CS197264B2 - Fungicide means and method of making the active agents - Google Patents

Description

The present invention relates to fungicidal compositions containing imidazole derivatives as active compounds and to a process for the preparation of such active compounds.

The imidazoles of the invention exhibit curative fungicidal properties and are unique in that they kill phytopathogenic fungi in infected plant tissues and can therefore only be used after fungal infestation. The disclosed compounds also have unique systemic properties and can move up and down in plant tissues. In addition, when applied to plants prior to fungal infection, the compounds exhibit protective effects on phytopathogenic fungi.

The present invention provides a fungicidal composition in the form of a wettable powder, an emulsifiable concentrate, a dust, a granulate, an aerosol or a liquid emulsion concentrate comprising a carrier, characterized in that it contains from 0.000001 to 99% by weight of the imidazole derivative of the formula

R 'f = N _:

ZC- (A) _n -C

R * in which

Z represents a phenyl group optionally substituted by one, two or three substituents independently selected from the group consisting of chlorine, bromine and fluorine, C 1 -C 4 alkyl, trifluoromethyl, methoxy, methylthio, methylsulfonyl, nitro and amino, furthermore represents naphthyl, diphenyl, pyridyl, indolyl, thienyl, benzodioxanyl, acenaphthalene or indanyl,

R ¹ represents hydrogen or cyano,

R ² represents a hydrogen atom, a chlorine atom, a C 1 -C 8 alkyl group, a propenyl group, a propynyl group, a cyclohexyl group, a cyclohexenyl group, a phenyl group, an ethylphenyl group, a chlorine or ethyl substituted phenyl group, benzyl group, naphthyl group or pyridines group,

R ³ represents a hydrogen atom, a C 1 -C 10 alkyl group, a C 3 -C 6 alkenyl group, a hexyl group, a phenyl group, an ethylphenyl group, a chloro, fluoro or methyl-substituted phenyl group (I), or a benzyl group,

R ⁴ represents a hydrogen atom or a methyl group, or

Z and R ² together may form a group of the formula

provided that when R @ ¹ , R @ ³ and R ^{@ 4} are hydrogen, R @ ^{2 is} not hydrogen or C1 -C3 alkyl,

A represents a methylene or 1,2-ethylene group,

B represents a methylene, 1,2-ethylene or 1,4-butylene group,

X represents a chlorine atom, a nitro group, a methyl group or a butyl group and is a number of 0 to 2, n has a value of 0 or 1, n 'has a value of 0 or 1, or an agronomically acceptable acid addition salt or a complex salt thereof a metal salt of formula MY, wherein M is a metal cation and Y is an anion of the corresponding valency.

The metal salt complexes of the above imidazoles correspond to the general formula II,

X and a have which can VA, IB, IIB in which

Z, A, B, R ¹ , R ² , R ³ , R ⁴ , n, n ', as defined above, -W represents a metal cation, be selected from groups IIA, IVA,

VIB, VIIB and VIII of the Periodic Table of the Elements,

Y is the solubilizing anion of the corresponding valence, and m is 1-4.

The alkyl groups R ² and R ³ may be straight or branched, as well as the alkenyl groups R ³ .

Preferred compounds of the invention are those compounds of formulas I and II above wherein n 'is 1. Even more preferred compounds of the invention are those compounds of formulas I and II above where n' has a lan value of 0. Most preferred compounds of the invention are then the corresponding compounds wherein n * is 1, n equals 0, R ¹ represents a hydrogen atom, a represents 0, Z represents a substituted phenyl group having 1 to 3 substituents selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, methoxy, ethoxy, chlorine, fluorine, bromine and iodine, nitro, amino and methylthio and R ² is as defined above.

The compound of the invention may be prepared by standard synthetic procedures. Typical preparation methods that can be used to produce these compounds include: J (II) include the following general syntheses wherein all temperatures, unless otherwise indicated, are in degrees Celsius.

1- (N-Substituted alkyl) imidazole

If the corresponding acetate of formula III is reacted with sodium hydride in tetrahydrofuran or ethylene glycol dimethyl ether, the corresponding sodium salt of formula IV is formed. Reaction of the sodium salt of formula IV with an organic halide yields an ester of formula V. Esters of formula V are converted to the corresponding carbinols of formula VI by reduction with suitable reagents such as lithium aluminum hydride in ether or bis- (2-methoxyethoxy) aluminum hydride in benzene. in the presence of triethylamine in an aromatic hydrocarbon solvent such as benzene or toluene, a saltphonate of formula VII is obtained by reaction of a compound of formula VI with thionyl chloride or phosphorus pentachloride in an aromatic hydrocarbon such as benzene or toluene. excess of imidazoles or reaction of a compound of Formula VIIa with sodium salt of imidazoles either in the absence or in the presence of solvents such as benzene, dimethyl ether, ethylene glycol, N, N-dimethylformamide and the like results in the resulting alkylated imidazoles of Formula VIII. described by the following reaction scheme:

β

ZC ^ CO ^ H ^ _{Ν Η} Z-CHN + COSfr

(Vlil)

1- (C 2-6 alkyl) imidazole

1- (α-Substituted alkyl) imidazoles se

Z-Ct ^ CL in different ways, according to the following reaction ´ scheme:

preparing> Z-CH = GCL _RCHO) (*) (XJ ^

Z-CH 2 CHROH (X) ^CH 3 ^SO Z ^{CL /} (W ₃ n

Z-CH 2 CHR (X),

Z-CH 2 CHROSO 4 CH,

4 / (XI)

By reacting the magnesium metal with the appropriate organic chloride in ether, a Grignard reagent of formula IX is prepared. This reagent of formula IX is then reacted with the corresponding aldehyde to give a carbinoil derivative of formula X. A sulfonate or chloride is prepared which then reacts with imidazole or its sodium salt as described above to give the product of formula XI.

Methylene chain extension - malonate process

In order to prepare starting materials for the preparation of some closely related analogs in which the methylene chain is extended, a malonate synthesis is carried out according to the following scheme:

(Kli)

Z-fCN ^ CHRCO4 (XV)

J. KOH

2. HCl

3.igo ° -co _z

Z-CH 2 CO 2, (XIII)

1. Ns.U

2. RX

Z- (CN _z ) _h CR (CO 2) _z (XIV)

LLAIH + z - (C ^ H CHRCUpU Z- (CuI _n - CHRCyOSO.CH, (XVI) (X) *

N.

Ν '/ - = rN • · Ό ~ (X).

(XII)

Reaction of an alkyl halide of formula XII with sodium ethyl malonate in a solvent such as tetrahydrofuran or ethylene glycol dimethyl ether gives the substituted malonate of formula XIII. Further reaction of the compound of formula XIII, first with sodium hydride in tetrahydrofuran and then the addition of the appropriate organic halide, affords the disubstituted ester of formula XIV. Reduction of the compound of formula XV with lithium aluminum hydride yields the corresponding carbinol derivative of formula XVI. The resulting alkylated imidazole of formula XVII is then prepared in a conventional manner. a process starting from the methanesulfonate of formula VII through the preparation of the nitrile of formula

Extension of the methylene chain XVIII according to the following reaction scheme:

Z-CURCU ^ CN (XVII)

Z-CW (CH 2, COOW 1 x w) = N z-CuRO-β 1

The sulfonate of formula VII in dimethylformamide is treated with sodium cyanide in dimethylformamide to give the nitrile derivative of formula XVIII. Hydrolysis of the compound of formula XVIII in boiling 50% sulfuric acid affords the acid of formula XIX, which subsequent reduction with 11th aluminum aluminum hydride affords the alcohol of formula XX. The desired imidazole derivative is then prepared in a conventional manner via a sulfonate or the sulfonate can be recycled to further extend the chain.

Phenylanalogy

Phenylsubstituted analogs are prepared

Darzen's reaction. The substituted benzophenone is reacted with ethyl chloroacetate in the presence of sodium hydride to form the glycidester of formula XXI.

Hydrolysis followed by decarboxylation of the compound of formula XXI affords the arylacetaldehyde of formula XXII. This aldehyde of formula XXII is reduced with lithium aluminum hydride to the corresponding alcohol of formula XXIII, which is then converted in the usual manner to the resulting imidazole derivative of formula XXIV. The procedure can be described by the following reaction scheme:

Z-C = O + Ν & μ

ClCH 2 CO 2 s

Z-CHCHO bar (XXII) _χ 160 '

Z-C 'cUC.O & Hf

W (XXI) hyd-olysax, OH

Z-C-CCO.H + Ws; LiAlH 4

Φ

Zucu, ou

I ^of QWs · (XXIII)

ΟΗβΟ £ 1 / (C ^ N Z-CHC ^ SOgCH ^)

ψ ·.

~ N i. ~ \ j ~ ^ÍXJ <

Z-CHCH3N (XXIV) α, + Disubstituted alkylimidazole

Friedel-Crafts acylation of a substituted aromatic hydrocarbon with an acyl halide in the presence of aluminum chloride, either with or without the halogenated hydrocarbon, provides the desired product of formula XXV.

Reaction of the compound of formula XXV with an excess of ethyl chloroacetate and sodium hydride affords the glycide ester of formula XXVI, which by saponification with base and hydrolysis with hot mineral acid followed by decarboxylation affords the aldehyde of formula XXVII. Grignard reaction with an alkyl or aryl magnesium halide yields an alcohol of formula XXVIII. Preparation of the sulfonate and its reaction with imidazole as described above gives the product of formula XXIX, which is described by the following reaction scheme:

197284

O

Z + CICR

Z-CHRCHO XXVII

R ¹ MgX

Ψ

Z-ČHRCHŘ ¹ Olympics (XXVIII)

Λ N&OH ⁽ 2.HCl

3. I R0 °

O

II

Z-CR (xyv)

1. eiCH 2 CO 3

2. Na.H

Z-C-CHCO & Hr (xxvi)

(XXIX) β, β-Disubstituted alkylimidazole

By reacting the corresponding sodium alkyl acetate derivative XXX as described above with an iodoalkane at elevated temperature in a solvent such as ether, tetrahydrofuran or dimethylformamide, the desired trisubstituted acetate XXXI is obtained.

Reduction of the compound of formula XXXI with lithium aluminum hydride in anhydrous ether affords the alcohol of formula XXXII. The above-described preparation of the sulfonate followed by reaction with imidazole affords the desired product of formula XXXIII. The procedure can be described by the following reaction scheme:

187284

Fr

Z-CH 2 / Na.

R (XXXI)

Li Alpha * _R 1 i

CMfiSapH, CH 2 CV 1 N 2 -CH 2 OH R ^X /

ÍXJL

R * (XXXII) / = rW

2 <σΗ _λ Ν 4-fx ^

R ^to (XXXtlI)

Alternative methods of preparation of phenylanogues

Reduction of the substituted phenylacetic acid of formula XXXIV with lithium aluminum hydride in tetrahydrofuran gives the alcohol of formula XXXV. Preparation of the sulfonate and reaction with imldazole affords the desired product of formula XXXVI. The procedure can be described by the following reaction scheme:

Z-CHCO.H LLAIH

I - * fy (XXXIV) XL

Ψ z-chc ^ rT + txL · H ....... ...

f XXXVI)

Z-CHCH3OH

CM-n ^ n (XXXV) cfysqpi /

Z-CHCfyOSOjCfy

1- (1S-Substituted diarylalkyl jimidazole)

Reaction of chloroacetaldehyde diethyl acetal with a substituted aromatic hydrocarbon in the presence of sulfuric acid at room temperature yields the substituted aryl ethyl chloride chloride of formula XXXVII. Treatment of the compound of formula XXXVII with the sodium salt of imidazole as described above affords the desired product of formula XXXVIII. The procedure follows the following reaction scheme:

Z + (CH 2 Cl 2)

Z-CHCH.Cl i *

Z (XXXVII) (Χ) _Λ ^N ó r

N &

/ = - N

Z-GHCH ^ N ^ -J-X ^ (XXXVIII)

1- [ε- (Substituted aryl) hexyl] imidazole

When a substituted aromatic hydrocarbon is treated with 1,2-epoxyhexane in the presence of aluminum chloride, hexanol XXXIX is formed after the rearrangement. Preparation of the methanesulfonate followed by reaction with imidazole yields the desired product of formula XL. The procedure can be described by the following reaction scheme:

Z + CN - CH.

I *

LiAtH * (X)

N / = - N

Z-CnCn ^ N ^ - ^ i +

Ν '

AND

CH, zinc

CH _} (XXXIX)

CN ^ C ^ s ^ N

Ψ

Z-CNfCH ^ OSO ^ N ^ ₃ (XL)

When benzene is substituted with electron donating groups

With 1,2-epoxyhexane in the presence of tin (II) chloride to give hexanol of formula XLI. The reaction can be described by the following reaction scheme:

Z-CH-CH, and ^Λ

CjjHg

Sn CL · _nll

-Z-CNCN, ON (XLI)

The imidazole derivative is then prepared via the methanesulfonate as described above.

