GB1601423A

GB1601423A - Optionally substituted 1- or 4-aralkyl-1,2,4-triazoles and their use as fungicides

Info

Publication number: GB1601423A
Application number: GB19466/78A
Authority: GB
Original assignee: Rohm and Haas Co
Current assignee: Rohm and Haas Co
Priority date: 1977-05-19
Filing date: 1978-05-15
Publication date: 1981-10-28
Also published as: CA1117537A; JPS5416474A; NL971010I1; DE2821971C2; NL971010I2; FR2391200B1; JPH0152390B2; NL189408B; NL189408C; DE2821971A1; NL7804341A; CH633281A5; FR2391200A1

Abstract

The 1,2,4-triazoles in question are represented by the following general formula: <IMAGE> where Z is an aryl radical; R<1> is a cyano and R<2> hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl or aralkyl radical; m is zero or one; n is one or two; and Q is a 1- or 4-(1,2,4-triazole) radical. The substances in question are broad-spectrum systemic fungicidal agents which can be used on many plant species.

Description

(54) OPTIONALLY SUBSTITUTED 1- OR 4-ARALKYL-l ,2,4-TRIAZOLES AND THEIR USE AS FUNGICIDES (71) We, ROHM AND HAAS COMPANY, a corporation organised and existing under the laws of the State of Delaware, United States of America, of Independence Mall West, Philadelphia, Pennsylvania 19105, United States of America, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention concerns novel substituted 1 2,4-triazoles and acid addition salts and metal salt complexes thereof, as well as their method of preparation and their use as broad-spectrum systemic fungicides. This invention provides new compounds of the formula:

wherein: Z is (C6-C10)aryl which is optionally substituted; R (when not joined to R) is cyano or any of the groups (2)-(8) as defined below for R; R (when not joined to R) is (1) hydrogen, (2) (C1-C12)alkyl, (3) (C3 C8)cycloalkyl, (4) (C2-C8)alkenyl, (5) (C5-C8)cycloalkenyl, (6) (C2-C8)alkynyl, (7) (C6-C10)aryl which is optionally substituted, (8) (C7-C14) aralkyl which is optionally substituted in the aryl portion or, in the case where R is cyano, (9) (C1 C4)alkoxy, (10) (C2-C4)alkenoxy, (11) (C2-C4)alkynoxy, (12) hydroxy, (13) (C6 C10)aryloxy which is optionally substituted or (14) (C7-C14)aralkyloxy which is optionally substituted in the aryl portion; R1 and R2 can be joined together in which case they collectively form, together with the carbon atom to which they are attached, a (C3-C8)cycloalkylene group; mis0or 1; n is 1 or 2; and Q is optionally substituted 1 - (1,2,4 - triazolyl) or 4 - (1,2,4 - triazolyl); The invention also provides agronomically acceptable acid addition salts and agronomically acceptable metal salt complexes of a compound of Formula I.

When any of Z, R' and R2 is optionally substituted aryl, such group is typified by phenyl or naphthyl which is optionally substituted with up to three of the same or different substituents, preferably up to two substituents, each selected from the group consisting of halogen, nitro, trihalomethyl, cyano, (C7C14)aralkyl. (C1- C4)aikyl, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfinyl, (C1- C4)alkylsulfonyl and (particularly in the case where R1 is other than cyano) phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, and phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl substituted with up to two of the same or different substituents each selected from halogen, nitro, trifluoromethyl, cyano, methyl, methoxy, methylthio, methylsulfinyl and methylsulfonyl.

Typical substituted aryl groups are 4 - chlorophenyl. 2,4 - dibromophenyl, 3,5 - difluorophenyl, 2,4,6 - trichlorophenyl, 2,3,5 - tribromophenyl 3,4 dichlorophenyl, 2 - chloro - 4 - iodophenyl, 3 - chloro - 4 - nitrophenyl, 2,4 dinitrophenyl, 4 - phenoxyphenyl, 2 - phenylthiophenyl, 3 - phenylsulfinylphenyl, 4 - phenylsulfonylphenyl, 4 - chlorophenyoxyphenyl, 2,4 dibromophenoxyphenyl, 3,5 - difluorophenylthiophenyl, 4- chloro - 2 methylphenylsulfinylphenyl, 3,4 - diiodophenylthiophenyl, 4 - trifluoromethyl 2 - chlorophenyl - sulfonylphenyl, 2 - cyano - 4 - methoxyphenylsulfinylphenyl, 4- methylthiophenoxyphenyl, 2- methylsulfinylphenylsulfinylphenyl, 4 methylsulfonyl - 3 - chlorophenoxyphenyl, 3,5,6 - trimethylphenyl, 2 - nitro - 4 methoxyphenyl, 2 - chloronaphthyl, 2 nitronaphthyl, 2,4 - dimethoxyphenyl, 4 trifluoromethylphenyl, 2- nitro - 4 - trifluoromethylphenyl, 3,5 dimethylthiophenyl, 2 - cyano - 5 - methylphenyl, 2,4 - dimethylsulfinylphenyl, 2,4 - dimethylsulfonylphenyl, 2,4 - diiodonaphthyl, 2 - iodo - 4 - benzylphenyl and (particularly in the case where R1 is cyano) 3,4,5 - trimethylphenyl and 2 iodo - 4 - methylphenyl. When either of R1 and R2 is substituted aralkyl, such group is typified by 2,4 - dichlorobenzyl, 2,4 - dibromobenzyl, 2,5 - dinitrobenzyl, 2,4,6 - trichlorobenzyl, 3,5 - dimethoxyphenethyl, 2,5 - dimethylthiophenylpropyl, 2,4 diiodophenyl- 2- methyl- propyl, 3,4 - dimethylsulfinylbenzyl, 2,3 dimethylsulfonylphenylethyl, 2,4,5 - trimethylphenylbutyl. 2,4 dicyanonaphthylmethyl, 2 - nitronaphthylpropyl, 2 - 4 - dibromonaphthylbutyl and (particularly when R' is other than cyano) 1 - nitronaphthylethyl and (particularly when R1 is cyano) 2 - nitronaphthylethyl.

The term "alkyl" as used herein encompasses both branched and straight chained alkyl groups. Typical alkyl groups are methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, neopentyl, iso-pentyl, n-hexyl, nheptyl, isooctyl, n-nonyl, n-decyl, iso-decyl, n-undecyl and n-dodecyl.

When Q is substituted 1 - (1,2,4 - triazolyl) or 4 - (1,2,4 - triazolyl), these two groups may contain up to two of the same or different substituents each selected from halogen, (C1-C4)alkyl, nitro and cyano.

The acids which can be utilized in making the acid addition salts of the present invention include hydrochloric, hydrobromic, nitric, sulfuric, phosphoric, hydroiodic, hydrofluoric, perchloric, p-toluenesulfonic, methanesulfonic, acetic, citric, tartaric, malic, maleic, oxalic, fumaric and phthalic.

