GB2095251A

GB2095251A - Imidazole derivatives

Info

Publication number: GB2095251A
Application number: GB8207746A
Authority: GB
Original assignee: Hokko Chemical Industry Co Ltd
Current assignee: Hokko Chemical Industry Co Ltd
Priority date: 1981-03-20
Filing date: 1982-03-17
Publication date: 1982-09-29
Also published as: FR2502150B1; DE3210009A1; JPS57156464A; DE3210009C2; IT1164462B; JPS605593B2; IT8209364A0; BR8201546A; FR2502150A1; GB2095251B

Abstract

Novel imidazole compounds are represented by the general formula <IMAGE> wherein R1 is naphthyl group, an arylalkyl group, a cycloalkyl group, a cycloalkyl group, an alkyl group, a lower alkenyl group, a lower alkoxy- lower alkyl group or a phenylthio- lower alkyl group or phenyl group or a substituted phenyl group; R2 is an unsubstituted or substituted alkyl group or an alkenyl group or an alkynyl group, naphthyl group, or an unsubstituted or substituted phenyl group; X is an oxygen atom or a sulfur atom; and Y is an unsubstituted or substituted alkylene group or an unsubstituted substituted alkenylene group. The imidazole compounds and their salts show a usefully high fungicidal activity against a wide variety of fungi which infest crop plants.

Description

SPECIFICATION New imidazole derivatives This invention relates to new imidazol derivatives and their salts which exhibit a high fungicidal activity against a wide variety of fungi which usually infest crop plants in the agricultural field. This invention also relates to the use of these new imidazole derivatives or their salts as fungicidal agent of agricultural and horticultural utilities.

Many kinds of fungicidal compounds are known, and among of them, some imidazole derivatives are known to have the fungicidal activity. For instance, from Japanese patent application unexamined prepublication "Kokai" Sho 52-27767 (published on 2nd March, 1977, corresponding to U.K. Patent applications No. 35208/75, No. 37241/75, No. 37244/7 5, No. 51039/75, No. 671/76 and No.

27649/76), it is known that an ester or an amide (including anilide) of an imidazol-1 -yl-alkanoic acid represented by the general formula

wherein R' and R2 are each a hydrogen atom, a halogen atom,-nitro or an alkyl group; R3 and R4 are each a hydrogen atom or a substituted or unsubstituted hydrocarbyl group; and R5 is a hydroxyl group, a substituted or unsubstituted hydrocarbyloxy group, or an amino group, or a substituted or unsubstituted hydrocarbyl group other than a substituted or unsubstituted phenyl; and Z is a group > C=O or > C=S or a derivative of the group > C=O is useful as a fungicidal agent of agricultural and horticultural utilities. However, these known imidazole derivatives have not always satisfactorily high fungicidal activity against a wide variety of the fungal pests.

An object of this invention is to provide a new imidazole derivative which exhibits a satisfactorily high fungicidal activity against a wide variety of the fungal pests infesting the crop plants. A further object of this invention is to provide a new imidazole derivative which is of a low toxicity and usable with safety and is useful as a broad-spectrum fungicide. Another objects of this invention will be clear from the following descriptions.

We, the present inventors, have synthetized a number of new imidazole derivatives, and we have now found that a particular class of the new imidazole derivatives now synthetized which is represented by the general formula [I] shown hereinafter has a satisfactorily high fungicidal activity against a wide variety of fungi and exhibits a high preventive effect as well as a high curative effect for treatment of the fungal infections of crop plants. Besides, the new imidazole derivative of the general formula [I] has neither any objectionable phytotoxicity to crop plants, nor any objectionable toxicity to mamalian animals and fishes.It has been found that the new imidazole derivative of the general formula [I] and a salt thereof with an acceptable, inorganic or organic acid, as well as a complex salt thereof with a metal salt have very excellent properties as fungicidal agent of agricultural and horticultural utilities.

According to a first aspect of this invention, therefore, there is provided as the new compound an imidazole derivative of the general formula

wherein R1 is naphthyl group, an arylalkyl group, a cycloalkyl group, a cycloalkylalkyl group, an alkyl group, a lower alkenyl group, a lower alkoxy-lower alkyl group, a phenylthio-lower alkyl group or phenyl group; the phenyl group being unsubstituted or substituted with 1 to 5 substituents which is or are the same or different from each other and selected from a halogen atom, nitro group, cyano group, a lower alkyl group, a lower alkenyl group, a halogenated lower alkyl group, a lower alkoxyl group, a lower alkenyloxy group, a lower alkylthio group, a lower alkylsulfinyl group, a lower alkylsulfonyl group, a lower alkylcarbonyl group, phenyl group, phenoxy group, a halogen-substituted phenoxy group, phenylthio group, a lower alkyl-substituted phenylthio group and a nitro-substituted phenylthio group;; R2 is a saturated alkyl group, an unsaturated alkyl group, a lower alkoxy-lower alkyl group, a lower aikylthio-lower alkyl group, a phenoxy-lower alkyl group, a phenylthio-lower alkyl group, a mono- or dilower alkylamino-lower alkyl group, a lower alkyl group substituted with a group --N(CH,), where n is an integer of 2 to 6, a lower alkylcarbonyl group, phenylcarbonyl group, a cycloalkyl group, a cycloalkylalkyl group, a halogenated lower alkyl group, a cyano-lower alkyl group, a lower alkoxycarbonyl-lower alkyl group, a lower alkylthiocarbonyl-lower alkyl group, an arylalkyl group, a lower alkylcarbonyl-lower alkyl group, a phenylcarbonyl-lower alkyl group, naphthyl group, furfuryl group or phenyl group; the latter phenyl group being unsubstituted or substituted with a substituent which is selected from a halogen atom, nitro group, cyano group and a lower alkyl group; Xis an oxygen atom or a sulfur atom: and Y is a straight or branched saturated alkylene group or unsaturated alkylene group, the saturated alkylene group being unsubstituted or substituted with a halogen group, a lower alkoxyl group, cyano group, phenyl group, a halogen-substituted phenyl group, a nitro-substituted phenyl group, a lower alkyl-substituted phenyl group and/or trifluoromethyl-substituted phenyl group, or a salt of said imidazole derivative.

The imidazole compound of the general formula [I] may be termed as an O-ether of imidazole-1-yl- isothioacetic acid anilide or an S-ether of imidazole-1-yl-isc. hioacetic acid anilide or a derivative thereof and may also be termed as an N-substituted α-(imidazol-1-yl-alkyl)-or α-(imidazol-1-yl-alkenyl)-imino- acid ester or an N-substituted α-(imidazol-1 -yl-alkyl)- or a-(imidazol-1 -yl-alkenyl)-thio-imino-acid ester or a derivative thereof.

The term "lower alkyl" means an alkyl containing 1 to 6 carbon atoms. Similarly, the term "lower" attached to "alkenyl" or "alkoxy" group indicates that the alkenyl or alkoxy group is containing 1 to 6 carbon atoms.

According to a first preferred embodiment of the first aspect invention, there is provided as the new compound an imidazole derivative which is of the formula

wherein R3 is naphthyl group, a phenyl-(C1-C4)alkyl group, a dichlorophenyl-(01-C4)alkyl group, a (C5-C6)cycloalkyl group, a (C5-C6)cycloalkyl-(C1-04)alkyl group, a (C1-C10)alkyl group, a (C2-C4)alkenyl group, a (C1-C4)alkoxy-(C1-C4)alkyl group, a phenylthio-(C1-C4)alkyl group, phenyl group, a chlorophenyl group, a fluorophenyl group, a bromophenyl group, a nitrophenyl group, a cyanophenyl group, a trifluoromethylphenyl group, a dichlorophenyl group, a dibromophenyl group, a difluorophenyl group, a bromochlorophenyl group, a chlorofluorophenyl group, a trifluoromethylchlorophenyl group, a trichlorophenyl group, a dichloro-dimethylphenyl group, a trichlorodimethylphenyl group, a chloro-methoxyphenyl group, a chloro-methylphenyl group, a (01-C4)alkylphenyl group, a di-(C1-C4)alkylphenyl group, a (C2-C4)alkenylphenyl group, a (C2-C4)alkenyloxyphenyl group, a (C1-C4)alkoxyphenyl group, a di-(C1-04)alkoxyphenyl group, a (01-C4)alkylthiophenyl group, a (C,-C,)alkylsulfinylphenyl group, a (C,-C,)alkylsulfonylphenyl group, a (C,-C,)alkylcarbonylphenyl group, diphenyl group, a phenoxyphenyl group, a chlorophenoxyphenyl group, a phenylthiophenyl group, a (C,-C,)alkylphenylthiophenyl group or a nitrophenylthiophenyl group, R4 is a (C1-C10)alkyl group, a (C2-C4)alkenyl group, a (C2-C4)alkynyl group, a (C1-C4)alkoxy- (C1-C4)alkyl group, a (05-C6)cycloalkyl-(C1-C4)alkyl group, a (C1-C4)-alkylthio-(C1-C4)alkyl group, a phenyl-(C1-C4)alkyl group, a phenoxy-(C1-C4)alkyl group, a dichlorophenoxy-(C1-C4)alkyl group, a phenylthio-(C1-C4)alkyl group, a (C1-C4)alkylamino-(C1-C4)alkyl group, a di-(C1-C4)alkylamino- (C1-C4)alkyl group, a pyrrolyl-(C1-C4)alkyl group, a chloro-(C1-C4)alkyl group, a cyano-(C1-04)alkyl group, a (C1-C4)alkoxycarbonyl-(C1-C4)alkyl group, a (C1-C4)alkylthiocarbonyl-(C1-C4)alkyl group, a (C1-C4)alkylcarbonyl-(C1-C4)alkyl group, a phenylcarbonyl-(C1-C4) alkyl group, a (C5-C6) cycloalkyl group, benzyl group, a chlorobenzyl group, a dichlorobenzyl group, a fluorobenzyl group, a methylbenzyl group, a dimethylbenzyl group, a methylbenzylethyl group, naphthyl group, furfuryl group, phenyl group, a chlorophenyl group, a dichlorophenyl group, a cyanophenyl group, a nitrophenyl group, a (C1-C4)alkylphenyl group, a (C14)alkylcarbonyl group, orbenzoyl group, X is an oxygen atom or a sulfur atom;; Y, is a (C1-C4)alkylene group or a (C2-04)alkenylene group; and Z is a hydrogen atom, a (C1-C6)alkyl group, a (C14)alkoxy-(C1-C4)alkyl group, a cyano (C1-C4)alkyl group, a(C2-C4)alkenyl group, phenyl group, a chlorophenyl group, a dichlorophenyl group, a methylphenyl group, a trifluoromethylphenyl group, a nitropheny group, benzyl grou, a chlorobenzyl group or a dichlorobenzyl group; or a salt of said imidazole derivative.

According to a second preferred embodiment of the first aspect invention, there is provided as the new compound an imidazole derivative which is of the formula

wherein R5 is phenyl group, a chlorophenyl group, a bromophenyl group, a nitrophenyl group, a trifluoromethylphenyl group, a dichlorophenyl group, a bromochlorophenyl group, a chlorofluorophenyl group, a trifluoromethyichlorophenyl group, a trichlorophenyl group, a dichlorodimethylphenyl group, a trichloro-dimethylphenyl group, a chloro-methoxyphenyl group, a chloro-methylphenyl group, a (C1-C4)alkylphenyl group, a di-(C1-C4)alkylphenyl group, a (C2-C4)alkenyloxyphenyl group, a (C1-C4)alkoxyphenyl group, a di-(C1-C4)alkoxyphenyl group, a methylsulfonylphenyl group, an acetylphenyl group, a phenoxyphenyl group, or a nitrophenylthiophenyl group; R6 is a (C1-C10)alkyl group, a (C2-C4)alkenyl group, a (C14)alkoxy-(C1-C4)alkyl group, a methylthio-(01-C4)alkyl group, a dichlorphenoxy-(C1-C4)alkyl group, a phenylthio-(C1-04)alkyl group, cyclohexyl group, an ethoxycarbonyl-(01-04)alkyl group, benzyl group, a chlorobenzyl group, a dichlorobenzyl group, naphthyl group, furfuryl group, phenyl group, a chlorophenyl group, a dichlorophenyl group, a cyanophenyl group, a nitrophenyl group, or a (C1-C4)alkylphenyl group, Y'' is a linear (C2-C4)alkylene group, Z' is a hydrogen atom, a(C1-C5)alkyl group, a (C2-C4)alkenyl group, a chlorophenyl group, a dichlorophenyl group, a methylphenyl group, a nitrophenyl group, or benzyl group or a salt of said imidazole derivative.

According to a third preferred embodiment of the first aspect of this invention, there is provided as the new compound an imidazole derivative which is of the formula

wherein R7 is phenyl group, a chlorophenyl group, a fluorophenyl group, a bromophenyl group, or a nitrophenyl group, a cyanophenyl group, a trifluoromethylphenyl group, a dichlorophenyl group, a dibromophenyl group, a bromochlorophenyl group, a chlorofluorophenyl group, a trifluoromethylchlorophenyl group, a trichlorophenyl group, a dichloro-dimethylphenyl group, a trichlorodimethylphenyl group, a chloro-methoxyphenyl group, a chloro-methylphenyl group, a (01-04)alkylphenyl group, a di-(C1-C4)alkylphenyl group, a (C2-C4)alkenylphenyl group, a (C1-C4)alkoxyphenyl group, a di-(C1-C4)alkoxyphenyl group, a methylthiophenyl group, a methylsulfinylphenyl group, a methylsulfonylphenyl group, an acetylphenyl group, diphenyl group, a phenoxyphenyl group, a chlorophenoxyphenyl group, a phenylthiophenyl group or a methylphenylthiophenyl group; R8 is a (C1-C10)alkyl group, a (C2-C4)alkenyl group, a (C2-C4)alkynyl group, a (C1-C4)alkoxy- (C1-04)alkyl group, a methylthio-(C1-C4)alkyl group, a phenoxy-(C1-C4)alkyl group, a phenylthio (01-C4)alkyl group, a (C1-C4)alkylamino-(C1-C4)alkyl group, a pyrrolyl-(C1-C4)alkyl group, a (C1-C4)alkylcarbonyl group, a (C5-C6)cycloalkyl group, a chloro-(C1-C4)alkyl group, a cyano (01-C4)alkyl group, a (C1-C4)alkylthiocarbonyl-(C1-C4)alkyl group, benzyl group, a chlorobenzyl group, a fluorobenzyl group, a dichlorobenzyl group, a methylbenzyl group, a methylbenzylethyl group, an acetyl-(C1-C4)alkyl group, benzoyl group, a phenylcarbonyl-(C1-04)alkyl group or phenyl group; Y"' is a linear(C1-C4)alkylene group or a linear (C2-C4)alkenylene group; and Z" is a hydrogen atom, a (01-C6)alkyl group, a (C1-04)alkoxy-(C1-04)alkyl group, a cyano (C1-C4)alkyl, a (C2-C4)alkenyl, phenyl group, a chiorophenyl group, a dichlorophenyl group, a methylphenyl group, benzyl group, a chlorobenzyl group or a dichlorobenzyl group; or a salt of the said imidazole derivative.

