Rl~ R2 and R3 are Cl- to 15 C5-alkyl or halogen. Suitable alkyl radicals are especially methyl and ethyl and suitable halogen radicals are Br, Cl and ~. The pyrazole derivatives of the formula I particularly preferably contain units which are derived from 4-halopyrazoles such as 4-bro ~pyLazole and 4-chloropyrazole, methylpyrazoles such as 20 4-methylpyrazole and 3-methylpyrazole, and 4-halo-3-methylpyra-zoles such as 4-bromo-3-methylpyrazole and 4-chloro-3-methylpyra-zole, and from 3,4-dimethylpyrazole.
Suitable R4 radicals are a) C6- to C20-, preferably C8- to C20-alkyl radicals, especially those having an even number of carbon atoms, in which 1 or 2 hydrogen atoms can possibly be replaced by halogen, or 30 b) Cl- to C20-alkyl radicals, in which 1 to 4, preferably 1 or 2, hydrogen atoms are replaced by a radical of the formula II
R6 ~ R7 II
R5J~N~N~
and 1 or 2 further hydrogen atoms of the Cl- to C20-alkyl radical are possibly replaced by halogen, preferably Cl or F.
Among the radicals R4 having the meaning indicated under (a) un-substituted branched and, especially, unbranched C8- to C20-alkyl radicals, in particular those having an even number of carbon atoms such as C8-, C10-, Cl2-, Cl4-, Cl6- or Cl8-radicals, are par-45 ticularly preferred.
' ' 0050/455~6 CA 02208~29 1997-06-16 .
Suitable R4 radicals having the meaning indicated under (b~ are in particular Cl- to C6-alkyl radicals in which 2, preferably one, hydrogen atom is substituted by a radical of the formula II, par-ticularly preferred compounds being those of the formula Ia.
AS R5, R6 and R7 substituents, those are preferred which are also preferred as Rl~ R2 or R3 substituents. Particularly simply accessible compounds are those in which each of Rl and R5, R2 and R6, and R3 and R7 in each case have the same meaning as those in 10 which each of Rl and R7, R2 and R6, and R3 and R5 in each case have the same meaning.
Among the compounds of the formula Ia, those are especially pre-ferred in which one or 2 of the radicals Rl, R2 or R3 and one or 2 15 of the radicals R5, R6 or R7 are halogen, preferably Cl or F, or methyl or ethyl, eg. the compound in which R3 and R5 are hydrogen, Rl and R7 are methyl and R2 and R6 are hydrogen, or in which R3 and R7 are hydrogen, Rl and R5 are methyl and R2 and R6 are hydrogen.
The pyrazole derivatives of the formula I can be used in free form or in the form of their salts, ie. as an acid addition or coordination compound. These salts are preferably derived from mineral acids such as hydrochloric acid, sulfuric acid, phospho-25 ric acid or nitric acid.
The compounds are accessible by generally known proce~ses, forexample as described in EP-A 0 474 037. In this process, a suit-able hydrazine derivative reacts with a suitable derivative of a 30 but-2-ene-1,4-diol, but-1-ene-3,4-diol or but-1-yn-3-ol to give the corresponding pyrazole derivatives.
The pyrazole derivatives of the formula I which carry a radical R4 having the meaning indicated under (a) can also be prepared in a 35 simple manner by reacting a pyrazole derivative of the formula III
RY ~ RZ III
~ RXJ~N~NH
where RX, RY and RZ radicals are the same radicals which are also suitable as Rl, R2, R3, R5, R6 or R7 radicals, with a C6- to 45 C20-haloalkane (haloalkane a), which carries at least one iodine, bromine or chlorine atom and possibly one or two further halogen atoms. In this reaction, an iodine, bromine or chlorine atom 0050/45506 CA 02208~29 1997-06-16 (substitutable halogen atom) is replaced by a unit derived from a pyrazole derivative of the formula III.
If it is desired that the substituent R4 in the pyrazole deriva-5 tive of the formula I should carry a number of substitutable halogen atoms as defined, a haloalkane (a) is employed which car-ries one substitutable halogen atom more than the desired number in the substituent R4. It is generally known in the technical world how to select the reaction conditions such that the sub-10 stitution of an iodine, bromine or chlorine atom in the halo-alkane (a) employed only takes place once. The desired result can be achieved, for example, by employing the haloalkanes (a) in a high molar excess based on the pyrazole derivatives of the for-mula III.
