CA1187085A - 2-imidazolylmethyl-2-phenyl-1,3-dioxolanes, a process for their preparation, and their use as fungicides - Google Patents
2-imidazolylmethyl-2-phenyl-1,3-dioxolanes, a process for their preparation, and their use as fungicidesInfo
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- CA1187085A CA1187085A CA000414986A CA414986A CA1187085A CA 1187085 A CA1187085 A CA 1187085A CA 000414986 A CA000414986 A CA 000414986A CA 414986 A CA414986 A CA 414986A CA 1187085 A CA1187085 A CA 1187085A
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- Prior art keywords
- compound
- methyl
- phenyl
- group
- dioxolane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- 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
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/16—Radicals substituted by halogen atoms or nitro radicals
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
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Abstract
A B S T R A C T
2-Imidazolylmethyl-2-phenyl-1,3-dioxolanes, a process for their preparation, and their use as fungicides 2-Imidazolylmethyl-2-phenyl-1,3-dioxolanes of the formula (I) In which R represents a grouping of the general formula R1 represents a hydrogen atom or an alkyl group, R2 represents a hydrogen or an alkyl or halogeno-alkyl group, X represents a hydrogen or halogen atom or an alkyl, alkoxy, nitro or cyano group, n is 1 or 2, and Y represents an optionally substituted phenoxy or substituted phenyl group, and their physiologically acceptable acid addition salts and metal salt complexes are novel, are produced as described and find use as fungicides.
1,3-Dioxolane derivates of the formula (II) in which R, R1 and R2 have the meanings given above, and Z represents a halogen atom or a grouping of the general formula -O-SO2-R3, ABSTRACT
wherein R3 represents a methyl or p-methylphenyl group, which are intermediates in the production of compounds of formula (I), are also novel and are prepared as described.
2-Imidazolylmethyl-2-phenyl-1,3-dioxolanes, a process for their preparation, and their use as fungicides 2-Imidazolylmethyl-2-phenyl-1,3-dioxolanes of the formula (I) In which R represents a grouping of the general formula R1 represents a hydrogen atom or an alkyl group, R2 represents a hydrogen or an alkyl or halogeno-alkyl group, X represents a hydrogen or halogen atom or an alkyl, alkoxy, nitro or cyano group, n is 1 or 2, and Y represents an optionally substituted phenoxy or substituted phenyl group, and their physiologically acceptable acid addition salts and metal salt complexes are novel, are produced as described and find use as fungicides.
1,3-Dioxolane derivates of the formula (II) in which R, R1 and R2 have the meanings given above, and Z represents a halogen atom or a grouping of the general formula -O-SO2-R3, ABSTRACT
wherein R3 represents a methyl or p-methylphenyl group, which are intermediates in the production of compounds of formula (I), are also novel and are prepared as described.
Description
s The present invention relates to certain new 2-imidazolylmethyl-2-phenyl-1 ,3 dioxolanes, to a process for thei.r production and to their use as fungicides.
It has already been disclosed that certain tri~
azolylalkanols possess fungicidal properties (see DE-OS
(German Published Specification) 2,431,407). Thus, for example, 4 chlorophenyl-(1,2,4-triazol-1-yl-methyl)-carbinol can be used for combating fungi. However, the action o this substance is not always adequate, particularly when low amounts are used.
Furthermore, it has already been disclosed that certaln imidazolyl-alkanols exhibit good actions against fungi which are pathogenic to humans ~see 7th Med. Chem.
12, 784 791 (1969)). Thus, for example, 4-bromophenyl-(imidazol-l-yl-methyl)-carbinoL and 2,4-dichlorophenyl-(imidazol-l-yl-methyl) carbinol can be employed for this indication. However, the action of these compounds against phytopathogenic fungi is not always satisfactory.
The present invention now provides, as new compound the' 2-'imida201'ylmethyl-2-phenyl-1,3-dioxola'lles of' the general formula /==N
R ~ CH2 - N ~
R1 R~ (I) in which R represents a grouping the the general formula CF3 or ~
~ represents a hydrogen atom or an alkyl group, R2 represents a hydrogen atom or an alkyl or halogenoalkyl group, Le A 21 387 s X represents a hydrogen or halogen atom or an alkyl, alkoxy, nitro or cyano group, n is 1 or 2, and : Y is a phenoxy or phenyl group optionally substituted by at least one radical selected from halogen and alkyl, or a non-phytotoxic acid addition salt or meta.l salt complex thereof wherein the metal is selected from those in main groups II to IV and sub-groups I, II and IV to VIII of the periodic table of elements.
The compounds of the formula (I) can occur in various stereoisomeric forms; preferably, they occur in the form of stereoisomer mixtures.
According to the present invention we further provide a process for the production of a compound of the present invention characterised in that a 1,3-dioxolane derivative of the general formula R ~ CH2 - Z
1 ~ ~ 2 ~II) in which R, R1 and R2 have the meanings given above and Z represents a halogen atom or a grouping of the general formula -o-So2-R3, wherein R3 represents a methyl or p-methylphenyl group, is reacted with an imidazole of the general formula r N
M - N
(III) 7a~8s in which M represents a hydrogen atom or an alkali metal, in the presence of a diluent and, if appropriate, in the presence of an acid-binding agent, and, iE desired, an acid or metal salt is then added onto the resulting compound of the formula (I).
2a-87~5 -Finally, it has bee.n found that the 2-i~idaz.ol.yl-
It has already been disclosed that certain tri~
azolylalkanols possess fungicidal properties (see DE-OS
(German Published Specification) 2,431,407). Thus, for example, 4 chlorophenyl-(1,2,4-triazol-1-yl-methyl)-carbinol can be used for combating fungi. However, the action o this substance is not always adequate, particularly when low amounts are used.
Furthermore, it has already been disclosed that certaln imidazolyl-alkanols exhibit good actions against fungi which are pathogenic to humans ~see 7th Med. Chem.
12, 784 791 (1969)). Thus, for example, 4-bromophenyl-(imidazol-l-yl-methyl)-carbinoL and 2,4-dichlorophenyl-(imidazol-l-yl-methyl) carbinol can be employed for this indication. However, the action of these compounds against phytopathogenic fungi is not always satisfactory.
The present invention now provides, as new compound the' 2-'imida201'ylmethyl-2-phenyl-1,3-dioxola'lles of' the general formula /==N
R ~ CH2 - N ~
R1 R~ (I) in which R represents a grouping the the general formula CF3 or ~
~ represents a hydrogen atom or an alkyl group, R2 represents a hydrogen atom or an alkyl or halogenoalkyl group, Le A 21 387 s X represents a hydrogen or halogen atom or an alkyl, alkoxy, nitro or cyano group, n is 1 or 2, and : Y is a phenoxy or phenyl group optionally substituted by at least one radical selected from halogen and alkyl, or a non-phytotoxic acid addition salt or meta.l salt complex thereof wherein the metal is selected from those in main groups II to IV and sub-groups I, II and IV to VIII of the periodic table of elements.
The compounds of the formula (I) can occur in various stereoisomeric forms; preferably, they occur in the form of stereoisomer mixtures.
