CA1065322A - Imidazole and 1,2,4-triazole compounds - Google Patents
Imidazole and 1,2,4-triazole compoundsInfo
- Publication number
- CA1065322A CA1065322A CA259,890A CA259890A CA1065322A CA 1065322 A CA1065322 A CA 1065322A CA 259890 A CA259890 A CA 259890A CA 1065322 A CA1065322 A CA 1065322A
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- Prior art keywords
- alkyl
- compound
- halogen
- substituted
- hydrogen
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Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Compounds of the formula:
Compounds of the formula:
Description
10~ 2 This invention relates to heterocyclic co~lpowlds wnici are imidazole or 1,2,4-triazole compounds, to a process for prep~ring them, to compositions containing them and to methods of con-~ating pests (particularly fungal pests) using them.
The compounds have the general formula (I):
Rl 1 N ~ R2 C - Z - R5 wherein Y is =N- or =C(R)-, each of R,Rl and R2, which may be the same or different, is hydrogen, halogen, nitro or alkyl, each of R3 and R4, which may be the same or different, : is hydrogen or hydrocarbyl which is alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl or aralkenyl, the aryl moieties of said aryl, aralkyl:and aralkenyl being optionally substituted with halogen, alkyl, nitro, trifluoromethyl, cyano, alkoxy, or alkylenedioxy, and R3 or R4 being hydrogen when R4 or R3 is optionally substituted phenyl and at least one of R3 and R4 being hydrocarbyl when Y is = C(R)-; R5 is hydroxy, hydro-carbyl which is alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl or aralkenyl, or hydrocarbyloxy which is alkyloxy, alkenyloxy, alkynyloxy, cycloalkoxy, aryloxy, aralkyloxy or aralkenyloxy~ the aryl moieties of said aryl, aralkyl, aralkenyl, aryloxy, aralkyloxy and aralkenyloxy being optionally sub-stituted with halogen, alkyl, nitro, trifluoromethyl, cyano, alkoxy or alkylenedioxy, or R5 is amino optionally substituted ,~
.
`` 10~53;~
with amino or one or two optionally substituted hydrocarbyls as defined above, subject to the proviso that when R5 is hydrocarbyl, it is other than substituted or unsubstituted phenyl, and Z is C = O or C = S or a derivative of said C = O
the derivative being a ketal, hydrazone, semicarbazone, imine or oxime, or a salt of such a compound.
The compounds can contain chiral centre(s). ~ormally the compounds are prepared in the form of racemic mixtures.
However these and other mixtures can be separated into the individual isomers by methods known in the art~
The halogen can be fluorine, chlorine, bromine or iodine.
The hydrocarbyl and hydrocarbyloxy groups may be saturated or unsaturated, straight or branched chain or cyclic or acyclic. These groups are alkyl, alkenyl, alkynyl, cyclo-alkyl, aryl (including alkaryl), aralkyl, aralkenyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, aryloxy (including alkaryl-oxy), aralkyloxy and aralkenyloxy.
When a hydrocarbyl or hydrocarbyloxy group is, or contains a phenyl group, the latter can be substituted by halo-gen, alkyl nitro, trifluoromethyl, cyano, alkoxy or alkylene-dioxy (e.g. methylenedioxy).
R3 and R4 are preferably Cl_l8, e-g- Cl_7, hydro carbyl; examples are methyl, ethyl, propyl (n- or i-propyl), butyl (n-, i_ or t-butyl), amyl (e.g. isopentyl), hexyl (e.g.
3,3-dimethylbutyl), heptyl, allyl, propynyl (e.g. propargyl), phenyl, tolyl (e.g. m-tolyl), 3-phenylallyl, benzyl, 2-,3- or 4-fluorobenzyl, 4-chlorobenzyl, 2-bromobenzyl, 3,4-, 2,6- or
The compounds have the general formula (I):
Rl 1 N ~ R2 C - Z - R5 wherein Y is =N- or =C(R)-, each of R,Rl and R2, which may be the same or different, is hydrogen, halogen, nitro or alkyl, each of R3 and R4, which may be the same or different, : is hydrogen or hydrocarbyl which is alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl or aralkenyl, the aryl moieties of said aryl, aralkyl:and aralkenyl being optionally substituted with halogen, alkyl, nitro, trifluoromethyl, cyano, alkoxy, or alkylenedioxy, and R3 or R4 being hydrogen when R4 or R3 is optionally substituted phenyl and at least one of R3 and R4 being hydrocarbyl when Y is = C(R)-; R5 is hydroxy, hydro-carbyl which is alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl or aralkenyl, or hydrocarbyloxy which is alkyloxy, alkenyloxy, alkynyloxy, cycloalkoxy, aryloxy, aralkyloxy or aralkenyloxy~ the aryl moieties of said aryl, aralkyl, aralkenyl, aryloxy, aralkyloxy and aralkenyloxy being optionally sub-stituted with halogen, alkyl, nitro, trifluoromethyl, cyano, alkoxy or alkylenedioxy, or R5 is amino optionally substituted ,~
.
`` 10~53;~
with amino or one or two optionally substituted hydrocarbyls as defined above, subject to the proviso that when R5 is hydrocarbyl, it is other than substituted or unsubstituted phenyl, and Z is C = O or C = S or a derivative of said C = O
the derivative being a ketal, hydrazone, semicarbazone, imine or oxime, or a salt of such a compound.
The compounds can contain chiral centre(s). ~ormally the compounds are prepared in the form of racemic mixtures.
However these and other mixtures can be separated into the individual isomers by methods known in the art~
The halogen can be fluorine, chlorine, bromine or iodine.
The hydrocarbyl and hydrocarbyloxy groups may be saturated or unsaturated, straight or branched chain or cyclic or acyclic. These groups are alkyl, alkenyl, alkynyl, cyclo-alkyl, aryl (including alkaryl), aralkyl, aralkenyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, aryloxy (including alkaryl-oxy), aralkyloxy and aralkenyloxy.
When a hydrocarbyl or hydrocarbyloxy group is, or contains a phenyl group, the latter can be substituted by halo-gen, alkyl nitro, trifluoromethyl, cyano, alkoxy or alkylene-dioxy (e.g. methylenedioxy).
R3 and R4 are preferably Cl_l8, e-g- Cl_7, hydro carbyl; examples are methyl, ethyl, propyl (n- or i-propyl), butyl (n-, i_ or t-butyl), amyl (e.g. isopentyl), hexyl (e.g.
3,3-dimethylbutyl), heptyl, allyl, propynyl (e.g. propargyl), phenyl, tolyl (e.g. m-tolyl), 3-phenylallyl, benzyl, 2-,3- or 4-fluorobenzyl, 4-chlorobenzyl, 2-bromobenzyl, 3,4-, 2,6- or
2,4-dichlorobenzyl, -methylbenzyl, 4-cyanobenzyl, 2-, 3- or 4-nitrobenzyl, 3-methylbenzyl, -methyl-4-chlorobenzyl, 3-nitro-4-chlorobenzyl, 2-methoxy-5-nitrobenzyl or 2-chloro-4,5-me~hylene-dioxybenzyl. Another possible group is n-dodecyl.
10653'~;~
R5 can be one of the hydrocarbyl groups listed above for R4 (with the exception of phenyl). Thus R5 can be substituted or unsubstituted aralkyl, cycloalkyl or branched chain alkyl. Suitable aralkyl groups are benzyl optionally substituted with halogen (e.g. fluorine, chlorine, bromine or iodine) or alkyl (e.g. methyl or ethyl). Examples of suitable cycloalkyl groups are cyclohexyl and cyclopentyl which can if desired be alkyl-substituted. R5 can also be Cl_7 hydrocarbyloxy for example methoxy, ethoxy, propoxy (e.g. i-propoxy), butoxy (e.g. n- or t-butoxy), allyloxy, -OC(CH3)2C2H5, -OCH2C(CH3)3, O(CH2)2C(CH3)3, benzyloxy, p-chlorobenzyloxy, cyclopentyloxy, phenoxy or p-chlorophenoxy.
Other examples of suitable R5 groups are phenylamino, n- or t-butylamino, 1,1- or 2,2-dimethylpropylamino, amino, hydrazlno, benzylamino, o- or p-chlorophenylamino, p-tolyl-amino, m-chloro-p-tolylamino, p-nitrophenylamino, -NHCH2C(CH3)3, m-chloro-p-nitrophenylamino, or m-trifluoromethylphenylamino.