According to the third preferred embodiment of the first aspect invention, it is especially preferred that the new compound of this invention is of the formula [Ic] where R7 is 2,4-dichlorophenyl, 2trifluoromethyl-4-chlorophenyl or 2-chloro-4-fluorophenyl; R8 is ethyl, benzyl or p-chlorobenzyl; Y"' is methylene; and Z" is hydrogen, methyl or ethyl.

According to a fourth preferred embodiment of the first aspect invention, there is provided as the new compound an imidazole derivative which is of the formula

wherein R9 is a (C1-C4)alkyl group, a phenyl-(C1-C4)alkyl group or a chloro-(C1-C4)alkyl group; and Y"" is a linear or branched (C1-C4)alkylene group, or a salt of the said imidazole derivative.

According to a fifth preferred embodiment of the first aspect invention, there is provided as the new compound an imidazole derivative which is of the formula

wherein R10 is a (C5-C6)cycloalkyl group or a (C1-C4)alkyl group which is unsubstituted or substituted with phenyl group, a dichlorophenyl group, a (C2-C4)alkenyl group, a (C1-C4)alkoxy group or phenylthio group; R11 is a (C1-C4)alkyl group which is unsubstituted or substituted with phenyl group, a di (C,-C,)alkylamino group, furanyl group or a (8-C6)cycloalkyl group; Y""' is a (C1-C4)alkylene group; and Z"' is a hydrogen atom, a (C1-C6)alkyl group, a chlorobenzyl group or a trifluoromethylphenyi group; or a salt of said imidazole derivative.

Particular examples of the new imidazole compounds according to the general formula [I] or the formula [la], [Ib], [Ic], [Id] or [le] are listed in Table 1 given hereinafter.

The new imidazole compound of this invention is belonging to a derivative of isoamides or isothioamides and is not described in any chemical literatures. The new imidazole compound of this invention is superior to the previously known fungicidal imidazole compounds in respect of the fungicidal activity to fungi of the fungal infections of crop plants. Thus, the new compound of this invention exhibits a wide ranged antifungal spectrum and is effective for treatment of a wide variety of fungal diseases of plants.In particular, the compound of this invention is effective to control fungal diseases of cereals such as leaf rust (Puccinia recondita), stripe rust (Puccinia striformus), stem rust (Puccinia graminis) or dwarf leaf rust tPuccinia horde!) in wheat or barley; powdery mildew {Erysiphe graminis) in wheat and barley, leaf spot (Helminthosporium maydis) in rice, brown spot lCochliobolus setariae) in corn; fungal diseases of beans such as rust (Phakopsora pachyrhizi) in soybean; rust (Uromyces fabae) in broad bean, and anthracnose (Collectotrichum lindemthianum) in kidney-bean; as well as fungal diseases of vegetables such as powdery mildew (Sphaerotheca fuliginea) in cucumber, powdery mildew (Sphaerotheca fuliginea) in water melon, powdery mildew fErysiphe cichoracearum) in egg plant and powdery mildew (Levelliula taurica) in sweet pepper; fungal diseases of cucurbitaceae such as anthracnose (Colletotrichum lagenarium) in cucumber, anthracnose (Colletotrichum lagenarium) in water melon, and anthracnose in sweet melon, and rust (Puccinia alliil in onion or stone leek.The new compound of this invention is also effective even at a low rate of application to control -tungal diseases of fruit-plants such as rust (Gymnosporangium yamadae), scaf(Venturia inaequalis) in apple, powdery mildew {Podosphaera leucotricha) in apple, rust {Gymnosporangium haraeanum), scab (Venturia mashicola) in pear, or rip rot (Glomerella cingulata) in grape.When the compound of this invention is used as seed disinfectant, it is highly effective to prevent brown spot and bakanae disease (Gibberella fujikuroi) on rice, and smuts (Urocystis tritici or Ustilago horde!) on barley and wheat, and barley bunt {Tilletia pancicii) on barley or wheat bunt (Tilletia canie) on wheat, and others.

The compound of this invention is much more effective for preventative treatment of the fungal diseases of plants and also much more effective for curative (protective) of the fungal diseases, as compared to-the previously known fungicidal imidazole compounds. Amongst the fungicidal compounds which have been used as the antifungal agent for treatment of fungal diseases of plants in practice, only a few of them is known to exert the curative effects to a satisfactory extent in fields, and much less fewer compounds are known to exert highly favorable results both in the preventative treatment and in the curative treatment of the fungal diseases of plants. Although the compound of this invention shows a high fungicidal activity, it has no or little phyto-toxicity to the useful plants and has not any objectionable toxicity to men and animals and also to fishes.Accordingly, the compound of this invention can be utilized with safety. Thus, the compound of this invention is highly safe as the fungicidal agent of agricultural and horticultural utilities and besides it is highly effective not only in the preventative treatment but also in the curative treatment of the various, fungal diseases of plants, so that the compound of this invention is greatly promising in the fields of agriculture and horticulture.

The imidazole compound of the formula [I] according to this invention can be produced, for example, by three different processes which are shown by the reaction equations (a), (b) and (c) given below, respectively.

In accordance with the first process, the imidazole compound of the formula [I] is produced by reacting an N-substituted a-(imidazol-1 -yl)alkyl- or a-(imidazol-1 -yl)alkenyl-imino (or thio-imino)-acid halide or a reactive equivalent thereof having the formula [II] given below, with an alcohol or a mercaptan having the formula [III] given below, according to the following reaction equation (a):-

wherein R1 and Y appearing in the formula Lll] have the same meanings as defined in the formula [I] and A is a halogen atom such as chlorine or bromine, imidazol-1 -yl group, an alkylsulfonyl group such as mesyl or an arylsulfonyl group such as tosyl group and wherein X and R2 in the formula [III] have the same meanings as defined in the formula [I].

The starting compound of the general formula [11] is containing the imidazole group like to the imidazole compound of the general formula [I] and hence may be provided also in the form of a salt thereof with an inorganic acid or organic acid or in the form of a metal salt complex. The reactant compound of the general formula [III] contains the groups X and R2 which are the same as those present in the final product compound of the formula [I], respectively. The reactant compound [III] belongs to the class of alcohols or mercaptans and may readily be prepared by known chemical methods.

In carrying out the reaction of the compound [II] with the compound villi according to the reaction equation (a), any solvent serving as the reaction medium may not always be used, though usually an organic solvent may preferably be used. In some cases, an excess of the compound [ill] may be used as the solvent. The organic solvent available for this purpose includes hydrocarbons, halogenated hydrocarbons, ethers, ketones, nitriles, acid-amides, dimethylsulfoxide and the like. If necessary, it is possible to provide the presence of an amount of an acid-binder which will bind the hydrogen halide as liberated during the reaction. However, the use of the acid-binder is not always required, as both the compound [II] and the compound [I] themselves are basic compounds.The acid-binder as used may be an organic amine such as triethylamine and pyridine or may be an inorganic base such as potassium carbonate and the like. The compound of the formula [III] may be provided in the form of its sodium or potassium salt (alcoholate or mercaptide) which has previously been prepared by reacting it with metallic sodium, metallic potassium, sodium amide or sodium hydride. The reaction may proceed at ambient temperature but may be promoted at an elevated temperature to be completed in a shorter reaction time. When the acid-binder is used, the reaction solution may be filtered after completion of the reaction, so that the salt of the acid-binder deposited in the reaction solution is removed. The resultant filtrate is distilled to remove the solvent for recovery of the compound of the invention.Alternatively, the reaction solution may be admixed with a volume of a water-immiscible organic solvent such as benzene, chloroform, ethylether or tetrahydrofuran and also with a volume of water and the admixture obtained is stirred, followed by separation of the organic phase from the aqueous phase and by removal of the organic solvent from the organic phase by distillation to afford the compound of the invention.

The first process of producing the compound of this invention according to the reaction equation (a) is illustrated with reference to Examples 1-6 given later.

In accordance with the second process, the imidazole compound of the formula [I] may be produced by reacting an N-substituted imino-ether or thioimino-ether of the formula [IV] given below, with imidazole of the formula [V] according to the foliowing reaction equation (b):-

wherein R,, X, R2 and Y appearing in the formula [iV] are as defined hereinbefore and B is a halogen atom such as chlorine or bromine, an alkylsulfonyl group such as mesyl or an arylsulfonyl group such as tosyl, or benzylsulfonyl.The compound c; the formula [V], namely imidazole is morphoteric and may be provided either as a salt of the anion-form of imidazole with an alkali metal cation, or as a salt of the cation-form of imidazole with an inorganic or organic acid or as a salt complex of the cation-form of imidazole with a metal salt.

In carrying out the reaction of the compound [IV] with the compound [V] according to the reaction equation (b), any solvent serving as the reaction medium is not necessary to be used, but usually an organic solvent may preferably be used as the reaction medium. In some cases, an excess of the compound of the formula [V] may be present as the reaction medium solvent. The organic solvent available for this purpose includes hydrocarbons, halogenated hydrocarbons, ethers, esters, ketones, nitriles, alcohols, acid amides, dimethylsulfoxide and the like. The presence of a polar organic solvent is useful to reduce the required reaction time. As the compound [Vj is basic, it is not necessary to provide the presence of an additional acid-binder in the reaction mixture.If desired, however, it is possible to use an organic amine such as triethylamine and pyridine or an inorganic base such as potassium carbonate as the acid-binder. The compound of the formula [V] may be provided in the form of its salt which has previously been prepared by reacting it with metallic sodium, metallic potassium, sodium amide or sodium hydride. The reaction may proceed at ambient temperature but a required reaction time may be reduced by warming the reaction mixture.

When the acid-binder is used in the reaction (b), the reaction solution is filtered after completion of the reaction to remove the salt of the acid-binder as formed during the reaction. The filtrate is distilled to remove the organic solvent and the compound of this invention is recovered. Alternatively, the reaction solution may be admixed with a volume of a water-immiscible organic solvent such as benzene, chloroform, ethylether or tetrahydrofuran and also with a volume of water, and the whole admixture is stirred, followed by separation of the organic phase from the aqueous phase and further by removal of the organic solvent from the organic phase by distillation to afford the compound of the invention.

The second process of producing the compound of the invention according to the reaction equation (b) is illustrated by Examples 7 and 8 given later.

In accordance with the third process, the compound of the invention may be made by reacting an N-substituted amide compound of the formula [VI] given below, with a halide compound or a reactive equivalent thereof having the formula [VII] given below, according to the following reaction equation

wherein P1, X and Y appearing in the general formula [Vl] are as defined hereinbefore. The starting compound of the formula [VI] contains the imid?zolyl group and may be provided in the form of a salt with an inorganic or organic acid or in the form of a metal salt complex.In the reactant compound of the general formula [Vll], the group R2 has the same meaning as that present in the compound of the general formula [I], and the group D denotes a halogen atom such as chlorine or bromine, an alkylsulfonyl group such as mesyl or an arylsulfonyl group such as tosyl. The reactant compound [VII] may easily be prepared by known chemical processes. The process of producing the compound [I] according to the reaction equation (c) may be carried out with advantage, particularly when the starting compound [VI] contains a sulfur atom as a value of X. The reaction of the compound [VI] with the compound [Vll] according to the reaction equation (c) may be conducted without any solvent as the reaction medium.Usually, however, an organic solvent may preferably be provided as the reaction medium. If desired, an excess of the compound [Vll] may be utilized as the reaction medium solvent.

The organic solvent available for this purpose includes hydrocarbons, halogenated hydrocarbons, ethers, esters, ketones, nitriles, alcohols, dimethylsulfoxide and the like. As the compound [VI] is basic, it is not necessary to provide the presence of an additional acid-binder in the reaction mixture. If desired, however, it is preferable to use an organic amine such as triethylamine and pyridine or an inorganic base such as potassium carbonate as the acid-binder. The compound of the formula [Vl] may be provided in the form of its salt which has previously been prepared by reacting it with metallic sodium, metallic potassium, sodium amide or sodium hydride or an alkali metal alcoholate. The reaction may proceed at ambient temperature but a required reaction time may be reduced by warming the reaction mixture.

When the acid-binder is used in the reaction (c), the reaction solution is filtered after completion of the reaction to remove the salt of the acid-binder as deposited during the reaction. The filtrate is distilled to remove the organic solvent and the compound of this invention is recovered. Alternatively, the reaction solution may be admixed with a volume of a water-immiscible organic solvent such as benzene, chloroform, ethylether or tetrahydrofuran and also with a volume of water, and the whole admixture is stirred, followed by separation of the organic phase from the aqueous phase and further by removal of the organic solvent from the organic phase by distillation to afford the compound of the invention.

The third process of producing the compound of the invention according to the reaction equation (c) is demonstrated by Example 9 shown later.

The imidazole compound of the formula [I] according to the invention may be in the form of its salt which includes a salt of the imidazole compound with an inorganic acid or a salt of the imidazole compound with an organic acid and a salt complex of the imidazole compound with a metal salt.

The inorganic acid suitable for the salt formation includes:-- hydrohalogenic acids such as hydrochloric, hydrobromic or hydroiodic acid; sulfuric acid, nitric acid, perchloric acid, phosphoric acid and sulfamic acid. The preparation of the salt of the imidazole compound with an inorganic acid may be achieved by dissolving or suspending the imidazole compound [I] in water or a suitable organic solvent and admixing the resultant solution or suspension with a stoichiometrical quantity of the acid which may be provided as such or may have been diluted with the organic solvent. If the acid used is gaseous, it may be blown into the solution or suspension of the imidazole compound. Generally, this salt-forming reaction may proceed rapidly at ambient temperature or even under cooling.When the inorganic acid salt formed is deposited as crystals, these may be separated by filtration. In some cases, the saltforming reaction solution may be distilled to remove the solvent therefrom, affording the compound of this invention in the salt form. The preparation of the inorganic acid salt of the compound of this invention is illustrated by Examples 1 0-12.

