GB2101994A - Microbidical and growth regulating 2-hydroxy-3-azolylpropane derivatives - Google Patents

Microbidical and growth regulating 2-hydroxy-3-azolylpropane derivatives Download PDF

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GB2101994A
GB2101994A GB08218713A GB8218713A GB2101994A GB 2101994 A GB2101994 A GB 2101994A GB 08218713 A GB08218713 A GB 08218713A GB 8218713 A GB8218713 A GB 8218713A GB 2101994 A GB2101994 A GB 2101994A
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triazolyl
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hydroxy
phenyl
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Robert Nyfeler
Alfred Meyer
Urs Muller
Elmar Sturm
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Novartis AG
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Ciba Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • 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
    • 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
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/34—Compounds containing oxirane rings with hydrocarbon radicals, substituted by sulphur, selenium or tellurium atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Saccharide Compounds (AREA)

Description

SPECIFICATION Microbicidal and growth regulating compositions The present invention relates to novel substituted 1 -azolyl-2-hydroxy-alkane derivatives and to the acid addition salts, quaternary azolium salts and metal complexes thereof. The invention relates further to the preparation of these compounds and to microbicidal and growth regulating compositions which contain at least one of these compounds as active ingredient. The invention also relates to the preparation of said compositions and to the use of the active ingredients or compositions for regulating plant growth and for controlling harmful organisms.
Comprised herein are compounds of the general formula I
wherein R1 is an azolyl group, R2 is C,-C4alkyl or an aryl group which is unsubstituted or substituted by halogen, cyano, C,-C3alkyl, C,-C3alkoxy, nitro, thiocyano, C,-C3alkylthio and/or C,-C4haloalkyl, R3 and R4, each independently of the other are C,-C4alkyl or one is hydrogen and the other is C1-C4alkyl, R5 is an unsubstituted or mono- or polysubstituted radical selected from the group consisting of phenyl, biphenyl, benzylphenyl, benzyloxyphenyl and phenoxyphenyl, said substituents being selected from the group consisting of halogen, cyano, C,-C3 alkyl, C,-Cs alkoxy, CI-Cshaloal- koxy, C,-C3alkylthio, C-C3haloalkyl, C,-C3-haloalkylthio, nitro and/or thiocyano; and X is oxygen or sulphur, and the acid addition salts quaternary azolium salts and metal complexes thereof.
The term azolyl denotes a 5-membered heterocyclic ring containing nitrogen as heteroatom and having aromatic character. Typical representatives are 1 H-i ,2,4-triazolyl, 4H-1,2,4-triazolyl and 1 H-imidiazole.
Depending on the indicated number of carbon atoms, alkyl by itself or as moiety of another substituent comprises e.g. the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl etc. and the isomers thereof, e.g. isopropyl, isobutyl, tert-butyl, isopentyl etc.
Haloalkyl is a mono- to perhlogenated alkyl substituent, e.g. CHCl2, CHF2, CH2CI, CCI3, CH2F, CH2CH2Cl,CHBr2, CF3 etc. Throughout this specification, halogen denotes fluorine, chlorine, bromine or iodine, with fluorine, chlorine or bromine being preferred. Napthyl is CL- or naphthyl, with a-naphthyl being preferred. Alkylene denotes an unbranched or branched alkylene bridge, e.g. methylene, ethylene, propylene etc., and is preferably a bridge member containing 4 to 6 carbon atoms. Aryl is e.g. naphthyl, especially phenyl; and aralkyl is a lower alkyl radical which is substituted by an aromatic group. Depending on the indicated number of carbon atoms, cycloalkyl is e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl etc.
Accordingly, the present invention relates to the free compounds of the formula I and to the acid addition salts, quaternary azolium salts and metal complexes thereof. The free compounds are preferred.
Examples of salt-forming acids are inorganic acids, e.g. hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid, and also sulfuric acid, phosphoric acid, phosphorous acid, nitric acid; and organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, salicyclic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid or 2-acetoxybenzoic acid.
Metal complexes of the formula I consist of the basic organic molecule and an inorganic or organic metal salt, for example the halides, nitrates, sulfates, phosphates, acetates, trifluoroacetates, trichloroacetates, propionates, tartrates, sulfonates, salicylates, benzoates etc. of the elements of the third and fourth main group of the Periodic Table such as aluminium, tin or lead, and of the first to eighth auxiliary group such as chromium, manganese, iron, cobalt, nickel, copper, zinc, silver mercury etc. Preferred elements are those of the auxiliary groups of the fourth period. The metals may exist in different valency states. The metal complexes of the formula I may be mononuclear or polynuclear, i.e. they can contain one or more parts of the organic molecule as ligands. Complexes with copper, zinc, manganese and tin are preferred.
The compounds of formula I are oils, resins or mainly solids which are stable at room temperature and have very valuable microbicidal and growth regulating properties. They can be used in agriculture or related field preventively and curatively for controlling phytopathological microoganisms and for regulating plant growth, for which utility the triazolylmethyl derivatives falling within the scope of formula I are preferred. The compounds of formula I are very well tolerated by cultivated plants.
On account or their pronounced growth regulating and/or microbicidal action, preferred compounds of the formula I are those compounds which contain the following substituents or combinations thereof.
For R,: a) 1 H-1.2,4-triazole, 4H-1,2,4-triazole, 1 H-imidazole.
b) 1 H-1,2,4-triazole, 4H-1 ,2,4-triazole c) 1 H-i ,2,4-triazole.
For R2: a) methyl, ethyl, isopropyl, tert-butyl, phenyl, phenyl substituted by C,-C3alkyl, C,-C3al- koxy, CF3, halogen and/or phenyl b) methyl, isopropyl, tert-butyl, phenyl, halophenyl, dihalophenyl, biphenyl c) tert-butyl, halophenyl, dihalophenyl d) tert-butyl, 4-chloropheny, 4-bromophenyl, 2,4-dichlorophenyl, 2-chloro-4-bromophenyl e) tert-butyl, 4-chlorophenyl, 2,4-dichlorophenyl f) tert-butyl, 2,4-dichlorophenyl g) tert-butyl.
For R3 and R4: a) each independently of the other is C,-C4alkyl or one is hydrogen and the other is C1-C4alkyl b) each independently of the other is C,-C4alkyl c) R3 is hydrogen, CH3, C2H5 and R4 is CH3 or C2H5 d) R3 is hydrogen and R4 is C,-C2alkyí.
For X: a) oxygen, sulfur b) oxygen.
For R5: a) a radical selected from the series consisting of phenyl, biphenyl, benzylphenyl and phenoxyphenyl, which radical may be unsubstituted or mono- or polysubstituted by halogen, cyano, C,-C2alkyl, C,-C2alkoxy, C,-C5haloalkoxy, C,-C2alkylthio, C,-C2haloalkyl, C1-C2haloalkylthio and/or nitro; b) an aromatic radical selected from the group consisting of phenyl, biphenyl, benzylphenyl, benzoxyphenyl and phenoxyphenyl, which radical may be unsubstituted or mono- or polysubstituted by C,-C2alkyl, C,-C2alkoxy, halogen, cyano, CF3, nitro and/or C1-C2alkyltio; c) phenyl or phenyl which may be mono- to trisubstituted by C1-C2alkyl, C1-C2alkoxy, halogen, cyano, CF3, nitro, and/or C,-C2alkythio; d) phenyl or phenyl which may be mono- to trisubstituted by methyl, methoxy, chlorine, bromine, fluroine, cyano, CF3, nitro or methylthio.
Accordingly, preferred compounds of the formula I are e.g. those of the groups a) to e) set forth below: a) compounds of the formula I, wherein R, is a 1 H-i ,2,4-triazolyl, 4H-1 2,4-triazolyl or 1 Himidazolyl group; R2 is methyl, ethyl, isopropyl, tert-butyl, phenyl or phenyl which is mono- or polysubstituted by C,-C3alkyl, C,-C3aikoxy, CF3, halogen and/or phenyl; each of R3 and R4 independently of the other is C,-C4 alkyl or one is hydrogen and the otheris C,-C4alkyI; R5 is a radical selected from the group consisting of phenyl, biphenyl, benzylphenyl and phenoxyphenyl, which radical may be unsubstituted or monc- or polysubstituted by halogen, cyano, C,-C2alkyl, C,-C ,alkoxy,C,-C,haloalkoxy, C,-C2alkylthio, C,-C 2haloalkyl, C,-C2haloalkylthio and /or nitro; and X is oxygen or sulfur; b) compounds of the formula I wherein R, is a 1 H-i ,2,4-triazolyl, 4H-1 ,2,4-traizolyl or 1 Himidazolyl group; R2 is methyl, ethyl, isopropyl, tert-butyl, phenyl which is mono- or polysubstituted by C,-C3alkyl, C,-C 3alkoxy, CF3, halogen and/or phenyl; each of R3 and R4 independently of the other is C1-C4alkyl; R5 is an aromatic radical selected from the group consisting of phenyl, biphenyl, benzylphenyl, benzoxyphenyl and phenoxyphenyl, which radical may be unsubstituted or mono- or polysubstituted by C,-C2alkyl, C,-C2alkoxy, halogen, cyano, CF3, nitro and/or C,-C2alkylthio; and X is oxygen or sulfur; including the non-phytotoxic acid addition salts, quaternary azolium salts and metal complexes thereof.
c) compounds of the formula I, wherein R, is a 1 H-i ,2,4-triazolyl, 4H-1,2,4-trizolyl or 1 Himidazolyl group; R2 is methyl, isopropyl, tert-butyl, phenyl, halophenyl, dihalophenyl or biphenyl; R3 is hydrogen and R4 is C1-C3alkyl; X is oxygen or sulphur; and R5 is an aromatio radical selected from the group consisting of phenyl, biphenyl, benzylphenyl, benzoxyphenyl and phenoxyphenyl, which radicals may be substituted or mono- or polysubstituted by C,-C2alkyl, C,-C2alkoxy, halogen, cyano, CF3, nitro and/or C,-C2alkylthio; d) compounds of the formula I, wherein R, is a 1 H-i ,2,4-triazolyl or 4H-1 ,2,4-triazolyl group; R2 is tert-butyl, halophenyl or dihalophenyl; R3 is hydrogen, methyl or ethyl;R4 is methyl or ethyl; R5 is phenyl or phenyl which may be mono- to trisubstituted by C,-C2alkyl, C,-C2alkoxy, halogen, cyano, CF3, nitro and/or C,-C2alkylthio; and X is oxygen or sulphur; e) compounds of the formula I, wherein R, is a 1 H-; 1 ,2,4-triazolyl or 4H-i ,2,4-triazolyl group; R2 is tert-butyl, 4-chlorophenyl, 4-bromophenyl, 2,4-dichlorophenyl or 2-chloro-4bromophenyl; R3 is hydrogen and R4 is methyl or ethyl; Rs is phenyl or phenyl which may be mono- to trisubstituted by methyl, methoxy, chlorine, bromine, fluroine, cyano, CF3, nitro or methylthio; and X is oxygen.
