WO1995015688A1 - Utilisation de derives d'azolyles comme inhibiteurs de la cristallisation - Google Patents

Utilisation de derives d'azolyles comme inhibiteurs de la cristallisation Download PDF

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Publication number
WO1995015688A1
WO1995015688A1 PCT/EP1994/003929 EP9403929W WO9515688A1 WO 1995015688 A1 WO1995015688 A1 WO 1995015688A1 EP 9403929 W EP9403929 W EP 9403929W WO 9515688 A1 WO9515688 A1 WO 9515688A1
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WIPO (PCT)
Prior art keywords
carbon atoms
formula
stands
phenyl
alkyl
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Application number
PCT/EP1994/003929
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German (de)
English (en)
Inventor
Wolfgang Wirth
Klaus Wangermann
Artur Botta
Original Assignee
Bayer Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU12408/95A priority Critical patent/AU1240895A/en
Publication of WO1995015688A1 publication Critical patent/WO1995015688A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur

Definitions

  • the present invention relates to the new use of certain azolyl derivatives to prevent crystallization when applying aqueous spray liquors based on certain fungicidal active ingredients.
  • filters and nozzles are present in spraying devices which are usually used for the application of aqueous formulations of plant treatment agents.
  • suction filters between the suction part and tank pump and also pressure filters, which are arranged after the pump in the pressure area.
  • nozzle filters can be included, which are located directly in front of the spray nozzles. All of these filters, as well as the nozzles, can more or less easily become blocked by crystallizing active ingredient when applying aqueous spray liquors based on solid active ingredients.
  • N-alkyl lactams and alkyl carboxylic acid dimethylamides can be used as crystallization inhibitors in the preparation and application of spray liquors of the active compounds mentioned (cf. EP 0 391 168, EP 0 453 915 and EP 0 453) 899).
  • N-octylpyrrolidone and / or a mixture which consists on average of 5% of hexanoic acid dimethylamide, 50% octanoic acid dimethylamide, 40% decanoic acid dimethylamide and 5% dodecanoic acid dimethylamide can be used when aqueous spray liquors containing l- (4-chlorophenyl) -4,4-dimethyl-3- (l, 2,4-triazol-l-yl-methyl) -pentan-3-ol are used as active ingredient, crystallize out to prevent this active ingredient in the sprayers. If such spray liquors are applied for a longer period of time, the effectiveness of the crystallization inhibitors mentioned is not always satisfactory.
  • R 1 represents alkyl with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, cycloalkyl with 5 to 7 carbon atoms, phenyl or aralkyl with 6 to 10 carbon atoms in the aryl part and 1 to 4 carbon atoms in the alkyl part,
  • R 2 represents hydrogen or alkyl having 1 to 4 carbon atoms
  • R 3 represents hydrogen or alkyl having 1 to 4 carbon atoms
  • X represents a nitrogen atom or a CR 4 group
  • R 4 represents hydrogen or alkyl having 1 to 4 carbon atoms or
  • R 3 and R 4 together with the part of the heterocycle to which they are attached represent a fused benzene ring
  • R 5 stands for -CHr— CH, -% —C ⁇
  • R 6 stands for tert-butyl and R 7 stands for hydroxy
  • R 5 represents 4-fluorophenyl
  • R 6 represents 2-fluorophenyl
  • R 7 represents hydroxy
  • R 5 stands for 2,4-dichlorophenyl
  • R 6 stands for n-butyl
  • R 7 stands for hydroxy
  • R 5 stands for
  • R 6 represents phenyl and R 7 represents cyano
  • R 5 represents 4-chlorophenyl
  • R 6 stands for and
  • R represents hydroxy
  • Y is -CH (OH)
  • R 8 represents chlorine or phenyl
  • R 8 represents chlorine, and or
  • R 9 represents hydrogen or chlorine
  • azolyl derivatives of the formula (I) in aqueous formulations based on fungicidally active azole derivatives of the formulas (U) to (VI) has a number of advantages.
  • the azolyl derivatives of the formula (I) are substances which are easy to handle and are also available in larger quantities. Furthermore, the use of the substances of the formula (I) prevents the spraying of aqueous formulations which contain the active compounds of the formulas (II) to (VI) from clogging both the filters and the nozzles of the spraying devices. It is also advantageous that azolyl derivatives of the formula (I) have no undesirable side effects in crop protection.