The organic acid suitable for the salt formation includes:- a saturated or unsaturated aliphatic acid, either substituted or unsubstituted; an arylcarboxylic acid such as benzoic acid; an alkyl- or arylsulfonic acid; a mono- or di-substituted aikyl- or aryl-sulfonic acid; and esters and amides of phosphoric acid or phosphorous acid, including their sulfur homologues.Particular examples of the suitable acids for this purpose may be, for example, formic acid, acetic acid, acrylic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, cyanoacetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid, succinic acid, malonic acid, glyoxalic acid, pyruvic acid, benzoic acid, p-nitrobenzoic acid, 2,4,6- trinitrobenzoic acid, methanesulfonic acid, octylsulfonic acid, benzenesulfonic acid, toluenesulfonic acid, dimethylsulfamic acid, cyclohexylsulfamic acid, phenylsulfamic acid, O,O-diethylphosphoric acid, 0,0diethylmonothiophosphoric acid, O,O,-diethyldithiophosphoric acid, O-ethyl-phenylphosphonic acid, 0ethylphosphoric acid or phenylphosphonic acid.The formation of the salt of the imidazole compound with an organic acid may be achieved by dissolving or suspending the compound [I] in water or a suitable organic solvent and admixing the resultant solution or suspension with a stoichiometric quantity of the organic acid which may optionally have been diluted with water or with the organic solvent. The salt-forming reaction may proceed at ambient temperature or even under cooling. The reaction mixture may be heated, if necessary. When the organic acid salt of the imidazole compound as formed is deposited as crystals, these may be separated by filtration. In some cases, the compound of the invention in the salt form may be recovered by removing the solvent from the salt-forming reaction solution by distillation.The preparation of the organic acid salt of the imidazole compound of the invention is illustrated by Examples 13-1 5.

The cation present in the metal salt suitable for the formation of the complex salt of the imidazole compound [I] includes:- metal cations such as copper, manganese, zinc, cobalt, nickel, iron, aluminum, silver, magnesium, tin, calcium and the like. The anion present in such metal salt includes an inorganic anion such as chlorine, bromine, iodine, fluorine anion; sulfuric, nitric or phosphoric acid anion; as well as an organic anion such as formic, acetic, methanesulfonic or toluenesulfonic acid anion and the like. The formation of the complex salt of the imidazole compound [I] with a metal salt may be achieved usually by reacting the compound [I] with a metal salt in water or an inert organic solvent. The inert organic solvent available for this purpose may be methanol, acetonitrile, dioxane, ethyl ether, dichloromethane, chloroform or hexane.The compound [I] and the metal salt reactant may properly be reacted with each other in a stoichiometrical or substantially stoichiometric molar proportion. When some metal cation is used for formation of the complex salt, there are formed two complexes of which the ligands are different from each other. The complex-forming reaction usually can proceed at ambient temperature without the necessity of heating the reaction mixture. If the complex salt of the imidazole compound with the metal salt is deposited as crystals, the latter may be recovered by filtration to afford the compound of the invention in the complex form. In some cases, the complex-forming reaction solution may be distilled to remove the solvent therefrom, yielding the complex form of the compound of the invention.The preparation of the metal salt complex is demonstrated by Examples 16-20 shown later.

The imidazole compound of the invention may be used as such for anti-fungal agent but more conveniently formulated into compositions for such antifungal purposes.

This invention therefore provides a fungicidal composition comprising, as an active ingredient, an imidazole compound of the general formula [I] or a salt thereof, in association with an acceptable carrier for the active ingredient.

The invention further provides a method of combating the fungal pests of plants, which comprises treating plants, seeds or trees with an imidazole compound of the formula [I] or a salt thereof as hereinbefore described.

The compound of the invention can be used to combat the fungal pests of plants or seeds in a number of ways, and for example, the compound of the invention as such or in the form of a formulation can be applied directly to the 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. Application can be made to any part ofthe plant, bush or tree, for example, to the foliage, stems, branches or roots, or to soil surrounding the roots.

The term "treating" as used means all these ways of application and the term "plant" includes seedlings, bushes and trees.

The compound of the invention are preferably used for agricultural and horticultural purposes in the form of a composition. The type of composition used in any instance will depend upon the particular purpose envisaged.

Generally, the composition of this invention may comprise any of the additive which are conventionally employed in the formulations of agricultural and horticultural usages, such as emulsifying agents, wetting agents, extending agents, dispersion agents and degradation-preventors, by which the effects of the composition as applied can be sured forthe intended pesticidal purposes.

The composition of this invention may be prepared by formulating the compound of the general formula [I] into the form of emulsifiable concentrate, wettable powder, sol (flowable powder), dusting powder, driftless (DL-type) powder, small granules or granules etc., according to conventional formulation technique. The carrier material which may be admixed with the active compound of this invention may be any solid or liquid ones which have been used conventionally in the preparations for agricultural and horticultural usages. The liquid carrier available in the formulation of this invention includes various solvents, such as, water, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, esters, ketones, acid amides, dimethylsulfoxide and the like. The solid carrier includes mineral powders such as clay, talc, kaolin, bentonite, diatomaceous earth, calcium carbonate and silica and the like, as well as organic powders such as wood powder and others.

More particularly, the composition of this invention may be in the form of dusting powder in which the active compound is mixed with a solid carrier such as kaolin, bentonite, or it may be in the form of granules in which the active compound is absorbed in a porous granular material such as pumice.

The composition of this invention may also be in the form of liquid preparations to be used as dips or sprays, which are usually aqueous dispersion or emulsion of the active ingredient compound of this invention together with one or more of the known wetting agents, dispersing agents or emulsifying agents.

Wetting agents, dispersing agents and emulsifying agents may be of the cationic, anionic or non ionic type. Suitable agents of the cationic type may be, for example, quaternary ammonium compounds, for example, cetyltrimethyl ammonium bromide. Suitable agents of the anionic type may be, for example, soaps, salts of aliphatic monoesters of sulphuric acid, for example sodium lauryl sulphate, salts of sulphonated aromatic compounds, for example sodium dedecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene sulphonate, and the sodium salts of diisopropyl- or triisopropylnaphthalene sulphonates. Suitable agents of the non-ionic type may be, for example, the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol or cetyl alcohol, or with alkyl phenols such as octyl phenol, nonyl phenyl and octyl cresol.Other non-ionic agents are the partial esters of long chain fatty acids and hexitol anhydrides and the condensation products of the said partial esters with ethylene oxide. The composition of the invention may contain a thickening agent such as gum, aliphatic acid salt, methyl cellulose and the like.

The compositions to be used as sprays may also be in the form of aerosols wherein the formulation is charged in a container under pressure together with a propellant such as fluorotrichloromethane or dichlorodifluoromethane. The compositions to be used in the form of aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient compound, and said concentrate may be diluted with water before use. These concentrates are often required to withstand storage for prolonged periods and after such storage, to be capable of dilution with water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment.

The composition of this invention in the form of the concentrates such as wettable powder, liquid preparations and emulsifiable concentrate may contain the active compound of the invention in an amount of 1 to 95% by weight and usually 2 to 75 ,0 by weight based on the whole weight of the composition. These preparations may be diluted with water upon use to give an aqueous preparation containing 0.0001 to 10% by weight of the active compound. The powders and granules may contain 0.1 to 10% by weight of the active compound. Such concentrates as oily solution or dispersion, emulsifiable concentrates and sol (flowable powder) may directly be applied as the spraying formulation at a minimized rate of application, without being diluted with water before use.The wettable powder or other powders may be used as such as the seed-dressing agent to over coat the seeds of crop plants.

The seeds may also be dipped in the liquid formulation which is prepared by diluting the wettable powder, sol or emulsifiable concentrate with water.

When the compound of this invention Is used as the fungicidal agent of agricultural and horticultural utilities, it may be applied in admixture with insecticides, another fungicides, bactericides, herbicides, plant-growth regulators and others, for broadening the range of applicability that the compound of this invention can be used effectively for the intended pesticidal purposes. In some cases, synergism can be expected by the combined use of the compound of this invention with another pesticides.

Examples of fungicides and bactericides which may be used in admixture with the compounds of this invention include the following: Ca rba mate fungicides such as 3,3'-ethylenebis(tetrahydro-4,6-dimethyl-2H-1 ,3,5-thiadiazine-2 thione), zinc or manganese ethylenebis(dithiocarbamate), bis(dimethyldithiocarbamoyl)disulfide, zinc propylenebis(dithiocarbamate), bis(dimethyldithiocarbamoyl)ethylenediamine; nickel dimethyldithiocarbamate, methyl 1 -(butylcarbamoyl)-2-benzimidazolecarbamate, 1 ,2-bis(3 methoxycarbonyl-2-thioureido)benzene, 1 -isopropylcarbamoyl-3-(3,5-dichlorophenyl)hydantoin, potassium N-hydroxymethyl-N-methyldithiocarbamate and 5-methyl- 1 0-butoxycarbonyla mi no- 10,11 - dehydrodibenzo (b,f)azepine; pyridine fungicides such as zinc bis(1-hydroxy-2(1 H)pyridinethionate) and 2-pyridine-thiol-1 -oxide sodium salt; phosphorus fungicides such as O,O-diisopropyl S benzylphosphorothioate and O-ethyl S,S-diphenyldithiophosphate; phthalimide fungicides such as N (2,6-diethylphenyl)phthalimide and N-(2,6-diethylphenyl)-4-methylphthalimide; dicarboxyimide fungicides such as N-trichloromethylthio-4-cyclohexene-1 ,2-dicarboxyimide and Ntetrachloroethylthio-4-cyclohexene-1 2-dicarboxyimide; oxathine fungicides such as 5,6-dihydro-2 methyl-l ,4-oxathine-3-carboxanilido-4,4-dioxide and 5,6-dihyd ro-2-methyl- 1 ,4-oxathine-3- carboxanilide; naphthoquinone fungicide such as 2,3-dichloro-1 ,4-naphthoquinone, 2-oxy-3-chloro- 1,4-naphthoquinone copper sulfate; pentachloronitrobenzene; 1 .4-dichloro-2,5-dimethoxybenzene; 5 methyl-s-triazol(3 ,4-b)benzthiazole; 2-(thiocya nomethylthio)benzothiazole; 3-hydroxy-5 methylisooxazole;N-2,3-dichlorophenyltetrachlorophthalamic acid; 5-ethoxy-3-trichloromethyl-1 ,2,4- thiadiazole; 2,4-dichloro-6-(0-chloroaniiino)-l ,3,5-triazine; 2,3-dicyano-1 ,4-dithioanthraquinone; copper 8-quinolinate; polyoxine; varidamycin; cycloheximide; iron methanearsonate; diisopropyl-1,3dithiolane-2-iridene malonate; 3-allyloxy-1 ,2-benzoisothiazol-1 ,1-dioxide; kasugamycin; Blasticidin S; 4,5,6,7-tetrachlorophthalide; 3-(3,5-dichlorophenyl)-5-ethenyl-5-methyloxazogizine-2,4-dione; N-(3,5dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboxyimide;S-n-butyl-5'-para-t-butylbenzyl-N-3pyridyldithiocarbonylimidate; 4-chlorophenoxy-3,3-dimethyl-1 -(1 H, 1 3,4-triazol- 1 -yl)-2-butanone; methyl-D,L-N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyl)alaninate; N-propyl-N-[2-(2,4,6 trichlorophenoxy)ethyl]imidazol-1 -carboxamide; N-(3,5-dichlorophenyl)succinimide; tetrachloroisophthalonitrile; 2-dimethylamino-4-methyl-5-n-butyl-6-hydroxypyrimidine; 2,6-dichloro-4nitroaniline; 3-methyl-4-chlorobenzthiazol-2-one; 1 ,2,5,6-tetrahydro-4H-pyrrolo[3,2, 1 -i,j]quinoline-2- one; 3'-isopropoxy-2-methylbenzanilide; 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxorane-2-ylmethyl]1 H,1,2,4-triazol; 1 ,2-benzisothiazoline-3-one; basic copper chloride; basic copper sulfate;N'dichlorofluoromethylthio-N,N-dimethyl-N-phenylsulfamide; ethyl-N-(3dimethyla minopropyl)thiocarbamate hydrochloride; piomycin; S,S-6-methylquinoxaline-2,3 diyldithiocarbonate; complex of zinc and maneb; dizinc bis(dimethyldithiocarbamate) ethylenebis (dithiocarbamate).

Examples of plant growth regulators and herbicides which may be used in combination with the compounds of this invention includes the following.

isourea plant growth regulators such as N-methoxycarbonyl-N'-4methylphenylca rbamoylethylisourea and 1 -(4-chlorophenylcarba moyl)-3-ethoxycarbonyl-2methylisourea; another type of plant growth regulators such as sodium naphthalene-acetate, 1,2- dihydropyridazine-3,6-dione and gibberellins; triazine herbicides such as 2-methylthio-4,6bisethylamino-1,3,5-triazine, 2-chloro-4,6-bisethylamino-1,3,5-triazine, 2-methoxy-4-ethylamino-6isopropylamino-1,3,5-triazine, 2-chloro-4-ethylamino-6-isopropylamino-s-triazine, 2-methylthio-4,6bis(isopropylamino)-s-triazine and 2-methylthio-4-ethylamino-6-isopropylamino-s-triazine; phenoxy herbicides such as 2,4-dichlorophenoxyacetic acid and methyl, ethyl and butyl esters thereof, 2-chloro4-methylphenoxyacetic acid, 4-chloro-2-methylphenoxyacetic acid and ethyl 2-methyl-4chlorophenoxybutylate; diphenylether herbicides such as 2,4,6-trichlorophenyl-4'-nitrophenylether, 2,4-dichlorophenyl-4'-nitrophenylether and 3,5-dimethylphenyl-4'-nitrophenylether; urea herbicides such as 3-(3,4-dichlorophenyl)-1 -methoxy-1 -methyl urea,3-(3,4-dichlorophenyl)-1,1-dimethylurea and 3-(4-chlorophenyl)-1 ,1 -dimethyl urea; carbamate herbicides such as 3-methoxyearbonylaminophenyl N-(3-methylphenyl)carbamate, isopropyl-N-(3-chlorophenyl)carba mate and methyl-N-(3,4'dichlorophenyl)carbamate; uracil herbicides such as 5-bromo-3-sec-butyl-6-methyluracil and 1 cyclohexyl-3,5-propyleneuracil; thiolcarbamate herbicides such as S-(4-chlorobenzyl)-N,Ndiethylthiolcarbamate, S-ethyl-N-cyclohexyl-N-ethylthiolcarbamate and S-ethyl-hexahydro-1 H-azepine 1 -carbothioate and S-ethyl-N,N-di-n-propylthiocarbamate; pyridinium herbicides such as 1,1 '-di methyl- 4,4'-bispyridinium dichloride; phosphoric herbicides such as N-(phosphonomethyl)glycine; aniline herbicides such as α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-tol uidine, 4-(methylsu Ifonyl)-2 ,6-dinitro N,N-dipropylaniline and N3,N3-diethyl-2,4-dinitro-6-trifluoromethyl-1 ,3-phenylene diamine; acid anilide herbicids such as 2-chloro-2',6'-diethyl-N-(butoxymethyl)acetoanilide, 2-chloro-2',6'-diethyl-N- (methoxymethyl)acetoanilide, and 3,4-dichloropropioneanilide; pyrazole herbicides such as 1,3dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole and 1 ,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-(p toluenesulfonyloxy)pyrazole; 5-tert-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxadiazoline-2 one; 2-[N-isopropyl, N-(4-chlorophenyl)carbamoyl]-4-chloro-5-methyl-4-isooxazoline-3-one; 3 isopropyl-benzo-2-thia-1 ,3-diazinone-(4)-2,4-dioxide and 3-(2-methylphenoxy)pyridazine.