It furthermore has to be taken into account in the choice of a pyrazole derivative of the formula III that a radical Rx in a pyrazole derivative of the formula III corresponds to a radical Rl in a pyrazole derivative of the formula I, a radical RY to a radi-20 cal R2 and a radical R2 to a radical R3.
As the pyrazole derivatives of the formula III tautomerize underthe reaction conditions in which the reaction is customarily car-ried out RY~r=q~ RZ = RY~ RZ
RX ~ W' H RX ~ N~
it can generally not be avoided that, if the substituents Rx and RY are different, isomer mixtures of the pyrazole derivatives of the formula I are formed which also contain a structural isomer in which a radical RZ from the pyrazole derivative of the for-35 mula III corresponds to the radical Rl and a radical Rx corre-sponds to the radical R3.
The pyrazole derivatives of the formula I in which the radical R4 has the meaning indicated under (b) are obtained in a similar 40 manner to those in which the radical R4 has the meaning indicated under (a), from a pyrazole derivative of the formula III and a Cl-to C20-di-bis-tetrahaloalkane (haloalkane b), at least 2 of the halogen atoms being iodine, chlorine or bromine. Correspondingly, the pyrazole derivatives of the formula Ib can be obtained from a 45 pyrazole derivative of the formula III and dibromo-, diiodo- or dichloromethane.
0050/45506 CA 02208~29 1997-06-16 In the reaction of one of the dihalomethane derivatives indicated with a pyrazole derivative of the formula III in which the radi-cals Rx and RZ are different, because of the tautomerization of the pyrazole derivatives of the formula III, both pyrazole deri-5 vatives of the formula Ib in which each of Rl and R5, and R3 and R7, have the same meaning in each case and those in which each of Rl and R7, and R3 and R5, have the same meaning in each case are customarily obtained.
10 The number of iodine, chlorine or bromine atoms in the haloalkane (b), which can be substituted by a pyrazole derivative of the formula III, can be determined by the choice of the stoichiomet-ric ratios.
15 More conveniently, the reaction of the haloalkanes (a) or (b) with a pyrazole derivative of the formula III is performed at from 0 to 80~C under normal pressure in an inert solvent, eg. a polyglycol, acetonitrile or dimethyl sulfoxide, in the presence of, based on the starting material of the formula III, approxi-20 mately equimolar amounts of an organic or inorganic base, eg. ofan alkali metal hydroxide or of a tertiary amine, and catalytic amounts of a phase-transfer catalyst. Suitable phase-transfer catalysts are C2- to C30-alkylammonium hydroxides, eg. octyltri-ethylammonium hydroxide or polyether compounds, eg. of a crown 25 ether.
The use of the pyrazole derivatives of the formula I as nitrifi-cation inhibitors takes place by the generally customary pro-cesses.
They can thus be applied directly to the soil, for example in the form of a powder or in granulated form and also in the form of an aqueous suspension.
35 Advantageously, mixtures of the nitrification inhibitor with a mineral fertilizer, in particular a nitrogen fertilizer, are also employed. Such mixtures preferably contain from 500 to 10,000 ppm by weight of nitrification inhibitor, based on the mineral fer-tilizer. Those mixtures which are described in DE-A 4 128 828 40 have proven particularly suitable here. According to this pre-ferred procedure, granules of mineral fertilizers are impregnated with a nitrification inhibitor by spraying them with a solution or suspension of the nitrification inhibitor and drying again.
The sealing of the impregnated granules with a paraffin wax pro-45 posed in DE-A 4 128 828 is in general unnecessary on account of 0050/45506 CA 02208~29 1997-06-16 the substantially lower volatility of the nitrification inhibi-tors according to the invention.
Customarily, the nitrification inhibitors are applied to the soil 5 in amounts from 100 g/ha to 10 kg/ha.
The pyrazole derivatives of the formula I which can be prepared in a simple manner from cost-effective starting materials are es-pecially distinguished in their use as nitrification inhibitors 10 in that they effectively inhibit the nitrification of ammonium nitrogen in the soil for a long period of time.
In addition, these compounds are hardly toxic, have a low vapor pressure and are well absorbed in the soil. This has the con-15 sequence that they are neither released into the atmosphere to anoticeable extent by sublimation nor easily leached out by water.