The metal salt complexes of the invention are typified by those of the formula

wherein Z, R', R2, Q, m and n are as defined in Formula (I) above, M is a cation selected from Groups IIA, IB, IIB, VIB, VIIB, and VIII of the Periodic Table and X is an anion counterion selected in such a manner that the sum of the valence charges of the cation M and anion equal zero. The Periodic Table referred to herein is that given at the beginning of the Merck Index, 9th Edition, 1976. Typical cations are magnesium, manganese, copper, nickel, zinc, iron, cobalt, calcium, tin, cadmium, mercury, chromium, lead and barium. Typical anions are chloride, bromide, iodide, fluoride, sulfate, bisulfate, perchlorate, nitrate, nitrite, phosphate, carbonate, bicarbonate, acetate, citrate, oxalate, tartrate, malate, maleate, fumarate, p-toluenesulfonate, methanesulfonate, (mono) or (di) (C1- C4)alkyl-dithiocarbamate and (C1C4)alkylenebisdithiocarbamate.

One sub-class of compounds, wherein R1 is other than cyano, which may be singled out for mention are the compounds, salts, and complexes of Formulae (l) and (II) wherein Z is phenyl or naphthyl group preferably a phenyl group optionally substituted with up to three of the same or different substituents, preferably with up to two substituents, each selected from the group consisting of halogen, nitro, trihalomethyl, cyano, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1 C4)alkylsulfinyl, (C1-C4)alkylsulfonyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, and phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl substituted with up to two of the same or different substituents each selected from the group consisting of halogen, nitro, trifluoromethyl, cyano methyl, methoxy, methylthio, methylsulfinyl and methylsulfonyl; R1 is hydrogen; R2 is selected from the group consisting of (C1-C12)alkyl, (C5-C7)cyclo- alkyl, (C2-C4)alkenyl, (C5-C6)cycloalkenyl, (C2-C4)alkynyl, unsubstituted phenyl, benzyl or phenethyl or phenyl, benzyl or phenethyl, the aromatic portion of which is substituted with up to two halogen atoms; or R1 and R2 are taken together with the carbon atom to which they are attached to form a (C4-C7)cycloalkylene group; Q is an unsubstituted 1 or 4triazole; m is zero; and n is the integer 1.

Another sub-class of compounds, acid addition salts and metal salt complexes are those where, in Formula I, Rl is other than cyano; Z is phenyl or naphthyl each optionally substituted with up to 3 of the same or different substituents each selected from halogen, nitro, trihalomethyl, cyano, (C7-C14)aralkyl, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)- alkylsulfinyl, (C1-C4)alkylsulfonyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, each of the last four groups being optionally substituted with up to two of the same or different substituents each selected from halogen, nitro, trifluoromethyl, cyano, methyl, methoxy, methylthio, methylsulfinyl and methylsulfonyl; R1, when optionally substituted aryl, is as defined for Z in this subparagraph and, when optionally substituted aralkyl, is phenyl(C1-C4)alkyl or naphthyl(C1-C4)alkyl each optionally substituted in the aryl portion as defined for Z in this sub-paragraph; R2, when optionally substituted aryl or optionally substituted aralkyl, is as defined for R1 in the immediately preceding sub-paragraph; and Q is I - (1,2,3 - triazolyl) or 4 - (1,2,4 - triazolyl) each optionally substituted with up to 2 of the same or different substituents each selected from halogen, (C1- C4)alkyl, nitro and cyano.

Yet another sub-class of compounds, acid addition salts and metal salt complexes are those where, in Formula I, R1 is cyano; Z is phenyl or naphthyl each optionally substituted with up to 3 of the same or different substituents each selected from halogen, nitro, trihalomethyl, cyano, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfinyl and (C1- C4)alkylsulfonyl, Z preferably being phenyl optionally substituted with up to 3 halogen atoms; R2, when optionally substituted aryl, is as defined for Z in the immediately preceding sub-paragraph and, when optionally substituted aralkyl, is phenyl(C1- C4)alkyl or naphthyl(C,C4)alkyl each optionally substituted in the aryl portion as defined for Z in this sub-paragraph, R2 preferably being (C1-C6)alkyl or (C2- C8)alkenyl; Q is 1 - (1,2,4 - triazolyl) or 4 - (1,2,4 - triazolyl) each optionally substituted with up to two of the same or different substituents each selected from halogen, (C1-C4)alkyl, nitro and cyano, Q preferably being unsubstituted; m is preferably 0 and n is preferably 1.

Examplary compounds of the sub-class described immediately above are those in which Z is 2,4-dichlorophenyl, R2 is CH3, n-C4H9, n--C,H,, or allyl and Q is unsubstituted 1 - (1,2,4 - triazolyl).

In the sub-class of compounds defined in the immediately preceding paragraph. typically: Z is phenyl optionally substituted with up to 3 of the same or different substituents each selected from (C1-C4)alkyl and halogen, particularly 2,4dichlorophenyl; R' (when not joined to R2) is (C1-C12)alkyl, particularly n-C4H6; R2 is hydrogen or is joined to R' to form, together with the attached carbon atom. a (C2-C6)cycloalkylene group; Q is an unsubstituted 1 - (1,2,4 - triazolyl) or 4 - (1,2,4 - triazolyl) group, particularly 1 - (1,2,4 - triazolyl): m is 0; and n is 1.

A more preferred sub-class of compounds, wherein R' is other than cyano, are the compounds, salts and complexes of Formulae (I) and (II) wherein Z is phenyl optionally substituted with up to 3 of the same or different substituents, preferably with up to 2 substituents, each selected from the group consisting of chlorine bromine, methyl, methoxy, nitro, methylthio, phenoxy, phenylthio, phenylsulfinyl and phenylsulfonyl; R' is hydrogen; R2 is (C1-C12)alkyl, cyclohexyl, allyl, cyclohexenyl, propargyl, phenyl, benzyl or phenethyl or monochloro substituted phenyl, benzyl or phenethyl; or R' and R2 are taken together with the carbon atom to which they are attached to form a cyclopentylene group; Q is an unsubstituted I or 4-triazole; m is zero; and n is the integer 1.