Particularly preferred compounds are those of groups d) and e). Among the growth regulating compounds, those compounds of the formula 1 are especially preferred in which R2 is a C1-C4 alkyl group, in particylar the tert-butyl group. Among the microbicidal compopounds, those compounds of the formula are especially preferred in which R2 is unsubstituted or substituted aryl, in particular monohalogenated or dihalogenated phenyl, in which the most preferred halogen substituents are chlorine and/or fluorine.
These compounds within the scope of formula I are also preferred in which R3 and R4 are methyl.
The following individual compounds are especially preferred: 1-[1H-1,2,4-triazolyl]-2-methyl-3-hydroxy-3-[4-chlorophenoxy]-3-methylbutane, 1-[1H-1,2,4-trizolyl]-2-methyl-2-methyl-2-hydroxy-3-[2,4-dichlorophenoxy]-3-methylbutane, 1-[1H-1,2,4-triazolyl]-2-methyl-2-hydroxy-3-[3,4-dichlorophenoxy]-3-methylbutane, 1-[1H-1,2,4-triazolyl]-2-methyl-3-hydroxy-3-[4-biphenyl]-3-methyl-butane, 1-[1H-1,2,4-triazolyl]-2-methyl-2-hydroxy-3-[4-isopropylphenoxy]-3-methylbutane, 1-[1H-1,2,4-triazolyl]-2-[2,4-dichlorophenyl]-2-hydroxy-3-[4-chlorophenoxy]-pentane, 1-[1H-1,2,4-triazolyl]-2-[2,4-dichlorophenyl]-2-hydroxy-3[4-flurophenoxy]-pentane, 1-[1 H-i , 2,4-triazolyl]-2-[2,4-dichlorophenyI2-hydroxy-3-[2, 3-dimethylphenoxy]-pentane, 1-[1 H-i , 2, 4triazoIyl]-2-[2,4-dichlorophenyl]-2-hydroxy-3-[4-chlornphenoxy]-hexane 1-[1 H-1,2,4-triazolyl]-2-[2,4-dichiorophenyl]-2-hydroxy-3-[phenoxy]-pentane, 1-[1H-1,2,4-triazolyl]-2-[2,4-dichlorophenyl]-2-hydroxy-3-[4-bromophenoxy]-pentane, 1-[1H-1,2,4-triazolyl]-2-[2-chloro-4-flurophenyl]-2-hydroxy-3-[4-chlorophenoxy]-butane, 1-[1H-1,2,4-triazolyl]-2-tert-butyl-2-hydroxy-3-[4-chlorophenoxy]-butane, 1-[1H-1,2,4-triazolyl]-2-tert-butyl-2-hydroxy-3-[4-flurophenoxy]-butane, 1-[1H-1,2,4-triazolyl]-2-tert-butyl-2-hydroxy-3-[4-methylphenoxy]-butane, 1-[1H-1,2,4-triazolyl]-2-tert-butyl-3-hydroxy-3-[4-chlorophenoxy]-pentane, 1-[1H-1,2,4-triazolyl]-2-tert-butyl-hydroxy-3-[4-chlorophenoxy]-butane, 1-[1H-1,2,4-triazolyl]-2-tert-butyl-2-hydroxy-3-[4-fluorophenoxy]-butane, 1-[1H-1,2,4-triazolyl]-2-[2,4-dichlorophenyl]-2-hydroxy-3-[4-chlorophenoxy]-butane.
The compounds of formula I are prepared by reacting an oxirane of the formula II
wherein R2, R3, R4, X and Rs are as defined for formula I, with an azole of the formula Ill M--R, (III), wherein M is hydrogen or preferably a metal atom, especially an alkali metal atom, and R, is as defined for formula I.
The reaction is conveniently conducted in the presence of a condensing agent or of an acid acceptor. Examples of such compounds are organic and inorganic bases, e.g. tertiary amines such as trialkylamines (trimethylamine, triethylamine, tripropylamine etc.), pyridine and pyridine bases (4-dimethylaminopyridine, 4-pyrrolidylaminopyridine etc.), oxides, hydrides and hydroxides, carbonates and bicarobonates of alkali metals and all < aline earth metals (CaO, BaO, NaOH, LiOH, KOH, NaH, Ca(OH)2, KHC03, NaHCO3, Ca(HCO3)2, K2 CO3, Na2CO3), as well as alkali acetates such as Ch3COONa or CH3COOK. Also suitable are alkali alcoholates such as C2H50Na, C3h7-nONa etc.In some cases it may be advantageous to convert the free azole of the formula Ill (M = hydrogen) first.g. in situ with the alcoholate-into the corresponding salt, and then reacting this latter with the oxirane of the formula 11 in the presence of one of the bases specified above. Parallel to the formation of the 1,2,4-triazolyl derivatives, there are usually also obtained 1,3,4-triazolyl isomers, which can be separated from one another in conventional manner, e.g. with different solvents. In some cases, hydrogen halide can be expelled from the reaction mixture by introducing inert gas, e.g. nitrogen, or by adding a molecular sieve.
The reaction of the oxirane of the formula II with the azole of the formula ill is preferably carried out in a relatively polar, but inert, organic solvent, e.g. N,N-dimethylformamide, N-Ndimethylacetamide, dimethylsulfoxide, acetonitrile, benzonitrile and others. Such solvents may be employed in combination with other inert solvents, e.g. benzene, toluene, xylene, hexane, petroleum ether, chlorobenzene, nitrobenzene etc. The reaction temperature is in the range from O' to 150"C, preferably from 20 to 100'C.
In other respects, this reaction may be carried out in the same manner as already known reactions of other oxiranes with azoles (cf. European published patent specification 0 015 756 and German Offenlegungsschrift 29 1 2 288).
The azoles of formula Ill are known or they may be obtained by methods which are known per se.
The oxiranes of formula II are novel and constitute specially developed intermediates for the preparation of the valuble compounds of the formula I. Their structural nature makes it possible for them to be converted in simple manner into compounds of the formula I.
The oxiranes of formula li can be prepared by reacting the ketones of the formula IV
with dimethylsulfonium methylide or dimethyloxosulfonium methylide, in dimethylsulfoxide or another suitable solvent. In formula IV, the substituents are as defined for formula 1. The reaction is carried out in the temperature from 0" to 1 20 C.
Simiiar reactions are known from the literature [q.v. JACS, 87, 1 353 (1 965) and Angew.
Chem. 85, 867 (1973)1. In principle, the reaction may be carried out in the same manner as the reactions described therein.
Ketones of the formula IV can be prepared from the e-haloketones known per se of the formula V
with compounds of the formula VI, in conventional inert solvents, and optionally at elevated temperature.
In formulae (V) and (VI) above, the substituents R2, R3, R4, Rs and X are as defined for formula 1 Hal is halogen, preferably chlorine or bromine, and M is a metal atom, especially sodium or potassium.
Ketones of the formula IV' may also be prepared from ketones of the formula VII by reaction with halides of the formula VIII and an alkali metal hydride of the formula IX in accordance with the following reaction scheme
in which formulae R2, R4 and R4 are as defined for formula I, Hal is halogen, preferably chlorine or bromine, and M is an alkali metal atom, preferably potassium or sodium. The reaction is normally carried out in a conventional inert solvent temperature range from about 30 to 1 00 C.
The compounds of formulae V to IX are known and some are commercially available or may be prepared by methods which are known per se.
Unless otherwise expressly specified, one or more inert solvents or diluents may be present in the preparation of all starting materials, intermediates and final products mentioned herein. Examples of suitable inert solvents or diluents are: aliphatic and aromatic hydrocarbons such as benzene, toluene, xylenes, petroleum ether; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloethylene; ethers and ethereal compounds such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butylmethyl ether etc.), anisole, dioxane, tetrahydrofuran; nitriles such as acetonitrile, propionitrile; N,Ndialkylated amides such as dimethyl formamide; dimethyl sulfoxide; ketones such as acetone, diethyl ketone, methyl ethyl ketone; and mixtures of such solvents with each other.It can often be convenient to carry out the reaction, or partial steps of a reaction, under an inert gas atmosphere and/or in absolute solvents. Suitable inert gases are nitrogen, helium argon or, in certain cases, also carbon dioxide.
The process for obtaining the compounds of formula I, including all partial steps, constitutes an important object of the present invention.
The compounds of formula I
contain an asymmetrical carbon atom (*) vicinal to the hydroxyl group and, where the substituents R3 and R4 are different, a further such carbon atom vicinal to the -XRs group.
Accordingly, the compounds of formula I are usually obtained in the form of mixtures of enantiomers and diastereoisomers and may either subsequently be separated by conventional methods into the pure isomers or obtained as pure isomers by selective synthesis from optically pure starting materials. The different individual isomers have different biological properties and, like the mixtures, constitute an important object of the invention, i.e. the pure diastereoisomers and the pure enantiomers, like the mixtures thereof, are an object of the present invention. For successful application in the field of agriculture it is sufficient to use the mixtures, although the pure isomers make it possible to lower the concentration in certain cases.
Surprisingly, it has now been found that the novel compounds of the formula I and compositions containing them are characterised in particular by their selective influence on plant metabolism. This selective influence on the physiological processes of plant development makes it possible to use the compounds of formula I for different purposes, especially for those in connection with increasing the yield of useful plants, with facilitating harvesting, and with labour-saving in measures taken in crops of cultivated plants.
Previous experience with the application of growth regulators has shown that the active ingredients can induce one or more different responses in the plants. Thes different responses depend largely on the time of application, based on the development stage of the seed or plant, as well as on the concentrations of active ingredient applied to the plants or the locus thereof.
Growth regulators should at all events induce positive responses in the cultivated plants in the desired manner.
Growth regulators may be used e.g. for inhibiting vegetative plant growth. Such a growth inhibition is of economic interest, inter alia, in respect of grasses, as the frequency of cutting in flower gardens, parks, sports fields or road shoulders can thereby be reduced. Of importance too is the inhibition of growth of herbaceous and ligneous plants on road shoulders and near transmission lines, or generally in areas in which strong growth is undesirable.
The use of growth regulators for inhibiting the growth of height of cereals is also important, as shortening the stalks diminishes or completely eliminates the danger of lodging before harvesting. In addition, growth regulators are able to bring about a strengthening of the stalks in crops of cereals and this too couteracts lodging.
In many cultivated plants inhibition of vegetative growth permits more plants to be sown in crop area, so that a higher yield may be obtained per unit of area. A further mechanism of yield increase using growth regulators resides in the fact that nutrients are able increasingly to promote flower formation and fruiting, whilst vegetative growth is restricted.