As a result, on the one hand economic advantages result such as high economy as a result of the longer-lasting action of the ni-trification inhibitors and on tXe other hand ecological advant-20 ages such as reduction in the pollution of air and surface watersand ground water.
A. Preparation examples 25 Example 1 (No. 319 784) 6.8 g of pyrazole (0.1 mol), 5.6 g of KOH, 50 mg of octyltri-ethylammonium hydroxide and 26 g of hexadecyl bromide were dis-solved in 100 ml of acetonitrile and stirred overnight at room 30 temperature. The solution was evaporated, the residue was taken up in water and the solution was extracted several times with ether. After drying over Na2SO4 and removing the ether, 25.6 g (88% of theory) of N-hexadecylpyrazole were obtained from the ethereal solution in >99% purity (m.p. 39~C).
Example 2 (No. 319 785) 8.2 g of 3-methylpyrazole were treated as in Example 1. After removing the ether, a colorless oil remained which crystallized 40 on standing in the refrigerator. Yield 27.8 g of N-hexadecyl-3-methylpyrazole (91% of theory).
Example 3 (No. 320 564) 45 10.3 g of 4-chloropyrazole were treated as in Example 1. Yield 29.8 g (88.5% of theory) of N-hexadecyl-3-methyl-4-chloropyrazole of m.p. 15~C.
- 0050/45506 CA 02208~29 1997-06-16 . g Example 4 (No. 319 781) 11.6 g of 3-methyl-4-chloropyrazole were treated as in Example 1.
Yield 29.8 g (88.5% of theory) of N-hexadecyl-3-methyl-4-chloro-5 pyrazole of m.p. 15~C.
Example 5 (No. 300 340) 8.2 g (0.1 mol) of 3-methylpyrazole, 5.6 g of KOH and 50 mg of 10 octyltriethylammonium hydroxide were initially introduced into 50 ml of dimethyl sulfoxide. A solution of 8.7 g (95 mmol) of methylene bromide in 50 ml of dimethyl sulfoxide was added drop-wise at room temperature in the course of 3 h. After about 12 h, the reaction mixture was evaporated to dryness under reduced 15 pressure. The residue was taken up in water and the solution was extracted several times with ether. After drying the ethereal phase over Na2SO4, the ether and solvent residues were removed.
Yield of N,N~-methylenebis-3-methylpyrazole: 7 g (78% of theory) of colorless oil.
Example 6 (No. 320 565) 11.6 g of 4-chloro-3-methylpyrazole were processed as in Example 1. 10.5 g (86% of theory) of N,N'-methylene-25 bis-3-methyl-4-chloropyrazole were obtained as a colorless powder of m.p. 97~C.
B. Application tests 30 Volatility at room temperature Examples Vapor pressure lmbar]
Example 2 7.9 x 10-7 35 Example 4 8.2 x 10-8 Comparison examples Vapor pressure [mbar]
3-Methylpyrazole 7.0 x 10-2 40 4-Chloro-3-methylpyrazole 2.8 x 10-3 The measurement of the vapor pressure was carried out at 20 C
according to OECD Guideline 79/831JEEC V, updated version of February 1990, part A4.
Claims (14)
1. The use of pyrazole derivatives of the formula I
I
or their salts, where the radicals R1 to R4 have the following meanings:
- R1, R2 and R3 are C1- to C20-alkyl, C3- to C8-cycloalkyl, C5- to C20-aryl or C6- to C20-alkylaryl, it being possible for these 4 radicals to be monosubstituted or disubstituted by halogen and/or hydroxyl; and halogen, nitro or hydrogen, and - R4 is either a) C6- to C20-alkyl, in which 1 or 2 hydrogen atoms may be replaced by halogen, or b) C1- to C20-alkyl, in which - 1 to 4 hydrogen atoms are replaced by a radical having the formula II
I I
where R5, R6 and R7 are C1- to C20-alkyl, C3- to C8-cycloalkyl, C5- to C20-aryl or C6- to C20-alkylaryl, it being possible for these 4 radicals to be monosubstituted or disubstituted by halogen and/or hydroxyl; and halogen, nitro or hydrogen, and - 1 to 2 hydrogen atoms may be replaced by halogen, as nitrification inhibitors.