Typical individual compounds, wherein R' is other than cyano, are: 1-[ -(2,4-dibromophenyl)hexyl]-1,2,4-triazole 4-[ -(2,5-dinitrophenyl)octyl]-1,2,4-triazole 1-[ -(4-phenoxyphenyl)hexyl]-1,2,4-triazole 4-[ -(2-phenylthiophenyl)propyl]-1,2,4-triazole 1-[ -(4-phenylsulfinylphenyl)octyl]-1,2,4-triazole 4-[ -(4-phenylsulfonylphenyl)pentyl]-1,2,4-triazole 4-[#-(3-bromophenylsulfinylphenyl)decyl]-1,2,4-triazole 4-[#-(3-bromophenylsulfinylphenyl)decyl]1,2,4-triazole 1-[#-(4-methylsulfonylphenylsulfonyl)tridecyl]-1,2,4-triazole 4-[γ-2-methyl-4-methoxyphenylthiophenyl)pentadecyl]-1,2,4-triazole 1-[ -(3,5-diiodophenylsulfinylphenyl)hexadecyl]-1,2,4-triazole 4-[ -(3-chloro-4-methylphenylsulfonylphenyl)hexyl]-1,2,4-triazole 1-[γ-(3,5-ditrifluoromethylphenyl)nonyl]-1,2,4-triazole 4-[#-(2,4,6-trichlorophenyl)dodecyl]-1,2,4-triazole 1-[ -(2,4,5-trimethylphenyl)tetradecyl]-1,2,4-triazole 4-[ -(2,4-dimethoxyphenyl)hexyl]3-methyl-1,2,4-triazole 1-[ -(2,4-dimethylthiophenyl)hexyl]5-chloro-1,2,4-triazole, 4-[ -(3-iodophenyl)decyl]-1,2,4-triazole 1-[ -(2,6-dichlorophenyl)pentyl]-1,2,4-triazole 4-[ -(4-cyanophenyl) -phenylpropyl]-1,2,4-triazole 1-[γ-(2,4-dichlorobenzyl)heptyl]-1,2,4-triazole 4-[ -(2,4-difluorobenzyl)octyl]-1,2,4-triazole 4-[ -(4-iodophenyl)undecyl]-1,2,4-triazole 1-[#-(2-methyl-4-chlorophenyl)dodecyl]-1,2,4-triazole 4-[#-(2methyl-4-methylthiophenyl)tridecyl]-1,2,4-triazole 1-[ -(4-tolyl)hexyl]-1,2,4-triazole 4-[ -(4-anisyl)hexyl]-1,2,4-triazole 4-[ -(2,4-dichlorophenyl)- -cyclopropylethyl]-1,2,4-triazole 4-[ -(2,4-dichlorophenyl)- -cyclopentylethyl]-1,2,4-triazole 1-[ -(2,4-dichloronaphthyl)hexyl]-1,2,4-triazole 4-[ -(2-fluoronaphthyl)hexyl]-1,2,4-triazole 1 -[ -(2-nitronaphthyl)hexyll- 1 2,4-triazole 4-[ -(3,4-dichlorophenyl)octyl]-1,2,4-triazole 1-[ -(2,3-difluorophenyl)propyl]-1,2,4-triazole 4-[ -(2,5-diethylphenyl)tetradecyl]-1,2,4-triazole 1-[γ-(2,3,5-trichlorophenyl)hexykl]-1,2,4-triazole 4-[ -(4-trichloromethylphenyl)pentyl]-1,2,4-triazole 1-[ -(4-ethylsulfonylphenyl)hexyl]-5-cyano-1,2,4-triazole 4-[ -(2-bromo-4-nitrophenyl)hexyl]3-bromo-1,2,4-triazole 1-[ -(3-methylsulfinylphenyl)butyl]3-ethyl-1,2,4-triazole 1-[ -(2,4-dichlorophenyl)-4-chlorophenethyl]-1,2,4-triazole 4-[4-benzylphenyl)-4-chlorophenethy]-1,2,4-triazole 1-[γ-83,5-dinitrophenyl)hexyl]-1,2,4-triazole and the agronomically acceptable acid addition salts and metal salt complexes thereof.

One sub-class of compounds, wherein R1 is cyano, which may be singled out for mention are the compounds, salts and complexes of Formulae (I) and (II) wherein Z is a phenyl or napthyl group preferably a phenyl group optionally substituted with up to three substitutents preferably with up to two substituents selected from the group consisting of halogen, nitro, trihalomethyl, cyano, (C1 C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfinyl and (C1- C4)alkylsulfonyl; R2 is selected from (C1-C12)alkyl (particularly (C1C8)alkyl), (C5-C7)cycloalkyl (e.g. cyclohexyl), (C2-C4)alkenyl (e.g. allyl), (C5- C6)cycloalkenyl (e.g. cyclohexenyl), (C2-C4)alkynyl (e.g. propargyl), unsubstituted phenyl, benzyl or phenethyl or phenyl, benzyl or phenethyl, the aromatic portion of which is substituted with up to two halogen atoms; Q is an unsubstituted 1- or 4 (1,2,4 - triazole); m is zero; and n is the integer 1.

A more preferred sub-class of compounds, wherein R1 is cyano, are the compounds salts and complexes of Formulae (I) and (II) wherein Z is phenyl optionally substituted with up to three substituents preferably with up to two substituents selected from chlorine, bromine, methyl, methoxy, nitro and methylthio; R2 is (C1-C12)alkyl, cyclohexenyl, propargyl, phenyl, benzyl or phenethyl or monochloro substituted phenyl, benzyl or phenethyl; Q is an unsubstituted I or 4 - (1,2,4 - triazole); m is zero; and n is the integer 1.

Typical individual compounds, wherein R is cyano, are: 1-[ -cyano- -(2,4-dibromophenyl)hexyl]1,2,4-triazole 4-[ -cyano- -(2,5-dinitrophenyl)octyl]1,2,4-triazole 1-[ -cyano- -(2,4,5-trimethylphenyl)tetradecyl]1,2,4-triazole 4-[p-cyano-p-(2,4-dimethoxyphenyl)hexyl] 3-methyl- 1 ,2,4-triazole I -[ -cyano-p-(2,4-dimethylthiophenyl)hexyll 5-chloro- 1 ,2,4-triazole 4-[ -cyano- -(3-iodophenyl)decyl]1,2,4-triazole 1-[ -cyano-0 -(2,6-dichlorophenyl)pentyl]1,2,4-triazole 4-[ -cyano- -(4-cyanophenyl)propyl]1,2,4-triazole 4-[ -cyano- -(2,4-difliuorobenzyl)octyl]1,2,4-triazole 4-[ -cyano- -(4-iodophenyl)undecyl]1,2,4-triazole 1-[ -cyano- --(4-tolyl)hexyl]1,2,4-triazole 4-[ -cyano- -(4-anisyl)hexyl]1,2,4-triazole 4-[ -cyano- -(2,4-dichlorophenyl)- -cyclopropylethyll 1 ,2,4-triazole 4-[ -cyano- -(2,4-dichlorophenyl)- -cyclopentylethyl]1,2,4-triazole 1-[ -cyano- -(2,4-dichloronaphthyl)hexyl]1,2,4-triazole 4- [P-cyan o-P-(2-fluoronaphthyl)hexyl] 1 ,2,4-triazole 1-[ -cyano- -(2-nitronaphthyl)hexyl]1,2,4-triazole 4-[ -cyano- -(3,4-dichlorophenyl)octyl]1,2,4-triazole 1-[ -cyano- -(2,3-digfluorophenyl)propyl]1,2,4-triazole 4-[ -cyano- -(2,45-diethylphenyl)tetradecyl]1,2,4-triazole 4-[ -cyano- -(4-trichloromethylphenyl)pentyl]1,2,4-triazole 1-[ -cyano- -(4-ethylsulfonylphenyl)hexyl]5-cyano-1,2,4-triazole 4-[ -cyano- -(2-bromo-4-nitrophenyl)hexyl]3-bromo-1,2,4-triazole 1-[ -cyano- -(3-methylsulfinyl)butyl]3-ethyl-1,2,4-triazole 1-[ -cyano- -(2,4-dichlorophenyl)-4-chlorophenethyl]1,2,4-triazole 4-[ -cyano- -(4-chlorophenyl)-4-chlorophenethyl]1,2,4-triazole and the agronomically acceptable acid addition salts and metal salt complexes thereof.