According to the present invention we further provide a process for the production of a compound of the present invention characterised in that a 1,3-dioxolane derivative of the general formula R ~ CH2 - Z
1 ~ ~ 2 ~II) in which R, R1 and R2 have the meanings given above and Z represents a halogen atom or a grouping of the general formula -o-So2-R3, wherein R3 represents a methyl or p-methylphenyl group, is reacted with an imidazole of the general formula r N
M - N
(III) 7a~8s in which M represents a hydrogen atom or an alkali metal, in the presence of a diluent and, if appropriate, in the presence of an acid-binding agent, and, iE desired, an acid or metal salt is then added onto the resulting compound of the formula (I).
2a-87~5 -Finally, it has bee.n found that the 2-i~idaz.ol.yl-
2-phenyl-1,3-dioxolanes according to the invention, of the formula (I), and plant-tolerated acid addition salts and metal salt complexes possess powerful fungicidal properties, Surprisingly, the substance~ according to the invention exhibit a better fungicidal activity than the compounds 4-chlorophenyl-(1,2,4-triazol-1-yl-methyl)-carbinol, 4-bromophenyl-(imidazol l-yl-methyl)-carbinol and 2,4-dichlorophenyl-(imidazol-1-yl-methyl)-carbinol, which are known from the prior art and which are con-stitutionally similar substances with the same direction of actlon.
Preferred 2~imidazolyl~2-phenyl-1,3-dioxolanes of formula (I) according to the present invention are those in which R represents a grouping of the general formula X ~ or ~
. R . re.pr.esents,a hydrogen,atom or,an,alkyl .group having 1 to 4 carbon atoms;
R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogenoalkyl group having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms (such as fluorine atoms and chlorine atoms);
X represents a hydrogen, fluorine, chlorine or bromine atom or an alkyl or alkoxy group, each having 1 to 4 carbon atoms;
.n.is l; and Y represents an optionally substituted phenoxy or substituted phenyl group, the following being suitable substituents: halogen or alkyl having 1 to 4 carbon,atoms.
Le A 21 387 8'7~85 Particularly preferred.-compounds of.the formula (I) are those in which R represents a grouping of the general formula 1 CF3 or ~
R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R represents a hydrogen atom or an unsubstituted alkyl group having 1 to 4 car.bon atoms, and a methyl group which is substituted by fluorine, or chlorine;
X represents a hydrogen, fluorine or chlorine atom or a methyl group;
n is l; and Y represents an optionally substituted phenoxy or ~ substituted phenyl group (fluorine, chlorine and ; methyl being mentioned as substituents).
Preferred substances accordins to the invention are : al.s.o .acid add.ition. s.al.ts of. 2.-imidazolylmeth.yl 2-phenyl-1,3-dioxolanes of the formula (I), in which R, Rl and R have the meanings mentioned as being preferred. Amongst these substances, particularly preferred acid addition salts are those which are formed b~ the addition of hydrohalic acid (such as hydrobromic acid, and especially, hydrochloric acid), phosphoric acid, nitric acid, sulphuric acid, monofunctional and bi~unctional carboxylic acids and hydrox~carboxylic acids (such as acetic acid, maleic acid, ~ succinic acid~ fumaric acid, tar.taric acid, citric acid, : salic~clic acid, sorbic acid and lactic acid) and sulphonic acids (such as p-toluenesulphonic acid and naphthalene-1,5-disulphonic acid) Metal salt complexes of 2-imidazolylmethyl-2-phenyl-1,3-dioxolanes. of.the .formula (I),. in. which. R, Rl and. R2 Le A ~1 387 1~8~85 have the meanings mentioned as being preferred, are also preferred substances according to the invention. Amongst these substances, particularly preferred metal salt complexes are those which contain, as cations, metals of main groups II to IV or sub-groups I and II or IV to VIII
of the periodic table of elements, copper~ zinc, manganese, magnesium, tin, iron and nickel ~eing mentioned as examples.
Anions of these metal salt complexes are preferably those which are derived from hydrohalic acids, in particular hydrochloric acid and hydrobromic acid, and also phosphoric acid, nitric acid and sulphuric acid.
If, for example, 2-bromoethyl 2-(4-chloro-2-tri-fluoromethyl-phenyl)-1,3-dioxolane and imidazole are used as startingmaterials, the course of the reaction in the process according to the invention can be represented by the following equation:
Cl ~ ~ / ;H2ar H N ~ N Base ~ -H3r 5F3 /=N
C 1~>~< C H 2 ~
Preferred 1,3-dioxolane derivatives of formula (II) re~uired as starting materials in carrying out the process according to the invention are those in which R, Rl and R2 have the meanings which have already been mentioned for ; these radicals in the description of the preferred and particularly preferred compounds according to the invention and Z represents a chlorine or bromine atom or a grouping ; 25 of th~ general formula -o-So2-R3, wherein R3 represents a methyl or p-methylphenyl group.
The 1,3-dioxolane derivatives of the formula (II) are Le A 21 387 novel and form a :further subject of the presenk invention.
The present Invention thus provides, as new compounds, the compounds of formula ~ , as deined above.
According to the present invention we further provide 5 a process ~or the production of compounds of formula (II~ -characterised in that a keto derivative of the general formula R-C-CH2-Z (IV) o in which lO R and 2 have the meanings given above, is reacted with a diol of the general formula HO OH (V) in which Rl and R2 have the meaning given above, in the present of an inert organic solvent (such as toluene) and. in the. pr.esence .of a s.trong a.cid as the catalyst (such as p-toluenesulphonic acid) at a temperature between 80 and lOO~C, if appropriate under elevated pressure.
The keto derivatives of the formu.la (IV) are known (see, for example, DE-OS (German Published Specification) 2,431,407), or are obtained in a generally known manner, by reacting the corresponding ketones, for example, with chlorine, or bromine in the presence of an inert organic solvent (such as an ether or a chlorinated or unchlorinated hydrocarbon) at room temperature, or reacting them with customary chlorinating agents (such as sulphuryl chloride) at 20 to 60~C. The sulphonic acid derivatives of the compounds of the formula (IV) can likewise be prepared according to known methods.
Le A 21 387 '7~8~;i The diols of the ormula (V) are generally known compounds of organic chemlstry; they are obtained in a generally known manner.
Preferred imidazoles of formula (III) additionally to be used as starting materials for the process according to the invention are those in which M represents a hydrogen atom, sodium or potassium.
The imidazoles of the formula (III) are generally known compounds of organic chemistry.
Suitable diluents for the process according to the invention are inert organic solvents. These pre-ferably include amides, such as dimethylformamide or dimethylacetamide; and also dimethylsulphoxide or hexa-methylphosphoric acid triamide.
The process according to the invention is carried out, if appropriate, in the presence of an acid binding agent. It ls possible to add all the customarily usable inorganic or organic acid-binding agents, such as alkali metal carbonates (for example sodium carbonate, potassium carbonate and sodium bicarbonate), or such as lower tertiary alkylamines, cycloalkylamines or aralkyl-amines (for example triethylamine, N,N~dimethylcyclo-hexylamine, dicyclohexylamine and N~N-dimethylbenzylamine, and Eurthermore pyridine and diazabicyclooctane). Pre-ferably, an appropriate excess of imidazole is used.