Examples of insecticides which may be mixed with the compounds of this invention include the following:- phosphoric insecticides such as O,O-diethyl 0-(2-isopropyl-4-methyl-6 pyrimidinyl)phosphorothioa:3, O,O-diethyl S-2-[(ethylthio)ethyl] phosphorodithioate, O,O-dimethyl 0-(3- methyl-4-nitrophenyl )thiophosphate, O,O-dimethyl S-(N-methylcarbamoylmethyl)phosphorodithioate, O,O-dimethyl S-(N-methyl-N-formylcarbamoylmethyl) phosphorodithioate, O,O-dimethyl S-2 [(ethylthio)ethyl] phosphorodithioate, O,O-di methyl- 1 -hydroxy-2,2,2-trich loroethylphosphonate, 0,0diethyl-O-(5-phenyl-3-isooxazolyl)phosphorothioate, O,O-dime bromophenyl)phosphorothioate, O,O-dimethyl O-(3-methyl-4-methylmercaptophenyl)thiophosphate, 0ethyl O-p-cyanophenyl phenylphosphorothioate, 0,O-dimethyl-S-( 1 2- dicarboethoxyethyl)phosphorodithioate, 2-chloro-(2,4,5-trichlorophenyl)vinyldimethyl phosphate, 2 chloro-1 -(2,4-dichlorophenyl)vinyldimethyl phosphate, O,O-dimethyl O-p-cyanophenyl phosphorothioate, 2,2-dichlorovinyl dimethyl phosphate, O,O-diethyl 0-2,4-dichlorophenyl phosphorothioate, ethyl mercaptophenylacetate O,O-dimethyl phosphorodithioate, S-[(6-chloro-2-oxo 3-benzooxazolinyl)methyi] O,O-diethyl phosphorodithioate, 2-chloro-1 -(2,4-dichlorophenyl)vinyl diethylphosphate, O,O-diethyl 0-(3-oxo-2-phenyl-2H-pyridazine-6-yl) phosphorothioate, O,O-dimethyl S-(1 -methyl-2-ethylsulf inyl)-ethyl phosphorothiolate, O,O-dimethyl S-phthalimidomethyl phosphorodithioate, O,O-di ethyl O,O-diethyl S-(N-ethoxyCarbonyl-N-methylcarbamoylmethyl)phosphorodithioate, O,O-dimethyl S-[2-methoxy-1,3,4-thiadiazol-5-(4H)-onyl-(4)-methyl] dithiophosphate, 2-methoxy-4H 1,3,2-benzooxaphosphorine 2-sulfide, O,O-diethyl O-(3,5,6-trichloro-2-pyridyl)phosphorothioate, Oethyl O-2,4-dichlorophenyl thionobenzene phosphonate, S-[4,6-diamino-s-triazine-2-yl-methyl] O,Odimethyl phosphorodithioate, O-ethyl O-p-nitrophenyl phenyl phosphorothioate, O,S-dimethyl N-acetyl phosphoroamidothioate, 2-diethylamino-6-methylpyrimidine-4-yl-diethylphosphorothionate, 2 diethylamino-6-methyl-pyrimidine-4-yl-di methylphosphorothionate, O,O-diethyl O-N-(methylsulfinyl) phenyl phosphorothioate, O-ethyl S-propyl 0-2,4-dichlorophenyl phosphorodithioate and cis-3 (dimethoxyphosphinoxy) N-methyl-cis-crotone amide, carbamate insecticides such as 1 -naphthyl Nmethylcarba mate, S-methyl N-[methylcarba moyloxy]thioacetoimidate, m-tolyl methylcarba mate, 3,4- xylyl methylcarbamate, 3 ,5-xylyl methylcarbamate, 2-sec-butylphenyl N-methylcarbamate, 2,3 dihydro-2,2-dimethyl-7-benzofuranylmethylcarbamate, 2-isopropoxyphenyl N-methylcarba mate, 1,3- bis(carbamoylthio)-2-(N,N-dimethylamino)propane hydrochloride and 2-diethylamino-6 methylpyrimidine-4-yl-di methylcarbamate; and another insecticides such as N,N-dimethyl N'-(2methyl-4-chlorophenyl)formamidine hydrochloride, nicotine sulfate, milbemycin, 6-methyl-2,3quinoxalinedithiocyclic S,S-dithiocarbonate, 2,4-dinitro-6-sec-butylphenyl dimethylacrylate, 1,1 -bis(p- chlorophenyl) 2,2,2-trichloroethanol,2-(p-tert-butylphenoxy)isopropyl-2'-chloroethylsu Ifite, azoxybenzene, di-(p-chlorophenyl)-cyclopropyl carbinol, di[tri(2,2-dimethyl-2-phenylethyl)tin] oxide, 1 - (4-chlorophenyl)-3-(2,6-difluorobenzoyl) urea and S-tricyclohexyltin 0,0diisopropylphosphorodithioate.

The compound of this invention may also be admixed with fertilisers such as nitrogen-containing fertiliser or phosphorous-containing fertiliser. The composition may comprise granules of fertiliser which have been coated with the compound of this invention or in which the compound of this invention has been incorporated.

This invention is now illustrated with reference to the following Examples. Examples 1 to 20 are illustrative of the production of the new compound of this invention. Examples 21 to 26 are illustrative of the formulations containing the compound of this invention. Examples 27 to 33 are illustrative of the tests of estimating the fungicidal activities of the compound of this invention.

EXAMPLE 1 Production of Compound No. 1 identified in Table 1 later and of the formula

To a mixture of 25.6 g of the compound (imidazol-1-yl-acetic acid phenylimidoyl chloride hydrochloride) of the formula

and 100 ml of methanol was added dropwise under ice-cooling a solution in methanol of sodium methoxide which was prepared by reacting 4.6 g of metallic sodium with 50 ml of methanol. The whole admixture obtained was stirred at ambient temperature for 30 minutes, and the salt deposited was removed from the reaction solution by sucking-filtration. The filtrate was concentrated under reduced pressure to give~imidazol-1 -yl-isoacetic acid anilide O-methylether (Compound No. 1) as a lightly yellow colored oil in a yield of 19.8 g.This substance was purified in silica gel column chromatography (developed with a mixed solvent of benzene and acetone) to give a pure product as a colorless oil which showed a refractive index n23 = 1.5738.

EXAMPLE2 Production of Compound No. 102 of Table 1 and of the formula

To a mixture of 32.5 g of the compound (imidazol-l -yl-acetic acid 2',4'-dichlorophenylimidoyl chloride hydrochloride) of the formula

and 12.4 g of benzylmercaptan and 200 ml of acetonitrile was added dropwise 21.0 g of triethylamine (as the acid-binder) under ice-cooling. The whole admixture obtained was stirred at ambient temperature for 10 minutes, and the reaction solution was admixed with water and benzene. After stirring, the organic layer was separated and washed with 1 N aqueous sodium hydroxide and then with water, followed by drying over anhydrous sodium sulfate.The dried solution was distilled under reduced pressure to remove the solvent, and there was afforded imidazol-1-yl-isothioacetic acid 2',4'dichloroanilide S-benzylether (Compound No. 1 02) as a lightly yellow colored oil in a yield of 31.6 g.

This oil was purified in silica gel column chromatography to give a pure product as colorless oil which showed a refractive index nD3 = 1.6411.

EXAMPLE 3 Production of Compound No.1 of Table 1 and of the formula

The compound (imidazol-1 -yl-acetic acid 2',4'-dichlorophenylimidoyl imidazol) (32.0 g) of the formula

and p-chlorobenzylmercaptan (16.0 g) were dissolved in 150 ml of acetonitrile, and the resultant solution was reflexed for 30 minutes.

The reaction solution, after cooling, was admixed with water and benzene. After stirring, the organic layer was separated and washed with 1 N aqueous sodium hydroxide and then with water, followed by drying over anhydrous sodium sulfate. The dried solution was distilled under reduced pressure to remove the solvent, and there was afforded imidazol-1 -yl-isothioacetic acid 2',4'dichloroanilide S-p-chlorobenzylether (Compound No. 11 5) as lightly yellow colored crystals.

Recrystallization from a mixed solvent of n-hexane/acetone gave the pure product as colorless crystals which showed a melting point of 94-950C.

EXAMPLE 4 Production of Compound No. 131 of Table 1 and of the formula

To a mixture of 30.3 g of a-imidazol-1-yl-propionic acid 2',4'-dichlorophenylimidoyl chloride of the formula

and 8.0 of n-propylmercaptan and 100 ml of acetone was added 14.0 g of anhydrous potassium carbonate (as the acid-binder). The whole admixture obtained was refluxed for one hour, and the reaction solution, after cooling, was admixed with water and benzene. After stirring, the organic layer was separated from the aqueous layer and washed with 1 N aqueous sodium hydroxide and then with water, followed by drying over an hydros sodium sulfate. The dried solution was distilled under reduced pressure to remove the solvent, and there was afforded a-imidazoi-1-yl-isothiopropionic acid 2',4'dichloroanilide S-n-propylether (Compound No. 131) as a yellow colored oil in a yield of 31.1 g. This oil was purified in silica gel column chromatography to give a pure product as a lightly colored oil which showed a refractive index n23 = 1.5928.

EXAMPLE 5 Production of Compound No.181 of Table 1 and of the formula

Imidazol-1 -yl-acetic acid 4'-chloro-2'-trifluoromethylphenylimidoyl imidazole (35.4 g) of the formula

was dissolved in 100 ml of n-butanol, and the resultant solution was refluxed for 5 hours. The reaction solution was distilled under reduced pressure to remove n-butanol and then admixed with water and benzene. After stirring, the resultant organic layer was separated and washed with 1 N aqueous sodium hydroxide and then with water, followed by drying over anhydrous sodium sulfate. The dried solution was distilled under reduced pressure to remove the solvent, and there was afforded imidazol-1-ylisoacetic acid 4'-chloro-2'-trifluoromethylanilide O-n-butylether (Compound No. 1 81) as a lightly colored oil in a yield of 29.5 g.This oil was purified in silica gel column chromatography to give a pure product as a colorless oil which showed a refractive index nD3 = 1.5900.

EXAMPLE 6 Production of Compound No. 1 95 of Table 1 and of the formula

To a mixture of 39.8 g of cg-imidazol-1-yl-phenyl acetic acid 4'-chloro-2'trifluoromethylphenylimidoyl chloride of the formula

and 7.0 g of ethylmercaptan and 150 ml of acetonitrile was added dropwise 11.0 g of triethylamine (as the acid-binder). The whole admixture obtained was stirred at ambient temperature for one hour, and the reaction solution was admixed with water and benzene. After stirring, the resultant organic layer was separated and washed with 1 N aqueous sodium hydroxide and then with water, followed by drying over anhydrous sodium sulfate.The dried solution was distilled under reduced pressure to remove the solvent, and there was afforded ct-imidazol-l -yl-isothiophenylacetic acid 4'-chloro-2'trifluoromethylanilide S-ethylether (Compound No. 195) as a yellow colored oil in a yield of 39.0 g. This oil was purified in silica gel column chromatography to give a pure product as a lightly colored oil which showed a refractive index nD3 = 1.5946.

EXAMPLE 7 Production of Compound No.85 of Table 1 and of the formula

6.8 g of imidazole was added to a solution in n-propanol of sodium n-propoxide which was prepared by reacting 2.3 g of metallic sodium with 200 ml of n-propanol, and the admixture obtained was refluxed for 30 minutes. The reaction solution, after cooling, was admixed with 28.1 g of chloroisoacetic acid 2',4'-dichloroanilide O-n-propylether of the formula

and the resultant admixture was refluxed for 2 hours. After cooling, the salt deposited was removed from the reaction solution by filtration under sucking, and the filtrate was concentrated under reduced pressure to give imidazol-1 -yl-isoacetic acid 2',4'-dichloroanilide O-n-propylether (Compound No. 85) as a lightly colored oil in a yield of 29.0 g.This oil was purified in silica gel column chromatography to give a pure product as a colorless oil which showed a refractive index nod3 = 1.5686.

EXAMPLE 8 Production of Compound No. of Table 1 and of the formula

Chloroisothioacetic acid 4'-chloro-2'-trifluoromethylanilide S-benzylether (37.8 g) of the formula

and imidazole (14.0 g) were dissolved in 100 ml of dimethylformamide, and the resultant solution was maintained at 1000C for 2 hours for reaction. The reaction solution, after cooling, was admixed with water and benzene. After stirring, the resultant organic layer was separated and washed with 1 N aqueous sodium hydroxide and then with water, followed by drying over anhydrous sodium sulfate.The dried solution was distilled under reduced pressure to remove the solvent, and there was afforded imidazol-1 -yl-isothioacetic acid 4'-chloro-2'-trifluoromethylanilide S-benzylether (Compound No. 1 86) as a lightly colored oil in a yield of 38.5 g (94%). This oil was purified in silica gel column chromatography to give a pure product as a colorless oil which showed a refractive index nD3 = 1.5792.