Growth regulators are also frequently able to promote vegetative growth. This is of great value when the vegetative parts of plants are to be harvested. However, promotion of vegetative growth can also result simultaneously in promotion of generative growth, so that e.g. more or larger fruit is formed.
Yield increases may also often be obtained by influencing the plant metabolism without any visible changes in vegetative growth. Growth regulators can also induce a change in the composition of plants, so that the quality of the harvest produce is improved. For example, it is possible to increase the sugar content of sugar beet, sugar cane, pineapples and citrus fruit, or to increase the protein content of soya beans or cereals.
The use of growth regulators can lead to the formation of parthenocarpic fruit. The sex of blossoms can also be influenced. The production or flow of secondary plant substances can also be positively influenced by growth regulators, for example the stimulation of the flow of latex in rubber trees.
During plant growth, the development of side-shoots can also be promoted by the chemical interruption of apical dominance using growth regulators. This is of interest e.g. in the propagation of plant cuttings. However, it is also possible to inhibit the growth of side-shoots, e.g. in tobacco plants after decapitation in order to prevent the formation of side-shoots and thus to promote leaf growth.
Plant foliage can be so controlled under the influence of growth regulators that defoliation of the plants is effected at a desired time. Such a defoliation is of interest in order to facilitate mechanical harvesting, e.g. in vines or cotton, or to lower transpiration at a time when it is desired to transplant the plant. Premature fruit drop can be prevented by the use of growth regulators. However it is also possible to promote fruitdrop--e.g. in fruit crops-by means of chemical thinning up to a specific degree. Growth regulators can also be used for reducing the force necessary for detaching fruit at harvesting, thus mal < ing possible mechanical of plants or facilitating manual harvesting.
With growth regulators it is also possible to sped up or delay the ripening of harvest products before or after harvesting. This is particularly advantageous, because a best possible accomodation to market requirements can thereby be achieved. In addition, growth regulators can often improve the colour of fruit. With the aid of growth regulators it is also possible to concentrate ripening at a particular time. The conditions are thus created for a complete mechanical harvesting of e.g. tobacco, tomatoes or coffee, or for manual harvesting, in only one single operation.
The application of growth regulators can also make it possible to influence the dormancy of seeds and buds of plants, i.e. the endogenic annual rhythm, so that plants such as pineapples or ornamentals in nurseries germinate, sprout or blossom at a time when they would normally not tend to do so.
With growth regulators it is also possible to delay budding or the germination of seeds, e.g. in order to avoid damage by late frosts in areas endangered thereby. Conversely, root growth and/or the formation of shoots can be stimulated, so that growth may be restricted to a shorter period.
Growth regulators can also impart halophilic properties to cultivated plants. The conditions are thus created for cultivating plants in salty soil. Growth regulators can also impart to plants resistance to frost and drought.
Under the influence of growth regulators, the ageing (senescence) of plants or parts of plants can be inhibited or delayed. Such an action can be of great economic importance, as the storability of treated parts of plants or whole plants such as fruit, berries, vegetables, salads or ornamentals can be improved or prolonged after harvesting. Likewise, a substantial yield increase can be obtained by treating cultivated plants by prolonging the phase of photsynthetic activity.
A further important field of use for growth regulators is the inhibition of excessive growth of tropical cover crops. In tropical and subtropical monocultures, e.g. in palm tree plantations, cotton and maize fields etc., cover crops, especially species of leguminosae, are often planted, with the object of maintaining or improving the quality of the soil (prevention of desiccation, supplying nitrogen) and for preventing erosion. By applying the compounds of this invention it is possible to control the growth of these cover crops and so keep the growth in height of these plants at a low level, thus ensuring healthy growth of the cultivated plants and the maintenance of favourable soil conditions.
Surprisingly, it has also been found that, in addition to their advantageous growth regulating properties, the compounds of formula I and the compositions containing them also have for practical purposes a very useful microbicidal spectrum. A further field of use of the compounds of formula I is therefore the control of harmful microorganisms, especially phytopathogenic fungi. The compounds of formula thus have for practical purposes a very useful curative, preventive and systemic action for protecting plants, especially cultivated plants, without adversely affecting these.With the compounds of formula lit is possible to inhibit or destroy the microoganisms which occur in plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different crops of useful plants, while at the same time the parts of plants which grow later are also protected from attack by such microorganisms.
The compounds of formula I are effective against the phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Uncinula); Basidomycetes (e.g. the genera Hemileia, Rhizoctonia, Puccinia); Fungi imperfecti (e.g. Botrytis, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria). In addition, the compounds of formula I have a systemic action. They can also be used as seed dressing agents for protecting seeds (fruit, tubers, grains) and plant cuttings against fungus infections as well as against phytopathogenic microoganisms which occur in the soil.
The compounds of the invention are also especially well tolerated by plants.
Accordingly, the invention also relates to microbicidal compositions and to the use of compounds of the formula I for controlling phytophatogenic microorganisms, especially harmful fungi, and for the preventive treatment of plants to protect them from attack by such microorganisms.
The invention further embraces the preparation of agrochemical compositions which comprises homogeneously mixing the active ingredient with one or more compounds or groups of compounds described herein. The invention furthermore relates to a method of treating plants, which comprises applying thereto the compounds of the formula I or the novel compositions.
Target crops to be protected within the scope of the present invention comprise e.g. the following species of plants: cereals (wheat, barley, rye, oats, rice, sorghum and related crops), beet (sugar beet and fodder beet), drupes, pomes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, rasberries and blackberries), leguminous plants (beans, lentils, peas, soybeans), oil plants (rape, mustard, poppy, olives, sunflowers, coconuts, castor oil plants, cocoa beans, groundnuts), cucumber plants (cucumber, marrows, melons) fibre plants (cotton, flax, hemp, jute), citrus fruit (oranges, lemons, grapefruit, mandarins), vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika), lauraceae (avocados, cinnamon, camphor), or plants such as maize, tobacco, nuts, coffee, sugar cane, tea, vines, hops, bananas and natural rubber plants, as well as ornamentals (composites), areas of grass, embankments or general low cover crops which counteract erosion or desication of the soil and are useful in cultures of trees and perennials (fruit plantations, hop plantations, maize fields, vineyards etc.).
The compounds of formula I are normally applied in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession, with further compounds. These compounds can be both fertilisers or micronutrient donors or other preparations that influence plant growth. They can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, mollusicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application-promoting adjuvants customarily employed in the art formulation. Suitable carriers and adjuvants can be solid or liquid and correspond to the substances ordinarily employed in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, binders or fertilisers.
A preferred method of applying a compound of the formula I or an agrochemical composition which contains at least one of said compounds, is leaf application. The number of applications and the rate of application depend on the intensity of infestation by the corresponding pathogen (type of fungus). However, the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by impregnating the locus of the plant with a liquid composition, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). The compounds of formula I may also be applied to seeds (coating) by impregnating the seeds either with a liquid formulation containing a compound of the formula I, or coating them with a solid formulation.In special cases, further types of application are also possible, e.g. selective treatment of the plant stems or buds.
The compounds of the formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation, and are therefore formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances. Like the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. Advantageous rates of application are normally from 50 g to 5 kg of active ingredient (a.i.) per hectare, preferably from 100 g to 2 kg a.i./ha, most preferably from 200 g to 600 9 a.i./ha.
The formulations, i.e. the compositions or preparations containing the compound (active ingredient) of the formula I and, where appropriate a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol monomethyl or monethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2pyrrolidone, dimethyl sulfoxide or dimethyl formamide, as well as epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water.
The solid carriers used e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitably granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used. e.g. especially dolomite or pulverised plant residues.
Depending on the nature of the compound of the formula I to be formulated, suitable surfaceactive compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.
Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds.
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C33), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyltaurin salts.
More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alakaline earth metal salts or unsubstituted or substituted ammoniums salts and contain a C8-C22 alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignonsulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfonic acid esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms.
Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensation product. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 1 4 moles of ethylene oxide.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 1 8 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediamine propylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Representative examples of non-ionic sufactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylpheoxypolyethoxyethanol, polyethylene glycol and octylphenoxyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which contain as N-substituent, at least one C8-C22alkyl radical and, as further substituents, lower unsubstituted or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g stearyltrimethylammonium chloride or benzyldi(2-chloroethyl) ethylammonium bromide.
The surfactants customarily employed in the art of formulation are described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp. Ringwood, New Jersey, 1979, and Sisely and Wood, "Encylopedia of Surface Active Agents", Chemical Publishing Co., Inc. New York, 1 980.
The agrochemical compositions usually contain 0.1 to 99 %, preferably 0.1 to 95 %, of a compound of the formula 1, 1 to 99.9%, preferably 99.8 to 5%, of a solid or liquid adjuvant, and 0 to 25 %, preferably 0.1 to 25%, of a surfactant.
Whereas commercial products are preferably formulated as concentrates, the end user will normally employ dilute formulations.
The compositions may also contain further ingredients, such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients in order to obtain special effects.
Such agrochemical compositions also constitute an object of the present invention.
The invention is illustrated in more detail by the following Examples, without implying any restriction to what is described therein. Parts and percentages are by weight.
Preparatory Examples Example 1: Preparation of: Preparation of
1-[1 H- 1,2, 4-triazolylj-2-tert-butyl-2-h ydroxy-3-f4-chlorophenoxyj-butane a) Preparation of the starting materials:
2, 2-dimethyl-4-[4-chlorophenoxy]pentan-3-one 1 4.2 g of a 50 % dispersion of NaH in oil are washed with hexane by decantation and then 30 ml of tetrahydrofuran are added. 67.8 9 of 2,2-dimethyl-4-[4-chlorophenoxy]butan-3-one and 57.6 g of methyl iodide are dissolved in 1 80 ml of tetrahydrofuran and this solution is then added dropwise at 40"-50"C to the NaH suspension. When the evolution of hydrogen has ceased, the reaction mixture is further stirred for 2 hours and excess NaH is destroyed with glacial actic acid.The reaction mixture is then poured into ice/water and the product is extracted with diethyl ether. The organic phase is washed with brine and dried over sodium sulfate, affording 72 g of crude product (98 %; analysis by gas chromotography) in the form of an oil.
b) Preparation of the intermediate
1-tert-butyl-1-[1-(4-chlorophenoxy)ethyl]-oxirane A mixture of 20.3 g of 50 % potassium hydroxide solution, 2 g of tetrabutylammonium bromide, 12.4 g of trimethylsulfoxonium iodide and 10.9 g of 2,2-dimethyl-4-(4-chlorophenox- y)pentan-3-one (crude product) is heated for 8 hours to 100 C. The phases are separated and the inorganic phase is washed with water, dried over Na2SO4 and concentrated, affording 21.59 of a yellow oil consisting of 0.60% of product, c.30 % of educt and c.10 % of unidentified byproducts (analysis by gas chromatography). This product is used for the subsequent reaction without further purification.
c) Preparation of the final product: 21 9 of the mixture obtained in b), 5.7 g of 1,2,4-triazole and 1 g of LiOH2O are dissolved in 100 ml of dimethylsulfoxide and the solution is heated overnight to 90 C The reaction mixture is then poured into ice/water and extracted with ethyl acetate. The ester phase is washed with water and brine, dried over Na2SO4 and concentrated. The resultant oil is stirred in ether and the crystallised 1-[4H-1,2, 4-triazolyl]2-tert-butyl-2-hyd roxy-3-[4-chlorophenoxylbutane derivative is isolated by filtration. The filtrate is concentrated and the product is crystallised from ether/hex ane. Yield: 7.8 g of 1-[1H-1,2,4-triazolyl]-2-tort-butyl-2-hydroxy-3-[4-chlorophenoxy]-butane with a melting point of 108 -109 C.
calculated C59.3 % H 6.85 % N 12.98 % Cl 10.95 % found C59.i % H 6.6 % N 12.9 % Cl 11.0 %.