1- [β- (Alkylthio- or alkylsulfonyl-phenyl) -alkyl] imidazoles

The alkylthio and alkylsulfonyl derivatives are prepared from the aldehyde XLII according to the following reaction scheme:

LiAlHn ^{R 5} -CHO --— + (XLII) w

(XLIII)

CH _Z OH

C ^ SO SO ^ ^ Í Í Í N

RS w

(XLV)

CWf N *

Na-CN

RS '^^ - CN ^ OSO ^ (' XUV)

RS

RS

1. N&H

2. R'X w

(XLVI)

CNCN i

R '

ΈΤ Wí ^HC0 * ^R ''

R '(XLVII) LiAlHu

W “€ ps” psaw

Ó XL (XLIX)

R (XLV Π i)

The aldehyde XLII is reduced with lithium aluminum hydride to an alcohol XLIII, which is converted to the sulfonate XLIV by reaction with methanesulfonyl chloride in the presence of triethylamine. Reaction of the methanesulfonate of formula XLIV with sodium cyanide affords a benzylnitrile derivative of formula XLV, alkylated by first methylating it with sodium hydride and subsequently reacting with an alkyl halide to provide the α-alkylbenzylnitrile derivative of formula XLVI. Hydrolysis of the nitrile of formula XLVI with sulfuric acid in an alcoholic solvent results in an α-alkylphenylacetic acid ester of formula XLVII which, by reduction with lithium aluminum hydride, provides the phenethyl alcohol of formula XLVIII. The resulting imidazole is then prepared as described above using the methanesulfonate. When the imidazole of formula XLIX is oxidized with hydrogen peroxide in acetic acid, an alkylsulfonyl derivative of formula I is obtained. This reaction is described in the following reaction scheme:

(XLIX) N ^ O / HOAC

RSO _to —N (Xh

R '(L)

1- [β- (Nitrosubst.phenyl) alkyl] imidazole

Nitrosubstituted phenyl derivatives of formula

LII are obtained by nitration of unsubstituted or substituted analogs of formula LI according to the following reaction scheme:

(X1) (X1)

NO-R (LID

1- [β- (Aminosubst.phenyl) alkyl] imidazole

Aminosubstituted phenyl derivatives of formula IIIa are prepared by reduction of nitrosubstituted phenyl derivatives. This reaction can be described by the following reaction scheme:

(III) FeMCtICHi ^{, R} ^

zxrN

CWCH3 in -4-oxAs

R '(LID)

Substituted imidazole derivatives

Analogues in which the imidazole rings are substituted, corresponding to formula LV, are prepared by reacting the corresponding methanesulfonate of formula LIV either with an excess of substituted imidazole or with an imidazole sodium salt, according to the following reaction scheme:

The arylcyanalkyl and diarylcyanalkylimidazoles of the present invention can be prepared by a variety of synthetic procedures, including the following.

Aralkylcyanalkylimidazoles can be obtained by alkylation of the arylacetonitrile of formula LVI:

Z-CH 2 CN (LVI), an alkyl halide and sodium hydride in a solvent such as ether, tetrahydrofuran, dioxane and the like, at a temperature of about 20 to 100 ° C, to give the aralkylacetonitrile of formula LVU:

Z-CH (R ²⁾ CN (LVII)

The aralkylacetonitrile of formula LVU is hydroxyalkylated by reaction with an aldehyde or ketone, which may be straight, cyclic or branched, in a solvent such as pyridine, Ν, dimethyl-dimethylformamide and the like, at a temperature of about 0 to 150 ° C for about 10 - 40 hours to give an alcohol of formula LVIII:

CN R2 Z-C (R ²⁾ COH

Rs (LVIII)

The resulting alcohol of formula LVIII is converted to chloride using phosphorus pentachloride or thionyl chloride in a solvent such as benzene, toluene and the like, at a temperature of about 10 to 110 ° C. The alcohol can also be converted to the methanesulfonic acid ester by reaction with methanesulfonyl chloride in a solvent such as benzene, toluene and the like at a temperature of about 10 to 110 ° C. Both the chloride and the methanesulfonic acid ester can be reacted with imidazole either in the absence of a solvent or in a solvent such as Ν, Ν-dimethylformamide, dimethylsulfoxide, diethylene glycol dimethyl ether, and the like at about 50-180 ° C for about 10 to 40 hours to give the desired product of formula (I) above, wherein a and b are 0.

Diarylcyanalkylimidazoles can be obtained by reacting an arylaldehyde with an arylmagnesium halide in an anhydrous ethereal solvent such as ether, tetrahydrofuran, dioxane and the like, at a temperature of about 25 to 100 ° C, lasting about 1 to 24 hours, resulting in an alcohol of formula LVU:

Z-CH ^(R2) OH (LVII)

The alcohol of formula LVU is converted to a halide by treatment with phosphorus tribromide or thionyl chloride in a solvent such as benzene, toluene and the like at a temperature of about 25 to 110 ° C. The alcohol can also be converted to the methanesulfonic acid ester by reaction with methanesulfonyl chloride in a solvent such as benzene, toluene and the like at a temperature of about 25 to 110 ° C. The methanesulfonic acid halide or ester can then be reacted with a metal cyanide in a solvent such as dimethylsulfoxide, N, N-dimethylformaimide and the like at a temperature of about 50 to 180 ° C for about 4 to 24 hours to give the diarylacetonitrile LVIII :

Z-CH (R ² JCN (LVIII)

The diarylacetonitrile of formula LVIII is hydroxyalkylated by reaction of about 10 to about 40 hours with an aldehyde or ketone in a solvent such as pyridine, N, N-dimethylformamide and the like at a temperature of about 0 to 150 ° C to give the corresponding alcohol of formula LVIII. This alcohol is converted to the halide or methanesulfonate as described above. Both the halide and the methanesulfonic acid ester can be reacted analogously to the above with imidazole, either in the absence of a solvent or in a solvent such as N, N-dimethylformamide, dimethylsulfoxide, diethylene glycol dimethyl ether and the like at about 50 to 180 Noc: 2 ° C. The reaction takes about 10 to 40 hours to yield the desired product of roughly formula I wherein R ¹ is cyano, R ² is aryl and a, b are 0.

Compounds of the invention may also be prepared using the procedure described by Markosza and Serafin in Roczniki Chem., 38, 1223 (1965); ibid. 40, 1839 (1966), and Branstrom and Junggren in Tet. Letters, 473 (1972), wherein quaternary ammonium salt of arylacetonitrile carbanion (prepared by treating arylacetonitrile of formula LVI with 25-50% sodium hydroxide solution and subsequent reaction with quaternary ammonium halideide) is extracted into an aprotic solvent such as chloroform or methylene chloride and alkylated by adding an alkyl halide to this solution to give an aralkylacetonitrile of formula LVU.

The carbanion of aralkylacetonitrile or diarylacetonitrile of formula LVU can be bromoalkylated with dibromoalkane under conditions analogous to those described by Markosza and Branstrom to give the bromide of formula LIX:

CN i

AND

Z-C (R ²⁾ (CH ₂₎ Br (LIX)

The bromide of formula LIX is then reacted with imidazole for about 10 to 40 hours either in the absence of a solvent or in a solvent such as Ν, Ν-dimethylformamide, dimethylsulfoxide, diethylene glycol dimethyl ether and the like, at a temperature of about 50 to 180 ° C. the product of formula (I) wherein R ² is hydrogen and b is 0.

The carbanion of aralkylacetonitrile or diarylacetoniltrile of formula LVU can be bromoalkylated with branched or aryl-substituted dibromoalkane under conditions similar to those described by Markosza and Brannder to give the bromide of formula LX:

7 2 6 4

CN R ³

ZC (R ² ) (CH 2) a C (R ² ) - (CH 2) _b Br (LX)

The bromide of formula LX is then reacted with imidazole for about 10 to 49 hours, either in the absence of a solvent or in a solvent such as N, N dimethylformamide, dimethylsulfoxide, diethylene glycol dimethyl ether, and the like, at a temperature of about 50 to 180 ° C. of the desired product of formula (I)

An improved process for the preparation of the aralkylcyanalkylimidazoles of the present invention comprises adding a solution of arylacetonitrile and an alkyl halide in dimethylsulfoxide to a 50% aqueous solution of sodium hydroxide and then adding dibromoalkane to the reaction mixture. The desired product of formula LIX is then isolated in good yield. The bromide of formula LIX is then subjected to about ten hours to forty-hour reaction with imidazole either in the absence of solvent or in the presence of a small amount Vysokov, roučího solvent at about 50 to 180 ^Q C, gives the desired product of Formula I.

Similarly, the diarylcyanalkylimidazoles of the present invention can be prepared by adding dibromoalkane to a solution of diarylacetonitrile in dimethylsulfoxide and 50% sodium hydroxide and maintaining the reaction temperature at about 20 to 50 ° C for about 1 to 8 hours. The resulting bromide is then converted to imidazole using the reaction conditions described above.

The acid addition salts of the arylcyanalkyl and diarylcyanalkylimidazoles of the invention may be prepared by adding an aqueous, alcoholic or ethereal solution of an organic or mineral acid to an aqueous, alcoholic or ethereal solution of a compound of Formula I. The precipitate formed is filtered. acid salt. Typical acids which may be used in the above-described preparation include hydrochloric, nitric, hydrobromic, sulfuric, perchloric, phosphoric, acetic, oxalic, malic, tartaric, citric and the like.

Acid addition salts

Salts of aralkylimidazole derivatives are prepared by adding an equivalent amount of the desired inorganic or organic acid dissolved in an ether or an alcohol to an ethereal solution of imidazole of formula LXI and filtering or first concentrating and then filtering to obtain the desired salt. The reaction proceeds according to the following reaction scheme:

(LXII)

Metal complexes

Complexes of aralkylimidazole derivatives with metal salts corresponding to the formula LXIII are prepared by reacting an alcoholic or aqueous solution of an imidazole of the formula

LXI adds an aqueous or alcoholic solution of a metal salt at a temperature of about 15 to 60 ° C. The precipitate was filtered off and washed with solvent and dried to give the desired metal salt complex. The reaction can be described by the following reaction scheme:

Z-C- (A) n-C- (B) h'-N '

IXK ft (LXI)

Metal salts which may be used in the above reaction include those formed by the combination of a metal cation such as magnesium, calcium, barium, tin, lead, copper, zinc, cadmium, chromium, manganese, iron, cobalt, nickel and the like. and a suitable anion such as chloride, bromide, iodide, sulfate, bisulfate, phosphate and nitrate.

The preparation of the imidazoles, their salts and their metal salt complexes according to the invention is illustrated by the following non-limiting examples.

Example 1

1 - ([3- (2,4-Dichlorophenyl) hexyl] imidazole

Ethyl 1- [3- (2,4-dichlorophenyl) hexanoate

To 58.6 g (1.22 mol) of 50% sodium hydride in 1 liter of anhydrous tetrahydrofuran at 40 ° C was added 50.0 g (0.215 mol) of ethyl 2,4-dichlorophenylacetate and the mixture was stirred for 10 minutes. hydrogen gas evolution began, the temperature was lowered to 10 ° C and an additional 200.0 g (0.858 mol) of the ester was added dropwise, after completion of the addition, the reaction mixture was allowed to slowly warm to room temperature while stirring. After cooling to room temperature, 198.0 g (1.076 mol) of 1-iodobutane was added at 20 ° C, after which the reaction mixture was stirred at 40 ° C for 16 hours, then cooled. The mixture was concentrated, and the residue was poured into 1.5 liters of water. The precipitated insoluble oil was separated, the aqueous layer was extracted with ether, and the extract was combined with the oil, washed first with 100 ml of dilute hydrochloric acid, then with 100 ml of sodium bicarbonate solution. eventually 1 100 ml of water, dried and concentrated

324.3 g of crude product which, by distillation, yielded 223.0 g (72%) of pure ester having a boiling point of 115-120 ° C / 33.33 Pa. The product was identified by IR spectroscopy and its purity determined by gas chromatography.

2,2- (2,4-dichlorophenyl) -1-hexanol

To 11.7 g (0.308 mol) of lithium aluminum hydride in 1 liter of anhydrous ether at 5-10 ° C was slowly added 140.0 g (0.486 mol) of the above-prepared ethyl 3- (2,4-dichlorophenyl) hexanoate. adding the reaction mixture while stirring, allowing it to slowly warm to room temperature, and as soon as hydrogen gas evolves vigorously, the resulting suspension is slowly added to ice water, after the addition is acidified with concentrated hydrochloric acid, the organic layer is separated and the aqueous layer The extract was combined with the organic phase and washed with water and dilute sodium bicarbonate solution, dried over anhydrous magnesium sulfate, concentrated, and distilled to give 110.8 g (92%) of the desired product. boiling point 118-123 ° C / 26.66 Pa.

3. 2- (2,4-dichlorophenyl) hexyl methanesulfonate

To 14.7 g (0.1 mol) of 2- (2,4-dichlorophenyl) -2-hexanol and 13.8 g (0.12 mol) of methanesulfonyl chloride in 200 ml of benzene are slowly added 14.2 at 10 ° C. triethylamine (0.14 mol) After the addition was complete, the reaction mixture was allowed to warm to room temperature with stirring for 30 minutes, the resulting suspension was refluxed for 30 minutes, cooled and poured into water. Dilute hydrochloric acid, then water and finally dilute sodium bicarbonate solution After drying over anhydrous magnesium sulfate, evaporation of benzene yields 31.8 g (98%) of the crude product, identified by IC and NMR spectroscopy and is determined by gas purity. chromatography.

4, Reaction with imidazole

To 27.2 g (0.4 mol) of imidazole at 95 ° C was added 31.8 g (0.098 mol) of 2- (2,4-dichlorophenyl) hexyl methanesulfonate, and the mixture was stirred at 95 ° C for 16 hours. The mixture is then cooled, poured into 500 ml of water, stirred for 1 hour, the organic phase is separated and the aqueous layer is extracted with ether, the ether extract is combined with the organic phase, washed with water and concentrated to dryness. 24.4 g (88%) of the desired product The resulting imidazole derivative was identified by IC and NMR spectroscopy and elemental analysis, and the purity of the product was greater than 95% by gas chromatography.

Example 2

1- [β- (2,4-Dichlorophenyl) hexyl] imidazole hydrochloride

To a solution of 30.0 g (0.101 mol) of 1- (β- (2,4-diohlorophenyl) hexyljimidazole in 200 ml of ether) is added dry hydrogen chloride gas until acidic reaction to litmus. Filtration of the precipitated colorless solid gives 24.5 g of the desired product. The hydrochloride was identified by NMR spectroscopy.