I
or their salts, where the radicals R1 to R4 have the following meanings:
- R1, R2 and R3 are C1- to C20-alkyl, C3- to C8-cycloalkyl, C5- to C20-aryl or C6- to C20-alkylaryl, it being possible for these 4 radicals to be monosubstituted or disubstituted by halogen and/or hydroxyl; and halogen, nitro or hydrogen, and - R4 is either a) C6- to C20-alkyl, in which 1 or 2 hydrogen atoms may be replaced by halogen, or b) C1- to C20-alkyl, in which - 1 to 4 hydrogen atoms are replaced by a radical having the formula II
I I
where R5, R6 and R7 are C1- to C20-alkyl, C3- to C8-cycloalkyl, C5- to C20-aryl or C6- to C20-alkylaryl, it being possible for these 4 radicals to be monosubstituted or disubstituted by halogen and/or hydroxyl; and halogen, nitro or hydrogen, and - 1 to 2 hydrogen atoms may be replaced by halogen, as nitrification inhibitors.
2. The use of pyrazole derivatives or their salts as claimed in claim 1, the radicals R1, R2 and R3 being C1- to C5-alkyl or halogen.
3. The use of pyrazole derivatives or their salts as claimed in claim 2, the radicals R1, R2 and R3 being methyl, ethyl, chlorine, bromine or fluorine.
4. The use of pyrazole derivatives or their salts as claimed in claims 1 to 3, the radicals R5, R6 and R7 being C1- to C5-alkyl or halogen.
5. The use of pyrazole derivatives or their salts as claimed in claims 1 to 4, the radicals R5, R6 and R7 being methyl, ethyl, bromine, chlorine or fluorine.
6. The use of pyrazole derivatives or their salts as claimed in claims 1 to 3, the radical R4 having the meaning indicated under (a) and being unsubstituted C8- to C20-alkyl.
7. A pyrazole derivative or its salts as claimed in claim 6, the number of carbon atoms in R4 being even.
8. A pyrazole derivative of the formula Ia Ia or its salts, the radicals R1, R2, R3, R5, R6 and R7 having the meanings indicated in claim 1, N,N'-methylene-bis-3-methylpyrazole being excluded.
9. A pyrazole derivative or its salts as claimed in claim 8, one of the radicals R1, R2 or R3 and one of the radicals R5, R6 or R7 being halogen.
10. A pyrazole derivative or its salts as claimed in claim 9, the radicals R3 and R5 being hydrogen, the radicals R1 and R5 being methyl or ethyl and the radicals R2 and R6 being chlorine or fluorine.
11. A process for preparing pyrazole derivatives or their salts as claimed in claims 8 to 10, which comprises reacting dibromo-, diiodo- or dichloromethane with an excess of a pyrazole derivative of the formula III
III
where RX, RY and RZ are C1- to C20-alkyl, C3- to C8-cycloalkyl, C5- to C20-aryl or C6- to C20-alkylaryl, it being possible for these 4 radicals to be monosubstituted or disubstituted by halogen and/or hydroxyl; and halogen, nitro or hydrogen.
III
where RX, RY and RZ are C1- to C20-alkyl, C3- to C8-cycloalkyl, C5- to C20-aryl or C6- to C20-alkylaryl, it being possible for these 4 radicals to be monosubstituted or disubstituted by halogen and/or hydroxyl; and halogen, nitro or hydrogen.
12. A process as claimed in claim 11, wherein the reaction is carried out in the presence of catalytic amounts of a phase-transfer catalyst.
13. A fertilizer mixture containing a mineral fertilizer and from 500 to 10,000 ppm by weight, based on the mineral fertilizer, of a pyrazole derivative or of one of its salts as claimed in claims 1 to 10.