Example 2: Preparation of
1-[1 H- 1,2, 4-triazolyl]-2-[2, 4-dichiorophen ylJ-2-h ydroxy-3-(4-chlorophenoxy)hexane a) Preparation of the starting material
1-[2,4-dichlorophenyl]-2-[4-chlorophenoxy]pentan-1-one With stirring a mixture of 129 g of p-chlorophenol and 138 g of potassium carbonate in 100 ml of acetone is hoated under reflux for 3 hours. With continued vigorous stirring, a solution of 310 g of a-bromo-2,4-dichlorovalerophenone in 500 ml of acetone is then added dropwise at room temperature and the reaction mixture is further stirred for 10 hours under reflux. The organic salts are then removed by filtration and the filtrate is then concentrated in vacuo. The residue is taken up in water and extracted with ethyl acetate.The extract is dried, filtered and concentrated. The organic phase yields a brown oil which is distilled in a high vacoum, affording 288 g of 1-[2,4-dichlorophenyl]-2-[4-chlorophenoxy]pentan-1-one in the form of a yellow viscous oil with a boiling point of 160"-168"C/0.001 mbar.
b) Preparation of the intermediate
2-[2, 4-dichiorophen yq-2-f2-(4-chlorophen oxy)butylj-oxirane 3.4 g of 55 % sodium hydride are added to 90 ml of absolute dimethyl-sulfoxide and then 17.8 g of trimethylsulfoxonium iodide are stirred in. The reaction mixture is stirred for 2 hours at room temperature and then a solution of 25 g of 1-[2,4-dichlorophenyl]-2-[4-chloro phenoxy]pentan-1-one in 80 ml of absolute tetrahydrofuran is added. The solution is stirred for 2 hours at about 55"-60"C and then poured into an ice-cold brine solution. Extraction with diethyl ether/ethyl acetate (1:1) yields 24.5 g of crude 2-[2,4-dichlorophenyl]-2-[2-(4-chloro phenoxy)butyl]-oxirane in the form of a yellow oil.
c) Preparation of the final product: To a solution of 91.4 g of 1H-1,2,4-triazole and 20 g of potassium tert-butoxylate in 850 ml of absolute dimethylformamide is added a solution of 197 g of 2-[2.4-dichlorophlorophenyl]-2-[2(4chlorophenyloxy)-butyl]-oxirane in 850 ml of dimkethylformaide, and the mixture is heated for 15 hours to 95 C. The mixture is cooled to room temperature, then poured into a solution of sodium chloride extracted with ethyl acetate. The combined extracts are washed with water, dried over sodium sulfate, filtered and concentrated in vacuo. The residue is crystallised by digestion with diethyl ether, yielding 999 of 1-[1H-1,2,4-triazolyl]-2-[2,4-dichlorophenyl]-2- hydroxy-3-(4-chloro-phenoxy)hexane with a melting point of 144"-145"C.
The following compounds of formula I and intermediates are prepared in analogous manner: Table 1: Compounds of the formula
Com- R2 R3 R4 R5 X Physical pound data [ C] 1.1 CH3 CH3 CH3 C6H4Cl(4) O m.p. 93-94 1.2 CH3 CH3 CH3 C6H3Cl2(2,4) O m.p. 94-95 1.3 CH3 CH3 CH3 C6H3Cl(3,4) O m.p. 126-128 1.4 CH3 CH3 CH3 4-biphenyl O m.p. 134-135 1.5 CH3 CH3 CH3 C6H4C3H7-i(4) 0 oil 1.6 C3H7-i CH3 CH3 C6H4Cl(4) O 1.7 C3H7-i CH3 CH3 C6H4F(4) O 1.8 C3H7-i CH3 CH3 C6H5 O 1.9 C3H7-i CH3 CH3 4-biphenyl O 1.10 C3H7-i CH3 CH3 C6H3Cl2(2,3 O 1.11 C3H7-i CH3 CH3 C6H4(OCF3)(4) O 1.12 C3H7-i CH3 CH3 C6H4(SCF3)(4) O 1.13 C3H7-i CH3 CH3 C6H4(OCHF2)(4) O 1.14 C6H3Cl2(2,4) H C2H5 C6H4CH3(4) O m.p. 98-100 1.15 C6H3Cl2(2,4) H C2H5 C6H4Cl(4) O m.p. 132-133 1.16 C6H3Cl2(2,4) H C2H5 C6H4F(4) O m.p. 139-141 1.17 C6H3Cl2(2,4) H C2H5 C6H4(CH3)2(2,3) O m.p. 121-122 1.18 C6H3Cl2(2,4) H C2H5 C6H4Cl(4) O m.p. 144-145 1.19 C6H3Cl2(2,4) H C2H5 C6H5 O m.p. 155-156 1.20 C6H3Cl2(2,4) H C2H5 C6H4Br(4) O m.p. 121-124 1.21 C6H3C1,F(2,4) H CH3 C6H4Cl(4) 0 m.p. 133-136 1.22 C6H3Cl,F(2,4) H CH3 C6H4(CH3)(4) O m.p. 116-119 1.23 C6H4Cl(4) H C3H7-n C6H4Cl(4) O 1.24 C6H3Cl(4) H C3H7-n C6H4F(4) O 1.25 C4H9-t H CH3 C6H4Cl(4) O m.p. 108-109 Table 1: (continuation)
Com- R2 R3 R4 R5 X Physical pound 2 3 4 5 data [ C] 1.26 C4H9-T H CH3 C6H4F(4) O m.p. 78-82 1.27 C4H9-t H CH3 C6H4CH3(4) 0 m.p, 136-138 1.28 C4H9-t H C2H5 C6H4Cl(4) O m.p. 135-137 1.29 C4H9-t H CH3 C6H5 O 1.30 C4H9-t H CH3 C6H4-CF3(4) O m.p. 123-124 1.31 C4H9-t H CH3 C6H3-OCF3(4) O 1.32 C4H9-t H CH3 C6H3(CH3)2(2,3) O 1.33 C4H9-t H CH3 C6H3Cl2(2,3) O 1.34 C4H9-t H CH3 C6H4Br(4) O 1.35 C4H9-t H CH3 C6H4SCHF2(4) O 1.36 C4H9-t H CH3 C6H4OCHF2(4) O 1.37 C4H9-t H CH3 C6H4C1(4) S 1.38 C4H9-t H C2H5 C6H4F(4) O 1.39 C4H9-t H C2H5 C6H4Br(4) O 1.40 C4H9-t H C2H5 C6H4CH3 (4) 0 1.41 C4H9-t H C2H5 C6H4CF3(4) 0 1.42 C4H9-t H C2H5 C6H40CF3(4) 0 1.43 C4H9-t H C2H5 C6H5 O 1.44 C4H9-t H C3H7-n C6H4Cl(4) O 1.45 C4H9-t H C3H7-n C5H4F(4) 0 1.46) C4H9-t H C3H7-n C6H3Cl2(2.4) O 1.47 C4H9-t H C3H7-n C6H4CH3(4) 0 1.48 C4H9-t H C3H7-n C6H4CF3(4) 0 1.49 C4 H -t H C3H7-n C H O 1.50 C4H9-t H C4H9-n C6H4Cl(4) O 1.51 C4H9-t H C4H9-n C6H4F(4) 0 1.52 C4H9-t H C4H9-n C6H4CF3(4) 0 1.53 C4H9-t H C4H9-n C6H4Br(4) 0 1.54 C4H9-t H C4H9-n C6H4CH3(4) O Table 1: (continuation)
Com- R2 R3 R4 R5 X Physical pound data [ C] 1.55 C3H7-i H CH3 C6H4Cl(4) O 1.56 C3H7-i H C2H5 C6H4Cl(4) O m.p. 69-73 1.57 C3H7-i H C3H7-n C6H4Cl(4) O 1.58 C3H7-i H CH3 C6H4F(4) O 1.59 C3H7-i H C2H5 C6H4F(4) O 1.60 C3H7-i H CH3 C6H4CF3(4) O 1.61 C3H7-i H C2H5 C6H4CF3(4) O 1.62 C3H7-i H CH3H7-n C6H4CF3(4) O 1.63 C3H7-i H CH3 C6H4Br(4) 0 1.64 C3H7-i H CH3 C6H4F(4) 0 1.65 C3H7-i H CH3 C6H4CH3(4) 0 1.66 C4H9-t H C3 C6H4CF3(3) O 1.67 C4H9-t H C3H5 C6H4CF3(3) O 1.68 C4H9-t H CH3 C6H4Cl(3) O 1.69 C4H9-t H C2H5 C6H4Cl(3) O 1.70 C4H9-t H C3H7-n C6H4Cl(3) O 1.71 C4H9-t H CH3 C6H3Cl(4)CH3(2) O 1.72 C4H9-t H C2H5 C6H3(CH3)2(2,3) O 1.73 C4Hg-t H C2H5 C6H3C12(2,3) 0 1.74 C4H9-t H C3H7-i C6H4Cl(4) O 1.75 C4H9-t H C3H7-i C6H4F(4) O 1.76 C4H9-t H C3H7-i C6H4Br(4) O 1.77 C4H9-t H C3H7-i C6H4CH3(4) O 1.78 C4H9-t H C3H7-i C6H4CF3(4) O 1.79 &alpha; ;-naphthylH CH3 C6H4Cl(4) O 1.80 ss-naphthyl H CH3 C6H3Cl2(2,4) O 1.81 a-naphthyl H H C6H3Cl2(2.4) 0 1.82 &alpha;-naphthyl H H C6H3Cl2(2,4) O 1.83 C2H5 H H C6H4Cl(4) O 1.84 C2H5 H CH3 C6H3Cl2(2,3) O 1.85 C2H5 CH3 CH3 C6H4(CH3)(4) O Table 1: (continuation)