Example 3

Complex of 1 - [[3- (2,4-dichlorophenyl) hexyl] imidazole with zinc chloride

Procedure A:

To a solution of 2.0 g (0.0067 mol) of 1- [[3- (2,4-dichlorophenyl) hexyl] imidazole in 10 ml of absolute ethanol is added dropwise a solution of 0.46 g (0.0036 mol) of zinc chloride in 30 ml of absolute The reaction mixture was stirred at room temperature for 10 minutes, then the solvent was evaporated in vacuo to give a white glassy solid which was identified by NMR spectroscopy.

Procedure B:

In a 40 ml solvent system consisting of a mixture of acetone, methanol and water (1: 1: 2), 2.0 g (0.0067 mol) of 1- (β- (2,4-dichlorophenyl) hexyl] imidazole and 0.1 g (0.0067 mol) were mixed. 92 g (0.0067 mol) of zinc chloride can be applied immediately to the leaves of plants.

Example 4

1 - ([3- (2,4-Dichlorophenyl) hexyl] imidazole oxalate)

To a solution of 4 g (0.0135 mol) of 1- [[3- (2,4-dichlorophenyl) hexyl] imidazole in ether was added dropwise a solution of 1.7 g (0.0135 mol) of oxalic acid in 10 ml of methanol at 39 ° C, immediately adding A white precipitate formed, which was filtered off and dried in vacuo to give 3.37 g of the desired solid, m.p. 126 DEG-128 DEG.

The compounds of Examples 5-25, summarized in Table I below, were also prepared in an analogous manner.

Example 26

1 - ([3- (p-Methylthiophenyl) hexyl] imidazole

1. p-Methylthiophenylmethanol

To 19.8 g (0.521 mol) of lithium aluminum hydride in 750 ml of anhydrous ether, at a temperature below 10 ° C, 98 g (0.64 mol) of p-methylmercaptobenzaldehyde in 250 ml of anhydrous ether are slowly added. After the addition was complete, the reaction mixture was stirred at 10 ° C for 0.5 h, then quenched by the gradual addition of 100 mL of acetone to remove unreacted lithium aluminum hydride.

After addition of 500 ml of water, the reaction mixture is acidified by the addition of concentrated hydrochloric acid, the ether layer is separated, dried over anhydrous magnesium sulphate and concentrated to give 89.6 g of crude product. This crude product was crystallized from ether / hexane

75.8 g of the desired product (yield 76%), m.p. 38-40 ° C.

2. p-Methylthiophenylacetonitrile

To 73.0 g (0.47 mol) of p-methylthiophenylmethanol and 59.6 g (0.52 mol) of methanesulfonyl chloride in 250 ml of benzene were slowly added over 1 hour at a temperature below 15 DEG C. 59 mol) of triethylamine. After the addition was complete, the reaction mixture was stirred for 1 hour while allowing to warm to room temperature.

After addition of 400 ml of dilute hydrochloric acid, the benzene layer is separated, washed with 250 ml of water and, after drying, concentrated to give 74.7 g of crude mesylate.

The residue obtained above is taken up in 25.5 g (0.52 mol) of sodium cyanide in 300 ml of dimethylsulfoxide, stirred for 1 hour, then poured into ice-water, the yellowish solid which precipitates is filtered off and recrystallized from benzene. hexane. 60.8 g (79%) of the desired product of melting point 44-45 ° C are obtained.

3. 2- (p-Methylthiophenyl) hexanenitrile

To 12.5 g (0.2.5 mol) of 50% sodium hydride in 300 ml of anhydrous distilled tetrahydrofuran was added 60.0 g (0.258 mol) of p-methylthiophenylacetonitrile over 1 hour. The reaction mixture was stirred for 1 hour, then 48.8 g (0.265 mol) of 1-iodobutane was slowly added. After the addition was complete, the resulting mixture was stirred for 2 hours, then 500 ml of water was added, the organic phase was separated, washed with water and concentrated. 80.1 g of crude product are obtained, which after distillation yields 65.7 g (85%) of the desired product with a boiling point of 126-130 ° C / 1.3 mm Hg.

The appropriate imidazole derivative is then prepared according to Example 68, paragraphs 2, 3, 4 and 5.

Example 27

1- [[3- (p-Methylsulfonylphenyl) hexyl] imidazole

To 7.0 g (0.021 mol) of 1- [β- (p-methylthiophenyl) hexyljimidazole salt with nitric acid in 75 ml of glacial acetic acid, 8.0 g (0.083 mol) of 35% peroxide are added dropwise at a temperature below 10 ° C. hydrogen. After the addition was complete, the reaction mixture was stirred for 1 hour, then heated on a steam bath for 1 hour, then poured into ice water. The solution was basified with sodium hydroxide to litmus and the product was extracted with ether.

Addition of nitric acid to the ether extract yields an oily salt. This material is treated with aqueous sodium hydroxide to give the desired product. Extraction with ether and concentration of the extract yielded 2.1 g (25%) of the resulting methylsulfonyl derivative.

The product of Example 28 shown in Table I was prepared in an analogous manner. Example 29 1-lp- (p-Nitrophenyl) hexyl] imidazole

To a mixture of 20 ml of nitric acid and 10 ml of sulfuric acid at 5 ° C was slowly added 10.0 g (0.044 mol) of 1- (3-phenylhexyl) imidazole in 10 ml of sulfuric acid. After the addition was complete, the reaction mixture was poured into ice-water to give an oily product. The acid solution was discarded, the residual oil was washed with water and basified with dilute sodium hydroxide solution. The product was extracted with ether, the extract was dried and the salt precipitated by the addition of nitric acid which melted at 98-100 ° C after recrystallization from acetone-ether. Yield 4.8 g. Treatment of the salt with dilute sodium hydroxide gives the desired product as the free base.

Example 30

1- ([3- (p-Aminophenyl) hexyl] imidazole)

To 5.0 g (0.0183 mol) of 1- [[3- (p-nitrophenyl) hexyl] imidazole in 50 ml of methanol was added 2.0 g of concentrated hydrochloric acid, the solution was heated to reflux and at five minute intervals. four one gram portions of iron filings are added. After the addition was complete, the resulting suspension was stirred at reflux for 14 hours, then the reaction mixture was cooled and poured into water. The organic material was extracted with toluene, the extract was dried and concentrated to give 4.5 g of crude product.

The oily product is dissolved in ether and nitric acid is added to the solution, whereupon an oily salt precipitates. The oily material was treated with dilute sodium hydroxide solution, extracted with ether, dried and concentrated to give a yellow solid.

3.5 g of the desired imidazole derivative.

Example 31

1 - ([3- (2,4-Dichloro-5-nitrophenyl) hexyl] imidazole

To a mixture of 40 ml of nitric acid and 10 ml of sulfuric acid, at a temperature below 5 ° C, 14.8 g (0.0498 mol) of 1- [3- (2,4-dichlorophenyl) hexyl] imidazole in 30 ml of sulfuric acid are added. . The reaction mixture was stirred for 1/2 hour and then poured into ice water. The resulting oily product is isolated by decanting off the dilute acid solution, the residue is washed and ammonium hydroxide solution is added.

The organic product was extracted with ether, the extract was dried, and dry hydrogen chloride gas was added to precipitate the hydrochloride, which was filtered off. 9.4 g of crude product are obtained. Recrystallization of 2.7 g of this material from methanol gave 1.8 g of purified hydrochloride, m.p. 99-100 ° C.

The products of Examples 32-45, summarized in Table I below, were prepared in an analogous manner.

Example 46

1- [p- (2,4-Dimethylphenylphenyl) hexyl] imidazole

1. 2- (2,4-Dimethylphenyl) -1-hexanol

To the mixture. 173 g (1.63 mol) of m-xylene and 78.0 g (0.30 mol) of anhydrous tin (II) chloride are added dropwise while stirring under nitrogen at 0 ° C 30.0 g (0.30 mol) of 1,2- epoxyhexane in 50 g m-xylene. During the exothermic addition rate is controlled so that the reaction mixture remained at 3 ^Q G. After completion of the addition, the reaction mixture containing 223 g (2.0 mol) of m-xylene, stirred for 30 minutes at 0 ° C and then poured into a mixture of ice and concentrated hydrochloric acid. The aqueous phase is separated from the organic layer, the aqueous phase is extracted with ethyl ether, and the extract is combined with the organic phase obtained above. The combined solutions were washed successively with water, sodium bicarbonate solution and again with water, dried, and ethyl ether and excess unreacted m-xylene were evaporated from the solvent mixture on a rotary evaporator. The concentrated residue is subjected to fractional distillation under vacuum. The third fraction boiling at 112 ° C / 66.66 Pa is the desired product according to spectral and analytical data. Yield: 35.6 g (57.6% of theory).

2. 1 - [(3- (2,4-Dimethylphenyl) hexyljimidazole)

The desired imidazole derivative is prepared from the above alcohol by the procedure of Example 1, paragraphs 3 and 4.

The products of Examples 47 to 61, summarized in Table I below, are also obtained in an analogous manner.

Example 62

1- [α] (2,4-dimethoxyphenyl) hexyl] imidazole

2- (2,4-Dimethoxyphenyl) -1-hexanol

To a mixture of 27.6 g (0.20 mol) of m-dlmethoxybenzene, 52.1 g (0.20 mol) of anhydrous tin (II) chloride and 200 ml of methylene chloride are added dropwise under stirring at 5 ° C to 20.0 g (0). 20 mol of 1,2-epoxyhexane in 50 ml of methylene chloride The exothermic reaction is controlled by dropwise addition to maintain the reaction temperature at 3 [deg.] C. After the addition is complete, the reaction mixture is stirred at 5 [deg.] C. for 30 min. The layers are separated and the aqueous layer is extracted with methylene chloride, the combined organic layers are washed first with water, then with 5% sodium bicarbonate solution, and finally with water.The aqueous phase from the last wash is neutral on pH papers. The residue is subjected to fractional distillation under vacuum and the third fraction boiling at 140-142 ° C / 26.66 Pa is formed by NMR and IR spectra. The desired product yields

25.32 g (55% of theory).

2. 1- [N- (2,4-Dimethoxyphenyl) hexyl] imidazole

The alcohol obtained above was converted to the methanesulfonate according to the procedure of Example 1 (3). However, the reaction of this methanesulfonate with imidazole according to the procedure described in Example 1 (4) results in a rearrangement to produce the α-substituted product identified by IR and NMR spectroscopy.

The compounds of Examples 63 to 65, summarized in Table I below, were prepared in an analogous manner.

Example 66

1- [α- (2,4-Dichlorobenzyl) pentyl] imidazole

1. 1- (2,4-Diohlorobenzyl) -1-pentanol

To 7.5 g (0.384 mol) of magnesium shavings in 150 ml of ether was added 10.0 g (0.051 mol) of α-2,4-trichlorotoluene and a few crystals of iodine. After the iodine color disappeared, the reaction mixture was heated to reflux and 58.0 g (0.297 mole) of additional α-2,4-trichloro toluene in 50 ml were added to the mixture at a rate that kept stirring ^. ml of ether. After the addition was complete, the reaction mixture was refluxed for 2 hours, cooled, 17.0 g (0.197 mol) of valeraldehyde was added thereto, and the resulting mixture was refluxed again for 2 hours, then cooled and poured into ice. cold dilute hydrochloric acid. The organic phase is separated, the aqueous solution is extracted with ether and the extract is combined with the organic phase. After washing with water, the organic solution was dried over anhydrous magnesium sulfate and the solvent was evaporated. 57.2 g of crude product are obtained, which is distilled to give 11.3 g (23%) of the desired product, the purity of which is determined by gas chromatography.

2. 1- (2,4-dichlorobenzyl) pentyl methanesulfonate

The title methanesulfonate was prepared as in Example 1 (3). The product was identified by IR spectroscopy and its purity determined by gas chromatography.

3. 1- [cis- (2,4-Dichlorobenzyl) pentyl] imidazole

The title imidazole derivative was prepared as described in Example 1 (4). The product was identified by IR and NMR spectroscopy, and elemental analysis; the purity of the product is greater than 95% by gas chromatography.

Example 67

1- [β- (2,4-dichlorobenzyl) hexyl] imidazole

Ethyl .alpha .- (2,4-dichlorobenzyl malonate)

To 4.6 g (0.095 mol) of 50% sodium hydride in 250 ml of anhydrous tetrahydrofuran was added with stirring 16.0 g (0.1 mol) of ethyl malonate, the resulting suspension was stirred for 1 hour, then heated at reflux for 3 hours. cooled and added to it

17.5 g (0.09 mol) α, 2,4-trichlorotoluene. The reaction suspension was refluxed for 16 hours, then cooled and the fetrahydrofuran was evaporated. The residue is stirred with water and the resulting ester is extracted with ether. The ethereal solution was washed with water, dried over anhydrous magnesium sulfate and concentrated. The crude product is obtained as a residue, which is heated to 110 DEG C. at a pressure of 13.33 Pa. Distillation of excess ethyl malonate left 27.1 g (94%) of the desired product, which was found to be &gt; 95% pure by gas chromatography.

2. Ethyl α-butyl-α- (2,4-dichlorobenzyl) malonate

To 6.7 g (0.14 mol) of 50% sodium hydride in 500 ml of anhydrous tetrahydrofuran was added 44.2 g (0.139 mol) of ethyl N- (2,4-dlchlorobenzyl) malonate and the resulting suspension was refluxed. The mixture was stirred at reflux for 16 hours. The reaction mixture was cooled, 26.6 g (0.14 mol) of 1-iodobutane was added thereto, and the resulting mixture was heated to reflux for 6 hours with stirring.