The substituted 1,2,4-triazoles of the invention can be prepared by standard synthetic routes particularly those known per se for analogous compounds.

A preferred method for preparing compounds within the scope of this invention is as follows:

R1 metal Z(CH2)rnC(CII2)nY + [Q] saltFormula (I) (III) R2 In this reaction sequence Z, R1, R2, Q, m and n are as defined in Formula (I); Y may be halide, alkanesulfonate, or arylsulfonate and the metal salt is preferably a sodium or potassium salt. This reaction can be run either without solvent or in an appropriate solvent such as benzene, toluene, xylene, glyme, N,Ndimethylformamide, or dimethylsulfoxide. Reaction temperatures may be from 0 C to 150"C.

When the starting material of Formula (III) is reacted with the 1H - 1,2,4 triazole free base instead of its metal salt (usually at temperatures from 500C to 1800C) a mixture of l-substituted and 4-substituted 1,2,4-triazoles is obtained and these triazoles can be easily separated by conventional chemical separation techniques such as extraction, chromatography. or crystallization.

Another preferred method for preparing the substituted triazoles is represented as follows:

R1 Z--(CH,),CC-(C H,),--NH, + CH CH3 R2 N-CR3=N-N=CR4-N Formula (I) / Compound CH3 CH3 (IV) (V) In this reaction sequence Z, R1, R2, m and n are as defined in Formula (I) and R3 and R4 are selected from hydrogen, halogen (C1-C4)alkyl, nitro or cyano. This reaction is usually run in an appropriate inert solvent such as benzene, toluene or xylene. The reaction is usually carried out at temperatures from 0 C to 1500C with or without the presence of a suitable catalyst such as p-toluenesulfonic acid, benzene sulfonic acid or methanesulfonic acid. Either reactant can be used in excess in this pre?aration and the mode of addition is not critical.

The starting materials of Formula (III) can be prepared by standard synthetic methods. Examples of such preparative methods can be found in Belgian Patent No. 838,928 or its West German equivalent OLS P2604047.

The starting materials of Formula (IV) can be prepared by making the corresponding Formula (III) starting materials wherein Y is chlorine or bromine and reacting them with ammonia, either without solvent or in an appropriate solvent such as diethyl ether, tetrahydrofuran or methanol at temperatures usually from 40or to 1000C.

The addition salts of the substituted 1,2,4-triazoles of this invention can be prepared by standard techniques well-known in the art. For example, a compound of Formula (I) can be dissolved in an appropriate solvent such as diethyl ether tetrahydrofuran, ethanol or methanol, and treated with an equivalent or excess amount of a mineral or organic acid which may or may not be dissolved in an appropriate solvent. The mixture is then either cooled or evaporated to give the salt which can either be used as such or recrystallized from an appropriate solvent or combination of appropriate solvents.

The metal salt complexes of compounds of Formula I can be prepared by adding dropwise, with stirring, a stoichiometric amount of a metal salt (dissolved in an appropriate solvent) to a solution of a compound of Formula (I) dissolved in an appropriate solvent. The reaction mixture may be briefly stirred and the solvent removed under reduced pressure to give the desired metal salt.

The metal salt complexes can also be prepared by mixing stoichiometric or excess amounts of the metal salt and a compound of Formula (I) in the desired amount of solvent containing the appropriate adjuvants just prior to spraying plants to combat fungi. Adjuvants that may be included in this in-situ preparation may be detergents, emulsifiers, wetting agents, spreading agents, dispersing agents stickers, adhesives and other adjuvants which are used in agricultural applications.

Solvents that can be utilized in such an in situ procedure include any polar solvent e.g., water, methanol, ethanol, isopropanol or ethylene glycol and any aprotic dipolar solvent e.g., dimethylsulfoxide, acetonitrile, dimethylformamide, nitromethane or acetone.

Metal containing fungicides can also act as safening agents (i.e. to reduce phytotoxicity) in place of non-fungicidal metal salts. Typical metal containing fungicides that can be utilized in these in situ procedures are: a) dithiocarbamates and derivatives such as: ferric dimethyldithiocarbamate (ferbam), zinc dimethyldithiocarbamate (ziram), manganese ethylenebisdithiocarbamate (maneb) and its coordination product - with zinc ion (mancozeb). zinc ethylenebisdithiocarbamate (zineb); b) copper-based fungicides such as cuprous oxide. copper naphthenate, and Bordeaux mixture; and c) miscellaneous fungicides such as: phenylmercuric acetate, N- ethylmercuri- 12,3,6 - tetrahydro - 3,6 - endomethano - 3,4,5,6,7,7, - hexachlorophthalmide. phenylmercuri monoethanolammonium lactate, nickel-containing compounds and calcium cyanamide.

The compounds of this invention, except for those wherein R1 and R2 are both hydrogen, possess an asymmetric carbon atom and thus exist as racemic mixtures.

The d and I enantiomorphs in these racemic mixtures can be separated via standard techniques, such as fractional crystallization with d-tartaric acid, /-tartaric acid or 1- quinic acid, followed by basification and extraction of the d or I enantiomorph free base.

The following Examples 1--5 are provided to show illustrative working preparations of compound wherein R1 is other than cyano. In these examples and those which follow later the temperatures expressed are in degrees Centigrade.

The compounds prepared by Examples 1--5, as well as other analogous compounds which have been prepared in accordance with the disclosure of this specification, are listed below in Table I; analytical data are given in Table II below.

Example I Preparation of 4-[2-(2,4-dichlorophenyl)hexyl]-1,2,4-triazole (Compound I, Table I) A. 2-(2,4-Dichlorophenyl)hexyl amine To a suspension of 9.0 g (0.24 mole) of lithium aluminum hydride in 200 ml of anhydrous ether is added 57 g (0.24 m) of a - n - butyl - 2,4 - dichlorobenzyl cyanide dropwise at 100. The reaction mixture is stirred at room temperature for 30 minutes and at 350 overnight. Excess lithium aluminum hydride is then decomposed by addition of saturated ammonium chloride solution (50 ml), followed by 20% hydrochloric acid (300 ml) at 00. The acidic aqueous layer is separated and extracted with ether. The combined ether portions are washed with water and dried over MgSO4. When ether is evaporated under vacuo, there isobtained 63 g of a yellow solid. The solid is then dissolved in 20% sodium hydroxide solution and extracted with ether. The combined ether extracts are dried over MgSO4. Solvent is evaporated to give 48 g of an oil. Vacuum distillation (101- 104 /0.1 mm) gives 38.3 of pure product.