EXAMPLE 9 Production of Compound No. 120 of Table 1 and of the formula

Imidazol-1 -yl-thioacetic acid 2',4'-dichloroanilide (28.6 g) of the formula

was admixed with a solution in ethanol of sodium ethoxide which was prepared by reacting 2.3 g of metallic sodium with 100 ml of ethanol. To the resultant admixture was then added a solution of pmethylbenzyl chloride (14.1 g) in ethanol (30 ml), and the whole admixture was refluxed for 30 minutes.

Subsequent to cooling, the salt deposited was removed from the reaction solution by filtration under sucking, and the filtrate was concentrated under sucking, and the filtrate was concentrated under reduced pressure to give imidazol-1-yl-isothioacetic acid 2',4'-dichloroanilide S-p-methylbenzylether (Compound No. 120) as lightly yellow colored crystals in a yield of 38.2 g. Recrystallization from a mixed solvent of cyclohexane/acetone gave the pure product as colorless crystals which showed a melting point of 77--78"C.

EXAMPLE 10 Production of Compound No. of Table 1 and of the formula

Imidazol-1 -yl-isothioacetic acid 2',4'-dichloroanilide S-benzylether (3.8 g) of the formula

was dissolved in 50 ml of acetone, followed by addition of 2 ml of 5 N hydrochloric acid. The whole admixture obtained was allowed to stand at ambient temperature for one hour. The colorless crystals thus deposited were isolated from the reaction solution by filtration and washed with acetone to afford imidazol-1 -yl-isothioacetic acid 2',4'-dichloroanilide S-p-chlorobenzylether hydrochloride (Compound No. 103) as colorless crystals in a yield of 3.5 g, which showed a melting point of 114-11 50C.

EXAMPLE 11 Production of Compound No. 116 of Table 1.

Imidazol-1 -yl-isothioacetic acid 2',4'-dichloroanilide S-p-chlorobenzylether (4.1 g) of the formula

was dissolved in 50 ml of dioxane, followed by addition of 1.5 g of 85% phosphoric acid. The whole admixture obtained was allowed to stand at ambient temperature for one hour. The colorless crystals thus deposited were isolated from the reaction solution by filtration and washed with dioxane to afford imidazol-1-yl-isothioacetic acid 2',4'-dichloroanilide S-p-chlorobenzylether phosphate (Compound No.

11 6) as colorless crystals in a yield of 4.5 g, which showed a melting point of 1 58-1 59.50C.

EXAMPLE 12 Production of Compound No. 1 60 of Table 1.

Imidazol-l -yl-isothioacetic acid 2',4'-dimethylanilide S-ethylether (2.7 g) of the formula

was admixed, with stirring, with a solution of sulfamic acid (1.0 g) in water (100 ml). The whole admixture obtained was stirred at ambient temperature for 1 0 minutes, and the colorless crystals deposited were isolated from the reaction solution by filtration, washed with water and then dried.

There was afforded imidazol-1 -yl-isothioacetic acid 2',4'-dimethylanilide S-ethylether sulfamate (Compound No. 160) as colorless crystals in a yield of 3.3 g, which showed a melting point of 140-141 0C.

EXAMPLE 13 Production of Compound No. 86 of Table 1.

lmidazol-1-yl-isoacetic acid 2',4'-dichloroanilide O-n-propylether (3.1 g) of the formula

was dissolved in 100 ml of dioxane, and the resultant solution was admixed with 2.0 g of ptoluenesulfonic acid monohydrate with stirring. The whole admixture obtained was stirred at ambient temperature for 30 minutes, and the colorless crystals deposited were isolated from the reaction solution by filtration and washed with dioxane to afford imidazol-1 -yl-isoacetic acid 2',4'dichloroanilide O-n-propylether p-toluenesulfonate (Compound No. 86) as colorless crystals in a yield oi 4.4 g, which showed a melting point of 175-1 76.50C.

EXAMPLE 14 Production of Compound No. 105 of Table 1.

was dissolved in 50 ml of ether, followed by addition of 5.0 g of formic acid. The whole admixture obtained was allowed to stand in a refrigerator for one day. The colorless crystals thus deposited were isolated from the reaction solution by filtration and washed with a small volume of ether to afford imidazol-1 -yl-isothioacetic acid 2',4'-dichloroanilide S-benzyletherformate (Compound No. 105) as colorless crystals in a yield of 2.9 g, which showed a melting point of 4470C.

EXAMPLE 1 5 Production of Compound No. 187 of Table 1.

lmidazol-1-yl-isothioacetic acid 4'-chloro-2'-trifluoromethylanilide S-benzylether (4.1 g) of the formula

was dissolved in 10 ml of methanol, and the resultant solution was admixed, with stirring, with a solution of oxalic acid (1 g) in water (1 00 ml). The whole admixture was stirred at ambient temperature for one hour, and the colorless crystals thus deposited were isolated from the reaction solution by filtration, washed with water and dried to give imidazol-1 -yl-isothioacetic acid 4'-chloro-2'trifluoromethylanilide S-benzylether oxalate (Compound No. 1 87) as colorless crystals in a yield of 4.7 g, which showed a melting point of 146-1 47.50C.

EXAMPLE 16 Production of Compound No.92 of Table 1 of the formula

Imidazol-1 -yl-isoacetic acid 2',4'-dichloroanilide O-phenylether (3.5 g) of the formula

was dissolved in 10 ml of methanol, and the resultant solution was admixed, with stirring, with a solution of zinc chloride (0.7 g) in water (100 ml). The whole admixture was stirred at ambient temperature for 30 minutes, and the colorless crystals deposited were isolated from the reaction solution by filtration and washed with water. There was afforded bis(imidazol-1 -yl-isoacetic acid 2',4'dichloroanilide O-phenylether) zinc chloride (Compound No. 92) as colorless crystals in a yield of 3.6 g, which showed a melting point of 88-890C.

EXAMPLE 17 Production of Compound No. 110 of Table 1.

was dissolved in 10 ml of methanol, and the resultant solution was admixed, with stirring, with a solution of manganese chloride tetrahydrate (1.2 g) in water (100 ml). The whole admixture was allowed to stand at ambient temperature for 3 hours, and the colorless crystals thus deposited were isolated from the reaction solution by filtration and washed with water. There was thus afforded bis(imidazol-1 -yl-isothioacetic acid 2',4'-dichloroanilide S-benzylether) manganese dichloride (Compound No. 110) as colorless crystals in a yield of 4.0 g, which showed a melting point of 39--420C.

EXAMPLE 18 Production of Compound No. 119 of Table 1.

Imidazol-l -yl-iSothioacetic acid 2',4'-dichloroanilide S-p-chlorobenzylether (4.1 g) of the formula

was dissolved in 10 ml of methanol, and the resultant solution was admixed with 0.7 g of anhydrous ferric chloride. The resultant admixture was stirred at ambient temperature for 10 minutes and admixed with 100 ml of water, and the crystals thus deposited were isolated from the reaction solution by filtration. The resultant crystals were washed with water and dried to give tris(imidazol-1 -ylisothioacetic acid 2',4'-dichloroanilide S-p-chlorobenzylether) ferric chloride (Compound No. 11 9) as colorless crystals in a yield of 4.0 g, which showed a melting point of 11 6-11 7.50C.

EXAMPLE 19 Production of Compound No. 122 of Table 1.

lmidazol-1-yl-isothioacetic acid 2',4'-dichloroanilide S-p-methylbenzylether (3.9 g) of the formula

was dissolved in 10 ml of ethyl acetate, and the resultant solution was admixed with 0.8 g of anhydrous cupric chloride. The resultant admixture was stirred at ambient temperature for 10 minutes and then admixed with 100 ml of n-hexane. The crystals deposited were isolated from the reaction solution by filtration and washed with n-hexane to afford bis(imidazol-1 -yl-isothioacetic acid 2',4'-dichloroanilide S-p-methylbenzylether) cupric chloride (Compound No. 122) as bluish white colored crystals in a yield of 4.1 9, which showed a melting pointof8l-830C.

EXAMPLE 20 Production of Compound No. 147 of Table 1.

Imidazol-1 -yl-isothioacetic acid 3',5'-dichloroanilide S-benzylether (3.8 g) of the formula

was dissolved in 10 ml of methanol, and the resultant solution was admixed, with stirring, with a solution of ferrous chloride tetrahydrate (2.2 g) in water (100 ml). The whole admixture obtained was allowed to stand for 3 hours, and the crystals deposited were isolated from the reaction solution by filtration, washed with water and dried. There was thus afforded bis(imidazol-1 -yl-isothioacetic acid 3',5'-dichloroanilide S-benzylether) ferrous chloride (Compound No. 1 47) as ocher colored crystals in a yield of 3.7 g, which showed a melting point of 57-590C.

Similarly to the procedures of the Examples 1 to 20, further examples of the new compound of the formula [I] were produced. Representative compounds are listed in Table 1 below. In Table 1, the column of "Salts" indicates the nature of the inorganic acid, organic acid or metal salt forming the salts (or complex) of the compound [I] of the invention, as well as the molar proportion of the compound [I] in the free form which are required to constitute one mole of the salt or complex of the compound of the invention. Compound Numbers shown in Table 1 are referred to in the following Examples 21 to 33. Table 1

and salts thereof Salts Refractive

Compound Salt-forming index or m.p.

No. R1 R2 X Y component moles ( C) 1 # -CH3 O -CH2- nD23 1.5738 2 " " " " (CO2H)2 1 m.p. 74 ~ 77 3 " -C3H7-n " " nD23 1.5748 4 " # " " nD23 1.5864 5 " # " " nD23=1,5908 6 " -CH3 S " m.p. 118 ~ 120 7 " -C2H5 " " nD23 1.6021 8 " " " " (CO2H)2 1 m.p. 137.5!~139.5 9 " -C3H7-n " " nD23 1.5907 cont'd....

10 # # S -CH2- nD23 1.5921 11 " # " " m.p. 50 ~ 52.5 12 " # " " nD23 1.6295 13 " # " " nD23 1.5841 14 " # O # nD23 1.5811 15 " -C2H5 S " nD23 1.5840 16 " # " " nD23 1.6162 17 " " " " # 1 m.p. 74 ~ 76 18 " -CH2CH-CH2 " # nD23 1.5712 19 " " " " (CO2H)2 1 m.p. 111 ~ 112.5 20 # -C4H9-1 " # nD23 1.5958 cont'd...

21 # -C4H9-1 S # CuCl2 2 m.p. 63 ~ 66 22 # -C10H21-n " -CH2 nD23 1.5934 23 " # O # nD23 1.5899 24 " -CH2SCH3 S # nD23 1.5941 25 # # O -CH2- nD23 1.5909 26 " -C2H5 S " m.p. 49 ~ 51 27 " " " " p-TsOH 1 m.p. 147.5~149 28 " # " " m.p. 103~104 29 " " " " NH2SO3H 1 m.p. 149~150.5 30 " -CH2CH2CH2Cl " # nD23 1.5876 31 # -C2H5 " -CH2- nD23 1.5856 cont'd...

32 # # S -CH2- m.p. 73.5 ~ 75.5 33 # # O " nD 23 1.5981 34 " " " " p-TsOH 1 m.p. 161 ~ 163.5 35 " n-C5H11 S " nD23 1.5964 36 " " " " (CO2H)2 1 m.p. 134.5 ~ 136 37 # -CH2SCH3 " " nD23 1.5918 38 " -C2H5 O # nD23 1.5930 39 # # S -CH2 nD23 1.5981 40 # -C2H5 " " m.p. 70 ~ 72 41 " " " " HCl 1 m.p. 142 ~ 144 42 " -CH2CO2C2H5 " " nD23 1.6020 43 " # " " m.p. 98 ~ 99.5 cont'd...

44 # # S -CH2- # 1 m.p. 126 ~ 128.5 45 " # O -CH2CH2- nD23 1.5976 46 " # S -CH2 nD23 1.5842 47 " # " # nD23 1.5907 48 # # " -CH2 nD23 1.5892 49 " -CH2CN " # nD23 1.5916 50 # -C2H5 " -CH2 nD23 1.5508 51 " " " " CuSO4 2 m.p. 1.5508 52 # # " " nD23 1.5679 53 " # O # nD23 1.5801 cont'd...

54 # # S -CH2- nD23 1.6004 55 " -CH2CH2OC2H5 O -CH2CH2CH2- nD23 1.5977 56 " # " # nD23 1.5963 57 # -CH3 O -CH2- nD23 1.5894 58 " -C2H5 S " nD23 1.5844 59 " " " " (CO2H)2 1 m.p. 135.5 ~ 138 60 " # " " m.p. 67 ~ 69 61 " -CH2CH2NHC2H5 " " nD23 1.5849 62 " # " # nD23 1.5906 cont'd...

63 # -CH3 S # nD23 1.5942 64 # -CH2CH2SCH3 O -CH2- nD23 1.5763 65 " -C8H17-n D " nD23 1.5911 66 # # " " nD23 1.5855 67 # -C4H9-n " " nD23 1.5894 68 # -C2H5 O " nD23 1.5814 69 " -CH2CH=CH2 S " nD23 1.5842 70 " # " " nD23 1.5865 71 " # " " nD23 1.5975 72 # -C6H13-n O # nD23 1.5841 cont'd...

73 # # S -CH2- nD23 1.5863 74 " # " " nD23 1.5909 75 # # " " nD23 1.6026 76 # -C5H11-n O " nD23 1.6041 77 # # S " nD23 1.6002 78 # # " # nD23 1.5998 79 # # " -CH2- nD23 1.6060 80 # -C2H5 O " nD23 1.5973 81 # -CH3 " " nD23 1.5866 82 " " " " (CO2H)2 1 m.p. 160 ~ 162 83 " -C2H5 " " nD23 1.5772 cont'd...

84 # -C2H5 O -CH2- CuCl2 2 m.p. 86 ~ 88.5 85 " -C3H7-n " " nD23 1.5686 86 " " " " p-TsOH 1 m.p. 175 ~ 176.5 87 " # " " nD23 1.5128 88 " " " " H3PO4 1 m.p. 124 ~ 126 89 " # " " nD23 1.5664 90 " " " " # 1 m.p. 112.5 ~ 114 91 " # " " nD23 1.5931 92 " " " " ZnCl2 2 m.p. 88 ~ 91 93 " -CH3 S " nD23 1.5922 94 " -C2H5 " " m.p. 95.5 ~ 97 cont'd...