The solvent is evaporated and the residue is stirred with 500 ml of water. The precipitated product is extracted with ether, the ether extract is washed twice with 100 ml of water each time, dried over anhydrous magnesium sulphate and the ether is evaporated. 60 g (&gt; 100%) of the desired crude product are obtained, the purity of which is 95% by gas chromatography.

3. α- (2,4-dichlorobenzyl) hexanoic acid

To 45.0 g (0.40 mol) of 50% sodium hydroxide is added 52.4 g (0.14 mol) of ethyl .alpha.-butyl-.alpha .- (2,4-dichlorobenzyl) malonate, the mixture is stirred under reflux for 16 hours. The reaction mixture was cooled and washed twice with 75 ml of benzene, concentrated hydrochloric acid was added to the aqueous solution, the oily malonic derivative was separated and the aqueous solution was extracted with xylene and the extract was combined with the oil phase and dried over anhydrous magnesium sulfate. After 2 hours, xylene is distilled off from the reaction mixture until the temperature of the mixture rises to 180 DEG C. 46.0 g of crude product are obtained by cooling the remaining mixture.

4. 2- (2,4-dichlorobenzyl) -1-hexanol

To 9.4 g (0.248 mole) of lithium aluminum hydride in 600 mL of tetrahydrofuran was slowly added 46.0 g of crude α- (2,4-dichlorobenzyl) hexanoic acid at below 10 ° C. The reaction mixture was allowed to slowly warm to room temperature while stirring. After 2 hours, the resulting suspension was heated to reflux and refluxed for 16 hours, then cooled and poured carefully into ice water to quench excess lithium aluminum hydride, acidified with concentrated hydrochloric acid, and the ethereal solution was separated. The aqueous phase is extracted three times with 200 ml of ether each time, the extracts are combined with an ethereal solution, washed first with 100 ml of dilute sodium bicarbonate solution and then with 100 ml of water, dried over anhydrous magnesium sulfate and the ether is evaporated.

35.9 g of crude alcohol are obtained, which is distilled to give 34.2 g (93%) of pure alcohol at a boiling point of 86.8 ° C / 20 Pa. The product is identified by IR spectroscopy and its purity determined by gas chromatography.

5. 2- (2,4-dichlorobenzyl) hexyl methanesulfonate

The title methanesulfonate was prepared as described in Example 1, paragraph 3. The product was identified by IR spectroscopy and its purity determined by gas chromatography.

6. 1- (3- (2,4-Di-chlorobenzyl) hexyl) imidazole

The title imidazole was prepared as described in Example 1 (4). The product was identified by IR spectroscopy, NMR spectroscopy and elemental analysis and its purity was greater than 95% by gas chromatography.

Example 68

1- [α- (2,4-dichlorophenyl) heptyl] imidazole

1. 2- (2,4-dichlorophenyl) hexyl cyanide

To a suspension of sodium cyanide (11.3 g, 0.23 mol) in dry dimethylformamide (100 ml) was added dropwise a solution of 50 g (0.154 mol).

2- (2,4-di-chlorophenyl) hexyl methanesulfonate in 50 ml of dimethylformamide. The reaction mixture was stirred at 70 ° C overnight, then poured into 500 mL of water and extracted with ether. The combined ether extracts were washed first with water and then with saturated sodium chloride solution, dried over magnesium sulfate and the solvent was evaporated under reduced pressure. 37 g of crude product are obtained, which is purified by vacuum distillation to give 33.9 g (86%) of the expected product, b.p. 107.5-110 ° C / 6.66 Pa.

2. 2- (2,4-dichlorophenyl) heptanoic acid

A mixture of 2- (2,4-dichlorophenyl) hexyl cyanide (15 g, 0.0596 mol) and 50% sulfuric acid (100 ml) was heated at 110 ° C overnight, then cooled and diluted with water (500 ml). the combined ether extracts were dried over magnesium sulfate and the solvent was evaporated under reduced pressure to give 15.02 g (93.7%) of a white solid, mp 65-68 ° C.

3. 3- (2,4-dichlorophenyl) -1-heptanol

To a suspension of 2.07 g (0.0545 mol) lithium aluminum hydride in 100 ml ether was added dropwise a solution of 15 g (0.054 mol) 2- (2,4-dichlorophenyl) heptanoic acid in 50 ml ether and the resulting mixture was stirred at room temperature for 3 hours. The excess lithium197264 aluminum hydride was decomposed by carefully adding first 100 ml of saturated ammonium chloride solution and then 100 ml of dilute sulfuric acid solution.The ether layer was separated from the aqueous layer and the aqueous phase was extracted again with ether. , then with water, saturated sodium bicarbonate solution and finally saturated sodium chloride solution, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure to give 12 g of an oily residue which was further purified by vacuum distillation to give ID, 2 g (72%). of the desired product with a boiling point of 120 to 125 ° C / 3.33 Pa.

4. 3- (2,4-dichlorophenyl) heptyl methanesulfonate

To 10.2 g (0.039 mol) of 3- (2,4-dichlorophenyl) -1-heptanol and 4.8 g (0.042 mol) of methanesulfonyl chloride in 100 ml of benzene are slowly added 4.4 g (0.043 mol) at 10 ^° C. After the addition is complete, the reaction mixture is allowed to warm to room temperature with stirring for 30 minutes, the resulting suspension is refluxed for 30 minutes, cooled and poured into water, and the organic solution is washed first with dilute hydrochloric acid, then water. and finally with dilute sodium bicarbonate solution. After drying over anhydrous magnesium sulfate, benzene was evaporated to give 10.6 g of crude methanesulfonate.

5. 1- [α- (2,4-dichlorophenyl) heptyl] imidazole

10.5 g (0.042 mol) of crude 3- (2,4-dichlorophenyl) heptyl methanesulfonate are added to 10.6 g (0.160 mol) of imidazoles at 95 ° C. The reaction mixture was stirred at 95 ° C for 16 h, then cooled and poured into 530 mL of water. After stirring for 1 hour, the organic material was separated, the aqueous layer was extracted with ether, the ether extract was combined with the organic phase and washed with water and dried. Concentration gave 10.6 g of crude product.

Example 69

1- (3- [2,4-dichlorophenyl) phenethyl] imidazole

1. α- (2,4-dichlorophenyl) phenylacetaldehyde

To 47.1 g (0.188 mol) of 2,4-dichlorobenzophenone and 36.2 g (0.289 mol) of ethyl chloroacetate are slowly added at 15 ° C to 14.9 g (0.31 mol) of 50% sodium hydride. The mixture was allowed to warm to room temperature with stirring overnight, then was poured into ice water and acidified with dilute hydrochloric acid.The organic material was extracted three times with 200 ml of benzene each time, the extracts were combined, washed twice each time.

100 ml of water and dried over anhydrous magnesium sulfate. The benzene was evaporated and the crude residue was added to 35.3 g (0.53 mol) of 85% potassium hydroxide in 350 ml of water. The mixture was refluxed for 20 hours, cooled and washed twice with 200 ml of benzene. The aqueous solution is acidified, whereupon the organic acid precipitates as an oil. The oil was separated and the aqueous solution was extracted twice with 200 ml of ether each time. The extracts were combined with the oily product, dried over anhydrous magnesium sulfate, and concentrated to give 30.7 g of hydroxy acid. The residue was decomposed by heating to 140 ° C for three hours to give 24.3 g of the desired crude aldehyde, which distilled to give 16.3 g (33%) of the aldehyde, b.p. 128-137 ° C / 6.66 Pa.

2. β- (2,4-dichlorophenyl) phenethanol

To 2.4 g (0.0615 mol) of lithium aluminum hydride in 140 ml of anhydrous tetrahydrofuran at 0 ° C was added dropwise at 0 ° C 16.3 g (0.0615 mol of α- (2,4-dichlorophenyl) phenylacetaldehyde in 60 ml of anhydrous tetrahydrofuran). The reaction mixture was stirred at 0 ° C for 2 hours, then at room temperature for 16 hours, then refluxed for 2 hours, poured into ice-water, cooled, acidified with concentrated hydrochloric acid and the organic material was evaporated. The extracts were combined, dried over anhydrous magnesium sulfate and concentrated to give 15.5 g of crude product which, by distillation, gave 10.6 g (65%) of the purified desired alcohol, b.p. 125-139 ° C. The product is identified by IR spectroscopy and its purity determined by gas chromatography.

3. β- (2,4-dichlorophenyl) phenethyl methanesulfonate

The title product was prepared as described in Example 1, paragraph 3. The product was identified by IR spectroscopy and its purity determined by gas chromatography.

4. 1- [β- (2,4-dichlorophenyl) phenethyl] imidazole

The title imidazole derivative was prepared as described in Example-1, paragraph 4. Recrystallization of the product from ether / acetone gave 2.6 g (32%) of the hydrochloride, m.p. 197-198 ° C.

Example 70

1- [ε - (2,4-dichlorophenyl) hexyl] imidazole

1. 5- (2,4-dichlorophenyl) -1-hexanol

A suspension of 735 g (5.0 moles) of m-dichlorobenzene and 162 g (1.1 moles) of anhydrous aluminum chloride was cooled to 10 ° C using a water-ice cooling bath and 100 g ( 1.0 mol) of 1,2-epoxyhexane while maintaining the temperature of the reaction mixture below 15 ° C. The resulting mixture was allowed to warm to room temperature and stirring was continued overnight. The reaction mixture was then poured into a 4L flask containing ice and 50 mL concentrated hydrochloric acid with stirring. The aqueous layer was separated from the organic layer and the aqueous phase was extracted three times with 150 ml of ether each time. The combined organic extracts were washed twice with 50 ml of water each time, dried over magnesium sulphate, the solvent was evaporated and the residue was distilled under vacuum. 114 g (46%) of the desired product with a boiling point of 160-172 DEG C./13.33 Pa are obtained.

2. 1- [ε- (2,4-dichlorophenyl) hexyl] imidazole

The primary alcohol obtained above is converted to the sulfonate and then to the imidazole derivative in a conventional manner.

Example 71

1- (α-methyl-1- (2,4-dichlorophenyl) hexyl) imidazole

1. 2,4-dichlorvalerophenone

To 48.0 g (0.398 mol) of valeryl chloride in 100.0 g (0.680 mol) of m-dichlorobenzene was added portionwise at a temperature below 5 ° C 66.7 g (0.5 mol) of aluminum chloride. After the addition was complete, the reaction mixture was stirred for 2 hours, allowed to warm slowly to room temperature, then refluxed for 3 hours, then stirred at room temperature for 16 hours. The reaction mixture is poured into ice-water, acidified with hydrochloric acid, the separated oil is separated and the aqueous phase is extracted twice with 200 ml of ether each time. The oily material was combined with the extracts, washed with water and concentrated to dryness. 122.2 g of crude product are obtained, which is distilled to give 55.2 g (60%) of the desired product, b.p. 89 DEG-93 DEG C./6 mm Hg.

2. α- (2,4-dichlorophenyl) hexanal

To 50.0 g (0.216 mol) of 2,4-dichlorvalerophenone in 42.4 g (0.346 mol) of ethyl chloroacetate was added portionwise at 0 ° C over 4 hours 8.7 g (0.363 mol) of sodium hydride. After the addition was complete, the reaction mixture was stirred for 2 hours while slowly warming to room temperature. The resulting mixture was poured into ice-water, acidified with hydrochloric acid, the organic material extracted with ether, dried and concentrated. 89.2 g of crude glycidester are obtained, to which 40 g (0.607 mol) of 85% potassium hydroxide in 400 ml of water are added and the mixture is heated on a steam bath for 2 hours. The basic solution was washed with benzene and acidified with hydrochloric acid. The precipitated oil is extracted with ether, the ether solution is dried and concentrated. The residue was dissolved in xylene and the solution was refluxed for 6 hours with evolution of carbon dioxide. Evaporation of the resulting solution to dryness yielded

32.4 g of crude aldehyde which, by distillation, gave 16.6 g (31% of the desired product, b.p. 112-117 ° C).

3- (2,4-dichlorophenyl) -2-heptanol

To 14.3 g (0.088 mol) of methylroagnesium iodide in 75 ml of ether was slowly added 14.5 g (0.059 mol) of N- (2,4-dichlorophenyl) hexanal at a temperature below 10 [deg.] C. The reaction mixture was stirred for 1 hour at the end of the addition. The reaction mixture was then acidified with hydrochloric acid and the resulting oil was extracted with ether, dried and concentrated to give 11.7 g (76%) of the crude product.

4. 3- (2,4-dichlorophenyl) -2-heptyl methanesulfonate

The title methanesulfonate was prepared as described in Example 1, paragraph 3. The product was identified by IR spectroscopy and its purity determined by gas chromatography.

5. 1- [α-Methyl-S- (2,4-dichlorophenyl) hexyl] imidazole

The title imidazole derivative was prepared as described in Example 1 (4). The product was identified by IR spectroscopy and its purity determined by gas chromatography, according to which the product consisted of approximately equal proportions of isomeric products.

Example 72

1 - [(S-butyl-S- (2,4-dichlorophenyl) hexyl] imidazole hydrochloride

Ethyl α-butyl-α- (2,4-dichlorophenyl) hexanoate

To 4.3 g (0.09 mol) of 50% sodium hydride in 200 ml of anhydrous tetrahydrofuran was added 23.6 g (0.0816 mol) of ethyl N- (2,4-dichlorophenyl) hexanoate, the reaction mixture was boiled under reflux for 72 hours. After stirring at room temperature for 72 hours, 16.6 g (0.09 mol) of iodobutane were added and the mixture was refluxed for 24 hours, then cooled, poured into ice water and poured into ice. The separated oil is separated, the aqueous phase is extracted with ether, the extract is combined with the oily material, the ether solution is dried and concentrated to give 14.2 g of crude product which is distilled off by distillation.