B. 4 - [2 - (2,4 - dichlorophenyl)hexyl] - 1,2,4 - triazole A mixture of 10 g (0.04 mole) of 2 - (2,4 - dichlorophenyl) hexyl amine, 5.7 g (0.04 mole) of N,N-dimethylformamide azine and 0.5 g of p-toluene sulfonic acid in 100 ml of dry toluene is heated under reflux for 16 hours. The solvent is evaporated to give 15 g of a white solid which can be further purified by recrystallization from benzene to give 7.5 g of pure product. nmr (CDCl3): 0.8-2.0 (complex multiplets, 9H), 3.8 (m, 1H), 4.3 (d, 2H), 7.3 (m, 3H), 8.0 (s, 2H) Example 2 Preparation of l-[2-(2,4-dichlorophenyl)hexyl]-1 2,4-triazole and 4-[2-(2,4-dichlorophenyl)hexyll- 1 ,2,4-triazole Compound 2, Table I) A. 2 - (2,4 - Dichlorophenyl)hexyl methane sulfonate For the preparation of this compound see Example 4 below.

B. 1 - [2 - (2,4 - dichlorophenyl)hexyl] - 1,2,4 - triazole and 4 - [2 - (2,4 - dichlorophenyl)hexyl] - 1,2,4 - triazole A mixture of 8 g (0.025 mole) of 2 - (2,4 - dichlorophenyl)hexyl methane sulfonate and 6 g (0.087 mole) of 1H - 1,2,4 - triazole is mixed and heated at 1200 for 4 hours. The reaction mixture is poured into water and extracted with ether.

The combined ether extracts are washed with water and dried over MgSO4. The drying agent is filtered and to the filtrate is added conc. nitric acid dropwise until no more precipitate forms. Solvent is then decanted and the residue is washed with ether and back neutralized with dilute NH4QM solution to give 3 g of an oil.

Analysis by glc and nmr reveals that this product contains a mixture of I - [2 (2,4 - dichlorophenyl)hexyl] - 1,2,4 - triazole and 4 - [2 - (2,4 dichlorophenyl)hexyl] - 1,2,4 - triazole in a ratio of 2:1. nmr (CDCl3): a 0.7-2.0 (m, 9H), 3.64.0 (m, 1H), 4.24.9 (m, 2H), 7.0-7.5 (m, 3H), and singlets at 7.8, 7.9 and 8.0 integrated for 2H Example 3 Preparation of 1 -[2-(2,4-dichlorophenyl)hexyl]- 1,2,4- triazole (Compound 3, Table I) The free base of 1 - [2 - (2,4 - dichlorophenyl)hexyl] - 1,2,4 - triazole is obtained when the nitrate salt of Example 4 is back neutralized with 100, ammonium hydroxide solution. nmr (CDCl3): 0.7-2.0 (complex multiplets, 9H), 3.9 (m, 1 H), 4.4 (d, 2H), 7.0 7.5 ( Example 4 Preparation of 1-[2-(2,4-dichlorophenyl)hexyl]-1,2,4 triazolium nitrate (Compound 4, Table I) A. 2 - (2,4 - Dichlorophenyl)hexyl methane sulfonate To 24.7 g (0.1 mole) of the 2 - (2,4 - dichlorophenyl)hexan - I - ol and 13.8 g (0.12 mole) of methane sulfonyl chloride in 200 ml of benzene at 100 is slowly added 14.2 g (0.14 mole) of triethylamine. When the addition is complete the reaction mixture is stirred and allowed to come up to ambient temperature over 1/2 hour period. The reaction slurry is then heated to reflux for 1/2 hour, cooled and poured into water. The organic solution is washed with dilute HCI then with water and finally with dilute sodium bicarbonate solution. After drying over anhydrous MgSO4, the benzene is stripped off to give 31.8 g (98%) of the crude product. This material is identified by ir and nmr. The purity is determined by glc.

B. 1 - [2 - (2,4 - dichlorophenyl)hexyl] - 1,2,4 - triazolium nitrate To a dimethyl sulfoxide solution (25 ml) of sodium 1,2,4-triazole, generated from 2.2 g (0.032 mole) of 1H - 1,2,4 - triazole and 1.3 g (0.032 mole) of sodium hydroxide, is added 10 g (0.03 mole) of 2 - (2,4 - dichlorophenyl) hexyl methane sulfonate in 10 ml of dimethyl sulfoxide dropwise at 1000. The reaction is maitained at 100 for 1 hour and then poured into water and extracted with ether. The combined ether extracts are washed with water and dried over MgSO4. Drying agent is then filtered and to the filtrate is added conc. nitric acid until no more precipitates form. The white precipitate (7.5 g) is filtered and is characterized as the nitric acid salt of the desired product. nmr (DMSO): ö 0.72.0 (complex multiplets, 9H), 3.9 (m, I H), 4.7 (d, 2H), 7.5 (m, 3H), 8.5 (s, IH), 9.0 (s, IH), 9.3 (s, 1H) Example 5 Preparation of zinc chloride complex of 1-[2-(2,4-dimethyl phenyl)hexyl]-l,2,4-triazole (Compound 7, Table I) To 3.0 g (0.01166 mole) of 1 - [2,4 - dimethylpenyl)hexyl] - 1,2,4 - triazole in 50 ml methanol is added 0.71 g (0.0052 mole) of zinc chloride and the mixture is allowed to stir for 15 minutes. The methanol is stripped to give 3.7 g of residue. The residue is triturated with hexane, and the solid which formed is filtered and dried to give 3.3 g. (71.9%) of the product, mp 85-6 TABLE I

Compound No. Z R R R Q M 1 2,4Cl2-C6h3 C4H9n H 4-(1,2,4-triazolyl) 2 2,4CI2-C6H3 C4Hgn H 1 & -(1,2,4-triazolyl) - 3 2,4C12-C6H3 C4Hgn H 1-(1,2,4-triazolyl) 4 2,4Cl2-C6H3 C4Hgn H 1-(1,2,4-triazolyl) HNO3 5 1,4-(CH3)2-C6H3 C4H9n H 1-(1m2m4-triazolyl) HCl 6 2,4(CH3)2-C6H3 C4H9n H 1-(1,2,4-triazolyl) 7 2,4(CH3)2-C8H3 C4Hgn H 1-(1,2,4-triazolyl) l/2ZnCl2 8 2,4,6-(CH3)3-C6H2 CH3 H 1-(1,2,4-triazolyl) HCl 9 2,4,6-(CH3)3-C6H2 CH3 H 1-(1,2,4-triazolyl) 10 C6H5 C12H25-n H 1-(1,2,4-traizolyl) HCl 11 C6H5 C12H25-n H 1-(1,2,4-traizolyl) 12 2,4Cl2-C6H3 (CH2)4-* 1-(1,2,4-triazolyl HCl 13 2-C6H5O-C6H4 C4H9n H 1,(1,2,4-triazolyl) HCl 14 3-C6HsO-C6H4 C4Hgn H l-(1,2,4-triazolyl) HNO3 *i.e. Rl and R2 joined together to form, minus the carbon atom to which they are attached. a tetramethylene group.