95 # -C3H7-n S -CH2- n23D 1.5936 96 " -C3H7-1 " " m.p. 64 ~ 65.5 97 " " " " HBr 1 m.p. 116.5 ~ 119 98 " -C4H9-n " " n23D 1.6161 99 " -CH2CH-CH2 " " n23D 1.6126 100 " " " " (CO2H)2 m.p. 123 ~ 125.5 101 " # " " n23D 1.5821 102 " -CH2-# " " n23D 1.6411 103 " " " " HCl m.p. 114 ~ 115.5 104 " " " " H3PO4 m.p. 160 ~ 161 105 " " " " HCO2H m.p. 44 ~ 47 106 # " " " (CO2H)2 m.p. 169 ~ 170 cont'd...

107 # # S -CH2- CHCO2H 1 m.p. 99 ~ 100.5 CHCO2H 108 " " " " CuCl2 2 m.p. 72 ~ 74.5 109 " " " " CuSO4 " m.p. 65 ~ 66 110 " " " " MnCl2 " m.p. 39 ~ 42 111 " " " " ZnCl2 " m.p. 68 ~ 70 112 " " " " CoCl2 " m.p. 63 ~ 65 113 " " " " NiCl2 " m.p. 76 ~ 78 114 " " " " FeCl2 " m.p. 60 ~ 62.5 115 " # " " " m.p. 94 ~ 95 116 " " " " H3PO4 " m.p. 158 ~ 159.5 117 " " " " NH2SO3H " m.p. 63 ~ 65 118 " " " " (CO2H)2 " m.p. 121 ~ 122 cont'd...

119 # # S -CH2- FeCl3 3 m.p. 116 ~ 117.5 120 " # " " m.p. 77 ~ 78.5 121 " " " " HCl 1 m.p. 122 ~ 123.5 122 " " " " CuCt2 2 m.p. 81 ~ 83 123 " # " " n23D 1,5681 124 " # " " n23D 138 ~ 139 125 " # " -CH- n23D 1.5735 126 " -CH3 O CH3 n23D 1.5945 127 " # " " n23D 1.6002 128 " -CH3 S " n23D 1.6129 129 " " " " (CO2H)2 1 m.p. 143 ~ 145 cont'd...

130 # -C2H5 S # n23D 1.6003 131 " -C3H7-n " " n23D 1.5928 132 " -C4H9-n " " n23D 1.5925 133 " " " " CuCl2 2 m.p. 51 ~ 53.5 134 " -CH2-# " " m.p. 74 ~ 75 135 " " " " p-TsCH 1 m.p. 154 ~ 156 136 " # " " n23D 1.6210 137 " " " " ZaCl2 2 m.p. 58 ~ 61 138 " # " # n23D 1.5845 139 " # O # n23D 1.6040 140 " # " # n23D 1.5942 cont'd...

141 # # O -CH2- n23D 1.5894 142 " -CH2SCH3 S " n23D 1.5886 143 " -CH2CH2-#-CH3 " -CH2-CH=CH- n23D 1.5873 144 # #Cl O -CH2- n23D 1.5983 145 " -C2H5 S " n23D 1.6081 146 " -CH2-# " " n23D 1,6290 147 " " " " FeCl2 2 m.p. 57 ~ 59 148 " -CH2CH2# " " n23D 1.6052 149 " # " # n23D 1.6024 150 # -C4H9-% " -CH2- n23D 1.5949 cont'd...

151 # -CH2OCH3 S # n23D 1.5859 152 # -C3H7-1 " -CH2- n23D 1.5950 153 " # " # n23D 1.5963 154 " # O # n23D 1.5951 155 # # " -CH2- n23D 1.5843 156 " -CH2C@CH S " n23D 1.5887 157 " -C4H9-n " # n23D 1.5892 158 # # O -CH2- n23D 1.5946 159 " -C2H5 S " n23D 1.5856 cont'd...

160 # -C2H5 S -CH2- NH2SO3H 1 m.p. 140 ~ 142 161 " # " " m.p. 70.5 ~ 72 162 " " " " NO2-#-CO2H 1 m.p. 100 ~ 102 163 " -C2H5 " # n23D 1.6027 164 " # O # n23D 1.5983 165 # -CH2-# " -CH2- n23D 1.5899 166 " -CH2H5 S " n23D 1.5390 167 " -CH2-# " " m.p. 83.5 ~ 55.5 168 " " " " p-TaOH m.p. 179 ~ 181 169 " -CH2CO2C2H5 " # n23D 1.5468 cont'd...

170 # -CH2OC2C2H5 S -CH- (OC2H)2 1 m.p. 61 ~ 64 CH3 171 " # " # n23D 1.5878 172 # # O -CH2- n23D 1.5907 173 " -C2H5 S " n23D 1.5889 174 " " " " (CO2H)2 1 m.p. 136 ~ 138 175 " " " " p-TsOH " m.p. 130.5 ~ 132 176 # # O " n23D 1.6029 177 " -C10H21-n S " n23D 1.5994 178 " # " # n23D 1.5849 179 " " " # n23D 1l.5820 cont'd...

180 # -CH3- O -CH2- n23D 1.5836 181 " -C4H9-n " " n23D 1.5900 182 " -C2H5 S " n23D 1.5631 183 " " " " H2PO3 1 m.p. 181 184 " -C3H7-n " " n23D 1.6139 185 " # " " n23D 1.5820 186 " -CH2-# " " n23D 1.5792 187 " " " " (CO2H)2 1 m.p. 146 ~ 147.5 188 " " " " p-TaCH " m.p. 133 ~ 121 189 " -CH2-# " " n23D 1.5881 190 " -CH2-# " " n23D 1.5948 191 " # " " n23D 1.5685 cont'd...

192 # # O # n23D 1.5937 193 " -CH2-# S " n23D 1.5949 194 " -CH3 " # n23D 1.5958 195 " -C2H5 " # n23D 1.5946 196 " -C2H11-n " -CH2CH2- n23D 1.5955 197 # # O -CH2- n23D 1.5964 198 " -CH2CH2S-# S " n23D 1.5843 199 # -C4H9-1 O " n23D 1.5826 200 " -C2H5 S " m.p. 81 ~ 83 201 " " " " H2SO4 1 m.p. 142 ~ 144 202 " " " " CH3COCO2H " m.p. 66 ~ 68.5 cont'd...

203 # -CH2-# S -CH2- m.p. 98 ~ 99 204 " " " " CuSO4 2 m.p. 74 ~ 6 205 " # " " n23D 1.5840 206 # -CH2CH2OC2H5 " # n23D 1.5852 207 " -CH2CH-CHCH3 O # n23D 1.5916 208 # -C3H7-1 S -CH2- n23D 1.5873 209 " -CH2CO2C2H5 O # n23D 1.5792 210 # -CH3 " -CH2- n23D 1.5944 cont'd..

211 # -C2H5 S -CH2- n23D 1,6387 212 " -CH2-# " " n23D 1,6489 213 " " " " CHCO2H 1 m.p. 107 ~ 110 CHCO2H 214 " " " " CuCt2 2 m.p. 68 ~ 70 215 " -CH2CH2CH2Cl " # n23D 1,5888 216 # -C2H5 " -CH2- n23D 1.5767 217 " " " " (CO2H)2 1 m.p. 84 ~ 86.5 218 " -CH2-# " " n23D 1.6111 219 " " " " ZnCt2 2 m.p. 42 ~ 45 220 # -C6H13-n O " n23D 1.5821 221m " -CH2CH2N(C2H5)2 S # n23D 1.5804 cont'd...

222 # # S # n23D 1.6021 223 #-CH2CH2- # O -CH2- n23D 1.6111 224 -C2H5 # " # n23D 1.5794 225 -C4H9-1 #-CH2CH2- S -CH2- n23D 1.5796 226 -C8H17-n -CH2CH=CH-CH=CH-CH3 O # n23D 1.5751 227 -CH2CH=CH2 -CH2-# S # n23D 1.5780 228 -CH2CH2OC2H5 -CH2-CH2-# " # n23D 1.5996 229 -CH2CH2S-# -CH2-# " -CH2- n23D 1.5804 230 # -CH2-#-Cl " " n23D 1,6218 cont'd...

231 # -CH2-#-F S -CH2- m.p. 77 ~ 79 232 " -CH2-#-Cl " " m.p. 113 # 115.5 233 " -CH2-# " " m.p. 69.5 ~ 71 234 " -CH2-#-CH3 " " m.p. 62 ~ 65 235 " -CH2-#-Cl " # m.p. 70.5 ~ 73 236 " -CH2-#-F " " m.p. 74.5 ~ 76 237 " -CH2-#-CH3 " " m.p. 69.5 ~ 71.5 238 " -CH2-#-Cl " # n23D 1.6242 239 # " " -CH2- m.p. 66.5 ~ 68 240 # -CH2# " " n23D 1.6212 cont'd...

241 # -CH2-#-Cl S -CH2- n23D 1.6235 242 # -CH2-# " " m.p. 67.5 ~ 69.5 243 " -CH2-#-Cl " " m.p. 99 ~ 101 244 # " " " m.p. 102 ~ 103 Notle : - p-TsOH dentoes p-tooluenesulfonic acid in the above tabel.

The following Examples 21 to 26 illustrate the procedures for preparing the fungicidal compositions of this invention but are not limitative of this invention. In Examples 21 to 26, "parts" are given by weight.

EXAMPLE 21 Wettable Powder 20 Parts of Compound No. 11 5, 5 parts of polyoxyethylene alkylarylethers, 3 parts of calcium ligninsulfonate and 72 parts of diatomaceous earth were mixed together and ground uniformly to give a wettable powder containing 20% by weight of the active ingredient compound.

EXAMPLE 22 Emulsifiable concentrate 30 Parts of Compound No. 102, 50 parts of xylene and 20 parts of polyoxyethylene alkylarylethers were mixed together to make a uniform dissolution, affording an emulsifiable concentrate containing 30% by weight of the active ingredient compound.

EXAMPLE 23 Oily formulation 50 Parts of Compound No. 85 and 50 parts of ethyl cellosolve were mixed together to make a uniform dissolution, affording an oily formulation containing 50% by weight of the active ingredient compound.

EXAMPLE 24 Sol (flowable powder) 40 Parts of finely divided Compound No. 106 having average particle size of not more than 10 microns, 2 parts of lauryl sulfate, 2 parts of sodium alkylnaphthalene sulfonate, 1 part of hydroxypropylcellulose and 55 parts of water were mixed together uniformly to give a sol containing 40% by weight of the active ingredient compound.

EXAMPLE 25 Dusting powder 0.5 Parts of Compound No. 212, 0.5 parts of finely divided silica, 0.5 parts of calcium stearate, 50 parts of clay and 48.5 parts of talc were mixed together and ground uniformly to give a dusting powder containing 1% of the active ingredient compound.

EXAMPLE 26 Granules 3 Parts of Compound No. 186, 1 part of calcium ligninsulfonate, 30 parts of bentonite and 66 parts of clay were mixed together and ground uniformly. The powdery mixture obtained was granulated with addition of water, followed by drying and screening. Granules containing 3% of the active ingredient compound were obtained.

EXAMPLE 27 This Example illustrates tests of controlling leaf rust in wheat for preventative treatment.

Wheat plants (variety: Norin No. 61) were grown in soil in 9 cm-diameter porous pots in a greenhouse. At the first true-leaf stage, the wheat seedlings were sprayed with the composition under test which was prepared by diluting the wettable powder of the Example 21 with water to a particular concentration of the active compound indicated in Table 2 below. The rate of application of the composition sprayed was 20 ml per three pots. One day after the treatment, the treated foliage was sprayed for inoculation with a suspension of uredo spores of wheat leaf rust fungi {Puccinis recondita) at such inoculum size that the number of the inoculated spores on leaf observed within the vision field of a microscope (x 150) amounted to approximately 50.The spore suspension used was prepared by suspending the uredo spores which were previously produced on another wheat leave, into a volume of sterilized water containing 50 ppm. of a dispersion agent "Tween 20" (a trade name of polyoxyethylene sorbitan monolaurate, a product of Kao Atlas Co., Japan). The spore-inoculated wheat plants were incubated overnight in a high-humidity room at 20 C and then transferred into a greenhouse at 20 C in which the environment was appropriate to allow the infection to take place. 10 Days after the inoculation, the infected wheat plants were removed out of the greenhouse and estimated for the degree of disease development. To this end, the number of uredosorus per leaf was assessed and the degree of control (%) was evaluated according to the under-mentioned equation.The degree of phyto toxicity of the test compound to wheat plant was assessed according to the under-mentioned grading.

The tests were conducted with three replicates for a particular value of the concentration of the test compound, and the average of the evaluated degree of control (%) was calculated. The test results (expressed as averaged Control (%)) are set out in Table 2 below.

Number of uredosorus in treated plot Control (%) = (1 ) x 100 Number of uredosorus in non-treated plot Grades for estimation of phyto-toxicity 5-Very much severe 4 - Severe 3-Strong 2 - Slight 1 - Very slight 0-None EXAMPLE 28 This Example illustrates tests of controlling powdery mildew in cucumber.

Cucumber plants (variety: Sagami-Hanjiro) were grown in soil in 9 cm-diameter porous pots in a greenhouse. At the first true-leaf stage, the cucumber seedlings were sprayed with 10 ml per pot of the composition under test which was prepared by diluting the wettable powder of the Example 21 with water to a particular concentration of the active compound indicated in Table 2 below. The treated cucumber plants were allowed to stand overnight and then sprayed for inoculation with a suspension of spores of cucumber powdery mildew fungi (Sphaerotheca fuliginea). 10 Days after the inoculation, the rate (%) of the area of the symptom on the infected leave was assessed, and the degree of control (%) was evaluated according to the under-mentioned equation. The degree of phyto-toxicity of the test compound to cucumber plant was estimated by the same grading as in Example 27. The tests were conducted with three replicates. The test results (expressed as averaged % Control) are given in Table 2.