72 DEG-84 DEG C. gives 13.3 g of the desired ester, b.p. 150 DEG-170 DEG C./0.2 mm Hg.

2. 2-Butyl-2- (2,4-dichlorophenyl) -1-hexanol

The title alcohol was prepared as described in Example 1 (2). 4.8 g of pure product were obtained, distilling at 133-138 ° C / 6.66 Pa and identified by NMR spectroscopy.

3. Reaction with imidazole

The desired imidazole was prepared by the procedures of Example 1, paragraphs 3 and 4, via the corresponding methanesulfonate. The final product (1.5 g, 28%) melts after recrystallization from acetone / ether at 103-105 ^° C and is identified by NMR spectroscopy and elemental analysis.

Example 73

1 - [[3, 3-Bis (p-chlorophenyl) ethyl] imidazole

1. 2,2-bis (p-chlorophenyl) ethanol

To 15.1 g (0.397 mol) of lithium aluminum hydride in 753 ml of anhydrous tetrahydrofuran was added portionwise 95.0 g (0.338 mol) of bis (p-chlorophenyl) acetic acid at 2 ° C over 2 hours. After the addition was complete, the reaction mixture was stirred at 5 ° C for 4 hours, then allowed to warm to room temperature overnight and poured slowly into ice water, evolving hydrogen. The resulting mixture is acidified with hydrochloric acid, the organic phase is separated, the aqueous phases are extracted twice with 200 ml of ether each time and the extracts are combined with the organic phase. Drying of the ether solution followed by concentration afforded 74.9 g of crude product which was distilled to give 35.3 g (39%) of the desired product, bp 157-162 ° C / 6.66 Pa.

2. Preparation of imidazole derivative

The desired imidazole derivative, m.p. 80 DEG-82 DEG C., is prepared in a conventional manner.

Example 74 1 - [[3- (oa and p-chlorophenyl) -p-chlorophenyl] imidazole

I. 2- (o- and p-chlorophenyl) -p-chlorophenethyl chloride

To a mixture of 12.5 ml of 30% oleate in 25 ml of sulfuric acid was added dropwise at a temperature below 35 ° C

II, 6 g (0.76 mol) of chloroacetaldehyde diethyl acetal in 34.0 g (0.30 mol) of chlorobenzene. After the addition was complete, the reaction mixture was stirred for 1 hour, allowed to warm to room temperature, then poured into ice water and extracted twice with 200 ml of ether each time.

The extracts were dried and concentrated to give 17.3 g of a yellow-orange crude product. This material was distilled to give 9.8 g of the product as isomers, b.p. 165-168 ° C.

2. Reaction with imidazole

To 75 mL of methanol was added 1.05 (0.0453 mol) of sodium and to the resulting solution was added 3.1 g (0.0458 mol) of imidazole. The reaction mixture is evaporated to dryness and 50 ml of N, N-dimethylformamide are added to the wet solid residue. The resulting solution was heated to 130 ° C, the remaining methanol was distilled off, to the remaining solution in dimethylformamide was added 8.7 g (0.0305 mol) of 2- (o- and p-chlorophenyl) -p-chlorophenethyl chloride, the reaction mixture was stirred for 48 min. The mixture was cooled to 130 ° C, poured into ice water and the organic material was extracted with ether. The ether extract was cooled and hydrogen chloride gas was introduced. The oily salt formed was separated and a solution of sodium bicarbonate was added. The resulting mixture was extracted with ether, the ether solution dried and concentrated to give 0.6 g of the desired product.

Example 75

1- [(3R) -N-tetramethylene- [3- (2,4-dichlorophenyl) ethyl] imidazolium nitrate

1. t, a-tetramethylene-2,4-dichlorobenzyl cyanide

A 500 ml three-necked flask was charged with 200 ml of 25% sodium hydroxide solution and 4 g of tetraethylammonium bromide. A solution of 33.5 g (0.2 mol) of 2,4-dichlorobenzyl cyanide and 43 g (0.2 mol) of 1,4-dibromobutane in 200 ml of methylene chloride was added dropwise under nitrogen. After the addition was complete, the reaction mixture was refluxed for 1.5 hours, then poured into water and the layers separated. The aqueous layer was extracted with 100 ml of methylene chloride, the combined organic extracts were washed with water and saturated sodium chloride solution, dried over magnesium sulfate and the solvent was evaporated. Vacuum distillation of the residual yellowish oil gave 30.4 g (63%) of pure product, boiling at 130-140 ° / 26.66 P, identified by NMR spectroscopy.

2. α, α-tetramethylene-2,4-dichlorophenylacetic acid

A mixture of 14 g (0.06 mol) of α, α-tetramethylene-2,4-dichlorobenzyl cyanide, 163 ml of 40% potassium hydroxide solution and 120 ml of diethylene glycol is refluxed for 3 days. The reaction mixture was poured into water and extracted with ether. The aqueous layer was acidified with hydrochloric acid, washed with water and saturated sodium chloride solution, dried over magnesium sulfate, and the solvent was evaporated. 12.4 g of crude acid are obtained which, after recrystallization from a mixture of hexane and benzene, gives 8 g of pure acid, m.p. 136-138 ° C.

3. 2,2-tetramethylene-2- (2,4-dichlorophenyl) ethyl alcohol

To a suspension of 3 g (0.08 mol) of lithium amine-anhydride in 300 ml of anhydrous ether, 13 g (0.05 mol) of α, α-tetramethylene-2,4-dichlorophenylacetic acid in 50 ml of ether was added dropwise under nitrogen. The reaction mixture was refluxed for 1 hour, then excess lithium aluminum hydride was carefully quenched by dropwise addition of 10% hydrochloric acid to the reaction mixture. The two layers were separated and the aqueous layer was extracted with ether. The combined ether extracts were washed with water, dried over magnesium sulfate and the solvent was evaporated. 9.8 g of the desired alcohol are obtained, which is identified by NMR spectroscopy.

4. 2,2-tetramethylene 2- (2,4-dichlorophenyl) ethyl methanesulfonate

To a mixture of 9.8 g (0.4 mol) of 2,2-tetramethylene-2- (2,4-dichlorophenyl) ethyl alcohol and 5 g (0.04 mol) of methanesulfonyl chloride in 30 ml of benzene is added dropwise 5 g (0.05 The reaction mixture is stirred at room temperature overnight, the precipitate formed is filtered off, the benzene solution is washed first with water and then with dilute hydrochloric acid and then dried over anhydrous magnesium sulphate, and the solvent is evaporated to give 12 g of the desired product. using NMR spectroscopy.

5. 1 - [(3,5-tetramethylene- (3- (2,4-dichlorophenyl) ethyl) imidazole

A mixture of 12 g (0.037 mol) of 2,2-tetramethylene 2- (2,4-dichlorophenyl ethyl methanesulfonate), g (0.15 mol) of imidazole and 1 ml of dimethylformamide was heated at 140 ° C for 24 hours. The combined ether extracts were washed with water, dried over magnesium sulfate, the desiccant was filtered off and concentrated nitric acid was added dropwise to the ether solution, and the white precipitate was filtered off and dried in vacuo to give a total of 3.7 g of the desired product. salts having a melting point of 176-179 ° C, identified by NMR spectroscopy.

The products of Examples 76-100, summarized in Table I below, are also prepared in an analogous manner.

Example 101

1- [β- (2,4-dichlorophenyl) hexyl] -4-nitroimidazole

To 1.3 g (0.0307 mol) of sodium hydroxide in 150 ml of methanol was added 3.5 g (0.0307 mol) of 4-nitroimidazole and the solution was heated while methanol was distilled off. Dimethylformamide (100 ml) was added to the concentrate and the resulting solution was heated to 120 ° C to remove excess methanol and water. The dimethylformamide solution was cooled to below 90 ° C, and 10.0 g (0.0307 mol) of 2- (2,4-dichlorophenyl) hexyl methanesulfonate was added and the reaction mixture was heated to 145 ° C for 2 hours. The organic material was extracted with ether, the extract was dried and evaporated, a residue of 11.2 g was triturated with hexane and then dissolved in 25 ml of methanol. The product is a gummy solid which is filtered off and recrystallized from acetone / hexane to dryness.

4.2 g (41%) of the desired product, m.p. 67-69 ° C.

Example 102

1 - ([3- (2,4-dichlorophenyl) hexyl] -4,5-dichloroimidazole

Sodium (1.7 g, 0.0735 mol) was added to 100 ml of methanol and, after dissolution, 10 g (0.0735 mol) of 4,5-dichloroimidazole was added. The mixture was stirred until a solution was formed, after which the methanol was evaporated. The wet residue is taken up in 50 ml of DMF and the solution is heated to 125 ° C to remove residual methanol and water. The solution was cooled to below 100 ° C, and 2.5 g (0.0735 mol) of 2- (2,4-dichlorophenyl) hexyl methanesulfonate was added and the reaction mixture was heated at 130 ° C for 2 hours. The combined extracts were washed with water (2 x 50 ml), dried over anhydrous magnesium sulfate and concentrated to give 15.8 g of a crude product which was dissolved in ether and into a solution. The ethereal solution was poured from the separated oil and the oily material was triturated twice with 150 ml of ether each, 10% sodium hydroxide solution was added to the oily residue, and the mixture was extracted twice with 200 ml of ether each time. and concentrated to give 12.6 g (47%) of an oily product.

Example 1 and d 103

1 - ([3- (2,4-dichlorophenyl) hexyl] -3-butylimidazolium iodide)

5.0 g (0.0168 mol) of 1- [[3- (2,4-dichlorophenyl] halo] imidazole] was heated on a steam bath for 3.1 hours (3.168 mol) of 1-iodobutane. The mixture was cooled, triturated three times with 50 ml of ether each time and the oily residue was evaporated to dryness to give 5.3 g (66%) of an oily product.

Example 104

1 - ([3- (2,4-dichloro-5-nitrophenyl) hexyl] nitroimidazole

To 20.0 g (0.067 mol) of 1- [3- (2,4-dichlorophenyl) hexyl] imidazole in 40 ml of sulfuric acid was slowly added 80 ml of nitric acid and 40 ml of sulfuric acid, and the reaction mixture was heated on a steam bath for 14 hours. The acidic aqueous solution is poured from the separated oil, washed twice with 75 ml of water each time, taken up in a mixture of acetone and benzene, dried and concentrated to give 14.9 g of crude product. Purification 3.0 g of the crude product are dissolved in hot methanol and cooled, and the precipitated product is filtered off and dried to give 1.6 g of the desired nitroimidazole derivative.

Tables I and II below show the compounds prepared by the procedures described in the previous examples, as well as the physical constants of these compounds. These tables are merely illustrative of the various types of compounds within the scope of the invention, but are not intended to limit the scope of the invention in any way.

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Elemental analysis, calculated (found)

point thaw C H Cl N 0 next 60.64 6.16 24.01 9.16 (60,62) (6,10) (23,86) (9,42) 139—141 51.48 5.60 30.30 7.89 (53,99) (5,74) (31,87) (8,40) 57—63 48.75 4.94 29.70 6.88 7.58 (49,31) (4,97) (29,11) (7,67) Zn = (8.95) 126—128 54.22 5.33 19.20 7.56 14.16 (52,73) (5,21) (18,31) (7,23) (16,53) 219—221 38,00 3.92 16.26 5.87 13.00 (44,06) (4,44) (17,34) (6,85) Cu = (7.77) 61—64 52.35 5.38 21.08 7.51 5.49 4.70 (47,79) (4,81) (18,81) (7.43). (8,49) Cu = (8.43) 53—58 49.68 5.16 7.10 28.45 7.60 (49,75) (5,01) (7,73) (29,37) Co = (8.14) 107—113 45.75 4.87 18.96 6.91 10.54 5.23 (48,05) (4,84) (15,23) (7,47) (8.53) Ni = (4.23) 45—50 49.77 5.13 30.12 6.92 5.70 (49,96) (5.03) (29,49) (7,77) Fe = (7.74) 44—49 40.67 4.81 16.78 10.14 18.97 3.2 (43,28) (4,36) (17,03) (11,78) (17,29) Cr = (6.24) 154—156 53.63 5.74 31.79 8.26 (53,99) (5,74) (31,87) (8,39) 77.93 9.21 - 11.32 (79,29) (9,15) (11,56) 78.36 9.11 - 11.75 (79,29) (9,15) (11,56) 126—128 68.65 8.47 12.21 9.75 (68,92) (8,32) (12,71) (10.05) 72.99 8.42 11.20 7.35 (74,40) (8,58) - (10,84) (6.17) 77.36 8.70 11.87 (78,90) (8,83) - (12,27) 72—73 56.82 6.26 22.24 8.91 (60,21) (6,74) (23,70) (9.36) 66.80 7.25 14.72 9.52 (68,56) (7,29) (13,49) (10,66) 66.08 7.19 12.78 10.25 (68,56) (7,29) (13,49) (10,66) 103—106 56.76 6.32 22.09 8.23 (60,21) (6,74) (23,70) (9.36) 60.25 6.27 24.91 8.30 (60,61) (6,10) (23,85) (9,42) 78.06 9.46 10.83 (79,64) (9,44) - (10,93) 63.31 6.34 10.84 18.62 (64,85) (6,46) - (9,45) F = (19.23) 72.06 8.05 10.20 7.96 (73,14) (7,77) - (11,37) F = (7.71) 51.62 6.00 9.15 7.62 22.76 (52,42) (5,87) (10.32) (8.15) Br = (23.25) 108—110 56.48 6.81 13.06 13.89 9.32 (56,95) (6,87) - (12,45) (14,22) S = (9.50) 62.06 7.48 8.57 10.86 9.62 (62,71) (7.24) - (9,14) (10.44) S = / (10.47) 79.96 10,06 9.75 (80,23) (9,92) - (9,85) 65.40 7.19 15.42 12.53 (65,91) (7,01) - (15,37) (11,71) 73.64 8.92 16.84 (74,03) (8,70) (17,27)