A preferred class of triazole compounds are those whereln Y is -N-, Rl, R2 and R3 are hydrogen, R4 is hydrogen, Cl_6 alkyl, alkenyl or alkynyl having up to 4 carbon atoms, phenylallyl, phenyl, benzyl optlonally ring-substituted with halogen, Cl_4 alkyl or alkoxy, nitro, trifluoromethyl, cyano or methylene dioxy, or ~ -(Cl_4 alkyl) benzyl optionally ring-substituted with halogen, and R5 is hydroxy, Cl_6 alkyl or alkoxy, amino, hydrazino, phenylamino optionally ring-iOf~5~
substituted with Cl 4 alkyl, halogen, nitro or trifluoro-methyl, (Cl_6 alkyl) amino, phenyloxy optionally substituted with halogen, benzylamino, benzyloxy, cycloalkoxy or cyclo-alkyl, and Z ls C = 0 or C = NH, or a salt of such a compound.
A preferred class of imidazole compounds are those wherein Y is = C(R)- wherein R is hydrogen, Rl, R2 and R3 are hydrogen, R4 is Cl 6 alkyl, benzyl optionally substituted with halogen, cyano or trifluoromethyl, or 0~-(Cl_4 alkyl) benzyl optionally ring-substituted with halogen, R5 is hydroxy, Cl 6 alkyl, Cl 4 alkoxy, phenylamino or benzyloxy optionally substituted with halogen, and Z is C = 0, or a salt of such a compound.
The salts of the compounds can be salts of organic or inorganic acids e.g. hydrochloric, sulphuric, acetic or oxalic acid, or, when R5 is hydroxy, salts with alkali metals, for example lithium, sodium or potassium, alkaline earth metals, for example calcium and magnesium, ammonia and primary, secondary or tertiary amines, for example mono-, di- or tri-(Cl_6 aliphatic) amines.
Examples of suitable triazole and imidazole compounds are shown in Tables I and II, respectively.
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The compounds may be made by reacting an optionally substituted imidazole or 1,2,4-triazole or a salt thereof with the appropriate activated halo compound (for example an ~-haloketone, ~ -haloacid, O~-haloester, ~-haloamide or substituted alkyl halide) using methods set out in the literature. Thus a compound of general formula (II):-Y -NH
Rl~N~R2 wherein Y, Rl and R2 are as defined above, or a salt thereof, can be reacted with a compound of general formula (III):-X-f -Z-R5 wherein X is halogen, preferably bromine or chlorine, and R3, R4, R5 and Z are as defined above.
Alternatively, the compounds wherein R3 and/or R4 are hydrocarbyl made by hydrocarbylating (e.g. with an appro-priately substituted alkylating or aralkylating agent) a compound of general formula (IV):-10~iS3~;~
wherein Z, Y, Rl, R2 and R5 are as defined above, or a salt thereof, suitably in the presence of a base in a hydroxylic or non-hydroxylic solvent using methods set out in the literature.
These processes may in some cases be carried out by heating the reactants together in the absence of a solvent or diluent, but preferably a solvent is present. Suitable solvents are non-hydroxylic solvents such as acetonitrile (which is preferred), dimethylformamide, dimethyl sulphoxide, sulpholane and tetrahydrofuran. Hydroxylated solvents, for example methanol and ethanol, may be used in certain circum-stances when the presence of the hydroxyl group does not interfere with the progress of the reaction. The processes may also be carried out in the presence of a base, but preferably excess imidazole or triazole is present to remove liberated HX from the reaction. Other suitable bases are sodium hydride (although not when a hydroxylated solvent or diluent is used), alkali metal carbonates (such as potassium carbonate) and alkali metal hydroxides (such as potassium hydroxide). The reaction temperature depends upon ~0~iS3;~;~
the choice of reactants, solvent and base, but generally the reaction mixture is refluxed.
The processes generally involve dissolving the reactants in a solvent and, after allowing reaction to occur, isolating the product by removal of the reactant solvent in vacuo.
The unreacted imidazole or triazole is removed by extraction of the product with a suitable solvent and the extract is washed with water. A crystallisation or other purification procedure may then be carried out if desired.
The activated halo compounds may be made by any of the methods set out in the literature.
The compounds wherein Z is a derivative of C = 0 may be made from the respective carbonyl compound using any of the standard techniques set out in the literature.
The compounds are active fungicides, particularly against the following diseases:-Piricularia oryzae on rice Puccinia recondita and other rusts on wheat and rusts on other hosts Plasmopara viticola on vines Erysiphe graminis (powdery mildew) on barley and wheat and other powdery mildews on various hosts such as Sphaerotheca fulginea on cucumbers, Podosphaera leucotricha on apples and Uncinula necator on vines i()f~S3'~'~
Botrytis cinerea (grey mould) on tomatoes, strawberries, vines and other hosts Gleosporiun musarum on bananas and Penicillium digitatum on oranges (Compounds 8 and 19 show activity against these latter two) Some of ~he compounds are active in the form of seed dressings against:
Fusarium spp., Septoria spp., Tilletia spp., and Pyrenophora spp. on cereals.
The compounds also have certain anti-bacterial and anti-viral activities.
They may be used as such for anti-fungal purposes but are more conveniently formulated into compositions for such usage.
The invention therefore also provides a fungicidal composition comprising, as an active ingredient, an imidazole or triazole compound or salt thereof, and a carrier for the active ingredient.
The invention also provides a method for combating pests, which are fungi, viruses or bacteria, which method comprises treating plants, seeds or trees with an imidazole or triazole compound or salt thereof as hereinbefore defined.
The compounds can be used to combat plant pests and treat plants or seeds in a number of ways, for example they can be applied, formulated or unformulated, directly to the iOf~53~;~
foliage of a plant which is infected or likely to become infected, or they can be applied also to bushes and trees, to seeds or to other medium in which plants, bushes or trees are growing or are to be planted, or they can be sprayed on, dusted on or applied as a cream or paste formulation.
Application can be to any part of the plant, bush or tree, for example to the foliage, stems, branches or roots, or to soil surrounding the roots.
The term "treating" as used herein refers to all these modes of application and the term "plant" includes seed-lings, bushes and trees. Furthermore, the method of the invention includes preventative, protectant, prophylactic and eradicant treatment.
The compounds are preferably used for agricultural and horticultural purposes in the form of a composition. The ~ype of composition used in any ins~ance will depend upon the particular purpose envisaged.
The compositions may be in the form of dusting powders or granules comprising the active ingredient and a solid diluent or carrier, for example, kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth, gypsum, Hewitt's earth, diatomaceous earth and China clay. Compositions for dressing seed, for example, may comprise an agent (for example a mineral oil) for assisting the adhesion of the composition to the seed.
lOtiS3~;~
The compositions may also be in the form of dispersible powders or grains comprising a wetting agent to facilitate the dispersion in liquids of the powder or grains which may contain also fillers and suspending agents.
The aqueous dispersions or emulsions may be prepared by dissolving the active ingredient(s) in an organic solvent optionally containing wetting, dispersing or emulsifying agent(s) and then adding the mixture to water which may also contain wetting, dispersing or emulsifying agent(s).
Suitable solvents are ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, the xylenes and trichloro-ethylene.
The compositions to be used as sprays may also be in the form of aerosols wherein the formulation is held in a container under pressure in the presence of a propellant, e.g. fluorotrichloromethane or dichlorodifluoromethane.
By including suitable additives, for example additives for improving the distribution, adhesive power and resis-tance to rain on treated surfaces, the different compositions can be better adapted for various utilities.
The compounds can be used as mixtures with fertilisers (e.g. nitrogen - or phosphorus - containing fertilisers).
Compositions comprising only granules of fertiliser incor-porating, for example coated with, the imidazole or triazole 10~532~
compound, are preferred. The invention therefore also provides a fertiliser composition comprising the imidazole or triazole compound.
The compositions may also be in the form of liquid preparations for use as dips or sprays which are generally aqueous dispersions or emulsions containing the active ingredient in the presence of one or more wetting agent(s), dispersing agent(s), emulsifying agent(s) or suspending agent(s). These agents can be cationic, anionic or non-anionic agents.
Suitable cationic agents are quaternary ammonium compounds for example, cetyltrimethylammonium bromide.
Suitable anionic agents are soaps, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), and salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of sodium diisopropyl- and triisopropyl-naphthalene sulphonates). Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol or cetyl alcohol, or with alkyl phenols such as octylphenol, nonylphenol and octylcresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of the said partial esters with ethylene oxide, and the lecithins.
10~;53;~
Suitable suspending agents are hydrophilic colloids (for example polyvinylpyrrolidone and sodium carboxymethylcel-lulose), and the vegetable gums (for example gum acacia and gum tragacanth).
