WO1995015686A1 - Utilisation d'esters de l'acide carbamique comme inhibiteurs de la cristallisation - Google Patents

Utilisation d'esters de l'acide carbamique comme inhibiteurs de la cristallisation Download PDF

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Publication number
WO1995015686A1
WO1995015686A1 PCT/EP1994/003927 EP9403927W WO9515686A1 WO 1995015686 A1 WO1995015686 A1 WO 1995015686A1 EP 9403927 W EP9403927 W EP 9403927W WO 9515686 A1 WO9515686 A1 WO 9515686A1
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Prior art keywords
carbon atoms
formula
phenyl
chain
alkyl
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PCT/EP1994/003927
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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.)
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Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU10679/95A priority Critical patent/AU1067995A/en
Publication of WO1995015686A1 publication Critical patent/WO1995015686A1/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 carbamic acid esters 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-alkyllactams and alkylcarboxylic acid dimethylamides can be used as crystallization inhibitors in the preparation and application of spray liquors of the active compounds mentioned (cf. EP-OS 0 391 168, EP-OS 0 453 915 and EP-OS 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.
  • carbamic acid esters can be used as insect repellents (cf. J. Pharm. Sei. 66, 587-589 (1977) and Chem. Abstr. 85, 123 067 g).
  • R 1 represents hydrogen, alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, cycloalkyl having 5 to 7 carbon atoms, cycloalkenyl having 5 to 7 carbon atoms, phenyl or phenylalkyl having 1 to 4 carbon atoms in the alkyl part,
  • R 2 represents hydrogen, alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, cycloalkyl having 5 to 7 carbon atoms, phenyl or phenylalkyl having 1 to 4 carbon atoms in the alkyl part and
  • R 3 represents alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, cycloalkyl having 5 to 7 carbon atoms, phenyl or phenylalkyl having 1 to 4 carbon atoms in the alkyl part, or
  • R 1 and R 2 together for an alkylene chain with 3 to 6 carbon atoms or for a group of the formula
  • R 2 and R 3 together represent an alkylene chain with 2 to 4 carbon atoms
  • R 5 stands for tert-butyl and R 6 stands for hydroxy
  • R 4 represents 4-fluorophenyl
  • R 5 stands for 2-fluorophenyl and R 6 stands for hydroxy
  • R 4 represents 2,4-dichlorophenyl
  • R 5 represents n-butyl
  • R 6 represents hydroxy
  • R 4 stands for R 5 represents phenyl and R 6 represents cyano
  • R 4 represents 4-chlorophenyl
  • R 5 stands for and
  • Y is -CH (OH)
  • R 7 represents chlorine or phenyl
  • R 8 represents hydrogen or chlorine
  • carbamic acid esters of the formula (I) in aqueous formulations based on fungicidally active azole derivatives of the formulas (II) to (VI) has a number of advantages.
  • the carbamic acid esters 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 carbamic acid esters of the formula (I) have no undesirable side effects in crop protection.
  • R 1 preferably represents hydrogen, straight-chain or branched alkyl having 1 to 10 carbon atoms, straight-chain or branched alkenyl having 2 to 10 carbon atoms, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, benzyl, phen-2-ethyl or phen-1-ethyl.
  • R 2 preferably represents hydrogen, straight-chain or branched alkyl having 1 to 10 carbon atoms, straight-chain or branched alkenyl having 2 to 10 carbon atoms, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, benzyl, phen-2-ethyl or phen-1-ethyl.
  • R 3 preferably represents hydrogen, straight-chain or branched alkyl having 1 to 10 carbon atoms, straight-chain or branched alkenyl having 2 to
  • R 1 and R 2 together also preferably represent an alkylene chain having 3 to 6 carbon atoms or a group of the formula
  • R 2 and R 3 also preferably together represent an alkylene chain having 2 to 4 carbon atoms.
  • R 1 particularly preferably represents hydrogen, straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched alkenyl having 3 to 8 carbon atoms, cyclopentyl, cyclohexyl, cycloheptyl,
  • R 2 particularly preferably represents hydrogen, straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched alkenyl having 3 to 8 carbon atoms, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, benzyl, phen-1-ethyl or phen-2-ethyl.
  • R 3 particularly preferably represents straight-chain or branched alkyl having 1 to 10 carbon atoms, straight-chain or branched alkenyl having 3 to 8 carbon atoms, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, benzyl, phen-1-ethyl or phen-2-ethyl.
  • R 1 and R 2 together also particularly preferably represent an alkylene chain having 3 to 6 carbon atoms or a group of the formula
  • R> 2 ⁇ , u, "ndJ ⁇ R3 are also particularly preferably together for an alkylene chain having 2 to 4 carbon atoms.
  • Examples of substances which can be used according to the invention are the carbamic acid esters listed in Table 1 below.
  • the carbamic acid esters of the formula (I) are known or can be prepared according to known ones
  • azole derivatives contained in the aqueous spray liquors which can be used according to the invention are defined by the formulas (II) 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 combating 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 may 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:
  • N-trichloromethylmercapto-4-cyclohexene-1,2-dicarboxamide Captan
  • N- (1,1, 2,2-tetrachloroethyl-sulfenyl) -cis-4-cyclohexene-1,2-dicarboxamide Captafol
  • N- Trichloromethylthio-phthalimide Fralpet
  • Dodine N-dodecyl-guanidine acetate
  • Dodine tetrachloroisophthalodinitrile
  • Chlorothalonil Chlorothalonil
  • 4,5,6,7-tetrachlorophthalide 4,5,6,7-tetrachlorophthalide
  • 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.
  • 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
  • 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 hydroxycarboxylic 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 natural phospholipids, such as cephalins and lecithins, and also synthetic phospholipids are suitable.
  • 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 (II) to (VI) to carbamic acid ester of formula (I) can also be varied within a certain range.
  • the weight ratio of active ingredient from group (A) to carbamic acid ester 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 that is usually the case in such aqueous spray flowers.
  • 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. It is also possible to add carbamic acid esters of the formula (I) when the concentrate is diluted with water to give the ready-to-use spray liquor.
  • All mixing devices and spraying devices that are usually suitable for these purposes can be used both for preparing the concentrated formulations and for producing and applying the spray liquors which can be used according to the invention.
  • a spray liquor is prepared by mixing with water of defined hardness (CEPAC-C water), in which the concentrate is contained in a concentration of 0.5% by weight.
  • CIPAC-C water water containing 4 mmol calcium chloride and 1 mmol 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., with the after every 30 minutes Spray broth 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 esters de l'acide carbamique de formule (I) dans laquelle R1 désigne l'hydrogène, 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 un phénylalkyle avec 1 à 4 atomes de carbone dans la partie alkyle; R2 désigne l'hydrogène, 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 un phénylalkyle avec 1 à 4 atomes de carbone dans la partie alkyle; et R3 désigne un alkyle avec 1 à 12 atomes de carbone, un cycloalkyle avec 5 à 7 atomes de carbone, un phényle ou un phénylalkyle avec 1 à 4 atomes de carbone dans la partie alkyle; ou R1 et R2 désignent ensemble une chaîne alkylénique avec 3 à 6 atomes de carbone ou un groupe de formule: -CH¿2?-CH2-O-CH2-CH2-, de formule (II) ou de formule (III), ou bien R?2 et R3¿ désignent ensemble une chaîne alkylénique avec 2 à 4 atomes de carbone, pour éviter, lors de 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/EP1994/003927 1993-12-09 1994-11-28 Utilisation d'esters de l'acide carbamique comme inhibiteurs de la cristallisation WO1995015686A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU10679/95A AU1067995A (en) 1993-12-09 1994-11-28 Use of carbamide acid esters as crystallisation inhibitors