Com- R2 R3 R4 R5 X Physical pound data [ C] 1.86 C6H4Cl(4) H C3H7-n C6H5 O 1.87 C6H4Cl(4) H C3H7-n C6H4CF3(4) O 1.88 C6H3C12(2,4) H CH3 C6H5 O m.p. 150-152 1.89 C6H3C12(2,4) H CH3 C6H4C1(4) O m.p. 130-132 1.90 C6H3C12(2,4) H CH3 C6H4CF3(4) 0 1.91 C6H3C12(2,4) H CH3 C6H40CF3(4) 0 1.92 C6H3C12(2,4) H CH3 C6H4F(4) 0 m.p. 121-124 1.93 C6H3C12(2,4) H C2H5 C6H4CF3(4) 0 1.94 C6H3Cl2(2.4) H C3H7-n C6H4F(4) O 1.95 C6H3Cl2(2.4) H C3H7-n C6H4OCF3(4) O 1.96 C6H3Cl2(2.4) H C4H9-n C6H4F(4) O m.p. 174-175 1.97 C6H3Cl2(2.4) H C4H9-n C6H4Cl(4) O m.p. 150-151 1.98 C6H3Cl2(2.4) H C3H7-n C6H4F(4) O 1.99 C6H3C1,F(2.4) H CH3 C6H4F(4) 1.100 C6H3Cl,F(2,4) H C2H5 C6H4Cl(4) O 1.101 C6H3Cl,F(2,4) H C2H5 C6H4Cl(4) O 1.102 C6H3Cl,F(2,4) H C3H7 C6H4Cl(4) O Table 2 @ (Compounds of the formula)
Com- R2 R3 R4 R5 X Physical pound data [ C] 2.1 CH3 CH3 CH3 C6H4Cl(4) O 2.2 CH3 CH3 CH3 C6H3Cl2(2,4) O 2.3 CH3 CH3 CH3 C6H3Cl2(3,4) 0 2.4 CH3 CH3 CH3 4-biphenyl O 2.5 CH3 CH3 CH3 C6H3C37-i(4) O 2.6 CH3 CH3 CH3 CH2CH2C6H4(CH3)(2) 0 2.7 C3H7-i CH3 CH3 C6H4Cl(4) 0 2.8 C3H7-i CH3 CH3 C6H4F(4) 0 2.9 C3H7-i CH3 CH3 C6H5 0 2.10 C3H7-i CH3 CH3 4-biphenyl O 2.11 C3H7-1 CH3 CH3 C6H3Cl3(2,3) O 2.12 C3H7-i CH3 CH3 C6H4(OCF3)(4) O 2.13 C3H7-i CH3 CH3 C6H4(SCF3)(4) O 2.14 C3H7-i CH3 CH3 C6H4(OCHF2)(4) O 2.15 C3H7-i CH3 CH3 C6H4CN(4) O 2.16 C6H3Cl2(2,4) C3H7-n H C6H4Cl(4) O 2.17 C6H3Cl2(2,4) C3H7-n H C6H4F(4) O 2.18 C6H3C12(2,4) CH3 H C6H4CF3(4) 0 2.19 C4H9-t H CH3 C6H4Cl(4) O m.p. 162-163 2.20 C4H9-t H C2H5 C6H4Cl(4) O 2.21 C4H9-t H C3H7-i C6H4Cl(4) O 2.22 C4H9-t H CH3 C6H4Br(4) O 2.23 C4H9-t H C2H5 C6H4Br(4) 0 2.24 C4H9-t H CH3 C6H4F (4) O m.p. 177-178 2.25 C4H9-t H CH3 C6H4CH3(4) O m.p. 172-173 2.26 C4H9-t H CH5 C6H4F (4) O Table 2: (continuation)
Com- R R R R X Physical pound R2 R3 R4 R5 X Physical data [ C] 2.27 C4H9-t H C2H5 C6H4CH3(4) O 2.28 C4H9-t H CH3 C6H4CF3(4) O 2.29 C4Hg-t H C2H5 C6H4CF3(4) 0 2.30 C3H7-i H CH3 C6H4C1(4) O 2.31 C3H7-i H C2H5 C6H4C1(4) 0 2.32 C3H7-i H CH3 C6H4Br(4) 0 2.33 C3H7-i H CH3 C6H4F(4) 0 2.34 3 7 H CH3 C6H4CF3(4) 0 2.35 C4H9-t H C2H5 C6H4OCF3(4) O 2.36 C4H9-t H C2H5 C6H5 O 2.37 C4H9-t H C3H7-n C6H4Cl(4) O 2.38 C4H9-t H C3H7-n C6H4F(4) O 2.39 C4H9-t H C3H7-n C6H4Cl2(2,4) O 2.40 C4H9-t H C3H7-n C6H4CH3(4) O 2.41 C4H9-t H C3H7-n C6H4CF3(4) O 2.42 C4H9-t H C3H7-n C6H5 O 2.43 C4Hg-t H C3H7-i C6H4CF3(4) 0 2.44 &alpha;;-naphthyl H CH3 C6H4Cl(4) O 2.45 ss-naphtahyl H CH3 C6H3C12(2,4) 0 2.46 a-naphthyl H H C6H3Cl2(2,4) 0 2.47 &alpha;-naphthyl H H C6H3C12(2,4) S 2.48 C2H5 H H C6H4Cl(4) O 2.49 C2H5 H CH3 C6H3Cl2(2,3) O 2.50 C2H5 CH3 CH3 C6H4(CH3)(4) O Table 3: Compounds of the formula
Corn- R R, R R 5 Physical pou d R2 R3 R4 5 j ^ ica 3.1 CH3 : H CH3 4-benzyloxyphenyl O 3.2 CH3 H CH3 r u cm(4) 7 3.3 CH3 H CH3 \ / \ /--CF3 3.3 \~~/ 3 3.4 CH3 H CH3 6 H C H (4) 0 6425 3.5 CH3 H CH3 C H,C H -i(4) 0 6437 3.6 CH3 CH3 CH3 C6H4C1(4) 0 3.7 CH3 CR 3 C6H3C12(2,4) 0 3.8 CH3 i CH3 CH3 C6H3C12(3,4) O 3.9 CH3 CH3 CH3 4-biphenyl O 3.10 CH3 CH3 CH3 C6H C3R7-i(4) 0 3.11 CH3 CH3 CH3 ,(CH )(2) 0 64 C3 C3 C, 6q 3 3.12 C3H7-i CH3 CH3 C6H4C1(4) g 3.13 C3H7-i CH3 CH3 C 4 0 64 3.14 C3R7-i CH3 CH3 C6H5 0 3.15 C3R7-i CH3 CH3 4-biphenyl O 3.16 C6H3C12(2,4) H CH3 C6H4C1(4) O m.p. 156-159 3.17 C6H3C12(2,4) H CH3 C6H3C12(2,4) 0 3.18 C6H3C12(2,4) H CH3 C6H5 0 i C6H.5 H CH3 C6R4F(4) O 3.20 C4R9-t H CH3 C6H4C1(4) 0 solid 3.21 C4H9-t H C2H5 C6H4C1(4) 0 3.22 jC4Hg-t H CH3 C6H4F(4) o m.p. 197-1950 13.23 jC4Hg-t H CH3 C6H4Br(4) 0 3.24 fC4R9-t H CR3 C6H4CH3(4) O 3 25 C H -t 13.25 |C4Hg-t 49 CH3 C6H5 O 326 C49-t H ICR C6H4CF3(4) O 3 Table 3: (continuation)
Com- R2 R3 R4 R5 X Physical pound data [ C] 3.27 C4H9-t H CH3 C6H4CH3(4) O 3.28 C3H7-i CH3 CH3 C6H4CL(2,3) O 3.29 C3H7-i CH3 CH3 C6H4(OCF3)(4) O 3.30 C3H7-i CH3 CH3 C6H4(SCF3(4) 0 3.31 C3H7-i CH3 CH3 C6H4(OCHF2)(4) O 3.32 C3H7-i CH3 CH2 C6H4CN(4) 0 3.33 C6H3Cl2(2,4) H C2H5 C6H2(CH3)2(3,5)Br(4) O m.p. 177-178 3.34 C6H3Cl2(2,4) H C2H5 C6H4F(4) O 3.35 C6H3Cl2(2,4) H C2H5 C6H3(CH3)2(2,3) O 3.36 C6H3Cl2(2,4) H C3H7-n C6H4Cl(4) O 3.37 C6H3Cl2(2,4) H C2H5 C6H5 O 3.38 C6H3Cl2(2,4) H C2H5 C6H4Br(4) O 3.39 C6H3C1,F(2,4) H CH3 C6H4Cl(4) O 3.40 C6H3Cl,F(2,4) H CH3 C6H4(CH3)(4) O 3.41 C4H9-t H C2H5 C6H4CF3(3) O 3.42 C4Hg-t H CH3 C6H4C1(3) O 3.43 C4Hg-t H C2R5 C6H4Cl(3) 0 3.44 C4H9-t H C3H7-n C6H4Cl(3) O 3.45 C4H9-t H CH3 C6H3Cl(4)CH3(2) O 3.46 C4H9-t H C2H5 C6H3(CH3)2(2,3) O 3.47 C4H9-t H C2H5 C6H3Cl2(2,3) O 3.48 C4Hg-t H C3H7-i C6H4C1(4) 3.49 C4Hg-t H C3H7-i C6H4F(4) 0 3.50 C4H9-t H C3H7-i C6H4CH3(4) O 3.51 C4H9-t H C3H7-i C6H4CH3(4) O 3.52 C4H9-t H C3H7-i C6H4CF3(4) O 3.53 &alpha;-naphthylH CH3 C6H4Cl(4) O 3.54 ss-naphtyl H CH3 C6H4Cl2(2,4) O 3.55 a-naphthyl H H C6H3C12(2,4) 0 Table 3: (continuation)
Com- R2 R3 R4 R5 X Physical pound data [ C] 3.56 a-naphthyl H H C6H3Cl2(2,4) S 3.57 C2H5 H H C6H4Cl(4) 0 3.58 C2H5 H CH3 C6H3Cl2(2,3) O 3.59 C2H5 CH3 CH3 C6H4(CH3)(4) O Table 4:Intermediates of the formula II
Com- R2 R3 R4 R5 X Physical pound data [ C] 4.1 CH3 CH3 CH3 C6H4C1(4) 0 oil 4.2 CH3 CH3 CH3 C6H3Cl2(2,4) O oil 4.3 CH3 CH3 CH3 C6H3C12(3,4) 0 oil 4.4 CH3 CH3 CH3 4-biphenyl 0 oil 4.5 CH3 CH3 CH3 C6H3C3H7-i(4) O oil 4.6 C3H7-i CH3 CH3 C6H4Cl(4) O 4.7 C3H7-i CH3 CH3 C6H4F(4) O 4.8 C3H7-i CH3 CH3 C6H5 O 4.9 C3H7-i CH3 CH3 4-biphenyl O 4.10 C3H7-i CR3 . CR3 C6H3C1(2,3) 0 4.11 C3H7-i CH3 CH3 C6H4(OCF3)(4) O 4.12 C3H7-i CH3 CH3 C6H4(SCF3)(4) 0 4.13 C3H7-i CH3 CH3 C6H4(OCHF2)(4) O 4.14 C3H7-i CH3 CH3 C6H4CN(4) O 4.15 C6H3Cl2(2,4) H C2H5 C6H4Cl(4) O oil 4.16 C6H3C12(2,4) H C2H5 C6H4F(4) O oil 4.17 C6H3Cl2(2,4) H C2H5 C6H3(CH3)2(2,3) O oil 4.18 C6H3Cl2(2,4) H C3H7-n C6H4Cl(4) O oil 4.19 C6H3Cl2(2,4) H C2H5 C6H5 O oil 4.20 C6H3Cl2(2,4) H C2H5 C6H4Br(4) O oil 4.21 C6H3Cl2(2,4) H CH3 C6H4Cl(4) O oil 4.22 C6H3Cl2(2,4) H CH3 C6H4(CH3)(4) O oil 4.23 C6H3Cl2(2,4) H C3H7-n C6H4Cl(4) O oil 4.24 C6H3Cl2(2,4) H C3H7-n C6H4F(4) O oil 4.25 C4H5-t H CH3 C6H4Cl(4) O oil Table 4: (continuation)