  • Formula (I) provides a general definition of the azolyl derivatives which can be used according to the invention.
  • R 1 preferably represents straight-chain or branched alkyl having 1 to 10
  • R 2 preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl or tert-butyl.
  • R 3 preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl or tert-butyl.
  • X also preferably represents a nitrogen atom or a CR 4 group.
  • R 4 preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl or tert-butyl.
  • R 3 and R 4 also preferably together with the part of the heterocycle to which they are attached represent a fused benzene ring.
  • R 1 particularly preferably represents straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched alkenyl having 2 to 8 carbon atoms, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, benzyl, phen-1-ethyl, phen-2-ethyl.
  • R 2 particularly preferably represents hydrogen, methyl or ethyl.
  • R particularly preferably represents hydrogen, methyl or ethyl.
  • X also particularly preferably represents a nitrogen atom or a CR 4 group.
  • R 4 particularly preferably represents hydrogen, methyl or ethyl.
  • R 3 and R 4 also particularly preferably together with the part of the heterocycle to which they are attached represent a fused benzene ring.
  • azolyl derivatives which can be used according to the invention are the substances listed in Tables 1 and 2 below.
  • azolyl derivatives of the formula (I) are known or can be prepared in a simple manner by known methods (cf. Ullmann "Encyclopedia of Industrial Chemistry", 4th edition, Verlag Chemie, Weinheim, Volume 13, pages 173-175 and Adv Heterocycl. Chem. 40: 130-197 (1987)).
  • azole derivatives contained in the aqueous spray liquors which can be used according to the invention are defined by the formulas (E) to (VI). Single or also several or following azole derivatives can be contained.
  • the active compounds of the formulas (II) to (VI) and their use for controlling phytopathogenic fungi are known (cf. EP-OS 0 040 345, US Pat. No. 4,551,469, EP-PS 0 015 756, EP-OS 0 068 813 , DE-OS 3 406 993, DE-PS 2 324 010, DE-PS 2 201 063, DE-OS 2 838 847, DE-OS 3 010 560, DE-OS 2 821 971 and EP-OS 0 196 038) .
  • the active compounds of the formulas (II) to (VI) can be used in customary formulations. The application is preferably carried out in the form of aqueous spray liquors.
  • the spray liquors which can be used according to the invention can also contain one or more further active compounds.
  • Compounds with fungicidal properties are preferred. The following may be mentioned as examples of such additional active substances:
  • Zinc-ethylene-bis-dithiocarbamate / manganese-ethylene-bis-dithiocarbamate (Mancozeb), zinc-propylene-l, 2-bis-dithiocarbamate (Propineb), l- [3- (4- (l, l-dimethylethyl) - phenyl) -2-methylpropyl] piperidine (fenpropidine),
  • Suitable additives which can be present in the spray liquors which can be used according to the invention are surface-active substances, organic diluents, acids, cold stabilizers and adhesives.
  • Nonionic, anionic, cationic and zwitterionic emulsifiers are suitable as surface-active substances. These substances include reaction products of fatty acids, fatty acid esters, fatty alcohols, fatty amines, alkylphenols or alkylarylphenols with ethylene oxide and / or propylene oxide, and their sulfuric acid esters, phosphoric acid monoesters and phosphoric acid di-esters, as well as reaction products of ethylene oxide with propylene oxide , furthermore alkyl sulfonates, alkyl sulfates, aryl sulfates, tetra-alkyl ammonium halides, trialkyl aryl ammonium halides and alkyl amine sulfonates.
  • the emulsifiers can be used individually or in a mixture. Reaction products of castor oil with ethylene oxide in a molar ratio of 1:20 to 1:60, reaction products of C 6 -C 20 fatty alcohols with ethylene oxide in a molar ratio of 1: 5 to 1:50, reaction products of fatty amines with ethylene oxide in a molar ratio of 1: 2 to 1:20, reaction products of 1 mol of phenol with 2 to 3 mol of styrene and 10 to 50 mol of ethylene oxide, reaction products of 1 mol of phenol with 2 to 3 mol of vinyl toluene and 10 to 50 mol of ethylene oxide, reaction products of C 8 -C 12 - Alkylphenols with ethylene oxide in a molar ratio of 1: 5 to 1:30, alkyl glycosides, C 8 -C 16 alkylbenzene sulfonic acid salts, such as calcium, monoethanolammonium, diethanolammonium and triethanolammoni