TABLE II Elemental Analysis: Calc'd (Found) Compound No. mp C C H Cl N O or Zn I 110-3 56.39 5.75 23.78 14.09 (56.55) (5.99) (23.38) (14.05) 2 oil 56.39 5.75 23.78 14.09 (55.11) (5.81) (23.89) (12.70) 3 oil 56.39 5.75 23.78 14.09 (56.19) (5.87) (23.95) (13.69) 4 108-10 46.55 5.02 19.64 15.51 13.29 (46.38) (5.01) (19.67) (15.22) (13.39) 5 145-51 65.40 8.23 12.07 14.30 (65.66) (8.37) (11.76) (14.47) 6 oil 74.67 9.00 - 16.33 (74.51) (9.19) - (16.49) 7 85-6 59.03 7.12 10.89 12.09 10.04 (58.72) (7.14) (10.56) (13.16) (10.47) 8 1807 63.26 7.59 13.34 15.81 (62.75) (7.42) (13.16) (15.90) 9 oil 73.32 8.35 - 18.33 (72.00) (8.05) - (18.33) 10 82-8 69.90 9.60 9.38 11.12 (69.34) (9.52) (8.83) (10.89) 11 oil 77.37 10.33 - 12.30 (77.32) (10.37) - (12.06) 12 175-9 50.55 4.85 31.97 12.63 (50.19) (4.83) (29.20) (12.68) 13 142-146 67.12 6.76 9.91 11.74 4.47 (67.23) (6.79) (10.11) (12.07) (5.04) 14 121-4 62.49 6.29 14.57 16.65 (61.11) (6.30) (14.30) (17.28) The following working Examples 6-9 are presented to show illustrative preparations of compounds wherein R' is cyano. The compounds prepared by Examples 6-9, as well as other analogous compounds which have been prepared by following one of the procedures given herein, are listed below in Table III, appropriate analytical data being given in Table IV.

Example 6 4-[2-Cyano-2-(2,4-dichlorophenyl)hexyl]- 1,2,4-triazole (Compound 15, Table III) A mixture of 12 g (0.036 mole) of 2 - cyano - 2 - (2,4 - dichlorophenyl)hexyl bromide and 10 g (0.145 mole) of IH - 1,2,4 - triazole is heated at 1850 overnight.

The reaction mixture is cooled and poured into water and extracted with ether.

When the combined ether extracts are washed with water, white precipitate separate from the ether layer. This precipitate is filtered and dried in vacuum to give 1 g of a white solid, mp 46-9 . Glc and nmr analysis reveal this material to be 4 - [2 - cyano - 2 - (2,4 - dichlorophenyl)hexyl] - 1,2,4 - triazole. nmr (CDCl3): # 80.7-3.2 (complex multiplets, 9H), 5.0 (q, 2H), 7.2-7.8 (m, 3H), 8.15 (s, 2H) Example 7 Preparation of 1-[2-Cyano-2-(2,4-dichlorophenyl)hexyl] 1,2,4-triazolium nitrate (Compound 17, Table III) A. 2 - Cyano - 2 - (2,4 - dichlorophenyl)hexyl bromide A solution containing 1.0 mole of n-butyl bromide and 1.0 mole of 2,4 dichlorophenyl cyanide in 250 ml of methylene chloride is added into a 250 aqueous solution of sodium hydroxide (500 ml) with 5.0 g of tetraethylammonium bromide. The reaction mixture is stirred vigorously under reflux for 3 hours to give 90% yield of desired product which is shown to be 90% pure by glc analysis and nmr spectroscopy. The cyanide is then mixed with 1.3 moles of methylene bromide and added into a 50% aqueous solution of sodium hydroxide with either tetraethylammonium bromide or benzyl triethyl ammonium chloride as catalyst.

The reaction mixture is heated to reflux (900) for three hours until 959;, of the starting material consumed. There is always about 5% of a - n - butyl, 2,4 dichlorobenzyl cyanide remain unreacted in this reaction.

B. 1 - [2 - Cyano - 2 - (2,4 - dichlorophenyl)hexyl] - 1,2,4 - triazole To a dimethyl sulfoxide solution (25 ml) of sodium 1,2,4 - triazole, generated from 3.2 g (0.046 m) of IH - 1,2,4 - triazole and 1.85 g (0.046 m) of sodium hydroxide, is added 2 - cyano - 2 - (2,4 - dichlorophenyl) hexyl bromide dropwise at 1100. The whole is stirred at 1100 for 1-1/2 hours. The reaction mixture is poured into 400 ml of water and extracted with ether. The combined ether extracts are washed with water and dried over MgSO4. Drying agent was filtered and to the filtrate is added conc. nitric acid dropwise until no more precipitates form. The precipitate (8.0 g) is filtered and is characterized as the nitric acid salt of the desired product. nmr (DMSO): # 0.6-2.5 (complex multiplets, 9H, 5.2 (q, 2H), 7.5-7.9 (m, 3H), 8.3 (s, IH), 8.7 (s, IH), 14.7 (s, IH) Example 8 The free base (Compound 18, Table III) is obtained when the nitrate salt of Example 7 is back neutralized with 10% ammonium hydroxide solution. nmr (CDCl3): a 0.7-2.8 (complex multiplets, 9H), 5.0 (q, 2H), 7.1-7.6 (m, 3H), 7.9 (s, 1H), 8.0 (s, IH) Example 9 Zinc chloride complex of 1-[2-cyano-2-phenylhexyl]-1,2,4 triazole (Compound 23, Table III) To 6.5 g (0.0256 mole) of I - 2 - cyano - 2 - phenyl - hexyl - 1,2,4 - triazole in 120 ml of methanol is added 1.5 g (0.0111 mole) of zinc chloride and stirring is carried out for 15 minutes. The methanol is stripped to give 9.6 g of residue. This material is taken up in warm ethanol, and the solid product precipitates. The material is separated by filtration to give 5.9 g (59%) of the product, mp 175-177 .

Tables III and IV referred to above now follow.