The compositions for use as aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient(s), the concentrate to be diluted with water before use. These concentrates often should be able to withstand storage for prolonged periods and after such storage be capable of dilution with water in order to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may conveniently contain 10-85%, generally 25-60%, by weight of the active ingredient(s). When diluted to form aqueous preparations, such preparations may contain varying amounts of the active ingredient(s) depending upon the intended purpose, but an aqueous preparation containing 0.0005% or 0.01% to 10% by weight of active ingredient(s) may be used.
The compositions of this invention can comprise also other compound(s) having biological activity, as well as stabilising agent(s), for example epoxides (e.g. epichlor-hydrin).
The following Examples illustrate the invention; the temperatures are given in degrees Centigrade (C).
l()~S3'~;~
~-1,2,4-Triazol-l-yl-pinacolone (Compound 1) 1,2,4-Triazole (33.4 g) and sodium ethoxide Cfrom sodium (11.6 g) and ethyl alcohol (250 ml)~7 were refluxed for 1 hour. To this solution at the reflux temperature was added bromopinacolone (87 g), and the mixture was then heated for 2 hours. It was then cooled to ambient temper-ature and filtered to remove the precipitated sodium bromide;
the solvent was removed in vacuo. The residue was extracted with chloroform (100 ml). The extract was washed with water (4 x 15 ml), dried (sodium sulphate) and filtered. Petroleum ether (50 ml; b.p. 60-80) was added and the solution concentrated to give ~-1,2,4-triazol-4-yl-pinacolone, m.p.
176. Further concentration of the solution gave the title compound, m.p. 63-65.
l-Imino-2-(1,2,4-triazol-1-yl)ethyl methyl ether (Compound 2) 1,2,4-Trlazole (3.45 g) was added to a sodium methoxide in methanol ~prepared from sodium (1.15 g) and methanol (40 ml) ~ , and the mixture was refluxed for 1 hour, and cooled to 25C; chloroacetonitrile (3.78 g) was then added and the lOt;S3'~;~
mixture was refluxed for a further 6 hours. The solution was filtered and the solvent removed in vacuo. The resultant mixture was dissolved in petroleum ether (50 ml; b.p. 40-60C) and the solution filtered to remove unreacted 1,2,4-triazole. Removal of the solvent in vacuo gave a residue which on distillation gave the title compound.
Ethyl ~-1,2,4-triazol-1-yl isovalerate. (Compound 4) Ethyl 0~-bromoisovalerate (5 g) was added dropwise to a solution of the sodium salt of 1,2,4-triazole Cprepared from reacting 1,2,4-triazole (1.8 gm) with sodium hydride (1.26 g; 50~ oil dispersion)~7 in dimethylformamide (30 ml).
The reaction mixture was kept at 55-60 for 5 hours, the solvent removed in vacuo, and the residue extracted with ether; the ethereal layer was then washed with water and dried (sodium sulphate). The solvent was removed in vacuo to leave a re9idual oil which was distilled, as an oil, to give the title compound.
~-1,2,4-Triazol-l-yl caproanilide. (ComPound 5) Stage 1 : Ethyl o~-bromocaproate (4.5 g) in dimethyl-formamide was added to the sodium salt of 1,2,4-triazole 10~;53'~'~
~prepared by reacting 1,2,4-triazole (3 g) with sodium hydride (1.8 g; 50~ dispersion in oil)~ in dimethylformamide (20 ml). The reaction mixture was maintained at 50C for 5 hours, the solvent removed in vacuo and the residue extracted with ether (100 ml). The ethereal phase was washed with water (2 x 50 ml) and dried (sodium sulphate), the solvent removed _ vacuo and the residue extracted with ether (100 ml). The ethereal phase was washed with water (2 x 50 ml), and dried (sodium sulphate); the solvent was removed in vacuo. Distillation of the residue gave a liquid, b.p. 86-90/0.2 mm. To this liquid (12 g) was added potassium hydroxide (6.5 g) in water (50 ml) and the mixture stirred for 15 minutes. The mixture was washed with ether (2 x 20 ml) and then acidified to pH 2 (concentrated hydrochloric acid).
The white solid so obtained was washed with cold water (50 mls) and dried. Recrystallisation of this solid gave o~-1,2,4-triazol-1-ylcaproic acid, m.p. 141-143.
Stage 2 : o~-1,2,4-Triazol-l-ylcaproic acid (1.83 g) and thionyl chloride (1.5 ml) were refluxed for 30 minutes.
Excess thionyl chloride was removed in vacuo and the result-ant gum extracted with methylene chloride (10 ml); the extract was added to aniline (2.83 g) in methylene chloride (10 ml) at 10-15. The mixture was stirred for 30 minutes, 10~53;~'~
washed with water (50 ml) and then dried ~magnesium sulphate).
Removal of the solvent in vacuo gave a solid which on recrystallisation from toluene gave the title compound.
Alternatively this compound can be made starting from o~-bromocapranilide as described in Example 1 using the sodium salt of the triazole.
0~-1,2,4-Triazol-l-yl-isovaleroylhydrazine.
(Compound 11) Stage 1 : To a solution of the sodium salt of 1,2,4-triazole (1.81 g) (prepared as described in Example 4) in dimethylformamide (30 ml) was added ethyl 0~-bromoisovalerate (5.0 g) dropwise with stirring and the mixture kept at 55-60 for five hours. The bulk of the solvent was removed in vacuo, and the residue was diluted with water and extracted with ether. The ethereal layer was washed with water and dried (magnesium sulphate), and the solvent was distilled off to give o~ 2~4-triazol-l-yl iso-valerate as a clear liquid.
Stage 2 : A solution of the above compound and hydrazine hydrate (3 ml) in ethanol (15 ml) was refluxed for two hours. Removal of solvent gave a white solid which was recrystallised from ethyl acetate to give the title compound.
10~;53;~;~
0~-p-Chlorobenzyl- ~-1,2,4-triazol-1-yl-pinacolone ~ (Compound 10) C~-1,2,4-Triazol-l-yl-pinacolone (3.3 g) in dimethyl-formamide (20 ml) was added dropwise to a suspension of sodium hydride (0.48 g; 100%) in dimethylformamide (10 ml) at room temperature with stirring. After stirring for two hours, p-chlorobenzyl chloride (3.2 g) in dimethylformamide (2-3 ml) was added dropwise and the reaction mixture was kept at 5-10 for two hours. The solvent was removed in vacuo and water was added to the residue. The aqueous solution was extracted with methylene chloride, the organic layer was washed with water and dried (magnesium sulphate).
The solvent was removed to give a yellow solid which was crystallised to give the title compound.
ExAMæLE 7 0~-1~2~4-Triazol-l-ylcaproamide. (Compound 8) Ethyl 0~ 2~4-triazol-l-ylcaproate (3. 0 g) was added to liquid ammonia (0.880, 15 ml) and the mixture was shaken well for a few minutes and then left overnight at room temperature. The white solid was filtered and washed with water to give, after recrystallisation from water, the title compound.
10~5~
ExAMæLE 8 Ethyl 2-(1-imidazolyl)-3-methylbutyrate. (Compound 69) Ethyl 2-bromo-2-isopropyl aceta~e (5 g), imidazole (4.2 g) and acetonitrile were refluxed for 72 hours. The solvent was removed in vacuo and the residue slurried with diethyl ether and poured into water. The ethereal layer was separated off and dried (magnesium sulphate). The solvent was removed in vacuo to give an oil which on distillation gave the title compound, b.p. 55-60/ 0.1 mm.
d -Imidazol-l-yl~ (p-chlorobenzyl)pinacolone (Compound 84) Stage I : To sodium ethoxide solution ~prepared by reacting sodium (6 g) with ethanol (200 ml 7 was added imidazole (17.3 g) in ethanol (S0 ml) and the mixture was refluxed for one hour. The mixture was cooled and bromo-pinacolone (45 g) in ethanol (60 ml) was added; the mixture was refluxed for two hours and left at room temperature overnight with stirring. The solvent was removed in vacuo, water was added and the mixture extracted with methylene chloride. The organic layer was washed with water and dried (MgS04), and the solvent was removed. The residual oil was 10~;53;~;~
distilled to give --imidazol-l-yl-pinacolone as a colour-less oil, b.p. 138-142/0.1 mm. The product contained unreacted imidazole, but was used for Stage II without further purification.
Stage II : To a suspension of sodium hydride ~480 mg;
100% 7 in dimethyl formamide (5 ml) was added C~-imidazol-l-yl-pinacolone (3.3 g) in dimethyl formamide (10 ml).