point thaw C H Cl N 0 99—100 45.37 5.11 26.73 10.55 11.72 (45,41) (5.06) (26,81) (10.59) (12,09) 78.23 9.85 10.77 (79,64) (9,44) '· - (10,93) 78.97 9.79 10.54 (79,64) (9,44) - (10,93) 79.73 7.71 8.75 (82,85) (7,95) - (9,20) 66.46 7.79 11.70 (66,62) (7,74) - (11,95) 103—105 47.38 6.06 19.96 26.24 (47,32) (5,96) - (19,71) (27,01) 128—130 61.90 6.49 11.88 20.59 (62,27) (6,60) - (11,46) (21,83) 81.47 8.17 9.41 (82,00) (7,95) - (10.05) 78.95 7.80 9.25 (82,00) (7,95) - (10.05) 78.20 9.99 9.34 (80,23) (9,92) - (9,85) 74.50 9.51 9.67 (79,94) (9,69) - (10.36) 79.63 9.48 9.87 (80,55) (9,01) - (10.44) 76.36 9.50 10.32 (79,64) (9,44) - (10,93) 76.82 9.46 10.13 (79,64) (9,44) - (10,93) 77.50 9,30 10.46 (78,28) (9,15) - (11,56) 78.81 »9.73 10.36 (79,64) (9,44) - (10,93) 78.30 8.49 9.19 (82,00) (7,95) - (10.05) 81.12 8.21 9.68 (82,85) (7,95) - (9,20) 108—110 48.87 4.44 20.94 11.92 13.44 (48,85) (4,39) (20,60) (12,21) (13,95) 58.68 4.54 28.86 7.44 (59,12) (4,13) (29,09) (7,66) 152—153 57.04 4; 58 26.60 7.17 (57,08) (4.54) (26,61) (7,01) 52.05 5.62 26.82 7.78 (51,55) (5,85) (26,85) (7.07) 74.45 8.90 11.92 (78,46) (8.46) - (13,09) 76.82 8.23 13.75 (77,96) (8.05) - (13,99) 111—112 62.28 7.16 13.87 (63,35) (6.98) - (13,85) 78.48 9.18 11.56 (78,90) (8,83) - (12,27) 77.14 8.54 12.96 (78,46) (8.46) - (13,09) 77.71 9.84 11.74 (78,90) (8,83) - (12,27) 79.35 10,03 9.14 (80,23) (9,92) - (9,85) 79.47 9.70 9.27 (79,94) (9,69) (10.36) 78.29 9.88 8.85 (80,23) (9,92) - (9,85) 70.60 8.10 9 _x 90 (70,80) (9,39) - (9,72)

next

13.42

S = (13.68)

4.50

F = (4.75)

Example number point thaw G H Cl N 0 63 78.80 10.21 8.93 (80,48) (10,13) - (9,39) 64 76.70 9.29 10.94 (79,28) (9,15) - (11,56) 65 79.75 9.96 10.20 (79,94) (9,69) - (10.36) 66 59.93 6.14 22.52 9.10 (60,61) (6,10) (23,86) (9,43) 67 61.31 6.86 23.28 8.62 (61,74) (6,48) (22,78) (9.00) 68 60.46 6.21 23.99 8.13 (61,74) (6,48) (22,78) (9.00) 69 197—198 58.82 4.38 28.44 8.04 (57,73) (4.28) (30,07) (7,92) 70 60.39 6.46 23.50 8.94 (60,62) (6,10) (23,86) (9,42) 71 61.33 6.42 23.10 8.34 (61,74) (6,48) (22,78) (9.00) 72 103—105 54.93 6.54 25.44 6.70 (58,55) (6.98) (27,29) (7,19) 73 80-82 64.59 4.44 21,81 ' 8.65 (64,37) (4,45) (22,35) (8,83) 74 75 176—179 49.78 4.78 20.07 11.60 13.86 (50,29) (4,78) 119.79) (11,79) (13,40) 76 195—197 69.42 6.81 11.15 8.75 (72,94) (6,77) (11,33) (8,96) 77 57.40 6.01 8.25 28.58 (58,64) (6,23) - (9,12) Br = 78 248—250 58.00 4,11 29.89 7.69 (57,73) (4.28) (30,07) (7,92) 79 63.38 4.60 22.11 8.03 (64,30) (4,41) (22,40) (8,85) 80 137—138 56.40 6.54 28.83 7.97 (56,44) (6,41) (29,40) (7,75) 81 109—111 43.13 3.74 22.98 13.99 (43,42) (3,61) (23,35) (13,81) 82 163—166 49.20 4.54 36.07 9.60 (49,42) (4,49) (36,47) (9.61) 83 56.68 4.88 27.37 11.11 (56,49) (4,74) (27,79) (10,98) 84 56.95 5.33 26.26 10,02 (58,01) (5,24) (26,34) (10,41) 85 61.92 6.84 22.27 8.57 (62,77) C6,82) (21,80) (8,61) 86 63.16 7.23 19.54 7.17 (64,59) (7,42) (20,07) (7,93) 87 65.32 8.05 18.35 5.84 (66,00) (7,86) (18,65) (7.35) 88 57.92 6.36 23.16 9.25 (60,60) (6.07) (23,90) (9,43) 89 64.42 5.01 21.85 8.13 (65,27) (4,87) (21,41) (8.46) 90 64.31 5.31 20.75 7.71 (66,19) (5,25) (20,54) (8,11) 91 175—177 54.33 5.39 28.91 7.38 (57,08) (5,35) (29,73) (7,83) 92 83—85 62.62 6.38 11.98 8.88 (71,70) (6,02) (12,45) (8,94) 93 71.38 5.41 12.81 9.90 (72,21) (5,35) (12,54) (9.91)

next (26.01)

1972B4

Example number point thaw C H Cl N O next 94 55.59 4.96 27.14 11.30 (56,49) (4,74) (27,79) (10,98) 95 76.62 8.67 12.52 (78,90) (8,83) - (12,27) 96 76.58 7.57 15.08 (77,38) (7,58) - (15,04) 97 165 58.92 6.64 15.61 12.56 (decomposition) (65,95) (7.24) (14,98) (11,83) 98 65.70 6.74 15.09 11.58 (66,52) (6,44) (15,10) (11,93) 99 168—175 53.56 6.15 25.16 11.13 (57,58) (5,95) (26,15) (10,33) 100 ALIGN! 58.73 6.70 23.79 7.86 (61,74) (6,47) (22,78) (9.00) 101 67—69 50.65 4.90 19.39 11.63 13.54 (50,05) (5,23) (19,70) (11,67) (13,33) 102 50.55 4.83 38.62 6.59 (49,21) (4,40) (38,74) (7,65) 103 47.67 5.98 15.39 5.87 24.39 (47,42) (5,66) (14,73) (5,82) 1 = (26.37) 104 46.60 4.20 18.34 14.37 17.00 (46,53) (4,17) (18,31) (14,47) (16,53)

The compounds of Examples 105-118, summarized in the table below, were also prepared in an analogous manner.

Example 119

1- [2-Cyano-2- (2,4-dichlorophenyl) hexyl] imidazole hydrochloride

a) α-n-Butyl-2,4-dichlorobenzyl cyanide

0.3 mol of sodium hydride as a 50% dispersion in mineral oil is washed to remove mineral oil with 100 ml of dry n-hexane, purged with dry nitrogen and suspended in 250 ml of freshly distilled tetrahydrofuran. To this suspension of sodium hydride was added dropwise a solution of 55.8 g (0.3 mol) of 2,4-dichlorobenzyl cyanide in 100 ml of tetrahydrofuran at room temperature. After the addition was complete, the mixture was maintained at 30 ° C for 0.5 h, then n-butyl iodide solution was added dropwise, the resulting mixture was stirred under nitrogen at 40 ° C overnight, then poured into 1 liter of water and extracted three times. 200 ml of ether each. The combined ether extracts were washed with water, dilute hydrochloric acid, saturated sodium bicarbonate solution and saturated sodium chloride solution, dried over anhydrous magnesium sulfate, and the solvent was evaporated. 71 g of crude brown colored product are obtained, which is further purified by vacuum distillation. (105 - 107 ° C / 13.33 Pa). 61.7 g (85%) of the desired product was identified by NMR spectroscopy.

b j 2-Cyano-2- (2,4-dichlorophenyl) -1-hexanol

To an ice-cooled solution of 5 g (0.02 mol) of n-butyl-2,4-dichlorobenzyl cyanide in 20 ml of pyridine containing a suspension of paraformaldehyde (2.4 g, 0.08 mol) was added with stirring 1 ml of benzyltriethylammonium hydroxide The mixture was stirred under nitrogen for 16 hours at room temperature, then poured into 300 ml of water and extracted with ether, and the combined ether extracts were washed with water, saturated sodium chloride solution, dried over magnesium sulfate and the solvent was evaporated. The product was identified by NMR spectroscopy.

c) 2-Cyano-2- (2,4-dichlorophenyl) hexyl methanesulfonate

To a mixture of 2-cyano-2- (2,4-dichlorophenyl) -1-hexanol (5.6 g, 0.02 mol) and 2.9 g (0.025 mol) of methanesulfonyl alcohol in 200 ml of benzene at 10 ° C 2.8 g (0.027 mol) of triethylamine are added dropwise. The reaction mixture was stirred at room temperature for 30 minutes and then heated on a steam bath for a further 30 minutes. The precipitate is filtered off, the filtrate is washed with dilute hydrochloric acid, water, saturated sodium bicarbonate solution and saturated sodium chloride solution and dried over magnesium sulfate. After evaporation of the solvent, 6.3 g of the desired product are obtained.

d) 1- [2-Cyano-2- (2,4-dichlorophenyl) hexyl] imidazole hydrochloride

A mixture of 100 g (0.29 mol) of 2-cyano-2- (2,4-dichlorophenyl) hexyl methanesulfonate, 100 g of imidazole (1.5 mol) and 5 ml of N, N-dimethylformamide was heated to 135 ° C with stirring overnight. The reaction mixture was poured into water and extracted with ether, the combined ethereal ex197264 traces were dried over magnesium sulfate, the desiccant was filtered off, and the ethereal solution was treated with dry hydrogen chloride gas, and the precipitated white precipitate was filtered and dried to give 70.4 g (68%). of the desired product identified by NMR spectroscopy.

The compounds of Examples 120-127, summarized in the table below, were also prepared in an analogous manner.

Example 128

Complex of 1- [2-cyano-2- (2,4-dichlorophenyl) hexyl] imidazole with zinc chloride

To a ethanolic solution of 3 g (0.01 mol) of 1- [2-cyano-2- (2,4-dichlorophenyl) hexyl) imidazole was added a solution of 0.63 g (0.01 mol) of zinc chloride in 10 ml of absolute , ethanol. The white precipitate was filtered, washed with ethanol and dried to yield 3.1 g of the desired product melting at 196 to 193 ^Q C, identified by NMR spectroscopy.

The compounds of Examples 129-134, summarized in the table below, were also prepared in an analogous manner.

Example 135

1- [2-cyano-2- (2,4-dichlorophenyl) decyl] imidazole hydrochloride

a) α-n-octyl-2,4-dichlorobenzyl cyanide

0.13 mol of sodium hydride as a 50% dispersion in mineral oil is washed with 100 ml of dry n-hexane to remove the mineral oil, then purged with dry nitrogen and suspended in 250 ml of freshly distilled tetrahydrofuran. A solution of 25 g (0.13 mol) of 2,4-dichlorobenzyl cyanide in 100 ml of tetrahydrofuran is added dropwise at room temperature to the obtained sodium hydride suspension. After completion of the addition, the temperature of the mixture was maintained at 30 ° C for 0.5 h, then 27 g (0.14 mol) of n-octyl bromide was added, the reaction mixture was stirred under nitrogen at 40 ° C overnight. 1 liter of water and extracted three times with 200 ml of ether each time. The combined ether extracts were washed with water, dilute hydrochloric acid, saturated sodium bicarbonate solution and saturated sodium chloride solution, dried over magnesium sulfate, and the solvent was evaporated, yielding 39.8 g (100%) of the desired product.

b) 2-cyano-2- (2,4-dichlorophenyl) -1-decanol

To an ice-cooled solution of 40 g (0.14 mol) of α-n-octyl-2,4-dichlorobenzyl cyanide in 250 ml of pyridine containing a suspension of paraformaldehyde (21 g, 0.7 mol) was added with stirring 1 ml of benzyltriethylammonium hydroxide. The mixture was stirred at room temperature under nitrogen for 72 hours, then poured into 2 L of water and extracted with ether. The combined ether extracts were washed with water, saturated sodium chloride solution and dried over magnesium sulfate. Evaporation of the solvent gave 40 g of the desired product as a thick oil.

c) 2-cyano-2- (2,4-dichlorophenyl) decyl methanesulfonate

To a mixture of 40 g (0.12 mol) of 2-cyano-2- (2,4-dichlorophenyl) -1-decanol and 15.3 g (0.13 mol) of methanesulfonyl chloride in 2 liters of benzene is added dropwise at 10 ° C. 14.8 g (0.14 mol) of triethylamine. The reaction mixture was first stirred at room temperature for 30 minutes and then heated on a steam bath for a further 30 minutes. The precipitate was filtered off, the filtrate was washed with dilute hydrochloric acid, water, saturated sodium bicarbonate solution, saturated sodium chloride solution, dried over magnesium sulfate and the solvent was evaporated. 41.3 g of the desired product identified by NMR spectroscopy are obtained.

d) 1- [2-cyano-2- (2,4-dichlorophenyl) decyl] imidazole hydrochloride

A mixture of 41.3 g (0.1 mol) of 2-cyano-2- (2,4-dichlorophenyl) decyl methanesulfonate, 27.7 g (0.4 mol) of imidazole and 1.5 ml of N, N-dimethylformamide was heated for 24 hours with stirring at 130 [deg.] C. The reaction mixture is poured into water and extracted with ether, the combined ether extracts are washed with water, dried over sodium sulphate and dry hydrogen chloride gas is added to the ether solution, the precipitated white product gives 11.7 after filtration and drying g (28%) of the desired product identified by NMR spectroscopy.