In carrying out the process according to the invention,the reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at a temperature between 20 and 150C, preferably between 60 and 150C.
In carrying out the process according to the invention 1 to 2 mol o the imidazole of the formula (III) and, if appropriate, 1 to 2 mol of an acid-binding agent are preferably employed per mol of the compounds of the formula (II). The compounds of the formula (I) are Le A 21 387 __,, . _ _ . , _ _ .. _ _ _ _ . . , . . .. . . . . . . __ _.. _ .
` i~l 3'7~35 isolated in a cus~omary manner. In some cases/ it is advantageous to prepare the compounds of the formula (I) in pure form via their salts.
Those acids which have already been mentioned in connection with the description of the acid addition salts according to the invention as being preferred acids are preferred for the preparation of plant-tolerated acid addition salts of the compounds of the formula (I).
These acid addition salts of the compounds of the formula (I) can be obtained in a simple manner by customary methods of salt formation for example by dissolving a compound of the formula (I) in a suitable inert solvent and adding the acid,for example hydrochloric acid, and they can be isolated in a known manner, for example by filtration, and if appropriate purified by washing with an inert organic solvent. `
Salts of those anions and cations which have already been mentioned in connection with the description of the metal salt complexes according to the invention as being preferred are preEerred for the preparation of metal salt complexes of compounds of the formula ~I).
The metal salt complexes of compounds of the formula (I) can be obtained in a simple manner by customary processes, thus, for example, by dissolving the metal salt in an alcohol, for example ethanol t and adding the solution to the compound of the formula (I)o The metal salt complexes can be isolated in a known manner, for example by filtration, and if appropriate purified by recrystallisation.
The active cornpounds according to the invention exhibit a powerful microbicidal action and can be employed in practice for combating undesired micro-organisms.
The active compounds are suitable for use as plant protec-tion agents.
Fungicidal agents in plant protection are employed Le A 21 387 1 ~37~ 8S
g for combating Plasmodiophoromycetes, Oomycetes, Chytridio-mycetes, Zyyomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
The good toleration by plants, of the active ocmpounds, at the concentrations required for combating plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.
As plant protection agents, the active compounds accordlng to the invention can be used with particularly good success for combating Podosphaera species r such as against the powdery mildew of apple causative organism (Podosphaera leucotricha), and for combating cereal dis-eases, such as against the powdery mildew 3~ cereals causative organism ~Erysiphe graminis) and against the stripe disease of barley (Helminthosporium gramineum).
The compounds according to the invention also exhibit a good m v o action, in particular against pathogens in rice plants.
When used in appropriate concentrations, the substances according to the invention also exhibit plant growth~
regulating properties.
The active compounds can be converted to the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, d~sting agents, foams, pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed-treatment powders, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances and in coating com positions for seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils as well as ULV cold mist and warm mist formulations.
Le A 21 387 87~
These formulations may -be produced in known manner, ~or e~ampleby mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of wa~er as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketoneg methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethyl-sulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meantliquids which ~ould be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
As solid carriers there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic
Preferred 2~imidazolyl~2-phenyl-1,3-dioxolanes of formula (I) according to the present invention are those in which R represents a grouping of the general formula X ~ or ~
. R . re.pr.esents,a hydrogen,atom or,an,alkyl .group having 1 to 4 carbon atoms;
R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogenoalkyl group having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms (such as fluorine atoms and chlorine atoms);
X represents a hydrogen, fluorine, chlorine or bromine atom or an alkyl or alkoxy group, each having 1 to 4 carbon atoms;
.n.is l; and Y represents an optionally substituted phenoxy or substituted phenyl group, the following being suitable substituents: halogen or alkyl having 1 to 4 carbon,atoms.
Le A 21 387 8'7~85 Particularly preferred.-compounds of.the formula (I) are those in which R represents a grouping of the general formula 1 CF3 or ~
R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R represents a hydrogen atom or an unsubstituted alkyl group having 1 to 4 car.bon atoms, and a methyl group which is substituted by fluorine, or chlorine;
X represents a hydrogen, fluorine or chlorine atom or a methyl group;
n is l; and Y represents an optionally substituted phenoxy or ~ substituted phenyl group (fluorine, chlorine and ; methyl being mentioned as substituents).
Preferred substances accordins to the invention are : al.s.o .acid add.ition. s.al.ts of. 2.-imidazolylmeth.yl 2-phenyl-1,3-dioxolanes of the formula (I), in which R, Rl and R have the meanings mentioned as being preferred. Amongst these substances, particularly preferred acid addition salts are those which are formed b~ the addition of hydrohalic acid (such as hydrobromic acid, and especially, hydrochloric acid), phosphoric acid, nitric acid, sulphuric acid, monofunctional and bi~unctional carboxylic acids and hydrox~carboxylic acids (such as acetic acid, maleic acid, ~ succinic acid~ fumaric acid, tar.taric acid, citric acid, : salic~clic acid, sorbic acid and lactic acid) and sulphonic acids (such as p-toluenesulphonic acid and naphthalene-1,5-disulphonic acid) Metal salt complexes of 2-imidazolylmethyl-2-phenyl-1,3-dioxolanes. of.the .formula (I),. in. which. R, Rl and. R2 Le A ~1 387 1~8~85 have the meanings mentioned as being preferred, are also preferred substances according to the invention. Amongst these substances, particularly preferred metal salt complexes are those which contain, as cations, metals of main groups II to IV or sub-groups I and II or IV to VIII
of the periodic table of elements, copper~ zinc, manganese, magnesium, tin, iron and nickel ~eing mentioned as examples.
Anions of these metal salt complexes are preferably those which are derived from hydrohalic acids, in particular hydrochloric acid and hydrobromic acid, and also phosphoric acid, nitric acid and sulphuric acid.
If, for example, 2-bromoethyl 2-(4-chloro-2-tri-fluoromethyl-phenyl)-1,3-dioxolane and imidazole are used as startingmaterials, the course of the reaction in the process according to the invention can be represented by the following equation:
Cl ~ ~ / ;H2ar H N ~ N Base ~ -H3r 5F3 /=N
C 1~>~< C H 2 ~
Preferred 1,3-dioxolane derivatives of formula (II) re~uired as starting materials in carrying out the process according to the invention are those in which R, Rl and R2 have the meanings which have already been mentioned for ; these radicals in the description of the preferred and particularly preferred compounds according to the invention and Z represents a chlorine or bromine atom or a grouping ; 25 of th~ general formula -o-So2-R3, wherein R3 represents a methyl or p-methylphenyl group.
The 1,3-dioxolane derivatives of the formula (II) are Le A 21 387 novel and form a :further subject of the presenk invention.
The present Invention thus provides, as new compounds, the compounds of formula ~ , as deined above.