Com- R2 R3 R4 R5 X Physical pound data [ C] 4.26 C4H9-t H CH3 C6H4F(4) O b.p. 76-78 / 4.27 C4H9-t H CH3 C6H4CH3(4) O 0.01 torr 4.28 C4H9-t H CH3 C6H4Cl(4) O b.p. 80-85 / 4.29 C4H9-t H CH3 C6H5 O 0.05 torr 4.30 C4H9-t H CH3 C6H4CF3(4) O b.p. 90-95 / 4.31 C4H9-t H CH3 C6H4OCF3(4) O 0.01 torr 4.32 C4H9-t H CH3 C6H3(CH3)2(2,3) O 4.33 C4H9-t H CH3 C6H3Cl2(2,3) O 4.34 C4H9-t H CH3 C6H4Br(4) O 4.35 C4H9-t H CH3 C6H4SCHF2(4) O 4.36 C4H9-t H CH3 C6H4OCUF2(4) O 4.37 C4H9-t H CH3 C6H4Cl(4) S 4.38 C4H9-t H C2H5 C6H4F(4) O 4.39 C4H9-t H C2H5 C6H4Br(4) O 4.40 C4H9-t H C2H5 C6H4CH3(4) O 4.41 C4H9-t H C2H5 C6H4CH3(4) O 4.42 C4H9-t H C2H5 C6H4OCF3(4) O 4.43 C4H9-t H C2H5 C6H5 O 4.44 C4H9-t H C3H7-n C6H4Cl(4) 0 4.45 C4H9-t H C3H7-n C6H4F(4) O 4.46 C H -t H C3H7-n C6H3Cl2(2,4) 0 4,47 C4H9-t H C3H7-n C6H4CH3(4) O 4.48 C4H9-t H C3H7-n C6H4CF3(4) O 4.49 C4H9-t H C3H7-n C6H5 O 4.50 C4H9-t H C4H9-n C6H4Cl(4) O 4.51 C4H9-t H C4H9-n C6H4F(4) O 4.52 C4H9-t H C4H9-n C6H4CF3(4) O 4.53 C4H9-t H C4H9-n C6H4Br(4) O 4.54 C4H9-t H C4H9-n C6H4CH3(4) O 4.55 C4H9-t H CH3 C6H4Cl(4) O Table 4: (continuation)
Com- R2 R3 R4 R5 X Physical pound data [ C] 4.56 C3H7-i H C2H5 C6H4Cl(4) O oil 4.57 C3H7-i H C3H7-n C6H4Cl(4) O 4.58 C3H7-i H CH35 C6H4F(4) O 4.59 C3H7-i H C2H5 C6H4F(4) O 4.60 C3H7-i H CH3 C6H4CF3(4) 0 4.61 C3H7-i H C2H5 C6H4CF3(4) O 4.62 C3H7-i H C3H7-n C6H4CF3(4) O 4.63 C3H7-i H CH3 C6H4Br(4) O 4.64 C3H7-i H CH3 C6H4F(4) 0 4.65 C3H7-i H CH3 C6H4CH3(4) O 4.66 C3H9-t H CH3 C6H4CF3(3) O 4.67 C3H9-t H C2H5 C6H4CF3(3) O 4.68 - C4Hg-t H CH3 C6H4C1(3) 0 4.69 C4H9-t H C2H5 C6H4Cl(3) O 4.70 C4H9-t H C3H7-n C6H4Cl(3) O 4.71 C4H9-t H CH3 C6H3CH(4)CH3(2) O 4.72 C4H9-t H C2H5 C6H3(CH3)2(2,3) O 4.73 C4H9-t H C2H5 C6H3Cl2(2,3) O 4.74 C4H9-t H C3H7-i C6H4Cl(4) O 4.75 C4H9-t H C3H7-i C6H4F(4) O 4.76 C4Hg-t H C3H7-i C6H4Br(4) 0 4.77 C4H9-t H C3H7-i C6H4CH3(4) O 4.78 C4H9-t H C3H7-i C6H4CF3(4) O 4.79 &alpha;-naphthylH CH3 C6H4Cl(4) O 4.80 ss-naphthyl H CH3 C6H3Cl2(2,4) O 4.81 &alpha;-naphthylH H C6H3Cl2(2,4) O 4.82 &alpha;-naphthylH H C6H3Cl2(2,4) S 4.83 C2H5 H H C6H 0 4.84 C2H5 H CH3 C6H3Cl2(2,3) O 4,85 C2H5 CH3 CH3 C6H4(CH3)(4) O Table 4: (continuation)
Com- R2 R3 R4 R5 X Physical pound data [ C] 4.86 C6H4Cl(4) H C3H7-n C6H5 O 4.87 C6H4Cl(4) H C3H7-n C6H4CF3(4) O 4.88 C6H3Cl2(2,4) H CH3 C6R5 0 4,89 C6H3Cl2(2,4) H CH3 C6H4Cl(4) O 4.90 C6H3Cl2(2,4) H CH3 C6H4CF3(4) 0 4,91 C6H3Cl2(2,4) H CH3 C6H4OCF3(4) O 4.92 C6H3Cl2(2,4) H CH3 C6H4F(4) O 4.93 C6H3Cl2(2,4) H C2H5 C6H4CF3(4) O 4.94 C6H3Cl2(2,4) H C3H7-n C6H4F(4) O 4.95 C6H3Cl2(2,4) H C3H7-n C6H4OCF3(4) O 4.96 C6H3C12(2,4) H C4Hg-n C6H4F(4) 0 4.97 C6H3Cl2(2,4) H C4H9-n C6H4Cl(4) O 4.98 C6H3Cl2(2,4) H C3H7-i C6H4F(4) 0 4.99 C6H3C1,F(2.4) H VH3 C6H4F(4) 0 4.100 C6H3C1,F(2,4) H C2H5 C6H4Cl(4) 0 4.101 C6H3Cl,F(2,4) H C2H5 C6H4F(4) O 4.102 C6H3Cl,F(2,4) H C3H7 C6H4F(4) O Formulation Examples 2 to 11 Formulation Examples for liquid active ingredients of the formula I (throughout, percentages are by weight) 2.Emulsifiable concentrates a) b) c) a compound of tables 1 to 3 25% 40% 50% calcium dodecylbenzenesulfonate 5% 8% 6% castor oil polyethylene glycol ether 5% (36 moles of ethylene oxide) tributylphenol polyethylene glycol ether 12% 4% (30 moles of ethylene oxide) cyclohexanone 15% 20% xylene mixture 65% 25% 20% Emulsions of any required concentration can be produced from such concentrates by dilution with water.
3. Solutions a) b) c) d) a compound of tables 1 to 3 80% 10% 5% 95% ethylene glycol monomethyl ether 20% polyethylene glycol 400 70% N-methyl-2-pyrrolidone 20 epoxidised coconut oil 1% 5% petroleum distillate (boiling range 94% 160-i 90') These solutions are suitable for application in the form of microdrops.
4. Granulates a) b) a compound of tables 1 to 3 5% 10% kaolin 94% highly dispersed silicic acid 1 % attapulgite 90% The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.
5. Dusts a) b) a compound of tables 1 to 3 2% 5% highly dispersed silicic acid 1% 5% talcum 97% kaolin 90% Ready-for-use dusts are obtained by intimately mixing the carriers with the active ingredient.
Formulation Examples for solid active ingredients of the formula I (throughout, percentages are by weight) 6. Wettable powders a) b) c) a compound of tables 1 to 3 25% 50% 75% sodium lignosulfonate 5% 5% sodium lauryl sulfate 3% 5% sodium diisobutylnapthalenesulfonate 6% 10% octylphenol polyethylene glycol ether 2% (7-8 moles of ethylene oxide) highly dispersed silicic acid 5% 10% 10% kaolin 62% 27% The active ingredient is thoroughly mixed with the adjuvants and the mixtures is thorougly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
7. Emulsifiable concentrate a compound of tables 1 to 3 10% octylphenol polyethylene glycol ether 3% (4-5 moles of ethylene oxide) calcium dodecylbenzenesulfonate 3% castor oil polyglycol ether 4% (36 moles of ethylene oxide) cyclohexanone 30% xylene mixture 50% Emulsions of any required concentration can be obtained from this concentrate by dilution with water.
8. Dusts a) b) a compound of tables 1 to 3 5% 8% talcum 95% kaolin 92% Ready-for-use dusts are obtained by mixing the active ingredient with the carriers, and grinding the mixture in a suitable mill.
9. Extruder granulate a compound of tables 1 to 3 10% sodium lignosulfonate 2% carboxymethylcellulose 1 kaolin 87% The active ingredient is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water. The mixture is extruded and then dried in a stream of air.
1 0. Coated granulate a compound of tables 1 to 3 3% polyethylene glycol 200 3% kaolin 94% The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.