TABLE Ill

Compound No. Z R2 Q Y 15 2,4-CIC6H3 C4Hg-n 4-(1,2,4-triazolyl) 16 2,4-ClC6H3 C4H9-n 1 & 4-(1,2,4-triazolyl) HNO3 17 2,4-CIC6H3 C4Hg-n 1-(1,2,4-triazolyl) HNO3 18 2,4-ClC6H3 C4Hg-n 1 -(1 ,2,4-triazolyl) 19 4-ClC6H4 CH3 1-(1,2,4-triazolyl) 20 4-ClC6H4 CH3 1-(1,2,4-triazolyl) HNO3 21 C6H5 C4H9-n 1-(1,2,4-triazolyl) HCl 22 C6H5 C4Hg-n I -(I ,2,4-triazolyl) - 23 C6H5 C4Hg-n 1-(1,2,4-triazolyl) l/2ZnCl2 24 2,4-CIC6H3 C8H17-n 1-(1,2,4-triazolyl) HCI 25 2,4-ClC6H3 C8H17-n 1-(1,2,4-triazolyl) 26 2,4-ClC6H3 CH2CH=CH2 1-(1,2,4-triazolyl) TABLE IV Elemental Analysis: Calc'd (found) Compound No. mp OC C H Cl N O or Zn 15 46-9 55.74 4.99 21.94 17.33 (55.40) (5.12) (21.82) (17.18) 16 110-120 46.65 4.44 18.36 18.13 12.43 (46.41) (4.30) (18.55) (18.36) (12.77) 17 156-8 46.65 4.41 18.36 18.13 12.43 (46.30) (4.61) (18.50) (18.27) (12.54) 18 oil 55.74 4.99 21.94 17.33 (55.91) (5.09) (22.07) (17.21) 19 114-6 58.43 4.49 14.37 22.71 (57.40) (5.03) (13.37) (19.48) 20 163(dec.) 46.54 3.90 11.45 22.61 15.50 (47.28) (3.90) (11.50) (21.97) (16.00) 21 16245 61.95 6.59 12.19 19.27 (61.10) (6.35) (10.49) (17.91) 22 oil 70.84 7.13 - 22.03 (71.36) (7.19) (20.82) 23 175-77 55.87 5.60 10.99 17.37 10.13 (56.10) (5.70) (12.05) (17.01) (9.04) 24 125-31 54.88 6.60 25.58 13.48 (54.80) (5.95) (24.77) (13.76) 25 oil 60.16 6.37 18.70 14.77 (56.97) (6.48) (17.93) (14.25) 26 88-90 54.74 3.94 23.08 18.24 (54.97) (3.97) (22.85) (18.59) The substituted 1,2,4-triazoles, acid addition salts and metal salt complexes of this invention are broad-spectrum fungicides which possess a high degree of activity against assorted phytopathogenic fungi. These compounds, salts and complexes are particularly effective at rates of application from about 50 to about 2000 ppm in controlling barley net blotch (Helminthosporium teres) on barley plants, grey mold (Botrvtis cinerea) on faba beans, bean powdery mildew (Erysiphe po4goni) on bean plants, grape downy mildew (Plasmopora viticola) on grape seedlings, rice blast {Piricularia oryzae) on rice plants, tomato late blight (Phvtophthora infestans) on tomato seedlings, and wheat stem rust (Puccinia graminis f. sp. tritici race (15B-2) on wheat seedlings.

In evaluating these compounds, a preliminary fungicidal evaluation is carried out using the compounds in a carrier at a concentration of 300 ppm and spraying the plants to run off in a carrier volume of about 150 gallons/acre.

The general procedure is to take potted plants in proper condition of growth for susceptibility to the fungal disease to be evaluated, to spray these on a moving belt with the fungicidal agents and allow them to dry. The plants are then inoculated with the appropriate fungal spores which are then allowed to incubate until the disease has developed and the percent control is read or estimated.

Typical compounds, acid addition salts and metal salt complexes of the invention, wherein R' is cyano or otherwise, have (when evaluated by the general procedure given above at 300 ppm concentration) shown complete or 7W90 fungicidal control of (1) Helminthosporium teres on barley plants (var. Wong), (2) Botrtis cinerea on broad bean plants (var. Vicia faba), (3) Erysiphe polygoni on bean plants (var. Drawf Hort), (4) Plasmopora viticola on grape seedlings (var. Siebel 1000), (5) Piricularia orizae on rice plants (var. Nova 66), (6) Pkvtophthora infe.sran.v on tomato plants (var. Rutgers) and (7) Puccinia gamins (f. sp. tritici race 15B-') on wheat plants.

The compounds of Formula I and their acid addition salts and metal salt complexes find a wide variety of uses as broad spectrum fungicides. e.g. in the storage of cereal grain and as fungicides on turf, fruit orchards, vegetables and golf courses.

In their use as fungicides, the active ingredients provided by the invention are usually applied to combat phytopathogenic fungi on plants by applying them to growing plants, plant seeds or the plant habitat, e.g. soil. in a fungicidally effective amount.

The substituted 1,2,4-triazoles, acid addition salts and metal salt complexes of the present invention in their application as agricultural fungicides can be applied to various loci such as the seed, the soil or the foliage, particularly where a vendible agronomic crop is concerned. For such purposes these compounds can be used in the technical or pure form as prepared, as solutions or as formulations. The compounds are usually used in admixture with an agronomically acceptable diluent or carrier so as to render them suitable for subsequent dissemination as fungicides.

For example, the active fungicidal ingredients can be formulated with a carrier or diluent as dusts, granules, aerosols, emulsifiable concentrates, wettable powders, or flowable emulsion concentrates, the last three formulations usually containing a surfactant with a liquid or solid carrier and, when desired, suitable surfactants are incorporated. Details of suitable methods of making formulations, and other pesticides which may be used in conjunction with the fungicidally active compounds concerned in the present invention are to be found in the specification of W. German OLS P2604047.

In conclusion, there should also be singled out for mention two further subclasses of compound in accordance with the invention.

The first sub-class of compounds are compounds of Formula I (and the metal salt complexes and acid addition salts thereof) wherein Z is (C6-C10)aryl optionally substituted in the aryl group with (C1-C6)alkyl, (C1-C6)alkoxy, halogen or nitro: the group

represents (C3-C4)alkyl and Q is unsubstituted 4 - (1,2,4 - triazolyl). Compounds of this first sub-class, when used as plant fungicides, show unexpected and beneficial properties in comparison with compounds similar in all respects but in which R' and R2 are both hydrogen.

The second sub-class of compounds are those of Formula I (including the acid addition salts and metal complexes thereof) wherein the group

represents an alkyl group containing more than 4 carbon atoms, e.g. 6 to 14 carbon atoms.

Claims

WHAT WE CLAIM IS:

1. A compound of the formula:

wherein Z is (C6-C10)aryl which is optionally substituted; R (when not joined to R) is cyano or any of the groups (2)-(8) as defined below for R2; R2 (when not joined to R') is (1) hydrogen, (2) (C1-C12)alkyl, (3) (C3- C8)cycloalkyl, (4) (C2-C8)alkenyl, (5) (C5-C8)cycloalkenyl, (6) (C2-C8)alkynyl, (7) (C6-C10)aryl which is optionally substituted, (8) (C7-C14)aralkyl which is optionally substituted in the aryl portion or, in the case where R is cyano, (9) (C1 C4)alkoxy, (10) (C2-C4)alkenoxy, (11) (C2-C4)alkynoxy, (12) hvdroxy, (13) (C6- C,O)aryloxy which is optionally substituted or (14) (C7-C14)aralkyloxy which is optionally substituted in the aryl portion; R' and R2 can be joined together in which case they collectively form, together with the carbon atom to which they are attached, a (C3-C8)cycloalkylene group; Q is optionally substituted 1 - (1,2,4 - triazolyl) or 4 - (1,2,4 - triazolyl); mis0or 1; n is 1 or 2; or an agronomically acceptable acid addition salt, or an agronomically acceptable metal salt complex, of a compound of Formula I.