After 3 hours, stirring at room temperature, p-chlorobenzyl chloride (3.2 g) in dimethylformamide (10 ml) was added and lQ the mixture stirred at room temperature overnight. The dimethylformamide was removed in vacuo, and the residue was diluted with water and extracted with methylene chloride.
The organic layer was washed with water, dried (Na2S04) and the solvent was removed to give a yellow oil. This slowly solidified and was recrystallised from ether/petrol (40-60) to give, as colourless plates, OL-imidazol-l-yl - L-(p-chlorobenzyl)-pinacolone, m.p. 98-100. Analysis;
Calculated : C, 66.08; H, 6.59; N, 9.64~. Found : C, 66.49;
H, 6.53; N, 9.58%.
~-Imidazol-l-yl- -benzylpinacolone (Compound 85), m.p. 64-66 (Analysis; Calculated : C, 74.04; H, 7.87; N, 11.51%. Found : C, 73.82; H, 7.87; N, 11.83~) was prepared as described in Example 9 using benzyl chloride as the aralkylating agent.
lO~S;~
/
d -Imidazol-l-yl- OL-p-fluorobenzylpinacolone (Compound 86) Stage I : OL-Imidazol-l-ylpinacolone.
To sodium ethoxide solution ~prepared by reacting sodium (6 g) with ethanol (200 ml) 7 was added imidazole (17.3 g) in ethanol (50 ml) and the mixture was refluxed for one hour. The mixture was cooled and bromopinacolone (45 g) in ethanol (60 ml) was added; the mixture was refluxed for two hours and left at room temperature overnight with stirring. The solvent was removed in vacuo, water was added and the mixture extracted with methylene chloride. The organic layer was washed with water and dried (MgS04), and the solvent was removed. The residual oil was distilled to give L-imidazol-l-yl-pinacolone as a colourless oil, b.p.
138-142/0.1 mm. The product contained unreacted imidazole, but was used for Stage II without further purification.
Stage II : To a suspension of sodium hydride C 480 mg;
100%~7 in dimethylformamide (5 ml) was added ~-imidazol-l-ylpinacolone (3.3 g) in dimethylformamide (10 ml). After stirring for 3 hours at room temperature, p-fluorobenzyl-chlorlde (2.9 g) in dimethylformamide (10 ml) was added and the mixture was stirred at room temperature overnight.
10~;53'~'~
The dimethylformamide was removed in vacuo and the residue diluted with water and extracted with methylene chloride.
The organic layer was washed with water, dried (Na2S04) and the solvent was removed to give an orange oil. This was chromatographed over silica gel eluting with ethyl acetate.
The product from the eluate was crystallised from petroleum ether (60-80) to give the title product as a white crystal-line solid.
The compounds were tested against a variety of foliar fungal diseases of plants. The technique employed was as follows.
The plants were grown in John Innes Potting Compost (No. 1, or Seed, as appropriate) in 4 cm diameter mini-pots.
A layer of fine sand was placed at the bottom of the pot to facilitate uptake of test compouna by the roots. Vermiculite was used to cover the seed in the soil tests.
The test compounds were formulated either by bead-milling with aqueous Dispersol T or as a solution in acetone/
ethanol which was diluted to the required concentration immediately before use. For the foliage diseases, 100 ppm a.i. suspensions were sprayed on to the foliage and applied to the roots of the same plant via the soil. (Sprays were 10~;53;~
applied to maximum retention, and root drenches to a flnal concentration equivalent to approximately 40 ppm a.i./dry soil). Tween 20* to give a final concentration of 0.1%, was added when the sprays were applied to the cereals.
For most of the tests, the test compound was applied to the soil and foliage one or two days before the plant was inoculated with the diseases. An exception was the test on Erysiphe graminis, in which the plants were inoculated 24 hours before treatment. After inoculation, ~he plants were l~ put into an appropriate environment to allow infection to take place and then incubated until the disease was ready for assessment. The period between inoculation and assess-ment varied from 3 to lO days according to the disease and environment.
The disease control was recorded by the following grading:
4 = No disease
10653'~;~
R5 can be one of the hydrocarbyl groups listed above for R4 (with the exception of phenyl). Thus R5 can be substituted or unsubstituted aralkyl, cycloalkyl or branched chain alkyl. Suitable aralkyl groups are benzyl optionally substituted with halogen (e.g. fluorine, chlorine, bromine or iodine) or alkyl (e.g. methyl or ethyl). Examples of suitable cycloalkyl groups are cyclohexyl and cyclopentyl which can if desired be alkyl-substituted. R5 can also be Cl_7 hydrocarbyloxy for example methoxy, ethoxy, propoxy (e.g. i-propoxy), butoxy (e.g. n- or t-butoxy), allyloxy, -OC(CH3)2C2H5, -OCH2C(CH3)3, O(CH2)2C(CH3)3, benzyloxy, p-chlorobenzyloxy, cyclopentyloxy, phenoxy or p-chlorophenoxy.
Other examples of suitable R5 groups are phenylamino, n- or t-butylamino, 1,1- or 2,2-dimethylpropylamino, amino, hydrazlno, benzylamino, o- or p-chlorophenylamino, p-tolyl-amino, m-chloro-p-tolylamino, p-nitrophenylamino, -NHCH2C(CH3)3, m-chloro-p-nitrophenylamino, or m-trifluoromethylphenylamino.
A preferred class of triazole compounds are those whereln Y is -N-, Rl, R2 and R3 are hydrogen, R4 is hydrogen, Cl_6 alkyl, alkenyl or alkynyl having up to 4 carbon atoms, phenylallyl, phenyl, benzyl optlonally ring-substituted with halogen, Cl_4 alkyl or alkoxy, nitro, trifluoromethyl, cyano or methylene dioxy, or ~ -(Cl_4 alkyl) benzyl optionally ring-substituted with halogen, and R5 is hydroxy, Cl_6 alkyl or alkoxy, amino, hydrazino, phenylamino optionally ring-iOf~5~
substituted with Cl 4 alkyl, halogen, nitro or trifluoro-methyl, (Cl_6 alkyl) amino, phenyloxy optionally substituted with halogen, benzylamino, benzyloxy, cycloalkoxy or cyclo-alkyl, and Z ls C = 0 or C = NH, or a salt of such a compound.
A preferred class of imidazole compounds are those wherein Y is = C(R)- wherein R is hydrogen, Rl, R2 and R3 are hydrogen, R4 is Cl 6 alkyl, benzyl optionally substituted with halogen, cyano or trifluoromethyl, or 0~-(Cl_4 alkyl) benzyl optionally ring-substituted with halogen, R5 is hydroxy, Cl 6 alkyl, Cl 4 alkoxy, phenylamino or benzyloxy optionally substituted with halogen, and Z is C = 0, or a salt of such a compound.
The salts of the compounds can be salts of organic or inorganic acids e.g. hydrochloric, sulphuric, acetic or oxalic acid, or, when R5 is hydroxy, salts with alkali metals, for example lithium, sodium or potassium, alkaline earth metals, for example calcium and magnesium, ammonia and primary, secondary or tertiary amines, for example mono-, di- or tri-(Cl_6 aliphatic) amines.
Examples of suitable triazole and imidazole compounds are shown in Tables I and II, respectively.
1()~53'~'~
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The compounds may be made by reacting an optionally substituted imidazole or 1,2,4-triazole or a salt thereof with the appropriate activated halo compound (for example an ~-haloketone, ~ -haloacid, O~-haloester, ~-haloamide or substituted alkyl halide) using methods set out in the literature. Thus a compound of general formula (II):-Y -NH
Rl~N~R2 wherein Y, Rl and R2 are as defined above, or a salt thereof, can be reacted with a compound of general formula (III):-X-f -Z-R5 wherein X is halogen, preferably bromine or chlorine, and R3, R4, R5 and Z are as defined above.
Alternatively, the compounds wherein R3 and/or R4 are hydrocarbyl made by hydrocarbylating (e.g. with an appro-priately substituted alkylating or aralkylating agent) a compound of general formula (IV):-10~iS3~;~
wherein Z, Y, Rl, R2 and R5 are as defined above, or a salt thereof, suitably in the presence of a base in a hydroxylic or non-hydroxylic solvent using methods set out in the literature.
These processes may in some cases be carried out by heating the reactants together in the absence of a solvent or diluent, but preferably a solvent is present. Suitable solvents are non-hydroxylic solvents such as acetonitrile (which is preferred), dimethylformamide, dimethyl sulphoxide, sulpholane and tetrahydrofuran. Hydroxylated solvents, for example methanol and ethanol, may be used in certain circum-stances when the presence of the hydroxyl group does not interfere with the progress of the reaction. The processes may also be carried out in the presence of a base, but preferably excess imidazole or triazole is present to remove liberated HX from the reaction. Other suitable bases are sodium hydride (although not when a hydroxylated solvent or diluent is used), alkali metal carbonates (such as potassium carbonate) and alkali metal hydroxides (such as potassium hydroxide). The reaction temperature depends upon ~0~iS3;~;~
the choice of reactants, solvent and base, but generally the reaction mixture is refluxed.