11. Suspension Concentrate a compound of tables 1 to 3 40% ethylene glycol 1 0% nonylphenol polyethylene glycol 6% (15 moles of ethylene oxide) sodium lignosulfonate 10% carboxymethylcellulose 1 % 37% aqueous formaldehyde solution 0.2% silicone oil in the torm of 75% 0.8% aqueous emulsion water 32% The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
Biological Examples 12 to 21 Example 12: Action against Puccinia graminis on wheat a) Residual-protective action Wheat plants are treated 6 days after sowing with a spray mixture prepared from wettable powder formulation of the active ingredient (0.06%). After 24 hours the treated plants are infected with a uredospore suspension of the fungus. The infected plants are incubated for 48 hours at 95-100% relative humidity and about 20"C and then stood in a greenhouse at about 22"C. Evaluation of rust pustule development is made 1 2 days after infection.
b) Systemic action Wheat plants are treated 5 days after sowing with a spray mixture prepared from a wettable powder formulation of the active ingredient (0,006% based on the volume of the soil). After 48 hours the treated plants are infected with a uredospore suspension of the fungus. The plants are then incubated for 48 hours at 95-100% relative humidity and about 20"C and then stood in a greenhouse at about 22"C. Evaluation of rust pustule development is made 1 2 days after infection. Compounds of Tables 1 to 3 are effective against Puccinia fungi. Puccinia attack is 100% on untreated and infected control plants. Among others, compounds 1.1 to 1.5, 1.15 to 1.20, 1.25 to 1.28, 3.20, 3.22 and 3.33 inhibit attack by Puccinia to 0 to 15%.
Example 13: Action against Cercospora arachidicola in groundnut plants a) Residual protective action Groundnut plants 10-15 cm in height are sprayed with a spray mixture (0.02 %) prepared from a wettable powder formulation of the active ingredient, and infected 48 hours later with a conidia suspension of the fungus. The infected plants are incubated for 72 hours at about 21 "C and high humidity and then stood in a greenhouse until the typical leaf specks occur. Evaluation of the fungicidal action is made 1 2 days after infection and is based on the number and size of the specks.
b) Systemic action Groundnut plants 10-15 cm in height are sprayed with a spray mixture prepared from a wettable powder formulation of the active ingredient (0.06 %, based on the volume of the soil).
The treated plants are infected 48 hours later with conidia suspension of the fungus and then incubated for 72 hours at about 21"C and high humidity. The plants are then stood in a greenhouse and evaluation of fungus attack is made 11 days later. Compared with untreated and infected controls (number and size of the specks = 100%), the plants treated with compounds of Tables 1 to 3 exhibit greatly reduced attack by Cercospora.
In the above tests, compounds 1.1 to 1.5, especially 1.15 to 1.20, and also 1.25 to 1.28, 3.20, 3.22 and 3.33 prevent speck development almost completely (0 to 10%).
Example 14: Action against Erysiphe graminis on barley a) Residual protective action Barley plants about 8 cm in height are sprayed with a spray mixture (0.02%) prepared from the active ingredient formulated as a wettable powder. The treated plants are dusted with conidia of the fungus after 3-4 hours. The infected barley plants are then stood in a greenhouse at about 22"C. The extent of the infestation is evaluated after 10 days.
b) Systemic action Barley plants about 8 cm in height are treated with a spray mixture (0.006%, based on the volume of the soil) prepared from the active ingredient formulated as wettable powder. Care is taken that the spray mixture does not come in contact with the parts of the plants above the soil. The treated plants are infected 48 hours later with a conidia suspension of the fungus. The infected barley plants are then stood ina greenhouse at about 22"C and evaluation of infestation is made after 10 days.
Compounds of the formula I are very effective against Erysiphe fungi. Erysiphe attack is 100% untreated and infected control plants. Among other compounds of Tables 1 to 3, compounds 1.1 to 1.5, especially 1.15 to 1.20, and also 1.25 to 1.28 and 3.20 reduce fungus attack in barley to 0 to 15%.
Example 15: Residual-protective action against Venturia inaequalis on apple shoots Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray mixture (0.06%) prepared from a wettable powder formulation of the active ingredient. The plants are infected 24 hours later with a conidia suspension of the fungus. The plants are then incubated for 5 days at 90-100% relative humidity and stood in a greenhouse for a further 10 days at 20"-24"C. Scab infestation is evaluated 1 5 days after infection.
Compounds 1.1 to 1.5, especially 1.15 to 1.20, and also 1.25 to 1.28 and 3.20 inhibit attack to less than 10 %. Venturia attack is 100 % on untreated and infected shoots.
Example 16: Action against Botrytis cinerea on beans Residual protective action Bean plants about 10 cm in height are sprayed witha spray mixture (0.2% concentration) prepared from the active ingredient formulated as wettable powder. After 48 hours, the treated plants are infected with a conidia suspension of the fungus. The infected plants are incubated for 3 days at 95-100% relative humidity and 21 C, and evaluation of the fungus attack is then made. Many compounds of Tables 1 to 3 very strongly inhibit fungus attack. For example, at a concentration of 0.02 % compounds 1.15, 1.16. 1.17, 1.18, 1.19 and 1.20 are very effective (0 to 5 % attack). Botrytis attack is 100 % on untreated and infected bean plants.
Example 1 7: Growth inhibition of cereals Summer barley (Hordeum volgare) and summer rye (Secale) are sown in sterilised soil in plastic beakers in a greenhouse and watered as required. The cereal shoots are treated about 21 days after sowing with an aqueous spray mixture of a compound of the formula I. The concentration corresponds to 0.5 and 2.5 kg respectively of active ingredient per hectare.
Evaluation of the growth of the cereals is made 'i 0 and 21 days after application. Compared with untreated controls, the growth of cereal plants treated with compounds of the formula I is greatly reduced. Compounds of Tables 1 to 3 are particularly effective. For example, compounds 1.1 to 1.5, especially 1.15 to 1.20, as well as 1.25 to 1.28 and 3.20 reduce the growth rate to less than 10%.
Example 18 Growth inhibition of grasses Seeds of the grasses Lolium perenne, Poa pratensis, Festuca ovina, and Cynodon dactylon are sown in plastic dishes filled with an earth/peat/sand mixture (6:3:1), in a greenhouse, and watered as reqired. The emergent grasses are cut back weekly to a height of 4 cm above the soil and, 50 days after sowing and 1 day after the last cut are sprayed with an aqueous spray mixture of an active ingredient of the formula I. The concentration of active ingredient corresponds to a rate of application of 0.5 and 2.5 kg per hectare respectively. The growth of the grasses is evaluated 10 to 21 days after application. The compounds of Tables 1 to 3 effect a marked reduction in growth. For example, compounds 1.1 to 1.5, 1.15 to 1.20, 1.25 to 1.28, 3.20, 3.22 and 3.33 reduce growth almost completely (growth rate 0 to 100%).
Example 19: Increase in crop yield by regulating the growth of soybeans Soybeans of the 'Hark" variety are sown in plastic containers in an earth/peat/sand mixture (6:3:1). The containers are put into a climatic chamber and the plants develop to the 5-6 trefoil leaf stage after about 5 weeks by optimum control of temperature, light, fertiliser addition, and watering. The plants are then sprayed with an aqueous mixture of a compound of the formula I until thoroughly wetted. Evaluation is made about 5 weeks after application. Compared with untreated controls, the compounds of the formula I markedly increase the number and weight of the harvested siliques. The compounds of Tables 1 to 3 are particularly effective.In particular, compounds 1.1 to 1.5, 1.15 to 1.20, 1.25 to '1.28, 3.20, 3.22 and 3.33 effect an increase in yield of 5 to 12 %.
Example 20: Growth inhibition of cover crops Test plants of the varieties Centrosema plumieri and Centrosema pubescens are reared from cuttings in plastic pots filled with an earth/turf/sand mixture (1:1:1). After they have grown roots, the plants are transplanted into 9 cm pots and watered as required. For further growth the plants are then kept in a greenhouse at a day temperature of 27"C and a night temperature of 21"C. The average light exposure is 14 hours (6000 lux) and the humidity is 70%. The plants are cut back to a height of about 1 5 cm and sprayed 7 days later with a spray mixture of the active ingredient (corresponding to a rate of application of 0.3 and 3 kg/a.i./ha respectively).
Four weeks after application the growth of the plants is compared with that of untreated control plants which have been cut back. Compounds of Tables 1 to 3 effect a marked growth inhibition of the cover plants. In particular compounds 1.1 to 1.5, 1.15 to 1.20, 1.25 to 1.28, 3.20, 3.22 and 3.33 induce a pronounced growth inhibition and reduce the growth rate to O to 20 %.
Example 21 inhibition of senescence in cereal plants Summer wheat of the 'Svenno" variety is sown in pots with compost soil and reared without special climatic conditions. About 10 days after emergence, 10 to 1 2 cm primary leaves are cut off and put Individual!v Into the test tubes containing 10 ml of an active ingredient suspension (1.25 to 10 ppm). The test tubes are kept in a climatic room at 23"C and 70% relative humidity and irradiated daily for an average of 1 4 hours (10,000 lux). Evaluation of senescence is made 7 days later by comparing the degree of yellowing with still fresh, green leaves. This test shows that compounds of Tables 1 to 3 markedly inhibit the senescence of the test plants. In particular, compounds 1.1, 1.2, 1.3. 1.4, 1.5, 1.25, 1.27, 3.20 and 3.33 inhibit yellowing of the leaves by more than 80 % during the test period.

Claims (47)

1. A compound of the formula I
wherein R, is an azolyl group, R2 is C,-C4 alkyl or an aryl group which is unsubstituted or substituted by halogen, cyano, C,-C3 alkyl, C,-C3alkoxy, nitro thiocyano, C,-C3 alkylthio and/or C,-C3 haloalkyl, P3 and R4, each independently of the other, are C,-C4alkyl or one is hydrogen and the other is C, -C4alkyl, R5 is an unsubstituted or mono- or polysubstituted radical selected from the group consisting of phenyl, biphenyl, benzylphenyl, benzyloxyphenyl and phenoxyphenyl, said substituents being selected from the group consisting of halogen, cyano, C,-C3alkyl, C,-C2-alkoxy, C,-Cshaloal- koxy, C,-C3alkylthio, C,-C3haloalkyl, C,-C 3haloalkylthio, nitro and/or thiocyano; and X is oxygen or sulfur, or an acid addition salt, quaternary azolium salt or metal complex thereof.
2. A compound of the formula I according to claim 1, wherein R, is a 1 H-1.2,4-triazolyl, 4H-1,2,4-triazolyl or 1 H-imidazolyl group; R2 is methyl, ethyl, isopropyl, tert-butyl, phenyl or phenyl which is mono- or polysubstituted by C,-C3alkyl, C,-C3alkoxy, CF3, halogen and/or phenyl; each of R3 and R4 independently of the other is C,-C4alkyl or one is hydrogen and the other is C,-C4alkyl; R5 is a radical selected from the group consisting of phenyl, biphenyl, benzylphenyl and phenoxyphenyl, which radical may be unsubstituted or mono- or polysubstituted by halogen, cyano, C,-C2alkyl, C,-C2alkoxy, C,-C5haloalkoxy, C,-C2alkylthio, C,-C2haloalkyl, C,-C2haloalkylthio and/or nitro; and X is oxygen or sulphur.