According to the present invention we further provide 5 a process ~or the production of compounds of formula (II~ -characterised in that a keto derivative of the general formula R-C-CH2-Z (IV) o in which lO R and 2 have the meanings given above, is reacted with a diol of the general formula HO OH (V) in which Rl and R2 have the meaning given above, in the present of an inert organic solvent (such as toluene) and. in the. pr.esence .of a s.trong a.cid as the catalyst (such as p-toluenesulphonic acid) at a temperature between 80 and lOO~C, if appropriate under elevated pressure.
The keto derivatives of the formu.la (IV) are known (see, for example, DE-OS (German Published Specification) 2,431,407), or are obtained in a generally known manner, by reacting the corresponding ketones, for example, with chlorine, or bromine in the presence of an inert organic solvent (such as an ether or a chlorinated or unchlorinated hydrocarbon) at room temperature, or reacting them with customary chlorinating agents (such as sulphuryl chloride) at 20 to 60~C. The sulphonic acid derivatives of the compounds of the formula (IV) can likewise be prepared according to known methods.
Le A 21 387 '7~8~;i The diols of the ormula (V) are generally known compounds of organic chemlstry; they are obtained in a generally known manner.
Preferred imidazoles of formula (III) additionally to be used as starting materials for the process according to the invention are those in which M represents a hydrogen atom, sodium or potassium.
The imidazoles of the formula (III) are generally known compounds of organic chemistry.
Suitable diluents for the process according to the invention are inert organic solvents. These pre-ferably include amides, such as dimethylformamide or dimethylacetamide; and also dimethylsulphoxide or hexa-methylphosphoric acid triamide.
The process according to the invention is carried out, if appropriate, in the presence of an acid binding agent. It ls possible to add all the customarily usable inorganic or organic acid-binding agents, such as alkali metal carbonates (for example sodium carbonate, potassium carbonate and sodium bicarbonate), or such as lower tertiary alkylamines, cycloalkylamines or aralkyl-amines (for example triethylamine, N,N~dimethylcyclo-hexylamine, dicyclohexylamine and N~N-dimethylbenzylamine, and Eurthermore pyridine and diazabicyclooctane). Pre-ferably, an appropriate excess of imidazole is used.
In carrying out the process according to the invention,the reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at a temperature between 20 and 150C, preferably between 60 and 150C.
In carrying out the process according to the invention 1 to 2 mol o the imidazole of the formula (III) and, if appropriate, 1 to 2 mol of an acid-binding agent are preferably employed per mol of the compounds of the formula (II). The compounds of the formula (I) are Le A 21 387 __,, . _ _ . , _ _ .. _ _ _ _ . . , . . .. . . . . . . __ _.. _ .
` i~l 3'7~35 isolated in a cus~omary manner. In some cases/ it is advantageous to prepare the compounds of the formula (I) in pure form via their salts.
Those acids which have already been mentioned in connection with the description of the acid addition salts according to the invention as being preferred acids are preferred for the preparation of plant-tolerated acid addition salts of the compounds of the formula (I).
These acid addition salts of the compounds of the formula (I) can be obtained in a simple manner by customary methods of salt formation for example by dissolving a compound of the formula (I) in a suitable inert solvent and adding the acid,for example hydrochloric acid, and they can be isolated in a known manner, for example by filtration, and if appropriate purified by washing with an inert organic solvent. `
Salts of those anions and cations which have already been mentioned in connection with the description of the metal salt complexes according to the invention as being preferred are preEerred for the preparation of metal salt complexes of compounds of the formula ~I).
The metal salt complexes of compounds of the formula (I) can be obtained in a simple manner by customary processes, thus, for example, by dissolving the metal salt in an alcohol, for example ethanol t and adding the solution to the compound of the formula (I)o The metal salt complexes can be isolated in a known manner, for example by filtration, and if appropriate purified by recrystallisation.
The active cornpounds according to the invention exhibit a powerful microbicidal action and can be employed in practice for combating undesired micro-organisms.
The active compounds are suitable for use as plant protec-tion agents.
Fungicidal agents in plant protection are employed Le A 21 387 1 ~37~ 8S
g for combating Plasmodiophoromycetes, Oomycetes, Chytridio-mycetes, Zyyomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
The good toleration by plants, of the active ocmpounds, at the concentrations required for combating plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.
As plant protection agents, the active compounds accordlng to the invention can be used with particularly good success for combating Podosphaera species r such as against the powdery mildew of apple causative organism (Podosphaera leucotricha), and for combating cereal dis-eases, such as against the powdery mildew 3~ cereals causative organism ~Erysiphe graminis) and against the stripe disease of barley (Helminthosporium gramineum).
The compounds according to the invention also exhibit a good m v o action, in particular against pathogens in rice plants.
When used in appropriate concentrations, the substances according to the invention also exhibit plant growth~
regulating properties.
The active compounds can be converted to the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, d~sting agents, foams, pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed-treatment powders, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances and in coating com positions for seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils as well as ULV cold mist and warm mist formulations.
Le A 21 387 87~
These formulations may -be produced in known manner, ~or e~ampleby mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of wa~er as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketoneg methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethyl-sulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meantliquids which ~ould be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
As solid carriers there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic
3 acid, alumina and silicates. As solid carriers for granules there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules o~ organic material such as sawdust, 35 coconut shells, maize cobs and tobacco stalks.
Le A 21 387 .. . _,, . _ . _ _ _ . _ . _ ... . _ . . .. . . . . .. . .. .. .. . . .. . . . . . . . . ... .
As emulsifying and/or foam-forming agents there may be used non-ionic and anionic emulsifiers, such as polyoxy-ethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products. Dispersing agents include 3 for example, lignin sulphite waste li~uors and methyl-cellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for example iron oxide~ titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestu~fs or metal phthalocyanine dyestuffs, and trace nutrients~ such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.
The active compounds according to the invention can be present in the formulations or in the various use forms as a mixture with other known active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides~ herbicides, bird repellants, growth factors, plant nutrients and agents for improving soil structure.
The active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in the customary manner, for example by watering 9 immersion, spraying, atomising, misting~ vaporising, injecting, forming a slurry, brushing on, dusting, scattering, dry dressing~ moist dressing~ wet Le A 21 387 37~85 dressing, slurry dressing or encusting.
Especially in the treatment of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are, in general, between l and 0.0001% by weight, preferably between 0.5 and O.C01%.
In the treatment of seed, amounts of active compound of 0.001 to 5~ g per kilogram of seed, preferably 0.01 to lO g are generally required.
For the treatment of soil, active compound concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%
by weight are generally required at the place of action.
The present invention also provides fungicidal composition containing as active ingredient a compound of the present invention in admixture with a solid or ; liquefied gaseous diluent or carrier or in admixture with a li~uid diluent or carrier containing a surface-active agent.
The present invention also provides a method of combating fungi which comprises applying to the fungi or to a habitat thereof, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by Pungi by being grown in areas in which immediately prior to and/or during the ~ime of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.
The preparation and the use of the active compounds according to the invention are illustrated by the Examples which follow.