  • the emulsifiers from the group of alkylaryl polyglycol ethers used in practice are often mixtures of several compounds.
  • these are mixtures of substances which differ in the degree of substitution on the phenyl ring connected to the oxyethylene unit and the number of oxyethylene units.
  • fractional numbers are also calculated as mean values for the number of substituents on the phenyl ring. Examples include substances for which the following average compositions result:
  • ketones such as methyl isobutyl ketone and cyclohexanone
  • amides such as dimethylformamide
  • cyclic compounds such as N-methyl-pyrrolidone, N-octyl-pyrrolidone, N-dodecyl-pyrrolidone, N-octyl-caprolactam , N-dodecyl-caprolactam and ⁇ -butyrolactone, moreover strongly polar solvents, such as dimethyl sulfoxide, also aromatic hydrocarbons, such as xylene, also esters, such as propylene glycol monomethyl ether acetate, adipic acid dibutyl ester, acetic acid hexyl ester, acetic acid heptyl ester, citric acid n-butyl ester and phthalic acid di-n-butyl ester, and furthermore alcohols, such as ethanol, n- and
  • Acids which can be used in the spray liquors which can be used according to the invention are all inorganic and organic acids which can customarily be used for such purposes.
  • Aliphatic and aromatic hydroxy carboxylic acids such as citric acid, salicylic acid, tartaric acid and ascorbic acid are preferred.
  • Cold stabilizers which can be used in the spray liquors which can be used according to the invention are all substances which are customarily suitable for this purpose. Urea, glycerol and propylene glycol are preferred.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and also synthetic phospholipids are preferred.
  • Other additives can be mineral and vegetable oils.
  • the spray liquors which can be used according to the invention each contain water.
  • the active substance concentrations in the spray liquors which can be used according to the invention can be varied within a certain range.
  • the active ingredient concentrations are between 0.0001 and 5 percent by weight, preferably between 0.001 and 3 percent by weight.
  • the ratio of active ingredient of formulas (E) to (VI) to azolyl derivative of formula (I) can also be varied within a certain range.
  • the weight ratio of active ingredient from group (A) to azolyl derivative of the formula (I) is between 1: 0.2 and 1: 5, preferably between 1: 0.6 and 1: 2.
  • the amounts of further active ingredients or additives can be varied within a substantial range in the spray liquors which can be used according to the invention. They are of the order of magnitude which is usually the case in such aqueous spray liquors.
  • the spray liquors which can be used according to the invention are produced by customary methods.
  • the procedure is that a concentrate is first prepared by combining the required components in any order at temperatures between 10 ° C. and 30 ° C. and mixing them homogeneously and, if necessary, filtering the resulting mixture.
  • the concentrated formulation is mixed with the desired amount of water, if appropriate with stirring and / or pumping, in such a way that the formulation is uniformly and finely dispersed in water.
  • a spray liquor is prepared from the concentrate thus obtained by mixing it with water of defined hardness (CIPAC-C water), in which the concentrate is contained in a concentration of 0.5% by weight.
  • CIPAC-C water water of defined hardness
  • CIPAC-C water water containing 4 mmol calcium chloride and 1 mmol magnesium chloride per liter
  • a spray liquor is prepared from the concentrate thus obtained by mixing it with water of defined hardness (CIPAC-C water; see Example I), in which the concentrate is contained in a concentration of 0.5% by weight.
  • aqueous spray liquor which has a concentrate content of 0.5% by weight, are continuously pumped through a fine-mesh sieve in a flow-through apparatus at a temperature of 5 ° C., the after every 30 minutes Spray broth is removed and replaced by a freshly prepared spray broth of the same composition.
  • the crystal deposition on the screen is determined by measuring the differential pressure on the screen. A sharp increase in pressure indicates that the meshes of the screen are largely blocked by crystal deposition.