3. A compound of the formula I according to either of claims 1 or 2, wherein R2 is tertbutyl.
4. A compound of the formula I according to claim 2, wherein R, is a 1 H-1,2,4-triazolyl, 4H-1,2,4-triazolyl or 1 H-imidazolyl group; R2 is methyl, ethyl, isopropyl, tert-butyl, phenyl or phenyl which is mono- or polysubstituted by C,-C3alkyl, C,-C3alkoxy, CF3, halogen and/or phenyl; each of R3 and R4 independently of the other is C,-C4alkyl; R5 is an aromatic radical selected from the group consisting of phenyl, biphenyl, benzylphenyl, benzoxyphenyl and phenoxyphenyl, which radical may be unsubstituted or mono- or polysubstituted by C,-C2alkyl, C,-C2alkoxy, halogen, cyano, CF3, nitro and/or C,-C2alkylthio; and X is oxygen or sulphur.
5. A compound of the formula I according to claim 4, wherein R, is a 1 H-1,2,4-triazolyl, 4H-1,2,4-triazolyl or 1 H-imidazolyl group; R2 is methyl, isopropyl, tert-butyl, phenyl, halophenyl, dihalophenyl or biphenyl; R3 is hydrogen and R4 is C,-C3alkyl; X is oxygen or sulfur; and R5 is an aromatic radical selected from the group consisting of phenyl, biphenyl, benzylphenyl, benzoxyphenyl and phenoxyphenyl, which radicals may be unsubstituted or mono- or polysubstituted by C,-C2alkyl, C,-C2alkoxy, halogen, cyano, CF3, nitro and/or C,-C2alkylthio.
6. A compound of the formula I according to claim 4, wherein the R, is d 1 H-1,2,4-triazolyl or 4H-1,2,4-triazolyl group; R2 is tert-butyl, halophenyl or dihalophenyl; R3 is hydrogen, methyl or ethyl; R4 is methyl or ethyl; R5 is phenyl which may be mono- to trisubstituted by C,-C2 alkyl, C,-C2alkoxy, halogen, cyano, CF3, nitro and or C,-C2alkylthio; and X is oxygen or sulfur.
7. A compound of the formula I according to claim 6, wherein R, is a 1 H-1,2,4-triazolyl or 4H-1,2,4-triazolyl group; R2 is tert-butyl, 4-chlorophenyl, 4-bromophenyl, 2,4-dichlorophenyl or 2-chloro-4-bromo-phenyl; R3 is hydrogen and R4 is methyl or ethyl; R5 is phenyl or phenyl which may be mono- to trisubstituted by methyl, methoxy, chlorine, bromine, fluorine, cyano, CF3, nitro or methylthio; and X is oxygen.
8. A compound of the formula I according to claim 7, wherein R5 is a 1 H-1,2,4-triazolyl group.
9. A compound according to any one of claims 1 to 6, wherein R3 and R4 are hydrogen.
10. 1-[1H-1,2,4-triazolyl]-2-methyl-2-hydroxy-3-[4-chlorophenoxy]-3-methylbutane.
11. 1-[1 H-i , 2,4-triazolyl]-2-methyl-2-hydroxy-3-[2,4-dichlorophenoxy]-3-methylbutane,
12. 1-[1 H-1,2,4-triazolyl]-2-methyl-2-hydroxy-3-[4.dichlorophenoxy]-3-methylbutane,
13. 1 -[i H- , 2,4-triazolyl]-2-methyl-2-hydroxy-3-[4-biphenyl3-3-methylbutane,
14. 1 -[1 H- 1,2,4-triazolyl]-2-methyl-2-hydroxy-3-[4-isopropylaphenoxy]-3-methylbutane,
15.1-[1H-1,2,4-triazolyl]-2-[2,4-dichlorophenyl-2-hydroxy-3-[4-chlorophenoxy]-pentane,
16.1-[1H-1,2,4-triazolyl]-2-[2,4-dichlorophenyl-2-hydroxy-3-[4-fluorophenoxy]-pentane,
17.1-[1H-1,2,4-triazolyl]-2-[2,4-dichlorophenyl-2-hydroxy-3-[2,3-dimethylphenoxy]-pentane,
1 8. 1-[1 H-1,2,4-triazolyl]-2-[2,4-dichlorophenyl]-2-hydroxy-3-[4-chlorophenoxy]-hexane,
19. 1-[1 H-i 2, 4-triazolyl]-2-[2, 4-d ich lorophenyl]-2-hydroxy-3-[phenoxy]-pentane,
20. 1 -[1 H-i ,2, 4-triazolyl]-2-[2, 4-dich lorophenyl]-2-hydroxy-3-[4-bromophenoxy]-pentane,
21. 1-[1 H-1,2,4-triazolyl]-2-[2-chloro-4-fluorophenyl]-2-hydroxy-3-[4-chlorophenoxy]-butane,
22. 1 -[i H-i , 2, 4-triazolyl]-2-tert-butyl-2-hyd roxy-3-[4-ch lorophenoxy]-butane,
23. 1-[1 H-1,2,4-triazolyl]-2-tert-butyl-2-hydroxy-3-[4-fluorophenoxy]-butane,
24. 1-[1 H-1,2,4-triazolyl]-2-tert-butyl-2-hydroxy-3-[4-methylphenoxy]-butane.
25. 1-[1H-1,2,4-triazolyl]-2-[2,4-dichlorophenyl-2-hydroxy-3- [4-chlorophenoxy]-pentane,
26. 1-[1H-1,2,4-triazolyl]-2-[2,4-dichlorophenyl-2-hydroxy-3-[4-chlorophenoxy-butane,
27. 1-[4H-1,2,4-triazolyl]-2-tert-butyl-2-hydroxy-3-[4-fluorophenoxy]-butane,
28. 1 -[4H- 1,2,4-triazolyl]-2-[2,4-dichlorophenyl]-2-hydroxy-3-[4-chlorophenoxy]-butane.
29. A compound of the formula I substantially as described with reference to Example 1.
30. A process for the preparation of a compound of the formula I as defined in claim 1, which process comprises reacting an oxirane of the formula II
wherein R2, R3, R4, X and R5 are as defined in claim 1, with an azole of the formula Ill M-R, (III) wherein M is hydrogen or a metal atom and R1 is as defined for formula I in claim 1.
31. A process according to claim 30, wherein the reaction is conducted in a relatively polar, inert organic solvent.
32. A process according to claim 31, wherein the solvent is N, N-dimethylformamide, N,Ndimethylacetamide. dimethylsulfoxide, acetonitrile or benzonitrile or a mixture of said solvents with one another or together with other customary inert organic solvents.
33. A process according to claim 30, wherein the reaction is carried out in the presence of a condensing agent or an acid acceptor.
34. A process for the preparation of a compound of formula I according to claim 30 substantially as described with reference to Example 1.
35. A compound of formula I when produced by a process claimed in any of claims 30 to 34.
36. A composition for controlling or preventing attack by microorganisms and/or for regulating plant growth, which composition comprises at least one compound of the formula I as claimed in claim 1.
37. A composition according to claim 36 which comprises at least one compound of the formula I as claimed in claim 2.
38. A composition for controlling microorganisms according to claim 36, which comprises at least one compound of the formula I as claimed in claim 3.
39. A composition according to claim 36, which comprises at least one compound of the formula I as claimed in any one of claims 4 to 29.
40. A composition according to any one of claims 36 to 39, which comprises 0.1 to 97% of a compound of formula 1, 99.9 to 1 % of a solid or liquid adjuvant and 0 to 25% of a surfactant.
41. A composition according to claim 40, which comprises 0.1 to 95% of a compound of formula 1, 99.8 to 5% of a solid or liquid adjuvsnt and 0.1 to 25% of a surfactant.
42. A composition according to claim 36 substantially as described with reference to any Formulation Examples 2 to 11.
43. A method of preparing an agrochemical composition as claimed in any one of claims 36 to 42, which method comprises homogeneously mixing at least one compound of the formula I as defined in any one of claims 1 to 29 with suitable solid or liquid adjuvants and surfactants.
44. A method of controlling phytopathogenic microorganisms or of protecting cultivated plants from attack by said microorganisms, which method comprises applying to plants or to the locus thereof a microbicidally effective amount of a compound of the general formula I as defined in any one of claims 1 to 29.
45. A method of regulating plant growth, which method comprises applying to plants an effective amount of compound of the formula I as defined in any one of claims 1 to 29.
46. A method according to any of claims 43 to 45 substantially as described with reference to any of Biological Examples 12 to 21.
47. An oxirane of the formula li
wherein R2, R3, R4, X and R5 are as defined for formula I.
GB08218713A 1981-07-02 1982-06-29 Microbidical and growth regulating 2-hydroxy-3-azolylpropane derivatives Withdrawn GB2101994A (en)

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DK161382C (en) * 1982-04-01 1991-12-09 Pfizer PROCEDURE FOR PREPARING 1,2,4-TRIAZOL COMPOUNDS OR PHARMACEUTICAL ACCEPTABLE ACID ADDITION SALTS
JPS5998073A (en) * 1982-11-02 1984-06-06 フアイザ−・コ−ポレ−シヨン Triazole fungicide
US4610716A (en) * 1982-12-14 1986-09-09 Ciba-Geigy Corporation Fluorinated azolyl ethanol growth regulators and microbicides
EP0113644A3 (en) * 1983-01-06 1984-09-26 Ciba-Geigy Ag Halogen azolyl propane derivatives as microbicides and plant growth regulators
AU572889B2 (en) * 1983-09-26 1988-05-19 Sumitomo Chemical Company, Limited 1,2,4 - triazolyl propanols
EP0145663B1 (en) * 1983-12-08 1989-06-21 Ciba-Geigy Ag 1-di- or triazolyl-2,3-diphenyl-propane-2,3-dioles as herbicides or plant growth regulators
KR930004193B1 (en) * 1984-10-02 1993-05-21 스미또모 세이야꾸 가부시끼가이샤 Process for preparing n-substituted triazole derivatives
CN1008735B (en) * 1984-11-02 1990-07-11 拜尔公司 Pyrrole ylmethyl-cyclopropyl-carbinol derivatives with replacement is a composition of active components
IT1198240B (en) * 1986-12-23 1988-12-21 Agrimont Spa FUNGICIDAL AZOLYL DERIVATIVES

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YU32302B (en) * 1968-10-31 1974-08-31 Krka Tovarna Zdravil Postopek za pripravo imidazolnih derivatov
DE2350121A1 (en) * 1973-10-05 1975-04-10 Bayer Ag ANTIMICROBIAL AGENTS
DE2350123C2 (en) * 1973-10-05 1983-04-14 Bayer Ag, 5090 Leverkusen 1-Propyl-imidazole derivatives and their salts, processes for their preparation and their use as fungicides
DE2350122C2 (en) * 1973-10-05 1982-06-24 Bayer Ag, 5090 Leverkusen 1-propyl-1,2,4-triazolyl derivatives and their salts, processes for their preparation and their use as fungicides
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