Le A 21 387 ~, 37~135 ti ~ rll~s CF3 ~= N
Cl ~O ~ / CH2 - N ~
0 0 ~ HCl 3.9 g (0.0116 mol) of 2-bromomethyl-2-(4-chloro-2-tri1uoeomethyl~phenyl)-1,3-dioxolane and 2.4 g (0.0348 mol) of imidazole in 50 ml of dimethylacetamide were heated under reflux for 4 days~ After the reaction mixture had cooled, it was dissolved in water and the solutlon was extracted with etherO The ether phase was washed with water, dried over sodium sulphate and concentrated.
Ethereal hydrochloric acid was added to the residual oil, and the latter was brought to crystallisation by tritura-tion. 2~(4-Chloro-2-trifluoromethyl-phenyl)-2-(imidazol-l-methyl)-1,3-dioxolane hydrochloride of melting point 174 to 83C was obtained.
Cl ~<, CH2-Br O O
35 g (0.12mol~ of 4-chloro-2-trifluoromethyl-phenacyl bromide and 9 g (0.15 mol) of glycol were heated in a water separator for 24 hours with 1.5 g of p-toluene-sulphonic acid in 80 ml of toluene, in the presence of 20 ml of butanol. After the reaction mixture had cooled, it was washed successively with dilute aqueous sodlum hydroxide solution and with water, dried over Le A 21 387 ; ., , ' .
.
. .
sodium sulphate and concentrated. 29.6 g (74~ of theory) of crude 2-bromomethyl-2-(4-chloro-2-trifluoromethyl-phenyl)-1,3-dioxolane were obtained as an oil, which was directly reacted further.
Cl- ~ \ CH2-Br ~ -1 ml o acetic acid was added to 22.3 g ( a .1 mol) of
Le A 21 387 .. . _,, . _ . _ _ _ . _ . _ ... . _ . . .. . . . . .. . .. .. .. . . .. . . . . . . . . ... .
As emulsifying and/or foam-forming agents there may be used non-ionic and anionic emulsifiers, such as polyoxy-ethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products. Dispersing agents include 3 for example, lignin sulphite waste li~uors and methyl-cellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for example iron oxide~ titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestu~fs or metal phthalocyanine dyestuffs, and trace nutrients~ such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.
The active compounds according to the invention can be present in the formulations or in the various use forms as a mixture with other known active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides~ herbicides, bird repellants, growth factors, plant nutrients and agents for improving soil structure.
The active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in the customary manner, for example by watering 9 immersion, spraying, atomising, misting~ vaporising, injecting, forming a slurry, brushing on, dusting, scattering, dry dressing~ moist dressing~ wet Le A 21 387 37~85 dressing, slurry dressing or encusting.
Especially in the treatment of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are, in general, between l and 0.0001% by weight, preferably between 0.5 and O.C01%.
In the treatment of seed, amounts of active compound of 0.001 to 5~ g per kilogram of seed, preferably 0.01 to lO g are generally required.
For the treatment of soil, active compound concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%
by weight are generally required at the place of action.
The present invention also provides fungicidal composition containing as active ingredient a compound of the present invention in admixture with a solid or ; liquefied gaseous diluent or carrier or in admixture with a li~uid diluent or carrier containing a surface-active agent.
The present invention also provides a method of combating fungi which comprises applying to the fungi or to a habitat thereof, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by Pungi by being grown in areas in which immediately prior to and/or during the ~ime of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.
The preparation and the use of the active compounds according to the invention are illustrated by the Examples which follow.
Le A 21 387 ~, 37~135 ti ~ rll~s CF3 ~= N
Cl ~O ~ / CH2 - N ~
0 0 ~ HCl 3.9 g (0.0116 mol) of 2-bromomethyl-2-(4-chloro-2-tri1uoeomethyl~phenyl)-1,3-dioxolane and 2.4 g (0.0348 mol) of imidazole in 50 ml of dimethylacetamide were heated under reflux for 4 days~ After the reaction mixture had cooled, it was dissolved in water and the solutlon was extracted with etherO The ether phase was washed with water, dried over sodium sulphate and concentrated.
Ethereal hydrochloric acid was added to the residual oil, and the latter was brought to crystallisation by tritura-tion. 2~(4-Chloro-2-trifluoromethyl-phenyl)-2-(imidazol-l-methyl)-1,3-dioxolane hydrochloride of melting point 174 to 83C was obtained.
Cl ~<, CH2-Br O O
35 g (0.12mol~ of 4-chloro-2-trifluoromethyl-phenacyl bromide and 9 g (0.15 mol) of glycol were heated in a water separator for 24 hours with 1.5 g of p-toluene-sulphonic acid in 80 ml of toluene, in the presence of 20 ml of butanol. After the reaction mixture had cooled, it was washed successively with dilute aqueous sodlum hydroxide solution and with water, dried over Le A 21 387 ; ., , ' .
.
. .
sodium sulphate and concentrated. 29.6 g (74~ of theory) of crude 2-bromomethyl-2-(4-chloro-2-trifluoromethyl-phenyl)-1,3-dioxolane were obtained as an oil, which was directly reacted further.
Cl- ~ \ CH2-Br ~ -1 ml o acetic acid was added to 22.3 g ( a .1 mol) of
4-chloro-2-trifluoromethyl-acetophenone in 200 ml of chloroform~ and the mixture was warmed to 40C. 5.1 ml (0.1 mol) of bromine in 50 ml of chloroform were added dropwise at this temperature. The reaction mixture was stlrred until the evolution of gas had ceased. After the mixture had cooled, it was washed successively with water and a~ueous sodium bicarbonate solution, dried over sodium sulphate and concentrated. 29O4 g (97% of theory) of crude 4-chloro-2-trifluoromethyl-phenacyl bromide were obtained as an oil, which is directly reacted further.
The compounds of the formula ~=~N
R ~ CH2-N
which are listed in Table 1 below were also prepared according to the method given in Example 1:
Le A 21 387 : ~ - .
, 1~8~ 3S
Table 1 r ample R Rl R2 Physical No. constants .
2 Cl ~ CH3 H viscous oil 3 Cl- ~ CH2Cl H viscous oil 4 Cl ~ C2H5 H viscous oil Cl ~ H H M.~.: 220C
(~H~l) ~0 6 ~ H H viscous oil ~o ~xHCl) 7 ~ CH3 H viscous oil (~ ~,~
CH2Cl H viscous oil 9 ~ ~ C2H5 H viscous oil 10 Cl ~ CH3 H viscous oil 11 Cl ~ ~ CH2Cl H viscous oil 12 Cl- ~ ~ C2H5 H viscous oil 13 Cl ~ ~ CH3 CH3 viscous oil 14 Cl ~ CH3 CH3 viscous oil 15 ~ O ~ CH3 ~H3 viscous oil Le A 21 387 - _ .
:~:
' -87~1~5 The fungicidal activity of the compounds of this invention is illustrated by the following biotest Examples.
In these Examples, the compounds according ~o the present invention are each identified by the number (given in brackets) of the corresponding preparative Example, which will be found later in this speci~ication.