The processes generally involve dissolving the reactants in a solvent and, after allowing reaction to occur, isolating the product by removal of the reactant solvent in vacuo.
The unreacted imidazole or triazole is removed by extraction of the product with a suitable solvent and the extract is washed with water. A crystallisation or other purification procedure may then be carried out if desired.
The activated halo compounds may be made by any of the methods set out in the literature.
The compounds wherein Z is a derivative of C = 0 may be made from the respective carbonyl compound using any of the standard techniques set out in the literature.
The compounds are active fungicides, particularly against the following diseases:-Piricularia oryzae on rice Puccinia recondita and other rusts on wheat and rusts on other hosts Plasmopara viticola on vines Erysiphe graminis (powdery mildew) on barley and wheat and other powdery mildews on various hosts such as Sphaerotheca fulginea on cucumbers, Podosphaera leucotricha on apples and Uncinula necator on vines i()f~S3'~'~
Botrytis cinerea (grey mould) on tomatoes, strawberries, vines and other hosts Gleosporiun musarum on bananas and Penicillium digitatum on oranges (Compounds 8 and 19 show activity against these latter two) Some of ~he compounds are active in the form of seed dressings against:
Fusarium spp., Septoria spp., Tilletia spp., and Pyrenophora spp. on cereals.
The compounds also have certain anti-bacterial and anti-viral activities.
They may be used as such for anti-fungal purposes but are more conveniently formulated into compositions for such usage.
The invention therefore also provides a fungicidal composition comprising, as an active ingredient, an imidazole or triazole compound or salt thereof, and a carrier for the active ingredient.
The invention also provides a method for combating pests, which are fungi, viruses or bacteria, which method comprises treating plants, seeds or trees with an imidazole or triazole compound or salt thereof as hereinbefore defined.
The compounds can be used to combat plant pests and treat plants or seeds in a number of ways, for example they can be applied, formulated or unformulated, directly to the iOf~53~;~
foliage of a plant which is infected or likely to become infected, or they can be applied also to bushes and trees, to seeds or to other medium in which plants, bushes or trees are growing or are to be planted, or they can be sprayed on, dusted on or applied as a cream or paste formulation.
Application can be to any part of the plant, bush or tree, for example to the foliage, stems, branches or roots, or to soil surrounding the roots.
The term "treating" as used herein refers to all these modes of application and the term "plant" includes seed-lings, bushes and trees. Furthermore, the method of the invention includes preventative, protectant, prophylactic and eradicant treatment.
The compounds are preferably used for agricultural and horticultural purposes in the form of a composition. The ~ype of composition used in any ins~ance will depend upon the particular purpose envisaged.
The compositions may be in the form of dusting powders or granules comprising the active ingredient and a solid diluent or carrier, for example, kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth, gypsum, Hewitt's earth, diatomaceous earth and China clay. Compositions for dressing seed, for example, may comprise an agent (for example a mineral oil) for assisting the adhesion of the composition to the seed.
lOtiS3~;~
The compositions may also be in the form of dispersible powders or grains comprising a wetting agent to facilitate the dispersion in liquids of the powder or grains which may contain also fillers and suspending agents.
The aqueous dispersions or emulsions may be prepared by dissolving the active ingredient(s) in an organic solvent optionally containing wetting, dispersing or emulsifying agent(s) and then adding the mixture to water which may also contain wetting, dispersing or emulsifying agent(s).
Suitable solvents are ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, the xylenes and trichloro-ethylene.
The compositions to be used as sprays may also be in the form of aerosols wherein the formulation is held in a container under pressure in the presence of a propellant, e.g. fluorotrichloromethane or dichlorodifluoromethane.
By including suitable additives, for example additives for improving the distribution, adhesive power and resis-tance to rain on treated surfaces, the different compositions can be better adapted for various utilities.
The compounds can be used as mixtures with fertilisers (e.g. nitrogen - or phosphorus - containing fertilisers).
Compositions comprising only granules of fertiliser incor-porating, for example coated with, the imidazole or triazole 10~532~
compound, are preferred. The invention therefore also provides a fertiliser composition comprising the imidazole or triazole compound.
The compositions may also be in the form of liquid preparations for use as dips or sprays which are generally aqueous dispersions or emulsions containing the active ingredient in the presence of one or more wetting agent(s), dispersing agent(s), emulsifying agent(s) or suspending agent(s). These agents can be cationic, anionic or non-anionic agents.
Suitable cationic agents are quaternary ammonium compounds for example, cetyltrimethylammonium bromide.
Suitable anionic agents are soaps, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), and salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of sodium diisopropyl- and triisopropyl-naphthalene sulphonates). Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol or cetyl alcohol, or with alkyl phenols such as octylphenol, nonylphenol and octylcresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of the said partial esters with ethylene oxide, and the lecithins.
10~;53;~
Suitable suspending agents are hydrophilic colloids (for example polyvinylpyrrolidone and sodium carboxymethylcel-lulose), and the vegetable gums (for example gum acacia and gum tragacanth).
The compositions for use as aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient(s), the concentrate to be diluted with water before use. These concentrates often should be able to withstand storage for prolonged periods and after such storage be capable of dilution with water in order to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may conveniently contain 10-85%, generally 25-60%, by weight of the active ingredient(s). When diluted to form aqueous preparations, such preparations may contain varying amounts of the active ingredient(s) depending upon the intended purpose, but an aqueous preparation containing 0.0005% or 0.01% to 10% by weight of active ingredient(s) may be used.
The compositions of this invention can comprise also other compound(s) having biological activity, as well as stabilising agent(s), for example epoxides (e.g. epichlor-hydrin).
The following Examples illustrate the invention; the temperatures are given in degrees Centigrade (C).
l()~S3'~;~
~-1,2,4-Triazol-l-yl-pinacolone (Compound 1) 1,2,4-Triazole (33.4 g) and sodium ethoxide Cfrom sodium (11.6 g) and ethyl alcohol (250 ml)~7 were refluxed for 1 hour. To this solution at the reflux temperature was added bromopinacolone (87 g), and the mixture was then heated for 2 hours. It was then cooled to ambient temper-ature and filtered to remove the precipitated sodium bromide;
the solvent was removed in vacuo. The residue was extracted with chloroform (100 ml). The extract was washed with water (4 x 15 ml), dried (sodium sulphate) and filtered. Petroleum ether (50 ml; b.p. 60-80) was added and the solution concentrated to give ~-1,2,4-triazol-4-yl-pinacolone, m.p.
176. Further concentration of the solution gave the title compound, m.p. 63-65.
l-Imino-2-(1,2,4-triazol-1-yl)ethyl methyl ether (Compound 2) 1,2,4-Trlazole (3.45 g) was added to a sodium methoxide in methanol ~prepared from sodium (1.15 g) and methanol (40 ml) ~ , and the mixture was refluxed for 1 hour, and cooled to 25C; chloroacetonitrile (3.78 g) was then added and the lOt;S3'~;~
mixture was refluxed for a further 6 hours. The solution was filtered and the solvent removed in vacuo. The resultant mixture was dissolved in petroleum ether (50 ml; b.p. 40-60C) and the solution filtered to remove unreacted 1,2,4-triazole. Removal of the solvent in vacuo gave a residue which on distillation gave the title compound.
Ethyl ~-1,2,4-triazol-1-yl isovalerate. (Compound 4) Ethyl 0~-bromoisovalerate (5 g) was added dropwise to a solution of the sodium salt of 1,2,4-triazole Cprepared from reacting 1,2,4-triazole (1.8 gm) with sodium hydride (1.26 g; 50~ oil dispersion)~7 in dimethylformamide (30 ml).
The reaction mixture was kept at 55-60 for 5 hours, the solvent removed in vacuo, and the residue extracted with ether; the ethereal layer was then washed with water and dried (sodium sulphate). The solvent was removed in vacuo to leave a re9idual oil which was distilled, as an oil, to give the title compound.