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

On peut utiliser des dérivés d'azolyles de formule (I), dans laquelle R1 désigne un alkyle avec 1 à 12 atomes de carbone, un alcényle avec 2 à 12 atomes de carbone, un cycloalkyle avec 5 à 7 atomes de carbone, un phényle ou aralkyle avec 6 à 10 atomes de carbone dans la partie aryle et 1 à 4 atomes de carbone dans la partie alkyle, R2 désigne l'hydrogène ou un alkyle avec 1 à 4 atomes de carbone et R3 désigne l'hydrogène ou un alkyle avec 1 à 4 atomes de carbone et X un atome d'azote ou un groupe CR?4, où R4¿ désigne l'hydrogène ou un alkyle avec 1 à 4 atomes de carbone ou R3 et R4 désignent avec la partie de l'hétérocycle à laquelle ils sont liés un noyau benzénique anellé, pour éviter, dans la pulvérisation de bouillies aqueuses contenant: A) certains dérivés d'azoles ayant tendance à cristalliser et B) le cas échéant une ou plusieurs autres substances actives ainsi que des additifs, une cristallisation, dans les pulvérisateurs, de ces substances actives ayant tendance à cristalliser.
PCT/EP1994/003929 1993-12-09 1994-11-28 Utilisation de derives d'azolyles comme inhibiteurs de la cristallisation WO1995015688A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU12408/95A AU1240895A (en) 1993-12-09 1994-11-28 Use of azolyl derivatives as crystallisation inhibitors

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4341982.8 1993-12-09
DE19934341982 DE4341982A1 (de) 1993-12-09 1993-12-09 Verwendung von Azolyl-Derivaten als Kristallisationsinhibitoren

Publications (1)

Publication Number Publication Date
WO1995015688A1 true WO1995015688A1 (fr) 1995-06-15

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Application Number Title Priority Date Filing Date
PCT/EP1994/003929 WO1995015688A1 (fr) 1993-12-09 1994-11-28 Utilisation de derives d'azolyles comme inhibiteurs de la cristallisation

Country Status (3)

Country Link
AU (1) AU1240895A (fr)
DE (1) DE4341982A1 (fr)
WO (1) WO1995015688A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103127897A (zh) * 2013-03-08 2013-06-05 南开大学 一种咪唑类离子液体的合成装置及应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0453915A1 (fr) * 1990-04-27 1991-10-30 Bayer Ag Utilisation de lactames N-alkylés comme inhibiteurs de cristallisation

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0453915A1 (fr) * 1990-04-27 1991-10-30 Bayer Ag Utilisation de lactames N-alkylés comme inhibiteurs de cristallisation

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
A. DE SAVIGNAC ET AL.: "Synthèse et propriétés antibactériennes et antifongiques d'une série de 1-alkylimidazoles", EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY, vol. 25, no. 5, June 1990 (1990-06-01), PARIS, FR, pages 449 - 454 *
ABH. AKAD. WISS. DDR, ABT. MATH., NATURWISS., TECH., 1979, pages 325 - 332 *
CHEMICAL ABSTRACTS, vol. 92, no. 17, 28 April 1980, Columbus, Ohio, US; abstract no. 141626v, G. MATOLCSY ET AL.: "Antifungal activity of several N-substituted heterocycles" *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103127897A (zh) * 2013-03-08 2013-06-05 南开大学 一种咪唑类离子液体的合成装置及应用
CN103127897B (zh) * 2013-03-08 2014-05-28 南开大学 一种咪唑类离子液体的合成装置及应用

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Publication number Publication date
AU1240895A (en) 1995-06-27
DE4341982A1 (de) 1995-06-14

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