; The known comparison compounds are identified as follows:
(A) = Cl ~ CH - CH2 - N
OH ~=N
(B) =Br ~ ~H-CH2-N ~
C1 OH ~--N
Example A
Erysiphe test (barley)/protective/
Solvent: 100 parts by weight of dimethylformamide Emulsifie;r: 0.25 part by weight. of..a.Lk.ylar.yl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of act.ive compound was mixed with the stated amounts of solvent and emulsifier, and the concentrate was diluted with water to the desired concen-tration.
To test for protective activity, young plants were sprayed with the preparation of active compound until dew-moist. After the spray coating had dried on, the Le A 21 387 . .
1~8~6~85 plants were dusted with spores of Erysiphe graminis f.sp.
hordei.
The plants were placed in a greenhouse at a temperature of about 20C and a relative atmospheric S humidity of about 80%, in order to promote the development of powdery mildew pustules.
Evaluation was carried out 7 days after the inoculation.
In this test, a clearly superior activity compared with the prior art was shown, for example, by the compounds (2) and (4).
Example_B
Drechslera graminea test (barley) / seed treatment (syn. Helminthosporium gramineum) The active compounds were used as dry dressingsO
These were prepared by extending the particular active compound with a ground mineral to give a finely pulverulent mixture, which ensured uniform distribution on the seed surface~
To apply the dressing, the infected seed was shaken with the dressing in a closed glass flask for 3 minutes.
The seed was embedded in sieved, moist standard soil and was exposed to a temperature of 4C in closed Petri dishes in a refrigerator for 10 days. Germination of the barl~y, and possibly also of the fungus spores, was thereby initiated. 2 batches of 50 yrains of the pregerminated barley were subsequently sown 3 cm deep in standard soil and were cultivated in a greenhouse at a temperature of about 18C, in seedboxes which were exposed to light for 15 hours daily.
About 3 weeks after sowing, the plants were evaluated for symptoms of stripe disease.
In this test, a clearly superior activity compared with the prior art was shown, for example, by the Le A 21 387 _ .. _ , , ,., .. _ _ .. . . . . .. . . . . ..... , . . . . . . . . . . ... . _ . .
'7~5 compounds (1) and (~).
Podosphaera test (apple) / protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether ~ To produce a suitable preparation of active : compound, 1 part by weight of active compound was mixed with ; the stated amounts of solvent and emulsifier, and the concentrate was diluted with water to the desired concen-tration.
To test for protective activity, young plants were sprayed with the preparation of ac~ive compound until dripplng wet. After the spray coating had dried on, the plants were inoculated by dusting with conidia of the powdery mildew of apple causative organism (Podosphaera leucotricha).
The plants were then placed in a greenhouse at 23C and a relative atmospheric humidity of about 70%.
Evaluation was carried out 9 days after the inoculation~
In this test, a clearly superior activity compared with the prior art was shown, for example, by the compounds (2)., (4) and (1).
Le A 21 387 .
~ , .
The compounds of the formula ~=~N
R ~ CH2-N
which are listed in Table 1 below were also prepared according to the method given in Example 1:
Le A 21 387 : ~ - .
, 1~8~ 3S
Table 1 r ample R Rl R2 Physical No. constants .
2 Cl ~ CH3 H viscous oil 3 Cl- ~ CH2Cl H viscous oil 4 Cl ~ C2H5 H viscous oil Cl ~ H H M.~.: 220C
(~H~l) ~0 6 ~ H H viscous oil ~o ~xHCl) 7 ~ CH3 H viscous oil (~ ~,~
CH2Cl H viscous oil 9 ~ ~ C2H5 H viscous oil 10 Cl ~ CH3 H viscous oil 11 Cl ~ ~ CH2Cl H viscous oil 12 Cl- ~ ~ C2H5 H viscous oil 13 Cl ~ ~ CH3 CH3 viscous oil 14 Cl ~ CH3 CH3 viscous oil 15 ~ O ~ CH3 ~H3 viscous oil Le A 21 387 - _ .
:~:
' -87~1~5 The fungicidal activity of the compounds of this invention is illustrated by the following biotest Examples.
In these Examples, the compounds according ~o the present invention are each identified by the number (given in brackets) of the corresponding preparative Example, which will be found later in this speci~ication.
; The known comparison compounds are identified as follows:
(A) = Cl ~ CH - CH2 - N
OH ~=N
(B) =Br ~ ~H-CH2-N ~
C1 OH ~--N
Example A
Erysiphe test (barley)/protective/
Solvent: 100 parts by weight of dimethylformamide Emulsifie;r: 0.25 part by weight. of..a.Lk.ylar.yl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of act.ive compound was mixed with the stated amounts of solvent and emulsifier, and the concentrate was diluted with water to the desired concen-tration.
To test for protective activity, young plants were sprayed with the preparation of active compound until dew-moist. After the spray coating had dried on, the Le A 21 387 . .
1~8~6~85 plants were dusted with spores of Erysiphe graminis f.sp.
hordei.
The plants were placed in a greenhouse at a temperature of about 20C and a relative atmospheric S humidity of about 80%, in order to promote the development of powdery mildew pustules.
Evaluation was carried out 7 days after the inoculation.
In this test, a clearly superior activity compared with the prior art was shown, for example, by the compounds (2) and (4).
Example_B
Drechslera graminea test (barley) / seed treatment (syn. Helminthosporium gramineum) The active compounds were used as dry dressingsO
These were prepared by extending the particular active compound with a ground mineral to give a finely pulverulent mixture, which ensured uniform distribution on the seed surface~
To apply the dressing, the infected seed was shaken with the dressing in a closed glass flask for 3 minutes.
The seed was embedded in sieved, moist standard soil and was exposed to a temperature of 4C in closed Petri dishes in a refrigerator for 10 days. Germination of the barl~y, and possibly also of the fungus spores, was thereby initiated. 2 batches of 50 yrains of the pregerminated barley were subsequently sown 3 cm deep in standard soil and were cultivated in a greenhouse at a temperature of about 18C, in seedboxes which were exposed to light for 15 hours daily.
About 3 weeks after sowing, the plants were evaluated for symptoms of stripe disease.
In this test, a clearly superior activity compared with the prior art was shown, for example, by the Le A 21 387 _ .. _ , , ,., .. _ _ .. . . . . .. . . . . ..... , . . . . . . . . . . ... . _ . .
'7~5 compounds (1) and (~).
Podosphaera test (apple) / protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether ~ To produce a suitable preparation of active : compound, 1 part by weight of active compound was mixed with ; the stated amounts of solvent and emulsifier, and the concentrate was diluted with water to the desired concen-tration.
To test for protective activity, young plants were sprayed with the preparation of ac~ive compound until dripplng wet. After the spray coating had dried on, the plants were inoculated by dusting with conidia of the powdery mildew of apple causative organism (Podosphaera leucotricha).
The plants were then placed in a greenhouse at 23C and a relative atmospheric humidity of about 70%.
Evaluation was carried out 9 days after the inoculation~
In this test, a clearly superior activity compared with the prior art was shown, for example, by the compounds (2)., (4) and (1).
Le A 21 387 .
~ , .