Rate of area of sympton in treated plot Control (%) = (1 ) x 100 Rate of area of sympton in non-treated plot TABLE 2 Control (%) Concentration of active ingredient compound sprayed (ppm) Compound Leafrust Powdery mildew Phytotoxiclty No. on wheat on cucumber 50 50 Wheat Cucumber 1 95 97 0 0 2 92 95 3 97 98 4 100 100 ,, 5 99 100 ,, 6 94 94 ,, 7 100 100 ,, 8 100 100 ,, 9 93 100 ,, 10 95 96 ,, TABLE 2 continued Control (%) Concentration of active ingredient compound sprayed (ppm) Compound Leaf rust Powdery mildew Phytotoxicity No. on wheat on cucumber 50 50 Wheat Cucumber 11 100 100 o O 12 90 95 13 89 90 14 98 99 15 100 100 16 100 100 17 100 100 18 90 100 19 98 100 20 95 97 21 95 90 22 92 90 23 93 95 24 90 92 25 98 98 26 100 100 27 100 100 28 100 100 29 100 100 30 95 96 31 98 100 ,, 32 100 100 33 100 100 ,, 34 99 99 ,, 35 100 100 ,, 36 100 98 ', 37 97 96 " " TABLE 2 continued Control (%) Concentration of active ingredient compound sprayed (ppm) Compound Leaf rust Powdery mildew Phytotoxicity No. on wheat on cucumber 50 50 Wheat Cucumber 38 95 94 0 0 39 90 91 40 99 100 41 98 100 42 87 85 43 100 90 44 97 96 45 92 93 46 94 92 47 92 93 48 91 92 49 94 95 50 100 100 51 100 99 52 100 100 53 95 96 54 92 94 55 93 91 56 85 90 57 98 96 58 100 100 ,, 59 100 100 ,, 60 100 100 ,, 61 98 96 " " 62 100 99 ,, 63 93 94 ,, 64 91 93 ,, TABLE 2 continued Control (%) Concentration of active ingredient compound sprayed (ppm) Compound Leaf rust Powdery mildew Phytotoxicity No. on wheat on cucumber 50 50 Wheat Cucumber 65 93 90 0 0 66 98 99 67 100 100 68 97 100 69 100 100 70 100 100 71 100 100 72 92 93 73 100 100 74 99 100 75 98 99 76 88 83 77 90 87 78 96 98 79 87 91 80 84 86 81 100 100 82 100 100 83 100 100 84 100 100 85 100 100 86 100 100 " " 87 87 92 88 85 90 89 90 100 90 89 96 91 100 100 TABLE 2 continued Control (%) Concentration of active ingredient compound sprayed (ppm) Compound Leaf rust Powdery mildew Pihytotoxicity No. on wheat on cucumber 50 50 Wheat Cucumber 92 100 100 93 100 100 94 100 100 95 100 100 96 100 100 97 100 100 98 100 100 99 100 100 100 100 100 101 100 100 102 100 100 103 100 100 104 100 100 105 100 100 106 100 100 107 100 100 108 100 100 109 100 100 110 100 100 111 100 100 112 100 100 " " 113 100 100 ,, 114 100 100 ,, 115 100 100 " " ,, 116 100 100 ', 117 100 100 ,, 118 100 100 ,, TABLE 2 continued Control (%) Concentration of active ingredient compound sprayed (ppm) Compound Leaf rust Powdery mildew Phytotoxicity No. on wheat on cucumber 50 50 Wheat Cucumber 119 100 100 0 0 120 100 100 121 100 100 122 100 100 123 100 100 124 80 84 125 81 80 126 98 96 127 100 98 128 93 100 129 90 99 130 100 100 131 100 100 132 100 100 133 100 100 134 100 100 135 100 100 136 96 100 137 94 96 138 100 100 139 95 92 140 92 88 141 91 93 142 100 100 ', 143 90 98 144 98 100 TABLE 2 continued Control (%) Concentration of active ingredient compound sprayed (ppm) Compound Leaf rust Powdery mildew Phytotoxicity No.

on wheat on cucumber 50 50 Wheat Cucumber 145 100 100 0 0 146 100 100 147 100 100 148 97 92 149 93 90 150 100 100 151 99 100 152 100 100 153 94 100 154 91 96 155 90 87 156 100 100 157 89 91 158 92 88 159 100 100 160 100 100 161 100 100 162 98 97 163 99 100 164 87 96 165 86 96 166 100 100 167 100 100 168 94 100 169 92 93 170 90 88 TABLE 2 continued Control (%) Concentration of active ingredient compound Compound Leafrust Powdery mildew Phytotoxicity No. on wheat on cucumber 50 50 Wheat Cucumber 171 80 85 0 0 172 86 87 173 98 100 174 98 100 175 92 96 176 83 88 177 90 91 178 89 90 179 92 92 180 99 100 181 100 100 182 100 100 183 100 100 184 99 100 185 100 100 186 100 100 187 100 100 188 100 100 189 100 100 190 100 100 191 99 100 192 89 95 193 100 100 ,' 194 93 95 195 100 100 196 82 86 " " TABLE 2 continued Control (%) Concentration of active ingredient compound sprayed (ppm) Compound Leaf rust Powdery mildew Phytotoxicity No.Leaf wheat on cucumber 50 50 Wheat Cucumber 197 90 92 0 0 198 87 85 199 85 82 200 100 100 201 100 100 202 100 100 203 100 100 204 100 100 205 81 80 206 90 86 207 88 89 208 89 94 209 80 83 210 92 96 211 100 100 212 100 100 213 100 100 214 100 100 215 98 100 216 82 86 217 80 82 218 93 95 219 90 90 220 92 86 221 90 92 222 87 85 TABLE 2 continued Control (%) Concentration of active ingredient compound sprayed (ppm) Compound Leaf rust Powdery mildew Phytotoxicity No. on wheat on cucumber 50 50 Wheat Cucumber 223 85 82 0 0 224 82 86 225 84 88 226 82 89 227 81 84 228 83 86 229 88 92 230 100 96 231 100 100 232 100 100 233 100 100 234 100 100 235 100 100 236 100 92 237 100 100 238 100 100 ,' 239 100 98 ,, 240 100 96 ,, 241 100 100 ,, 242 98 94 ,, 243 100 99 ,, 244 100 100 ,, TABLE 2 continued ,Control % Concentraion of active ingredient compound sprayed (ppm) Compound Leaf rust Powdery mildew Phytotoxicity No. on wheat on cucumber ~~~~~~~~~~~~~~~~~~~~~~~~~~ 50 50 Wheat Cucumber Comparative compound A 75 73 0 O Comparative compound B 78 78 Comparative compound C 85 Comparative compound D 86 No treatment 0 0 - Notes: Comparative compound A:

(a compound described in Japanese patent application unexamined prepublication "Kokai" Sho 52-27767) Comparative compound B:

(a compound described in Japanese patent application unexamined prepublication "Kokai" Sho 52-27767) Comparative compound C: Ethylene-bis dithiocarbamic acid) manganese salt (known under the tradename "Manneb") Comparative compound D: Dithiocarbonic acid S,S-6-methylquinoxaline-2,3-di-yl ester (known under the tradename "Quinomethionate") EXAMPLE 29 This Example illustrates tests of controlling leaf rust in wheat in preventative treatment when the test compound is applied at low concentrations.

The effects of the test compounds against leaf rust disease in wheat were estimated in the same manner as in Example 27, while the test compounds were applied at low concentrations as indicated in Table 3 below. The tests were conducted with three replicates. The test results (expressed as averaged % Control) are given in Table 3.

TABLE 3 Control (%) Concentration of active ingredient compound sprayed (ppm) Compound No. 25 12.5 6.25 7 100 92 84 16 100 98 86 28 100 92 81 52 100 98 86 70 100 96 92 71 100 99 91 85 100 98 92 86 100 92 86 95 100 100 98 99 100 100 94 102 100 100 98 103 100 100 97 106 100 100 94 108 100 100 96 115 100 100 99 118 100 100 96 120 100 100 95 121 100 100 96 131 100 100 92 134 100 100 95 138 100 98 89 152 100 98 91 159 98 92 80 181 100 98 90 182 98 99 92 186 100 100 98 187 100 100 95 189 100 100 97 TABLE 3 continued Control (%) Concentration of active ingredient compound sprayed (ppm) Compound No. 25 12.5 6.25 190 100 100 95 193 100 100 92 195 99 94 86 200 100 92 86 203 100 100 99 212 100 100 97 213 100 100 92 214 100 100 91 231 100 100 100 232 100 100 100 233 100 100 100 235 100 100 100 236 100 100 100 238 100 100 100 240 100 99 96 241 100 100 98 243 100 99 97 244 100 100 99 Comparative compound A 51 32 5 Comparative compound B 62 38 10 Comparative compound C 72 55 20 EXAMPLE 30 This Example illustrates tests of controlling leaf rust in wheat in curative treatment.

The procedures of Example 27 for controlling the wheat leaf rust disease were used but except that the spraying of the composition under test was made one day after the inoculation of the wheat leaf rust fungi on the wheat leave. The test results obtained are set out in Table 4 below.

TABLE 4 concentration of test compound Phyto Compound No. sprayed (ppm) Contro (%) toxicity 7 50 92 0 11 " 99 " 16 " 100 " 28 " 100 " 32 " 98 " 35 " 96 " 43 " 96 " 52 " 100 " 58 " 93 " 70 " 100 " 71 " 100 " 73 " 100 " 75 " 96 " 83 " 100 " 85 " 100 " 86 " 100 " 91 " 91 " 94 " 100 " 95 " 100 " 96 " 100 " 99 " 100 " 102 " 100 " 103 " 100 " 106 " 100 " 108 " 100 " 115 " 100 " 118 " 100 " 120 " 100 " 121 " 100 " 130 " 100 " TABLE 4 (Continued) Concentration of test compound Phyto Compound No. sprayed (ppm) Control (%) toxicity 131 50 100 0 134 ,, 100 138 ,, 100 152 " 100 159 ,, 100 166 " 93 167 " 97 181 ,, 100 182 ,, 100 186 " 100 187 ,, 100 189 ,, 100 190 " 100 193 ,, 100 195 ,, 100 200 ,, 100 203 ,, 100 212 " 100 213 ,, 100 214 " 100 Comparative compound A 50 40 0 Comparative compound B " 47 Comparative compound C ,, 40 No treatment 0 EXAMPLE 31 This Example illustrates tests of controlling powdery mildew in cucumber when the test compound was applied at low concentrations.

The effects of the test compounds for controlling the cucumber powdery mildew disease were estimated in the same manner as in Example 28, while the test compounds were applied at low concentrations as indicated in Table 5 below. The test results obtained (expressed as averaged % Control) are tabulated in Table 5 below.

TABLE 5 Control (%) Concentration of test compound sprayed (ppm) Compound No. 20 5 1.25 16 100 86 53 71 100 96 71 85 100 98 70 99 100 100 66 102 100 100 72 103 100 100 65 106 100 100 68 108 100 100 63 115 100 100 83 118 100 100 76 120 100 100 62 131 100 100 82 138 100 100 70 146 100 98 50 161 100 99 54 167 100 84 60 181 100 97 51 182 100 100 56 184 100 98 59 186 100 99 96 187 100 92 88 189 100 100 92 190 100 99 90 193 100 98 86 195 100 86 58 200 100 98 58 201 100 92 50 212 100 96 72 TABLE 5 continued Control (%) Concentration of test compound sprayed (ppm) Compound No. 20 5 1.25 214 100 90 66 232 ' 100 93 65 233 100 96 75 234 100 93 55 238 100 100 98 241 100 87 68 244 100 100 73 Comparative compound A 51 23 0 Comparative compound B 56 31 5 Comparative compound D 61 25 0 EXAMPLE 32 This Example illustrates tests of controlling brown spot in rice.

Rice plants (variety: Asahi) were grown in soil in 9 cm-diameter porous pots in a greenhouse. At the four true-leaf stage, the rice plants were sprayed with the composition under test which was prepared by diluting the wettable powder of Example 21 with water to a concentration of the active compound as indicated in Table 6 below. One day after the treatment, the treated rice plants were sprayed for inoculation with a suspension of conidiospores of rice brown spot fungi lCochliobolus miyabeanus). 5 Days after inoculation, the number of the lesions on the fourth leaf developed by infection was counted. The degree of control (%) was then evaluated according to the under-mentioned equation. Degree of phyto-toxicity of the test compound was also estimated by the same grading as in Example 27.The test results are set out in Table 6 below.

Number of lesions developed by infection in a treated leaf Control (%) = (1- ) x 100 Number of lesions developed by infection in a non-treated leaf TABLE 6 Concentration of test com pound sprayed Phyto Compound No. (ppm) Control (%) toxicity 5 100 96 0 7 " 100 9 " 95 11 " 93 15 " 91 16 " 100 " 17 " 98 " 26 " 100 " 27 " 100 " 35 " 96 " 40 " 100 " 52 " 98 " 58 " 88 " 71 " 99 " 73 " 98 " 81 " 93 " 83 " 100 " 85 " 98 " 86 " 96 " 87 " 94 " 93 " 100 " 94 " 100 " 95 " 100 " 96 " 94 " 99 " 100 " 100 " 100 " 102 " 100 " 103 " 98 " 115 " 96 " 128 " 100 " TABLE 6 continued Concentration of test com pound sprayed Phyto Compound No. (ppm) Control (%) toxicity 130 100 100 0 131 " 98 138 " 96 145 " 89 152 ,, 100 159 " 100 161 " 98 167 " 90 181 " 98 182 ,, 100 184 ,, 100 191 " 97 195 " 90 200 " 93 211 " 93 212 ,, 90 216 ,, 90 230 " 100 239 " 98 240 ,, 100 243 " 95 Comparative compound A 100 45 Comparative compound B " 36 Comparative compound E ,, 84 No treatment 0 Note: Comparative compound E: 2.4-Dichloro-6-(D-chloranllino)-1,3,5-triazlne (Triazine).

TABLE 7 continued Fungi and conditions of growth the fungal growth

Compound No. A B C D E F G H I J K 186 10 - I I - + - - - I 200 ,, - - - 1 - - 203 ,, 1 I - ++ - - - I I 212 ,, - - I I + - - - I 230 " - - - - + - - - 234 ,, - - I - + - - - I 235 " - - - - + - - - - I 236 ,, - - I - + - - - - 239 ,, - - I - + - - - - 240 " - - L - ++ - - I - 241 " - - - - + - - - - 242 SE - - I - ++ - - - - 243 " - - - - 1 - - - - No addition 0 +++ +++ +++ +++ +++ +++ +++ +++ +++ +++ Note: A-Concentration of test compound (ppm).

B - Cladosporium fulvum in tomato.

C - Gibberella fujikuroi in rice.

D -Glomerella cingulata in vine.

EAlternaria kikuchiana in pear.

F -- Valsa mali in apple.

G -- Piricularia oryzae in rice.

H - Cochliobolus miyabeanus in rice.

- - Cercospora beticola in beet.

J-Colletotrichum Tagenarium in cucumber.

K-Fusarium oxysporum in cucumber.