14. A fertilizer mixture as claimed in claim 13, obtainable by spraying a mineral fertilizer present in granulated form with a solution or a suspension of a pyrazole derivative or of one of its salts as claimed in claims 1 to 10, and drying.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4446194A DE4446194A1 (en) | 1994-12-23 | 1994-12-23 | Use of pyrazole derivatives with hydrophobic residues as nitrification inhibitors |
| DEP4446194.1 | 1994-12-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2208529A1 true CA2208529A1 (en) | 1996-07-04 |
Family
ID=6536849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002208529A Abandoned CA2208529A1 (en) | 1994-12-23 | 1995-12-14 | Use of pyrazole derivatives containing hydrophobic radicals as nitrification inhibitors |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0799168A1 (en) |
| JP (1) | JPH10511336A (en) |
| AU (1) | AU4345096A (en) |
| CA (1) | CA2208529A1 (en) |
| DE (1) | DE4446194A1 (en) |
| WO (1) | WO1996020146A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6139596A (en) * | 1996-08-06 | 2000-10-31 | Basf Aktiengesellschaft | Nitrification inhibitors and the use of polyacids to treat mineral fertilizers containing a nitrification inhibitor |
| US6451734B1 (en) | 1996-11-04 | 2002-09-17 | Basf Aktiengesellschaft | Substituted 3-benzylpyrazoles and their use as herbicides |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10343277A1 (en) | 2003-09-18 | 2005-04-21 | Piesteritz Stickstoff | N- (1H-Azolyl-methyl) amides, process for their preparation and their use as nitrification inhibitors |
| DE102006015705B4 (en) | 2006-04-04 | 2018-07-19 | Skw Stickstoffwerke Piesteritz Gmbh | 1,2-bis (azol-1-yl) ethane-1,2-diol derivatives, processes for their preparation and their use as nitrification inhibitors |
| DE102008020785B4 (en) | 2008-04-25 | 2021-11-04 | Skw Stickstoffwerke Piesteritz Gmbh | Use of simple derivatives of 5-amino-1,2,4-thiadiazole to inhibit or control nitrification |
| DE102011120098B4 (en) | 2011-12-02 | 2021-02-11 | Skw Stickstoffwerke Piesteritz Gmbh | N- (1H-pyrazolyl-methyl) formamides, process for their preparation and their use as nitrification inhibitors |
| EP3124473A1 (en) | 2015-07-31 | 2017-02-01 | Ludwig-Maximilians-Universität München | Bis(3,4,5-trinitropyrazolyl)methane and bis(3,5-dinitro-4-aminopyrazolyl)methane as explosives |
| DE102017201608A1 (en) | 2017-02-01 | 2018-08-02 | Eurochem Agro Gmbh | 3,4-dimethylpyrazole-containing mixture and its use |
| CN111683938B (en) * | 2018-02-28 | 2024-01-23 | 巴斯夫欧洲公司 | Use of N-functional alkoxypyrazole compounds as nitration inhibitors |
Family Cites Families (4)
| 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 |
| US4522642A (en) * | 1984-06-25 | 1985-06-11 | The Dow Chemical Company | Soil treating method and composition for conserving nitrogen in soil |
| US4969946A (en) * | 1986-01-29 | 1990-11-13 | The Dow Chemical Company | Soil treating method and composition for conserving nitrogen in naturally alkaline soil |
| DE3704359A1 (en) * | 1987-02-12 | 1988-08-25 | Basf Ag | AZOLHALBAMINAL DERIVATIVES AND THEIR USE AS NITRIFICATION INHIBITORS |
-
1994
- 1994-12-23 DE DE4446194A patent/DE4446194A1/en not_active Withdrawn
-
1995
- 1995-12-14 WO PCT/EP1995/004953 patent/WO1996020146A1/en not_active Ceased
- 1995-12-14 EP EP95942160A patent/EP0799168A1/en not_active Withdrawn
- 1995-12-14 CA CA002208529A patent/CA2208529A1/en not_active Abandoned
- 1995-12-14 AU AU43450/96A patent/AU4345096A/en not_active Abandoned
- 1995-12-14 JP JP8520169A patent/JPH10511336A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6139596A (en) * | 1996-08-06 | 2000-10-31 | Basf Aktiengesellschaft | Nitrification inhibitors and the use of polyacids to treat mineral fertilizers containing a nitrification inhibitor |
| US6802882B2 (en) | 1996-08-06 | 2004-10-12 | Basf Aktiengesellschaft | Nitrification inhibitors, and the use of polyacids which contain a nitrification inhibitor for the treatment of inorganic fertilizers |
| US6451734B1 (en) | 1996-11-04 | 2002-09-17 | Basf Aktiengesellschaft | Substituted 3-benzylpyrazoles and their use as herbicides |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4446194A1 (en) | 1996-06-27 |
| EP0799168A1 (en) | 1997-10-08 |
| AU4345096A (en) | 1996-07-19 |
| WO1996020146A1 (en) | 1996-07-04 |
| JPH10511336A (en) | 1998-11-04 |
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