Claims (24)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A 2-imidazolylmethyl-2-phenyl-1,3-dioxolane of the formula in which R is R1 is a hydrogen atom or an alkyl group, R2 is a hydrogen atom or an alkyl or halogenoalkyl group, X is a hydrogen or halogen atom or an alkyl, alkoxy, nitro or cyano group, n is 1 or 2, and Y is a phenoxy or phenyl group optionally substituted by at least one radical selected from halogen and alkyl, or a non-phytotoxic acid addition salt or metal salt complex thereof wherein the metal is selected from those in main groups II to IV and sub-groups I, II and IV to VIII of the periodic table of elements.
2. A compound according to claim 1, in which R1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
R2 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogenoalkyl group having 1 or 2 carbon atoms and 1 to 5 halogen atoms, X is a hydrogen, fluorine, chlorine or bromine atom, or an alkyl or alkoxy group each having 1 to 4 carbon atoms;
n is 1; and Y is an optionally substituted phenoxy or substituted phenyl group, the substituents being selected from halogen and alkyl having 1 to 4 carbon atoms.
R2 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogenoalkyl group having 1 or 2 carbon atoms and 1 to 5 halogen atoms, X is a hydrogen, fluorine, chlorine or bromine atom, or an alkyl or alkoxy group each having 1 to 4 carbon atoms;
n is 1; and Y is an optionally substituted phenoxy or substituted phenyl group, the substituents being selected from halogen and alkyl having 1 to 4 carbon atoms.
3. A compound according to claim 2, in which R2 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a methyl group substituted by fluorine or chlorine;
X is a hydrogen, fluorine or chlorine atom or a methyl group;
n is 1; and Y is an optionally substituted phenoxy or substituted phenyl group, the substituents being selected from fluorine, chlorine and methyl.
X is a hydrogen, fluorine or chlorine atom or a methyl group;
n is 1; and Y is an optionally substituted phenoxy or substituted phenyl group, the substituents being selected from fluorine, chlorine and methyl.
4. 2-(4-Chloro-2-trifluoromethyl-phenyl)-2-(imidazol-1-yl-methyl)-1,3-dioxolane of the formula
5. 2-(4-Chloro-2-trifluoromethyl-phenyl)-2-(imidazol-1-yl-methyl)-4-methyl-1,3-dioxolane of the formula
6. 2-(4-Chloro-2-trifluoromethyl-phenyl)-2-(imidazol-1-yl-methyl)-4-ethyl-1,3-dioxolane of the formula
7. 2-(3-Phenoxy-phenyl)-2-(imidazol-1-yl-methyl)-4-ethyl-1,3-dioxolane of the formula
8. 2-(4-Phenoxy-phenyl)-2-(imidazol-1-yl-methyl)-4,5-dimethyl-1,3-dioxolane of the formula
9. A non-phytotoxic acid addition salt of the compound of claim 4, 5 or 6.
10. A non-phytotoxic acid addition salt of the compound of claim 7 or 8.
11. A process for the production of a compound according to claim 1, characterised in that a 1,3-dioxolane derivative of the general formula (II) in which R, R1 and R2 have the same meanings as in claim 1 and Z represents a halogen atom or a group of the general formula -O-SO2-R3, wherein R3 represents a methyl or p-methylphenyl group, is reacted with an imidazole of the general formula (III) in which M represents a hydrogen atom or an alkali metal, in the presence of a diluent and, where required, a suitable acid or a suitable metal salt is then added onto the resulting compound of the formula (I).
12. A method of combating fungi comprising applying to the fungi, or to a habitat thereof, a fungicidally effective amount of a compound according to claim 1.
13. A method according to claim 12 wherein the compound is applied in the form of a composition containing said compound as active ingredient, in admixture with a suitable diluent or carrier.
14. A method according to claim 13, wherein a composition is used con-taining from 1 to 0.0001% of said compound, by weight.
15. A method according to claim 14, wherein a composition is used con-taining from 0.5 to 0.001% of said compound by weight.
16. A method according to claim 12, 13 or 15, wherein said compound is applied to soil in an amount of 0.00001 to 0.1 per cent by weight.
17. A method according to claim 12, 13 or 15, wherein said compound is applied to soil in an amount of 0.0001 to 0.02 per cent by weight.
18. A method according to claim 12, 13 or 15, wherein said compound is applied to seed in an amount of 0.001 to 50 g per kg of seed.
19. A method according to claim 12, 13 or 15, wherein said compound is applied to seed in an amount of 0.01 to 10 g per kg of seed.
20. A method according to claim 12, 13 or 15, wherein such compound is 2-(4-chloro-2-trifluoromethyl-phenyl)-2-(imidazol-1-yl-methyl)-1,3-dioxolane.
21. A method according to claim 12, 13 or 15, wherein such compound is 2-(4-chloro-2-trifluoromethyl-phenyl)-2-(imidazol-1-yl-methyl)-4-methyl-1,3-dioxolane.
22. A method according to claim 12, 13 or 15, wherein such compound is 2-(4-chloro-2-trifluoromethyl-phenyl)-2-(imidazol-1-yl-methyl)-4-ethyl-1,3-dioxolane.
23. A method according to claim 12, 13 or 15, wherein such compound is 2-(3-phenoxy-phenyl)-2-(imidazol-1-yl-methyl)-4-ethyl-1,3-dioxolane.