Claims

1. An imidazole derivative of the general formula

wherein R, is naphthyl group, an arylalkyl group, a cycloalkyl group, a cycloalkylalkyl group, an alkyl group, a lower alkenyl group, a lower alkoxy-lower alkyl group, a phenylthio-lower alkyl group or phenyl group; the phenyl group being unsubstituted or substituted with 1 to 5 substituents which is or are the same or different from each other and selected from a halogen atom, nitro group, cyano group, a lower alkyl group, a lower alkenyl group, a halogenated lower alkyl group, a lower alkoxyl group, a lower alkenyloxy group, a lower alkylthio group, a lower alkylsulfinyl group, a lower alkylsulfonyl group, a lower alkylcarbonyl group, phenyl group, phenoxy group, a halogen-substituted phenoxy group, EXAMPLE 33 This Example sets out the tests of estimating the activities of the test compounds against various kinds of phyto-pathogenic fungi.

A compound of this invention was dissolved in acetone, and 1 ml of the resultant solution was admixed with 20 ml of an incubation agar medium at 600C (for incubation of fungi: PSA-medium, pH 5.8) in a Petri dish of 9 cm diameter to prepare an agar plate containing the test compound at a predetermined concentration as indicated in Table 7 below. The Petri dish, without the upper cover, was allowed to stand overnight to evaporate acetone off, and the agar plate so prepared was inoculated with a loopful amount of a suspension of spores of the test microorganism which were previously incubated on agar slant medium. After incubation for 48 hours at 240C, the conditions of the growth of the test microorganisms were assessed by the following grading. The results are listed in Table 7 below.

Grades of growth of the fungi -: No growth at all.

I: Formation of a few colonies was observed in the inoculated region of the agar plate where the spore suspension had been applied, and the growth was greatly suppressed.

+: Formation of many colonies was observed in the inoculated region of the agar plate where the spore suspension had been applied, but the growth was so suppressed not to cover the whole surface of said region.

++: Growth covered the whole surface of the inoculated region of the agar plate where the spore suspension had been applied, but the growth was still poor.

+++: Growth covered the whole surface of the inoculated region of the agar plate where the spore suspension had been applied, and the growth was good.

TABLE 7 Fungi and conditions of growth of the fungal growth

Compound No. A B C D E F G H 1 J K 16 10 - 28 " - - I I + - - - I 32 " - - 1 + + - I - I 43 " - - 1 - + - - - - 85 " - - - - + - - - - 86 " - - - - I - - - - 95 , I - - - + - - - I 99 " - - - - 1 - - - - 102 ,, - - - - + - - - - 106 ,, - I - ~ I - I - ~ I 115 ,, - - - - + - ~ ~ ~ ~ 118 ,, - - - - I 1 - - - 120 ,, - - I - I - - - - 131 ,, - - - - + - I - - 134 ,, - - - - I - - - - 161 " - I I - ++ - - - I I 167 ,, " I 1 ~ ~ + 182 ,, - 1 I - + - - - I I phenylthio group, a lower alkyl-substituted phenylthio group and a nitro-substituted phenylthio group;; R2 is a saturated alkyl group, an unsaturated alkyl group, a lower alkoxy-lower alkyl group, a lower alkylthio-lower alkyl group, a phenoxy-lower alkyl group, a phenylthio-lower alkyl group, a mono- or dilower alkylamino-lower alkyl group, a lower alkyl group substituted with a group N(CH2)n where n is an integer of 2 to 6, a lower alkylcarbonyl group, phenylcarbonyl group, a cycloalkyl group, a cycloalkylaikyl group, a halogenated lower alkyl group, a cyano-lower alkyl group, a lower alkoxycarbonyl-lower alkyl group, a lower alkylthiocarbonyl-lower alkyl group, an arylalkyl group, a lower alkylcarbonyl-lower alkyl group, a phenylcarbonyl-lower alkyl group, naphthyl group, furfuryl group or phenyl group; the latter phenyl group being unsubstituted or substituted with a substituent which is selected from a halogen atom, nitro group, cyano group and a lower alkyl group; X is an oxygen atom or a sulfur atom; and Y is a straight or branched saturated alkylene group or unsaturated alkylene group, the saturated alkylene. group being unsubstituted or substhuted with a halogen grou. a lower alkoxyl group, cyano group, phenyl grou, a halogen-substituted phenyl group, a nltro-substituted phenyl group, a lower alkyl-substituted phenyl group and/or trifluoromethyl-substituted phenyl group, and a salt of said imidazole derivative.

2. An imidazole derivative as claimed in Claim 1 which is of the formula

wherein R3 is naphthyl group, a phenyl-(C,C4)alkyl group, a dichlorophenyl-(C1-C4)alkyl group, a (C5-C6)cycloalkyl group, a (C5-C6)cycloalkyl-(C1-C4)alkyl group, a (C1-C10)alkyl group, a (C2-C4)alkenyl group, a (C1-C4)alkoxy-(C1-C4)alkyl group, a phenylthio-(C1-C4)alkyl group, phenyl group, a chlorophenyl group, a fluorophenyl group, a bromophenyl group, a nitrophenyl group, a cyanophenyl group, a trifluoromethylphenyl group, a dichlorophenyl group, a dibromophenyl group, a difluorophenyl group, a bromochlorophenyl group, a chlorofluorophenyl group, a trifluoromethylchlorophenyl group, a trichlorophenyl group, a dichloro-dimethylphenyl group, a trichlorodimethylphenyl group, a chloro-methoxyphenyl group, a chloro-methylphenyl group, a (C1-C4)alkylphenyl group, a di-(C1-C4)alkylphenyl group, a (C2-04)alkenylphenyl group, a (C2-C4)alkenyloxyphenyl group, a (C1-C4)alkoxyphenyl group, a di-(C1-C4)alkoxyphenyl group, a (C1-C4)alkylthiophenyl group, a (C1-C4)alkylsulfinylphenyl group, a (C,-C,)alkylsulfonylphenyl group, a (C,-C,)alkylcarbonylphenyl group, diphenyl group, a phenoxyphenyl group, a chlorophenoxyphenyl group, a phenylthiophenyl group, a (C,-C,)alkylphenylthiophenyl group or a nitrophenylthiophenyl group, R4 is a (C1-C10)alkyl group, a (C2-C4)alkenyl group, a (C2-C4)alkynyl group, a (C1-C4)alkoxy- (C1-C4)alkyl group, a (C5-C6)cycloalkyl-(C1-C4)alkyl group, a (C1-C4)-alkylthio-(C1-C4)alkyl group, a phenyl-(C1-C4)alkyl group, a phenoxy-(C1-C4)alkyl group, a dichlorophenoxy-(C1-C4)alkyl group, a phenylthio-(C1-C4)alkyl group, a (C1-C4)alkylamino-(C1-C4)alkyl group, a di-(C1-C4)alkylamino- (C1-C4) alkyl group, apyrrolyl-(C1-C4]alkyl group, a chloro-[C1-C4]alkyl group, a cyano-(C1-C4)alkyl group, a (C1-C4)alkoxycarbonyl-(C1-C4)alkyl group, a (C1-C4)alkylthlocarbonyl-(C1-C4) alkyl group, a (C1-C4)alkylcarbonyl-(C1-C4)alkyl group, a phenylcarbonyl-(C1-C4)alkyl group, a (C5-C8)cycloalkyl group, benzyl group, a chlorobenzyl group, a dichlorobenzyl group, a fluorobenzyl group, a methylbenzyl group, a dimethylbenzyl group, a methylbenzylethyl group, naphthyl group, furfuryl group, phenyl group, a chlorophenyl group, a dichlorophenyl group, a cyanophenyl group, a nitrophenyl group, a (C1-C4)alkylphenyl group, a (C1-C4)alkylcarbonyl group, or benzoyl group, X is an oxygen atom or a sulfur atom;; Y' is a (C1-C4)alkylene group or a (C2-C4)alkenylene group; and Z is a hydrogen atom, a (C1-C6)alkyl group, a (C1-C4)alkoxy-(C1-C4)alkyl group, a cyano (C1-C4)alkyl group, a (C2-C4)alkenyl group, phenyl group, a chlorophenyl group, a dichlorophenyl group, a methylphenyl group, a trifluoromethylphenyl group, a nitrophenyl group, benzyl group, a chlorobenzyl group or a dichlorobenzyl group; or a salt of said imidazole derivative.

3. An imidazole derivative as claimed in Claim 1 which is of the formula

wherein R@ is phenyl group, a chlorophenyl group, a bromophenyl group, a nitrophenyl group, a trifluoromethylphenyl group, a dichlorophenyl group, a bromochlorophenyl group, a chlorofluorophenyl group, a trifluoromethylchlorophenyl group, a trichlorophenyl group, a dichlorodimethylphenyl group, a trichloro-dimethylphenyl group, a chloro-methoxyphenyl group, a chloro-methylphenyl group, a (C1-C4)alkylphenyl group, a di-(C1-C4)alkylphenyl group, a (C2-C4)alkenyloxyphenyl group, a (C1-C4)alkoxyphenyl group, a di-(C1-C4)alkoxyphenyl group, a methylsulfonylphenyl group, an acetylphenyl group, a phenoxyphenyl group, or a nitrophenylthiophenyl group; R6 is a (C1-C10)alkyl group, a (C2-04)alkenyl group, a (C1-C4)alkoxy-(C1-C4)alkyl group, a methylthio-[C1-C4)alkyl group, a dichlorophenoxy-(C1-C4)alkyl group, a phenylthio-(C1-C4)alkyl group, cyclohexyl group, an ethoxycarbonyl-(C1-C4)alkyl group, benzyl group, a chlorobenzyl group, a dichlorobenzyl group, naphthyl group, furfuryl group, phenyl group, a chlorophenyl group, a dichlorophenyl group, a cyanophenyl group, a nitrophenyl group, or a (C1-C4)alkylphenyl group, Y" is a linear (C2-C4)alkylene group, Z' is a hydrogen atom,a (C1-C8)alkyl group, a(C2-C4)alkenyl group, phenyl group, a chlorophenyl group, a dichlorophenyl group, a methylphenyl group, a nitrophenyl group, or benzyl group, and a salt of said imidazole derivative.

4. An imidazole derivative as claimed in Claim 1 which is of the formula

wherein R7 is a phenyl group, a chlorophenyl group, a fluorophenyl group, a bromophenyl group, or a nitrophenyl group, a cyanophenyl group, 9 trifluoromethylphenyl group, a dichlorophenyl group; a dibromophenyl group, a bromochlorophenyl group, a chlorofluorophenyl group, a trifluoromethylchlorophenyl group, a trichlorophenyl group, a dichloro-dimethylphenyl group, a trichlorodimethylphenyl group, a chloro-methoxyphenyl group, a chloro-methylphenyl group, a (C1-C4)alkylphenyl group, a dl-(C1-C4)alkylphenyl group, a (C2-C4)alkenylphenyl group, a (C1-C4)alkoxyphenyl group, a di-(C1-C4)alkoxyphenyl group, a methylthiophenyl group, a methylsulfinylphenyl group, a methylsulfonylphenyl group, an acetylphenyl group, diphenyl group, a phenoxyphenyl group, a chlorophenoxyphenyl group, a phenylthiophenyl group or a methylphenyithiophenyl group;; R8 is a (C1-C10)alkyl group, a (C2-C4)alkenyl group, a (C2-C4)alkynyl group, a (C1-C4)alkoxy- (C1-C4)alkyl group, a methylthlo-(C1-C4)alkyl group, a phenoxy-(C1-C4)alkyl group, a phenylthio (C1-C4)alkyl group, a (C1-C4)alkylamino-(C1C4)alkyl group, a pyrrolyl-(C1-C4)alkyl group, a (C1-C4)alkylcarbonyl group, a (C5-C4)cycloalkyl group, a chloro-(C1-C4)alkyl group, a cyano (C1-C4)alkyl group, a (C1-C4)alkylthiocarbonyl-(C1-C4)alkyl group, benzyl group, a chlorobenzyl group, a fluorobenzyl group, a dichlorobenzyl group, a methylbenzyl group, a methylbenzylethyl group, an acetyl-(C1-C4)alkyl group, benzoyl group, a phenylcarbonyl-(C,-C,)alkyl group or phenyl group; Y"' is a linear (C1-C4)alkylene group or a linear (C2-C4)alkenylene group; and Z" is a hydrogen atom, a (C1-C8)alkyl group, a (C1-C4)alkoxy-(C1-C4)alkyl group, a cyano (C1-C4)alkyl, a (C2-C4)alkenyl, phenyl group, a chlorophenyl group, a dichlorophenyl group, a methylphenyl group, benzyl group, a chlorobenzyl group or a dichlorobenzyl group; and a salt of the said imidazole derivative.

5. An imidazole derivative as claimed in Claim 1 which is of the formula

wherein R8 is a (C1-C4)alkyl group, a phenyl-(C1-C4)alkyi group or a chlorn-(C1-C4)alkyl group; and Y"" is a linear or branched (C1-C4)alkylene group, or a salt of the said imidazole derivative.

6. An imidazole derivative as claimed in Claim 1 which is of the formula

wherein R10 i is a (C5-C6)cycloalkyl group or a (C1-C4)alkyl group which is unsubstituted or substituted with phenyl group, a dichlorophenyl group, a (C2-C4)alkenyl group, a (C1-C4)alkoxy group or phenylthio group; R1l is a (C1-C4)alkyl group which is unsubstituted or substituted with phenyl group, a di (C1-C4)alkylamino group, furanyl group or a (C5-C6)cycloalkyl @ group; Y""' is a (C1-C4)alkylene group; and Z"' is a hydrogen atom, a (C1-C6)alkyl group, a chlorobenzyl group or a trifluoromethylphenyl group; and a salt of said imidazole derivative.

7. An imidazole derivative as claimed in Claim 1, which is the compound of the formula

(Compound No. 94), (Compound No. 102), (Compound No. 115), (Compound No. 134), (Compound No. 186), (Compound No. 238), (Compound No. 241).

8. An imidazole derivative substantially as described herein with reference to Examples 1-20.

9. A method of making an imidazole derivative substantially as described herein with reference to Examples 1-20.

10. A fungicidal composition comprising as the active ingredient a fungicidally effective amount of an imidazole derivative as defined in Claim 1, or a salt thereof, in association with an acceptable carrier for the active ingredient.

11. A method of combating the fungal pests of plants, which comprises treating plants, seeds or trees with a fungicidally effective amount of an imidazole derivative as defined in Claim 1 or a salt thereof.

1 2. A fungicidal composition substantially as described herein with reference to Examples 21-26.