Example 131

1- [2-cyano-2- (4-chlorophenyl) propyl] imidazole hydrochloride

(a) 2-cyano-2- (4-chlorophenyl) -1-propanol

To an ice-cooled solution of 50 g (0.3 mol) of commercially available α-methyl-4-chlorobenzyl cyanide in 500 ml of pyridine containing a suspension of paraformaldehyde (36 grams, 1.2 mol) was added with stirring 1 ml of benzyltriethylammonium hydroxide. The reaction mixture was stirred under nitrogen at room temperature for 72 hours, then poured into water and extracted with ether. The combined ether extracts were washed with water and saturated sodium chloride solution, dried over magnesium sulfate and the solvent was evaporated. 58.4 g of a thick oily product identified by NMR spectroscopy are obtained.

b) 2-cyano-2- (4-chlorophenyl) propyl methanesulfonate

To a mixture of 68 g (0.3 mol) of 2-cyano-2- (4-chlorophenyl) -1-propanol and 37.5 g (0.33 mol) of methanesulfonyl chloride in 2 liters of benzene is added dropwise at 10 DEG C. 36 g. (0.36 mol) of triethylamine. The reaction mixture was first stirred at room temperature for 30 minutes and then heated on a steam bath for a further 30 minutes. The precipitate was filtered off, the filtrate was washed with dilute hydrochloric acid, water, saturated sodium bicarbonate solution and saturated sodium chloride solution, dried over magnesium sulfate and the solvent was evaporated. 63 g of the expected product are obtained.

c] 1- [2-Cyano-2- (4-chloro-phenyl) -propyl] -imidazole hydrochloride

A mixture of 63 g (0.23 mol) of 2-cyano-2- (4-chlorophenyl) propyl methanesulfonate, 62.6 g (0.9 mol) of imidazole and 3 ml of Ν, Ν-dimethylformamide was heated to 130 ° C with stirring for 24 hours. The reaction mixture is poured into water and extracted with ether, the combined ether extracts are washed with water, dried over magnesium sulphate and dry hydrogen chloride gas is added to the ether solution to give 38 g (58.6%) of the desired product by filtration and drying. identified by NMR spectroscopy.

Example 132

1- [2-cyano-2- (2-chlorophenyl) -2- (4-chlorophenyl) ethyl] imidazolium nitrate

(a) 2,4‘-dichlorobenzhydrol

To 12.7 g (0.52 mol) of magnesium shavings in 200 ml of anhydrous ether was added 10.0 g (0.052 mol) of p-bromochlorobenzene and the mixture was heated to reflux. Once the Grignard reaction has started, the heating is discontinued and an additional 80.0 g (0.47 mole) of p-bromochlorobenzene in 80 mL of ether is added at such a rate that the mixture boils continuously. After the addition was complete, the reaction mixture was refluxed for 2 hours, then 73.4 g (0.52 mole) of o-chlorobenzaldehyde was slowly added, the resulting mixture was refluxed for 2 hours, cooled, poured into water. ice, the resulting mixture was acidified with hydrochloric acid and the organic phase separated. The aqueous layer was extracted with ether and the extract was added to the organic phase. The resulting solution was washed with water, dried over anhydrous magnesium sulfate and concentrated to a viscous residue which crystallized from petroleum ether to give 109.4 g (83%) of the desired product, m.p. 68-70 ° C.

b) 2,4‘-dichlorodiphenylbromoethane

68.4 g (0.253 mol) of phosphorus tribromide are slowly added to 109.4 g (0.432 mol) of 2,4‘-dichlorobenzhydrol in 125 ml of benzene at 10 ° C. After the addition was complete, the reaction mixture was stirred for a further 2 hours, after which the benzene was evaporated at atmospheric pressure up to 115 ° C (measured in the reaction mixture). The residue is cooled, poured into ice-water, stirred for minut5 minutes, then the organic materials are extracted three times with 100 ml of ether each time. The extracts were combined, washed with brine and dried over anhydrous magnesium sulfate. 116.5 g of crude product are obtained, which is distilled to give 97.2 g (69%) of pure resultant bromomethane having a boiling point of 140-145 [deg.] C./13.33 Pa.

c) 2,4‘-dichlorodiphenylacetonitrile

25.5 g (0.285 mol) of anhydrous cuprous cyanide are added to 85.0 g (0.27 mol) of the above bromomethanedivative at 125 ° C. As a result of the exothermic reaction taking place, the temperature of the mixture rises to 140 ° C. The reaction mixture was recooled to 125 ° C, stirred at 125 ° C for 1 hour and then heated to 150 ° C for another hour. The resulting mixture is cooled, stirred with 200 ml of benzene, the insoluble solid is filtered off and the filtrate is evaporated to dryness. 70.6 g of crude product are obtained, which is distilled to give 63.3 g (90%) of the desired acetonitrile derivative having a boiling point of 140-144 ° C / 13.33 Pa.

d) 2-cyano-2- (2-chlorophenyl-2- (4-chlorophenyl) ethanol)

To an ice-cooled solution of 20 g (0.08 mol) of 2,4‘-dichlorodiphenylacetonitrile in 100 ml of pyridine containing a suspension of p-formaldehyde (9.2 g, 0.3 mol) was added 1 ml of benzyltriethylammonium hydroxide. The reaction mixture was stirred at room temperature under nitrogen for 63 hours, then poured into 1.5 L of water and extracted with ether. The combined ether extracts were washed with water and saturated sodium chloride solution, dried over magnesium sulfate and the solvent was evaporated. 18 g of a thick oily product identified by NMR spectroscopy are obtained.

e) 2-cyano-2- (2-chlorophenyl) -2- (4-chlorophenyl) ethyl methanesulfonate

To a mixture of 18 g (0.06 mol) of 2-cyano-2- (2-chlorophenyl) -2- (4-chlorophenyl) ethanol and 7.8 g (0.07 mol) of methanesulfonyl chloride in 200 ml of benzene was added at 10 ° C. ° C, triethylamine (7.5 g, 0.08 mol) was added dropwise and the reaction mixture was stirred for 30 minutes at room temperature and then heated on a steam bath for a further 30 minutes, and the precipitate was filtered off, washed with dilute hydrochloric acid, water, saturated sodium bicarbonate solution and saturated sodium chloride solution, dried over magnesium sulfate and the solvent evaporated to give 22 g of the desired product, mp 124-127 ° C, identified by NMR spectroscopy.

f) 1- [2-cyano-2- (2-chlorophenyl-2- (4-chlorophenyl) ethyl] imidazolium nitrate

A mixture of 22 g (0.06 mol) of 2-cyano-2- (2-chlorophenyl) -2- (4-chlorophenyl) ethylmethanesulfonate, 16.3 g (0.24 mol) of imidazole and 1 ml of N _; The N-dimethylformamide was heated to 150 ° C with stirring for 24 hours. The reaction mixture was poured into water and extracted with ether, the combined ether extracts washed with water and dried over magnesium sulfate. Excess concentrated nitric acid is added to the ether solution with vigorous stirring, the precipitate formed is filtered off and washed with ether and dried. 10.8 g (44.4%) of the desired product is identified by NMR spectroscopy.

The compounds of Examples 136-140, summarized in the table below, were prepared in an analogous manner.

Example 141

1- [2-cyano-2- (2-pyridyl) -2-phenylethyl] imidazole

a) 2-cyano-2- (2-pyridyl) -2-phenylethanol

To an ice-cooled solution of 50 g (0.26 mol) of commercially available phenyl-2-pyridylacetonitrile in 350 ml of pyridine containing a suspension of paraformaldehyde (31 g, 1.0 mol) was added with stirring 1 ml of benzyltriethylammonium hydroxide. The mixture was stirred under nitrogen at room temperature for 24 hours, then poured into water and extracted with ether. The combined ether extracts were washed with water and saturated sodium chloride solution, dried over magnesium sulfate and the solvent was evaporated. 58 g of a thick oily product identified by NMR spectroscopy are obtained.

b) 2-cyano-2- (2-pyridyl) -2-phenylmethyl methanesulfonate

To a mixture of 25 g (0.1 mol) of 2-cyano-2- (2-pyridyl) -2-phenylethanol and 14 g (0.11 mol) of methanesulfonyl chloride in 600 ml of benzene at 10 ^{0 |} 13.5 g (0.12 mol) of triethylamine are added dropwise. The reaction mixture was first stirred at room temperature for 30 minutes and then heated on a steam bath for 30 minutes. The precipitate was filtered off, the filtrate was washed with dilute hydrochloric acid, water, saturated sodium bicarbonate solution and saturated sodium chloride solution, dried over magnesium sulfate and the solvent was evaporated. It is obtained

14.2 g of the desired product identified by NMR spectroscopy.

c) 1- [6-cyano-2,4-dichlorophenyl) decyljimidazole

A mixture of 14.2 g (0.036 mol) of 6-cyano-6- (2,4-dichlorophenyl) decyl bromide, 10 g (0.15 mol) of imidazole and 5 ml of N, N-dimethylformamide was heated at 120 ° C for 24 hours. The mixture was poured into water and extracted with ether, the combined ether extracts were dried over magnesium sulfate, filtered, and the ethereal solution was treated with dry hydrogen chloride gas until an oily precipitate ceased to form. The purified free base was extracted with ether, the extract was dried over magnesium sulfate and the solvent was evaporated, yielding 6.5 g (47.8%) of the desired product identified by NMR spectroscopy.

The products of Examples 142-144, summarized in the table below, were prepared in an analogous manner.

Example 145

1- [2-cyano-2- (2,4-dichlorophenyl) -4-phenylbutyl] imidazolium nitrate

(a) α-phenethyl-2,4-dichlorobenzyl cyanide

0.13 mol of sodium hydride as a 50% dispersion in mineral oil is washed with 100 ml of dry N-hexane to remove the mineral oil, then purged with dry nitrogen and suspended in 250 ml of freshly distilled tetrahydrofuran. A solution of 25 g (0.13 mol) of 2,4-dichlorobenzyl cyanide in 100 ml of tetrahydrofuran is added dropwise at room temperature to the obtained sodium hydride suspension. After the addition was complete, the mixture was kept at 30 ° C for 5 hours, then a solution of 26 g (0.14 mol) of phenethyl bromide was added dropwise, the reaction mixture was stirred under nitrogen at 40 ° C overnight, then poured into 1 liter. water and extracted three times with 200 ml of ether each time. The combined ether extracts were washed with water, dilute hydrochloric acid, saturated sodium bicarbonate solution and saturated sodium chloride solution, dried over magnesium sulfate, the solvent was evaporated and the residue was distilled. There were obtained 26.6 g (70.5%) of the desired product, b.p. 144 to 156 ^Q C / 4 mm Hg, identified by NMR spectroscopy.

b) 2-cyano-2- (2,4-dichlorophenyl) -4-phenyl-1-butanol

To an ice cooled solution of 26.5 g (0.09 mol) of ^{.alpha.-phenethyl-2,4-dichloro-1} orbenzylkyanidu in 200 ml of pyridine containing a suspension of paraformaldehyde (11 g, 0.35 mol), was added 1 ml benzyltriethylamoniumhydroxidu. The reaction mixture was stirred under nitrogen at room temperature for 24 hours, then poured into 1 liter of water and extracted with ether. The combined ether extracts were washed with water and saturated sodium chloride solution, dried over magnesium sulfate and the solvent was evaporated. 25.4 g of a thick oily product identified by NMR spectroscopy are obtained.

c) 2-cyano-2- (2,4-dichlorophenyl) -4-phenylbutyl methanesulfonate

To a mixture of 25.4 g (0.08 mol) of 2-cyano-2- (2,4-dichlorophenyl) -4-phenyl-1-butanol and 10 g (0.09 mol) of methanesulfonyl chloride in 1 liter of benzene at a temperature of 9.6 g (0.09 mol) of triethylamine are added dropwise at 10 ° C. The reaction mixture was first stirred at room temperature for 30 minutes and then heated on a steam bath for a further 30 minutes. The precipitate was filtered off, the filtrate was washed with dilute hydrochloric acid, water, saturated sodium bicarbonate solution and saturated sodium chloride solution, dried over magnesium sulfate and the solvent was evaporated. 25.1 g of the desired product are identified by NMR spectroscopy.

d) 1- [2-cyano-2- (2,4-dichlorophenyl) -4-phenylbutyl] imidazolium nitrate

A mixture of 25 g (0.063 mol) of 2-cyano-2- (2,4-dichlorophenyl) -4-phenylbutylmethanesulfonate, g (0.25 mol) of imidazole and 1 ml of N, N-dimethylformamide was stirred for 24 hours. with stirring at 159 ° C. The reaction mixture was poured into water and extracted with ether. The combined ether extracts were washed with water, dried over magnesium sulfate and excess concentrated nitric acid was added to the ether solution with vigorous stirring. The precipitate formed is filtered off and washed with ether and dried to give 17.5 g (64%) of the desired product identified by NMR spectroscopy.

The compounds of Examples 146-162 summarized in the table below are also prepared in an analogous manner.