~-1,2,4-Triazol-l-yl caproanilide. (ComPound 5) Stage 1 : Ethyl o~-bromocaproate (4.5 g) in dimethyl-formamide was added to the sodium salt of 1,2,4-triazole 10~;53'~'~
~prepared by reacting 1,2,4-triazole (3 g) with sodium hydride (1.8 g; 50~ dispersion in oil)~ in dimethylformamide (20 ml). The reaction mixture was maintained at 50C for 5 hours, the solvent removed in vacuo and the residue extracted with ether (100 ml). The ethereal phase was washed with water (2 x 50 ml) and dried (sodium sulphate), the solvent removed _ vacuo and the residue extracted with ether (100 ml). The ethereal phase was washed with water (2 x 50 ml), and dried (sodium sulphate); the solvent was removed in vacuo. Distillation of the residue gave a liquid, b.p. 86-90/0.2 mm. To this liquid (12 g) was added potassium hydroxide (6.5 g) in water (50 ml) and the mixture stirred for 15 minutes. The mixture was washed with ether (2 x 20 ml) and then acidified to pH 2 (concentrated hydrochloric acid).
The white solid so obtained was washed with cold water (50 mls) and dried. Recrystallisation of this solid gave o~-1,2,4-triazol-1-ylcaproic acid, m.p. 141-143.
Stage 2 : o~-1,2,4-Triazol-l-ylcaproic acid (1.83 g) and thionyl chloride (1.5 ml) were refluxed for 30 minutes.
Excess thionyl chloride was removed in vacuo and the result-ant gum extracted with methylene chloride (10 ml); the extract was added to aniline (2.83 g) in methylene chloride (10 ml) at 10-15. The mixture was stirred for 30 minutes, 10~53;~'~
washed with water (50 ml) and then dried ~magnesium sulphate).
Removal of the solvent in vacuo gave a solid which on recrystallisation from toluene gave the title compound.
Alternatively this compound can be made starting from o~-bromocapranilide as described in Example 1 using the sodium salt of the triazole.
0~-1,2,4-Triazol-l-yl-isovaleroylhydrazine.
(Compound 11) Stage 1 : To a solution of the sodium salt of 1,2,4-triazole (1.81 g) (prepared as described in Example 4) in dimethylformamide (30 ml) was added ethyl 0~-bromoisovalerate (5.0 g) dropwise with stirring and the mixture kept at 55-60 for five hours. The bulk of the solvent was removed in vacuo, and the residue was diluted with water and extracted with ether. The ethereal layer was washed with water and dried (magnesium sulphate), and the solvent was distilled off to give o~ 2~4-triazol-l-yl iso-valerate as a clear liquid.
Stage 2 : A solution of the above compound and hydrazine hydrate (3 ml) in ethanol (15 ml) was refluxed for two hours. Removal of solvent gave a white solid which was recrystallised from ethyl acetate to give the title compound.
10~;53;~;~
0~-p-Chlorobenzyl- ~-1,2,4-triazol-1-yl-pinacolone ~ (Compound 10) C~-1,2,4-Triazol-l-yl-pinacolone (3.3 g) in dimethyl-formamide (20 ml) was added dropwise to a suspension of sodium hydride (0.48 g; 100%) in dimethylformamide (10 ml) at room temperature with stirring. After stirring for two hours, p-chlorobenzyl chloride (3.2 g) in dimethylformamide (2-3 ml) was added dropwise and the reaction mixture was kept at 5-10 for two hours. The solvent was removed in vacuo and water was added to the residue. The aqueous solution was extracted with methylene chloride, the organic layer was washed with water and dried (magnesium sulphate).
The solvent was removed to give a yellow solid which was crystallised to give the title compound.
ExAMæLE 7 0~-1~2~4-Triazol-l-ylcaproamide. (Compound 8) Ethyl 0~ 2~4-triazol-l-ylcaproate (3. 0 g) was added to liquid ammonia (0.880, 15 ml) and the mixture was shaken well for a few minutes and then left overnight at room temperature. The white solid was filtered and washed with water to give, after recrystallisation from water, the title compound.
10~5~
ExAMæLE 8 Ethyl 2-(1-imidazolyl)-3-methylbutyrate. (Compound 69) Ethyl 2-bromo-2-isopropyl aceta~e (5 g), imidazole (4.2 g) and acetonitrile were refluxed for 72 hours. The solvent was removed in vacuo and the residue slurried with diethyl ether and poured into water. The ethereal layer was separated off and dried (magnesium sulphate). The solvent was removed in vacuo to give an oil which on distillation gave the title compound, b.p. 55-60/ 0.1 mm.
d -Imidazol-l-yl~ (p-chlorobenzyl)pinacolone (Compound 84) Stage I : To sodium ethoxide solution ~prepared by reacting sodium (6 g) with ethanol (200 ml 7 was added imidazole (17.3 g) in ethanol (S0 ml) and the mixture was refluxed for one hour. The mixture was cooled and bromo-pinacolone (45 g) in ethanol (60 ml) was added; the mixture was refluxed for two hours and left at room temperature overnight with stirring. The solvent was removed in vacuo, water was added and the mixture extracted with methylene chloride. The organic layer was washed with water and dried (MgS04), and the solvent was removed. The residual oil was 10~;53;~;~
distilled to give --imidazol-l-yl-pinacolone as a colour-less oil, b.p. 138-142/0.1 mm. The product contained unreacted imidazole, but was used for Stage II without further purification.
Stage II : To a suspension of sodium hydride ~480 mg;
100% 7 in dimethyl formamide (5 ml) was added C~-imidazol-l-yl-pinacolone (3.3 g) in dimethyl formamide (10 ml).
After 3 hours, stirring at room temperature, p-chlorobenzyl chloride (3.2 g) in dimethylformamide (10 ml) was added and lQ the mixture stirred at room temperature overnight. The dimethylformamide was removed in vacuo, and the residue was diluted with water and extracted with methylene chloride.
The organic layer was washed with water, dried (Na2S04) and the solvent was removed to give a yellow oil. This slowly solidified and was recrystallised from ether/petrol (40-60) to give, as colourless plates, OL-imidazol-l-yl - L-(p-chlorobenzyl)-pinacolone, m.p. 98-100. Analysis;
Calculated : C, 66.08; H, 6.59; N, 9.64~. Found : C, 66.49;
H, 6.53; N, 9.58%.
~-Imidazol-l-yl- -benzylpinacolone (Compound 85), m.p. 64-66 (Analysis; Calculated : C, 74.04; H, 7.87; N, 11.51%. Found : C, 73.82; H, 7.87; N, 11.83~) was prepared as described in Example 9 using benzyl chloride as the aralkylating agent.
lO~S;~
/
d -Imidazol-l-yl- OL-p-fluorobenzylpinacolone (Compound 86) Stage I : OL-Imidazol-l-ylpinacolone.
To sodium ethoxide solution ~prepared by reacting sodium (6 g) with ethanol (200 ml) 7 was added imidazole (17.3 g) in ethanol (50 ml) and the mixture was refluxed for one hour. The mixture was cooled and bromopinacolone (45 g) in ethanol (60 ml) was added; the mixture was refluxed for two hours and left at room temperature overnight with stirring. The solvent was removed in vacuo, water was added and the mixture extracted with methylene chloride. The organic layer was washed with water and dried (MgS04), and the solvent was removed. The residual oil was distilled to give L-imidazol-l-yl-pinacolone as a colourless oil, b.p.
138-142/0.1 mm. The product contained unreacted imidazole, but was used for Stage II without further purification.
Stage II : To a suspension of sodium hydride C 480 mg;
100%~7 in dimethylformamide (5 ml) was added ~-imidazol-l-ylpinacolone (3.3 g) in dimethylformamide (10 ml). After stirring for 3 hours at room temperature, p-fluorobenzyl-chlorlde (2.9 g) in dimethylformamide (10 ml) was added and the mixture was stirred at room temperature overnight.
10~;53'~'~
The dimethylformamide was removed in vacuo and the residue diluted with water and extracted with methylene chloride.
The organic layer was washed with water, dried (Na2S04) and the solvent was removed to give an orange oil. This was chromatographed over silica gel eluting with ethyl acetate.
The product from the eluate was crystallised from petroleum ether (60-80) to give the title product as a white crystal-line solid.
The compounds were tested against a variety of foliar fungal diseases of plants. The technique employed was as follows.
The plants were grown in John Innes Potting Compost (No. 1, or Seed, as appropriate) in 4 cm diameter mini-pots.
A layer of fine sand was placed at the bottom of the pot to facilitate uptake of test compouna by the roots. Vermiculite was used to cover the seed in the soil tests.