2. A compound, acid addition salt or metal salt complex according to Claim 1, wherein: R' is other than cyano: Z is phenyl or naphthyl each optionally substituted with up to 3 of the same or different substituents each selected from halogen, nitro, trihalomethyl, cyano, (C7-C14)aralkyl, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1- C4)alkylsulfinyl, (C1-C4)alkylsulfonyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl each of the last four groups being optionally substituted with up to two of the same or different substituents each selected from halogen, nitro, trifluoromethyl, cyano, methyl methoxy, methylthio, methylsulfinyl and methylsulfonyl; R', when optionally substituted aryl, is as defined for Z in this claim and, when optionally substituted aralkyl, is phenyl(C1-C4)alkyl or naphthyl(C1- C4)alkyl each optionally substituted in the aryl portion as defined for Z in this claim; R2, when optionally substituted aryl or optionally substituted aralkyl, is as defined for R' in this claim; and Q is 1 - (1,2,4 - triazolyl) or 4 - (1,2,4 - triazolyl) each optionally substituted with up to 2 of the same or different substituents each selected from halogen, (C,- C4)alkyl, nitro and cyano.

3. A compound, acid addition salt or metal salt complex according to Claim I wherein: R' is cyano; Z is phenyl or naphthyl each optionally substituted with up to 3 of the same or different substituents each selected from halogen, nitro, trihalomethyl, cyano, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfinyl and (C,- C4)alkylsulfonyl R2, when optionally substituted aryl, is as defined for Z in this claim and, when optionally substituted aralkyl, is phenyl(C1-C4)alkyl or naphthyl(C1-C4)alkyl each optionally substituted in the aryl portion as defined for Z in this claim; and Q is I - (1,2,4 - triazolyl) or 4 - (1,2,4 - triazolyl) each optionally substituted with up to two of the same or different substituents each selected from halogen, (C1-C4)alkyl, nitro and cyano.

4. A compound, acid addition salt or metal salt complex according to Claim 2, wherein: Z is phenyl optionally substituted with up to 3 of the same or different substituents each selected from (C1-C4)alkyl and halogen; R' (when not joined to R2) is (C1-C12)alkyl R2 is hydrogen or is joined to Rl to form, together with the attached carbon atom, a (C3-C8)cycloalkylene group; Q is an unsubstituted 1 - (1,2,4 - triazolyl) or 4 - (1,2,4 - triazolyl) group; m is 0; and n is 1.

5. A compound. acid addition salt or metal salt complex according to Claim 4, wherein Z is 2,4 - dichlorophenyl, R1 is n-C4Hg and Q is 1 - (1,2,4 - triazolyl).

6. A compound, acid addition salt or metal salt complex according to Claim 3, wherein: Z is phenyl optionally substituted with up to 3 halogen atoms; R2 is (C1-C8)alkyl or (C2-C8)alkenyl; Q is an unsubstituted I - (1,2,4 - triazolyl) or 4 - (1,2,4 - triazolyl) group: m is 0: and n is 1.

7. A compound, acid addition salt or metal salt complex according to Claim 6, wherein Z is 2,4 - dichlorophenyl, R2 is CH3, n-C4Hg, n-C8Hl7 and allyl and Q is unsubstituted I - (1,2,4 - triazolyl).

8. A compound, salt or complex according to Claim 2, being any one of those individual compounds, salts or complexes listed in foregoing Table 1.

9. A compound, salt or complex according to Claim 3, being any one of those individual compounds, salts or complexes listed in foregoing Table III.

10. A fungicidal composition containing (A) as an active ingredient, a compound, acid addition salt or metal salt complex according to Claim I and (B) an agronomically acceptable carrier or diluent for said active ingredient.

II. A composition according to Claim 10 in the form of (a) a dust or granules or (b) an emulsifiable concentrate, flowable emulsion concentrate or wettable powder each containing a surfactant.

12. A composition according to Claim 10 or 11 containing, as active ingredient, a compound, acid addition salt or metal salt complex according to any of Claims 2, 4, 5 and 8.

13. A composition according to Claim 10 or 11, containing, as active ingredient, a compound, acid addition salt or metal salt complex according to any of Claims 3, 6, 7 and 9.

14. A method of combating phytopathogenic fungi or plants which yield an agronomic crop which comprises applying, in a fungicidally effective amount, a compound, acid addition salt or metal salt complex according to Claim I to growing plants, plant seeds or the plant habitat.

15. A method according to Claim 14, wherein there is applied a compound, salt or complex according to any one of Claims 2, 4, 5 and 8.

16. A method according to Claim 14, wherein there is applied a compound, salt or complex according to any one of Claims 3, 6, 7 and 9.

17. A metal salt complex according to Claim 1, a composition according to Claim 10 or 11 containing a metal salt complex as active ingredient or a method according to Claim 14 employing a metal salt complex according to Claim I, wherein the metal salt complex is of the formula:

wherein M is a cation selected from Group IIA, IB, IIB, VIB, VIIB, and VIII of the Periodic Table (hereinbefore identified) and X is an anion counterion selected in such a manner that the sum of the valence charges of the cation M and anion X equal zero and wherein the metal salt complex is an accordance with any one of Claims 2, 4 and 5.

18. A complex, composition or method according to Claim 17 modified in that the metal salt complex of Formula II is in accordance with any of Claims 3 and 6 and 7.

19. A method of preparation of a compound of the formula:

which comprises reacting a compound of the formula:

with a compound of the formula:

wherein Z, m, R', R2 and n are as defined in Claim I and R3 and R4, which may be the same or different, represent hydrogen, halogen, (C1-C4)alkyl, nitro or cyano.

20. A method according to Claim 19 as applied to the preparation of a compound according to any one of Claims 2, 4, 5 and 8.

21. A method according to Claim 19 as applied to the preparation of a compound according to any one of Claims 3, 6, 7 and 9.

22. A compound, acid addition salt or metal salt complex according to any one of Claims 2, 4, 5 and 8 when prepared by any of the general methods of preparation hereinbefore described.

23. A compound, acid addition salt or metal salt complex according to Claim 2, when prepared substantially as hereinbefore described with reference to any one of foregoing Examples 1--5.

24. A compound, acid addition salt or metal salt complex according to any one of Claims 3, 6, 7 and 9, when prepared by any of the general methods of preparation hereinbefore described.

25. A compound, acid addition salt or metal salt complex according to Claim 3, when prepared substantially as hereinbefore described with reference to any one of foregoing Examples 6-9.