24. A method according to claim 12, 13 or 14, wherein such compound is 2-(4-phenoxy-phenyl)-2-(imidazol-1-yl-methyl)-4,5-dimethyl-1,3-dioxolane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3144318.4 | 1981-11-07 | ||
| DE19813144318 DE3144318A1 (en) | 1981-11-07 | 1981-11-07 | 2-IMIDAZOLYLMETHYL-2-PHENYL-1, 3-DIOXOLANE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1187085A true CA1187085A (en) | 1985-05-14 |
Family
ID=6145891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000414986A Expired CA1187085A (en) | 1981-11-07 | 1982-11-05 | 2-imidazolylmethyl-2-phenyl-1,3-dioxolanes, a process for their preparation, and their use as fungicides |
Country Status (18)
| Country | Link |
|---|---|
| EP (1) | EP0080071B1 (en) |
| JP (1) | JPS5888377A (en) |
| AT (1) | ATE27158T1 (en) |
| AU (1) | AU555638B2 (en) |
| BR (1) | BR8206434A (en) |
| CA (1) | CA1187085A (en) |
| CS (1) | CS235971B2 (en) |
| DD (1) | DD208534A5 (en) |
| DE (2) | DE3144318A1 (en) |
| DK (1) | DK494482A (en) |
| ES (1) | ES8307799A1 (en) |
| GR (1) | GR77371B (en) |
| HU (1) | HU188333B (en) |
| IL (1) | IL67178A (en) |
| NZ (1) | NZ202385A (en) |
| PL (1) | PL133350B1 (en) |
| PT (1) | PT75759B (en) |
| ZA (1) | ZA828134B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5274108A (en) * | 1992-06-18 | 1993-12-28 | Syntex (U.S.A.) Inc. | Process for preparing 1,3-dioxolane derivatives |
| CN109803965A (en) * | 2016-09-29 | 2019-05-24 | 拜耳作物科学股份公司 | The imidazolyl methyl dioxolane derivatives that 5- as fungicide replaces |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI77458C (en) * | 1981-05-12 | 1989-03-10 | Ciba Geigy Ag | NYA MICROBICIDES ARYLFENYLETTERDERIVAT, FOERFARANDE FOER DERAS FRAMSTAELLNING OCH DERAS ANVAENDNING. |
| FI834141A (en) * | 1982-11-16 | 1984-05-17 | Ciba Geigy Ag | FOERFARANDE FOER FRAMSTAELLNING AV NYA ARYLFENYLETERDERIVAT. |
| ZA853066B (en) * | 1984-05-02 | 1985-12-24 | Uniroyal Inc | Substituted imidazoles and triazoles |
| AU575163B2 (en) * | 1984-05-09 | 1988-07-21 | Hunter Douglas Limited | Roof insert |
| IT1186784B (en) * | 1985-11-04 | 1987-12-16 | Montedison Spa | AZOLIDERIVATED ANTI-FUNGAL ACTIVITIES |
| DE3914632A1 (en) * | 1989-05-03 | 1990-11-08 | Basf Ag | 1-HYDROXI AZOL COMPOUNDS AND FUNGICIDES CONTAINING THEM |
| TW457240B (en) * | 1995-04-20 | 2001-10-01 | Janssen Pharmaceutica Nv | Novel triazolones as apolipoprotein-B synthesis inhibitors |
| CN100347166C (en) * | 2002-08-09 | 2007-11-07 | 中央硝子株式会社 | Process for producing trifluoromethyl- substituted 2- alkoxyacetophenone derivatives |
| EP2745691A1 (en) | 2012-12-19 | 2014-06-25 | Basf Se | Substituted imidazole compounds and their use as fungicides |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3575999A (en) * | 1968-08-19 | 1971-04-20 | Janssen Pharmaceutica Nv | Ketal derivatives of imidazole |
| CA1065873A (en) * | 1975-01-27 | 1979-11-06 | Janssen Pharmaceutica Naamloze Vennootschap | Imidazole derivatives |
| DE2967202D1 (en) * | 1978-07-03 | 1984-10-11 | Janssen Pharmaceutica Nv | Derivatives of (4-(piperazin-1-yl-phenyloxymethyl)-1.3-dioxolan-2-ylmethyl)-1h-imidazoles and -1h-1.2.4-triazoles, their preparation and use as fungicides and bactericides |
| CH637392A5 (en) * | 1978-07-24 | 1983-07-29 | Janssen Pharmaceutica Nv | 2-Phenyl-2-azolylmethyl-cyclohexa(d)-1,3-dioxolane derivatives, processes for their preparation, compositions containing these active substances as microbicides, and their use |
| AU526321B2 (en) * | 1978-07-24 | 1983-01-06 | Janssen Pharmaceutica N.V. | 1-(2-aryl-4,5-disubstituted-1,3-dioxolan-2-yl-methyl)-1h- imidazoles and 1h-1,2,4-triazoles |
| CA1173449A (en) * | 1979-11-16 | 1984-08-28 | Adolf Hubele | 1-¬2-(4-diphenyl)ethyl|-1h-azolylketals |
| TR21964A (en) * | 1981-05-12 | 1985-12-11 | Ciba Geigy Ag | NEW ARILFENILETER TUEREVLER AS MICROBICIDES PROCEDURES AND USES FOR THE PREPARATION OF THEM |
| FI77458C (en) * | 1981-05-12 | 1989-03-10 | Ciba Geigy Ag | NYA MICROBICIDES ARYLFENYLETTERDERIVAT, FOERFARANDE FOER DERAS FRAMSTAELLNING OCH DERAS ANVAENDNING. |
-
1981
- 1981-11-07 DE DE19813144318 patent/DE3144318A1/en not_active Withdrawn
-
1982
- 1982-10-28 DE DE8282109961T patent/DE3276315D1/en not_active Expired
- 1982-10-28 PT PT75759A patent/PT75759B/en unknown
- 1982-10-28 EP EP82109961A patent/EP0080071B1/en not_active Expired
- 1982-10-28 AT AT82109961T patent/ATE27158T1/en not_active IP Right Cessation
- 1982-10-29 AU AU90018/82A patent/AU555638B2/en not_active Ceased
- 1982-11-02 JP JP57191946A patent/JPS5888377A/en active Granted
- 1982-11-04 DD DD82244560A patent/DD208534A5/en unknown
- 1982-11-04 HU HU823553A patent/HU188333B/en not_active IP Right Cessation
- 1982-11-04 NZ NZ202385A patent/NZ202385A/en unknown
- 1982-11-04 IL IL67178A patent/IL67178A/en unknown
- 1982-11-05 ZA ZA828134A patent/ZA828134B/en unknown
- 1982-11-05 PL PL1982238886A patent/PL133350B1/en unknown
- 1982-11-05 CS CS827905A patent/CS235971B2/en unknown
- 1982-11-05 CA CA000414986A patent/CA1187085A/en not_active Expired
- 1982-11-05 BR BR8206434A patent/BR8206434A/en unknown
- 1982-11-05 GR GR69731A patent/GR77371B/el unknown
- 1982-11-05 DK DK494482A patent/DK494482A/en not_active Application Discontinuation
- 1982-11-05 ES ES517158A patent/ES8307799A1/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5274108A (en) * | 1992-06-18 | 1993-12-28 | Syntex (U.S.A.) Inc. | Process for preparing 1,3-dioxolane derivatives |
| CN109803965A (en) * | 2016-09-29 | 2019-05-24 | 拜耳作物科学股份公司 | The imidazolyl methyl dioxolane derivatives that 5- as fungicide replaces |
Also Published As
| Publication number | Publication date |
|---|---|
| PT75759A (en) | 1982-11-01 |
| AU555638B2 (en) | 1986-10-02 |
| ZA828134B (en) | 1983-09-28 |
| BR8206434A (en) | 1983-09-27 |
| JPH0422913B2 (en) | 1992-04-20 |
| CS235971B2 (en) | 1985-05-15 |
| IL67178A (en) | 1986-12-31 |
| EP0080071A3 (en) | 1983-09-07 |
| DE3144318A1 (en) | 1983-05-19 |
| PL238886A1 (en) | 1983-06-06 |
| IL67178A0 (en) | 1983-03-31 |
| ATE27158T1 (en) | 1987-05-15 |
| DK494482A (en) | 1983-05-08 |
| PT75759B (en) | 1985-07-26 |
| ES517158A0 (en) | 1983-08-01 |
| JPS5888377A (en) | 1983-05-26 |
| NZ202385A (en) | 1985-02-28 |
| ES8307799A1 (en) | 1983-08-01 |
| EP0080071B1 (en) | 1987-05-13 |
| DE3276315D1 (en) | 1987-06-19 |
| DD208534A5 (en) | 1984-04-04 |
| HU188333B (en) | 1986-04-28 |
| PL133350B1 (en) | 1985-05-31 |
| GR77371B (en) | 1984-09-11 |
| AU9001882A (en) | 1983-05-12 |
| EP0080071A2 (en) | 1983-06-01 |
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