The test compounds were formulated either by bead-milling with aqueous Dispersol T or as a solution in acetone/
ethanol which was diluted to the required concentration immediately before use. For the foliage diseases, 100 ppm a.i. suspensions were sprayed on to the foliage and applied to the roots of the same plant via the soil. (Sprays were 10~;53;~
applied to maximum retention, and root drenches to a flnal concentration equivalent to approximately 40 ppm a.i./dry soil). Tween 20* to give a final concentration of 0.1%, was added when the sprays were applied to the cereals.
For most of the tests, the test compound was applied to the soil and foliage one or two days before the plant was inoculated with the diseases. An exception was the test on Erysiphe graminis, in which the plants were inoculated 24 hours before treatment. After inoculation, ~he plants were l~ put into an appropriate environment to allow infection to take place and then incubated until the disease was ready for assessment. The period between inoculation and assess-ment varied from 3 to lO days according to the disease and environment.
The disease control was recorded by the following grading:
4 = No disease
3 = 0-5%
2 = 6-25%
1 = 26-60%
0 = ~ 60%
The results are shown in Table III.
~Trade Mark for a surfactant which is a condensate of sorbitan monolaurate and ethylene oxide, 1()~5~
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Claims (7)
1. A compound of general formula (I):
wherein Y is =N- or =C(R)-, each of R, R1 and R2, which may be the same or different, is hydrogen, halogen, nitro or alkyl, each of R3 and R4, which may be the same or different, is hydrogen or hydrocarbyl which is alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl or aralkenyl, the aryl moieties of said aryl, aralkyl and aralkenyl being otionally substituted with halogen, alkyl, nitro, trifluoromethyl, cyano, alkoxy, or alkylenedioxy, and R3 or R4 being hydrogen when R4 or R3 is optionally.
substituted phenyl and at least one of R3 and R4 being hydrocarbyl when Y is = C(R)-; R5 is hydroxy, hydrocarbyl which is alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl or aralkenyl, or hydrocarbyloxy which is alkyloxy, alkenyloxy, alkynyloxy, cycloalkoxy, aryloxy, aralkyloxy or aralkenyloxy, the aryl moieties of said aryl, aralkyl, aralkenyl, aryloxy, aralkyloxy and aralkenyloxy being optionally substituted with halogen, alkyl, nitro, trifluoromethyl, cyano, alkoxy or alkylenedioxy, or R5 is amino optionally substituted with amino or one or two optionally substituted hydrocarbyls as defined above, subject to the proviso that when R5 is hydrocarbyl, it is other than substituted or unsubstituted phenyl, and Z is C = O or C = S or a derivative of said C = O, the derivative being a ketal, hydrazone, semicarbazone, imine or oxime; or a salt of such a compound.
wherein Y is =N- or =C(R)-, each of R, R1 and R2, which may be the same or different, is hydrogen, halogen, nitro or alkyl, each of R3 and R4, which may be the same or different, is hydrogen or hydrocarbyl which is alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl or aralkenyl, the aryl moieties of said aryl, aralkyl and aralkenyl being otionally substituted with halogen, alkyl, nitro, trifluoromethyl, cyano, alkoxy, or alkylenedioxy, and R3 or R4 being hydrogen when R4 or R3 is optionally.
substituted phenyl and at least one of R3 and R4 being hydrocarbyl when Y is = C(R)-; R5 is hydroxy, hydrocarbyl which is alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl or aralkenyl, or hydrocarbyloxy which is alkyloxy, alkenyloxy, alkynyloxy, cycloalkoxy, aryloxy, aralkyloxy or aralkenyloxy, the aryl moieties of said aryl, aralkyl, aralkenyl, aryloxy, aralkyloxy and aralkenyloxy being optionally substituted with halogen, alkyl, nitro, trifluoromethyl, cyano, alkoxy or alkylenedioxy, or R5 is amino optionally substituted with amino or one or two optionally substituted hydrocarbyls as defined above, subject to the proviso that when R5 is hydrocarbyl, it is other than substituted or unsubstituted phenyl, and Z is C = O or C = S or a derivative of said C = O, the derivative being a ketal, hydrazone, semicarbazone, imine or oxime; or a salt of such a compound.
2. A compound according to Claim 1 wherein Y is =N-, R1, R2 and R3 are hydrogen, R4 is hydrogen; C1-6 alkyl;
alkenyl or alkynyl having up to 4 carbon atoms; phenyl-alkyl; phenyl; benzyl optionally ring substituted with halogen, C1-4 alkyl or alkoxy, nitro, trifluoromethyl, cyano or methylenedioxy; or .alpha.-(C1-4 alkyl)benzyl optionally ring substituted with halogen; and R5 is hydroxy; C1-6 alkyl or alkoxy; amino; hydrazino;
phenylamino optionally ring substituted with C1-4 alkyl, halogen, nitro or trifluoromethyl; (C1-6 alkyl)amino;
phenyloxy optionally substituted with halogen, benzylamino;
benzyloxy, cycloalkyloxy or cycloalkyl; and Z is C = O or C = NH, or a salt of such a compound.
alkenyl or alkynyl having up to 4 carbon atoms; phenyl-alkyl; phenyl; benzyl optionally ring substituted with halogen, C1-4 alkyl or alkoxy, nitro, trifluoromethyl, cyano or methylenedioxy; or .alpha.-(C1-4 alkyl)benzyl optionally ring substituted with halogen; and R5 is hydroxy; C1-6 alkyl or alkoxy; amino; hydrazino;
phenylamino optionally ring substituted with C1-4 alkyl, halogen, nitro or trifluoromethyl; (C1-6 alkyl)amino;
phenyloxy optionally substituted with halogen, benzylamino;
benzyloxy, cycloalkyloxy or cycloalkyl; and Z is C = O or C = NH, or a salt of such a compound.
3. A compound according to Claim 1 wherein Y is =C(R)-wherein R is hydrogen, R1, R2 and R3 are hydrogen, R4 is C1-6 alkyl; benzyl optionally substituted with halogen cyano or trifluoromethyl or .alpha.-(C1-4 alkyl) benzyl optionally ring substituted with halogen; R5 is hydroxy;
C1-6 alkyl; C1-4 alkoxy; phenylamino; or benzyloxy optionally substituted with halogen; and Z is C = O, or a salt of such a compound.
C1-6 alkyl; C1-4 alkoxy; phenylamino; or benzyloxy optionally substituted with halogen; and Z is C = O, or a salt of such a compound.
4. A compound according to Claim 1 which is .alpha.-(p-chloro-benzyl)-.alpha.-1,2,4-triazol-1-ylpinocolone or .alpha.-(2,4-dichloro-benzyl)-.alpha.-1,2,4-triazol-1-ylpinacolone.
5. A process for preparing a compound or a salt thereof according to Claim 1, the process comprising (a) reacting a compound of general formula (II):
wherein Y, R1 and R2 are as defined in Claim 1, or a salt thereof, with a compound of general formula (III):
wherein R3, R4, R5 and Z are as defined in Claim 1 and X is halogen, or (b) when a compound according to Claim 1 wherein R3 and/or R4 is substituted or unsubstituted hydrocarbyl is required, hydrocarbylating a compound or a salt thereof according to Claim 1 wherein R3 and/or R4 is hydrogen.
wherein Y, R1 and R2 are as defined in Claim 1, or a salt thereof, with a compound of general formula (III):
wherein R3, R4, R5 and Z are as defined in Claim 1 and X is halogen, or (b) when a compound according to Claim 1 wherein R3 and/or R4 is substituted or unsubstituted hydrocarbyl is required, hydrocarbylating a compound or a salt thereof according to Claim 1 wherein R3 and/or R4 is hydrogen.
6. A method of combating fungal diseases in a plant, which method comprises applying to the plant, or the the locus of the plant, a compound or salt according to any one of Claims 1 to 3.