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19934341985 DE4341985A1 (de) 1993-12-09 1993-12-09 Verwendung von Carbamidsäure-estern als Kristallisationsinhibitoren
DEP4341985.2 1993-12-09

Publications (1)

Publication Number Publication Date
WO1995015686A1 true WO1995015686A1 (fr) 1995-06-15

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AU (1) AU1067995A (fr)
DE (1) DE4341985A1 (fr)
WO (1) WO1995015686A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010013399A (ja) * 2008-07-04 2010-01-21 Nippon Nyukazai Kk ２−オキサゾリジノン化合物の製造方法
WO2011060890A1 (fr) * 2009-11-17 2011-05-26 Cognis Ip Management Gmbh Compositions biocides comprenant des carbamates

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0453899A1 (fr) * 1990-04-27 1991-10-30 Bayer Ag Utilisation de diméthyl-amides alkylcarboxyliques comme inhibiteurs de cristallisation
EP0453915A1 (fr) * 1990-04-27 1991-10-30 Bayer Ag Utilisation de lactames N-alkylés comme inhibiteurs de cristallisation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0453899A1 (fr) * 1990-04-27 1991-10-30 Bayer Ag Utilisation de diméthyl-amides alkylcarboxyliques comme inhibiteurs de cristallisation
EP0453915A1 (fr) * 1990-04-27 1991-10-30 Bayer Ag Utilisation de lactames N-alkylés comme inhibiteurs de cristallisation

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 73, no. 3, 20 July 1970, Columbus, Ohio, US; abstract no. 14653j, L.K.MASILI ET AL.: "N,N-Disubstituted esters of carbamic acid" *
SAUL RICH & JAMES G. HORSFALL: "Fungitoxicity of Carbamic and Thiocarbamic Acid Esters", THE CONNECTICUT AGRICULTURAL EXPERIMENT STATION, BULLETIN, no. 639, March 1961 (1961-03-01), NEW HAVEN, US;, pages 1 - 95 *
W.A. SKINNER ET AL.: "Topical Mosquito Repellents X: 2-Oxazolidones", JOURNAL OF PHARMACEUTICAL SCIENCES, vol. 66, no. 4, April 1977 (1977-04-01), WASHINGTON,DC, US;, pages 587 - 589 *
ZH. ORG. KHIM., vol. 6, no. 4, 1970, pages 706 - 707 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010013399A (ja) * 2008-07-04 2010-01-21 Nippon Nyukazai Kk ２−オキサゾリジノン化合物の製造方法
WO2011060890A1 (fr) * 2009-11-17 2011-05-26 Cognis Ip Management Gmbh Compositions biocides comprenant des carbamates
EP2327302A1 (fr) 2009-11-17 2011-06-01 Cognis IP Management GmbH Compositions biocides comportant des carbamates
CN102595880A (zh) * 2009-11-17 2012-07-18 科宁知识产权管理有限公司 包含氨基甲酸酯的杀生物剂组合物
US8790675B2 (en) 2009-11-17 2014-07-29 Cognis Ip Management Gmbh Biocide compositions comprising carbamates

Also Published As

Publication number Publication date
AU1067995A (en) 1995-06-27
DE4341985A1 (de) 1995-06-14

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