7. A method of combating fungal diseases in a plant, which method comprises applying to the plant, or to the locus of the plant, a compound or salt according to Claim 4.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB35208/75A GB1535777A (en) | 1975-08-26 | 1975-08-26 | Imidazole and 1,2,4-triazole compounds and their use as pesticides |
| GB3724475 | 1975-09-10 | ||
| GB3724175 | 1975-09-10 | ||
| GB5103975 | 1975-12-12 | ||
| GB67176 | 1976-01-08 | ||
| GB2764976 | 1976-07-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1065322A true CA1065322A (en) | 1979-10-30 |
Family
ID=27546446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA259,890A Expired CA1065322A (en) | 1975-08-26 | 1976-08-26 | Imidazole and 1,2,4-triazole compounds |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS6029389B2 (en) |
| AU (1) | AU502265B2 (en) |
| BE (1) | BE845433A (en) |
| CA (1) | CA1065322A (en) |
| DE (1) | DE2638470A1 (en) |
| FR (1) | FR2346338A1 (en) |
| GB (1) | GB1535777A (en) |
| IE (1) | IE43937B1 (en) |
| IL (1) | IL50367A (en) |
| IT (1) | IT1064994B (en) |
| NL (1) | NL7609439A (en) |
| NZ (1) | NZ181823A (en) |
Families Citing this family (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ186257A (en) * | 1977-01-20 | 1980-03-05 | Ici Ltd | 1,2,4-triazole and imidazole compounds and fungicidal and plant growth regulating compositions |
| JPS6053018B2 (en) * | 1977-09-07 | 1985-11-22 | 住友化学工業株式会社 | Azole compounds, their production methods, and fungicides comprising the compounds |
| JPS6050190B2 (en) * | 1978-05-02 | 1985-11-07 | 小野薬品工業株式会社 | Imidazole derivative |
| GB2016452B (en) * | 1978-02-18 | 1982-07-21 | Kissei Pharmaceutical | Imidazole compounds |
| IT1162310B (en) * | 1978-05-02 | 1987-03-25 | Ono Pharmaceutical Co | IMIDAZOLE DERIVATIVES AND PROCEDURE TO PRODUCE THEM |
| JPS6054307B2 (en) * | 1978-06-09 | 1985-11-29 | 小野薬品工業株式会社 | Imidazole derivative |
| DE2826760A1 (en) * | 1978-06-19 | 1980-01-03 | Hoechst Ag | DERIVATIVES OF 1,2,4-TRIAZOLE |
| DE2845293A1 (en) * | 1978-10-18 | 1980-05-08 | Basf Ag | ALPHA -AZOLYL- ALPHA -PHENYLESSIGAIC DERIVATIVES |
| DE3019049A1 (en) * | 1980-05-19 | 1981-12-03 | Basf Ag, 6700 Ludwigshafen | NEW AZOLES |
| GB2078719B (en) * | 1980-06-02 | 1984-04-26 | Ici Ltd | Heterocyclic compounds |
| DE3049542A1 (en) * | 1980-12-31 | 1982-07-29 | Basf Ag, 6700 Ludwigshafen | AZOLYLALKYL-2,3-DIHYDROBENZOFURANE, FUNGICIDES CONTAINING THEM AND METHOD FOR THE PRODUCTION THEREOF |
| FR2499078A1 (en) * | 1981-02-05 | 1982-08-06 | Ciba Geigy Ag | N-Azolyl-acyl-N-alkyl aniline derivs. - useful as microbicides, esp. fungicides for plant protection |
| JPS605593B2 (en) * | 1981-03-20 | 1985-02-12 | 北興化学工業株式会社 | Imidazole derivatives and agricultural and horticultural fungicides |
| DE3126022A1 (en) * | 1981-07-02 | 1983-01-13 | Basf Ag, 6700 Ludwigshafen | AZOLE COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND FUNGICIDES CONTAINING THEM |
| JPS6026391B2 (en) * | 1981-10-15 | 1985-06-24 | 北興化学工業株式会社 | 1,2,4-triazole derivatives and agricultural and horticultural fungicides |
| EP0084236A3 (en) * | 1981-12-22 | 1983-08-03 | Fbc Limited | Fungicidal heterocyclic compounds and compositions containing them |
| DE3222220A1 (en) * | 1982-06-12 | 1983-12-15 | Bayer Ag, 5090 Leverkusen | AZOLYL METHYL KETONES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INTERMEDIATE PRODUCTS |
| GB8308506D0 (en) * | 1983-03-28 | 1983-05-05 | Ici Plc | Heterocyclic compounds |
| DE3321422A1 (en) * | 1983-06-14 | 1984-12-20 | Basf Ag, 6700 Ludwigshafen | NEW AZOLES |
| GB8330715D0 (en) * | 1983-11-17 | 1983-12-29 | Ici Plc | Extraction of metal values |
| US5254695A (en) * | 1983-11-17 | 1993-10-19 | Imperial Chemical Industries Plc | Substituted triazoles |
| DE3511922A1 (en) * | 1985-04-01 | 1986-10-09 | Basf Ag, 6700 Ludwigshafen | AZOLE COMPOUNDS, METHOD FOR THEIR PRODUCTION AND MEANS FOR REGULATING PLANT GROWTH |
| DE3417468A1 (en) * | 1984-05-11 | 1985-11-14 | Bayer Ag, 5090 Leverkusen | AZOLYLVINYLETHER |
| DE3417467A1 (en) * | 1984-05-11 | 1985-11-14 | Bayer Ag, 5090 Leverkusen | CYCLIC AZOLYLVINYL ETHER |
| DE3546017A1 (en) * | 1985-12-24 | 1987-06-25 | Basf Ag | (ALPHA) -ALLYLATED ARYLALKYLTRIAZOLES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
| DE3600812A1 (en) | 1986-01-14 | 1987-07-16 | Basf Ag | AZOLE COMPOUNDS AND FUNGICIDES AND GROWTH REGULATORS CONTAINING THEM |
| DE3601430A1 (en) * | 1986-01-20 | 1987-07-23 | Basf Ag | HALOGENED AZOL COMPOUNDS AND FUNGICIDES CONTAINING THEM |
| US5484802A (en) * | 1995-03-29 | 1996-01-16 | Patel; Bomi P. | Fungicidal α-(dioxoimidazolidine)acetanilide compounds |
| JP6397482B2 (en) | 2013-04-12 | 2018-09-26 | バイエル・クロップサイエンス・アクチェンゲゼルシャフト | New triazole derivatives |
| CN105283450B (en) | 2013-04-12 | 2018-12-18 | 拜耳作物科学股份公司 | Triazole derivative |
| US9550752B2 (en) | 2013-04-12 | 2017-01-24 | Bayer Cropscience Aktiengesellschaft | Triazolinthione derivatives |
| BR112017021109A2 (en) | 2015-04-02 | 2018-07-03 | Bayer Cropscience Ag | triazole derivatives as fungicides |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3255201A (en) * | 1965-04-09 | 1966-06-07 | Hoffmann La Roche | 2-nitroimidazoles |
| FR1520920A (en) * | 1966-04-18 | 1968-04-12 | Hoffmann La Roche | Process for the preparation of imidazole derivatives |
| DE2037610A1 (en) * | 1970-07-29 | 1972-02-03 | Bayer Ag | New alpha-substituted benzyl-azoles, processes for their production and their use as pharmaceuticals |
| DE2431407C2 (en) * | 1974-06-29 | 1982-12-02 | Bayer Ag, 5090 Leverkusen | 1,2,4-Triazol-1-yl-alkanones and alkanols, processes for their preparation and their use as fungicides |
-
1975
- 1975-08-26 GB GB35208/75A patent/GB1535777A/en not_active Expired
-
1976
- 1976-08-17 IE IE1814/76A patent/IE43937B1/en not_active IP Right Cessation
- 1976-08-20 NZ NZ181823A patent/NZ181823A/en unknown
- 1976-08-23 BE BE170008A patent/BE845433A/en not_active IP Right Cessation
- 1976-08-25 NL NL7609439A patent/NL7609439A/en not_active Application Discontinuation
- 1976-08-25 AU AU17126/76A patent/AU502265B2/en not_active Expired
- 1976-08-25 FR FR7625732A patent/FR2346338A1/en active Granted
- 1976-08-25 IT IT26548/76A patent/IT1064994B/en active
- 1976-08-26 JP JP51101189A patent/JPS6029389B2/en not_active Expired
- 1976-08-26 DE DE19762638470 patent/DE2638470A1/en active Granted
- 1976-08-26 CA CA259,890A patent/CA1065322A/en not_active Expired
- 1976-08-26 IL IL7650367A patent/IL50367A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE2638470A1 (en) | 1977-03-31 |
| BE845433A (en) | 1977-02-23 |
| FR2346338B1 (en) | 1981-03-06 |
| JPS5227767A (en) | 1977-03-02 |
| FR2346338A1 (en) | 1977-10-28 |
| IL50367A (en) | 1980-05-30 |
| AU1712676A (en) | 1978-03-02 |
| IE43937B1 (en) | 1981-07-01 |
| IE43937L (en) | 1977-07-14 |
| NZ181823A (en) | 1979-06-08 |
| DE2638470C2 (en) | 1988-03-31 |
| IT1064994B (en) | 1985-02-25 |
| GB1535777A (en) | 1978-12-13 |
| NL7609439A (en) | 1977-03-01 |
| JPS6029389B2 (en) | 1985-07-10 |
| AU502265B2 (en) | 1979-07-19 |
| IL50367A0 (en) | 1976-10-31 |
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