The following Table III gives an overview of the compounds prepared by the process of the invention, the melting points and which are shown in Table IV. The scope of the invention is not limited to the compounds listed in these tables.

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Complexes of the above imidazole with metal salts can be prepared by dropping a stoichiometric amount of the metal salt dissolved in a suitable solvent with stirring to a solution of 1-substituted aralkylimidazole in a similar suitable solvent. The reaction mixture is stirred for a short time and then the solvent is evaporated off under reduced pressure to give the corresponding 1-substituted aralkylimidazole metal salt complex. The identification and purity determination of the product is carried out by elemental analysis.

Metal salt complexes can also be prepared by mixing stoichiometric amounts (or excess) of the metal salt and the 1-substituted aralkylimidazole in the necessary amount of solvent containing suitable excipients just prior to spraying the plants. Excipients which may be present in such formulations prepared immediately before use are, for example, detergents, emulsifiers, wetting agents, distribution aids, dispersants, binders, adhesives and the like used in agrochemical applications.

Solvents useful in these processes include all polar solvents such as water, methanol, ethanol, isopropanol or ethylene glycol, and all aprotic dipolar solvents such as dimethylsulfoxide, acetonitrile, dimethylformamide, nitromethane, or acetone.

The metal salt cations useful in these processes may be selected from the group consisting of calcium, magnesium, manganese, copper, nickel, zinc, iron, cobalt, tin, cadmium, mercury, chromium, lead, barium and the like.

Any of the suitable anions such as anionic chloride, bromide, iodide, sulfate, bisulfate, phosphate, nitrate, perchlorate, carbonate, bicarbonate, hydrosulfide, hydroxide, acetate, oxalate, citrate, anionic charge-balancing anions in these metal salts can be used. etc.

It has also been found that any metal-containing fungicides can be used for the same purpose and with the same result instead of metal salts. Typical metal-containing fungicides useful herein include

(a) dithiocarbamates and their derivatives, such as ferric dimethyldithiocarbamate (ferbam), zinc dimethyldithiocarbamate (ziram), manganese ethylene bis-dithiocarbamate (maneb), and its zinc ion coordinate product (manzoceb) and ethylene bisamine zinc dithiocarbamate;

(b) copper-based fungicides such as cuprous oxide, cuprous naphthenate and Bordeaux broth;

c) various fungicides such as phenylmercuriacetate, N-ethylmerkuri-1,2,3,6-tetrahydro-3,6-endomethano-3,4,5,6,7,7-hexachlorophthalimide, phenylmercuron monoethanolammonium lactate, compounds with containing nickel and calcium cyanamide.

The compounds of the invention and their metal salt complexes have excellent activity as systemic protective and / or curative fungicides and show high activity against certain phytopathogenic fungi. Some of these substances are particularly effective against gray mold (Botrytis cinerea) on beans and beans, disease caused by the fungus Piricularia oryzae on rice, potato mold (Phytophthora infestans) on young tomato plants, powdery mildew (Erysiphe polygoni) on bean plants, brown spots barley (Helminthosporium teres) on barley, peronospora of grapevine (Plasmospara viticola) on young grapevine plants, rotting of citrus fruits caused by the fungus Penicillium digitatum, scab of apple tree (Ventu.ria inaequalis) on apple seedlings (Escherichia seedlings) the blackening of wheat kernels induced by the fungus Alternarla teuuis, the black rot of the vine (Gulguardia bidwellii) on young vine plants, the powdery mildew (Erysiphe cichoracearum) on cucumbers and against the organism responsible for the production of aflatoxin (Aspergillus flavus).

The curative fungicidal properties of the compounds of the invention are unique in that said compounds kill Helminthosporium teres in infected plant tissues. None of the known fungicides commonly used to combat diseases caused by Helminthosporium fungi has this property. Also unique are the systemic properties of the compounds described, since the compounds of the invention can move both acropetally (towards the vegetation peak) and basipetally (towards the roots) in plant tissue.

The disclosed free base compounds can be used to control the fungus Helminthosporium oryzae (brown speckled rice), a property not found in any other fungicide except organic mercury compounds.

The free base compounds of the present invention exhibit growth regulator properties in both monocotyledonous and dicotyledonous plants, with the most significant effect being the inhibition of plant growth. In some cases, especially in dicotyledonous plants, these growth regulator properties may be considered unfavorable and in such cases the plant growth and phytotoxicity regulatory properties can be suppressed by converting imidazole derivatives to complexes with elements selected from groups IIA, IVA, VA, IB , IIB, VIB, VIIB and VIII of the Periodic Table of the Elements.

A preliminary evaluation of the fungicidal activity of the compounds according to the invention is carried out by adjusting the compound to a concentration of 300 ppm of active ingredient and

197284 plants are sprayed with this product, using about 1000 liters of spray per hectare.

The general procedure for testing fungicidal efficacy is then carried out by spraying the plants grown in the dishes at the appropriate growth stage to assess their fungal diseases, spraying the test preparation on the moving belt and allowing them to dry. The treated plants are then inoculated with fungal spores and incubated until disease develops, whereupon the disease control is detected or calculated. Percentage of disease control is expressed on a scale of A-E, where each value has the following meanings:

A = 97-100% disease control,

B = 90-96% disease control,

C = 70-89% disease control,

D = 50-69% disease control,

E = Inactive dose or preparation (less than 50% disease control).

The disease control in% is calculated from the following formula:

range of disease to non-range of disease on o, ',,, treated plants sparing plants. disease control in% = ---—----——-——— x 100 range of disease on untreated plants

Table VI shows the results of the above-described fungieid activity tests of some of the compounds of the invention and their salts applied at 300 ppm. Fungi used for these tests are indicated in the table by symbols with the following meanings:

HT = Helminthosporium teres (brown spots of barley),

BC = Botrytis cinerea (Gray mold),

EP = Erysiphe polygoni (powdery mildew), PV = Plasmopara viticola (vine peronospora),

PI = Phytophthora infestans,

PO = Piricularia oryzae

PG = Puccinia graminis sp. tritici (grass rust),

PR = Puccinia recondita.

TABLE VI Compound HT BC EP PV PI PO PG PR of Example Number

9

21 22

AND

AND

AND

E

AND

AND

AND

AND

AND

AND

E

AND

E

AND

AND

AND

AND

AND

E

AND

AND

AND

E

AND

AND

E

AND

E

E

(B)

(B)

(B)

AND

(B)

C

AND

AND

AND

AND

AND

E

E

E

E

E

E

E

E

E

E

(B)

E

E

C

C c

E

E

C

E

C

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

E

AND

AND

AND

AND

AND

AND

E

AND

AND

AND

E

AND

AND

(B)

AND

AND

(B)

AND

AND

AND

AND

(B)

AND

AND

AND

AND

(B)

E

(B)

(B)

E

(B)

AND

(B)

(B)

(B)

AND

E

C

E

E

E

E

C

C

E

E

E

(B)

(B)

AND

(B)

(B)

AND

(B)

AND

(B)

(B)

(B)

E

AND

E

C

AND

AND

(B)

AND

(B)

AND

E

E

E

E

(B)

E

E

E

E

(B)

AND

(B)

(B)

E

E

AND

(B)

AND

AND

(B)

AND

E

(B)

AND

E

E

(B)

E

(B)

(B)

E

C

E

E

E

(B)

C

AND

E

C

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

E

E

C

C

(B)

AND

AND

AND

AND

And the compound of Example HT

BC EP PV PI

PO PG PR

E

E

AND

E

AND

AND

E

E

E

E

E

AND

AND

AND

E

AND

(B)

AND

E

E

E

AND

E

AND

AND

E

E

AND

E

AND

AND

(B)

AND

AND

AND

AND

AND

E

AND

AND

AND

E

E

AND

E

AND

E

AND

AND

AND

E

AND

AND

E

E

E

AND

E

AND

AND

E

E

E

C A C C A C EAC E A E

E - E E - E E - E E - E

E A E C A E EAC C A C E A B E A E E A C Ε E CAA Β E C BAB A A B A A B E A E E A E E A E E A E C and E, and Ε E E A E C A E C A E C A E Β E C E A E E A E CAA D and Ε B A A B Ε Ε B E A A B A E Β Β E A A A A E A B EAC and E BAB E A B E A E CAA C A B E A E C A E C A E C Ε E E A E C A B BAB BAB E A E E A E E A E E A E Ε Ε E Ε Ε E

E

AND

E

AND

E

E

E

E

E

E

(B)

E

E

E

E

E

E

E

E

E

E

C

E

AND

AND

(B)

(B)

AND

(B)

(B)

E

(B)

AND

AND

(B)

E

(B)

C

E

C

(B)

E

E

E

E

E

(B)

(B)

(B)

(B)

(B)

E

E

E

E

(B)

AND

AND

E

AND

(B)

AND

(B)

(B)

E

AND

(B)

(B)

(B)

(B)

E

E

E

E

AND

(B)

(B)

(B)

(B)

(B)

(B)

(B)

(B)

E

E

C

E

E

E

C

C

AND

(B)

AND

(B)

AND

C

E

E

E

E

E

(B)

E

E

C

C

C

E

C

AND

C

AND

E

AND

AND

AND

AND

(B)

E

AND

AND

AND

E

E

(B)

(B)

AND

AND

AND

AND

AND

AND

AND

E

AND

AND

AND

E

E

compound: example number HT BC EP 98 E E E 99 AND E AND 100 ALIGN! E E E 101 E E AND 102 E E AND 103 E AND AND 104 E E (B) Arylkyanalkyl- a diarylkyanalkylimidazo-

The present invention is particularly effective against phytopathogenic fungi such as gray mold (Botrytis cinerea) on broad bean (Vicia fabaj, powdery mildew (Erysiphe polygoni) on broad bean (Vicia faba var. Dwarf. Hort.j), late blight (Phytophthora infestansj) on young tomato plants, Piricularia oryzae on rice, peronospora grapevine (Plasmopara viticolaj on young grapevine plants, brown barley (Helminthosporium teres) on barley, wheat rust (Puccinia recondita) on wheat and grass rust (Puccinia sp. tritici) on wheat.

To evaluate the fungicidal activity of the other compounds of the invention, their acid addition salts and metal salt complexes, the following tests are performed:

To assess efficacy against gray mold (Botrytis cinerea), bean plants are trimmed to a height of about 10-13 cm 24 hours prior to chemical treatment, the test preparation is applied by spraying until run-off and after spraying the plants are allowed to dry. Botrytis cinerea and incubated for 66 hours in a humid environment at 24-30 ° C. The extent of disease on plants is evaluated 66-68 hours after inoculation.

To determine fungicidal activity against powdery mildew (Erysiphe polygonij), the bean plants (var. Dwarf Hort.j, cultivated in bowls) are torn 24 hours before chemical treatment, leaving only two plants in each dish. The polygons are cultivated on green bean leaves for 20-21 days, and the spores are isolated by cutting off the leaves of the bean infested with powdery mildew, placing them in a 1 liter glass container and then pouring the deionized glass into the container. water containing 0.05 ml of Tween 80 surfactant in 500 ml of water The spores are released from the leaf surface by shaking the container, the suspension obtained is filtered through a smooth gray cotton cloth to dilute the plant material and diluted to a content of 2 - 2.5 χ 10 ⁴ spores / ml Treated broad-bean plants are inoculated by spraying their leaves and stems from above suspensions until a visible film is formed on the plants, and the inoculated plants are then u62

PV PI AFTER PG PR E E (B) - E E - E - AND E (B) (B) - E C E AND AND - ' C E AND AND - (B) (B) - E - (B) E AND AND - behave in the greenhouse. Za 8 - - 10 days after inoculation is then evaluated and compares the

sah disease. Typical symptoms of powdery mildew on bean plants are circular white matt coatings on the leaf surface.

The fungicidal activity against Phytophthora infestans is evaluated by spraying young tomato plants with the respective test compound at a given concentration until the suspension of the test compound is run off. for incubation for about 40 hours in a humid chamber at 1001% relative air humidity and at a temperature of 15-17 ° C, then transferred to a greenhouse and after 5-6 days to evaluate and compare the disease state.

To assess the fungicidal activity against Piricularia oryzae, the crop is cut to a height of about 13 cm 24 hours before the chemical treatment of the rice plant. The test preparation is applied by spraying until run-off, treated plants are allowed to dry, then inoculated with Piricularia oryzae, incubated in a humid chamber at 24-30 ° C for 24 hours, then transferred to a greenhouse and 7-8 days after inoculation the extent of the disease is determined.

In assessing fungicidal activity against grapevine peronospora, the young grapevine plants are sprayed until the suspensions of the respective test compound at a given concentration are run off. The treated plants are allowed to dry, inoculated with a spore suspension of Plasmopara viticola, kept for 48 hours at 18-21 ° C in a humid chamber for incubation, then left in the light for 4 days, then transferred to a humid chamber for 24 hours. temperature 18 - 21 ° C. After this time, fungal growth was evaluated.

To assess fungicidal activity against barley blotch (Helminthosporium teres), the barley plants are trimmed to a height of about 6 cm 24 hours prior to chemical treatment. The test preparation is applied by spraying until run-off. The treated plants are allowed to dry, inoculated with Helminthosporium teres, kept for 24 hours in a humid chamber at 24-27 ° C for incubation, and then transferred to a greenhouse at 21-24 ° C. After 6-7 days, the disease was then suppressed.

Another test used for evaluation

The broad spectrum of efficacy of the fungicidal compositions of the present invention is to test their action against wheat rust (Puccinia recondltaj). This test is performed by cutting the wheat plants to a height of about 6 cm prior to application of the test wheat preparation. Plants are sprayed with the test preparation until run-off, allowed to dry, inoculated into Puccinia recondita, incubated for 24 hours in a humid chamber at 21-24 ° C, and then transferred to a greenhouse at a temperature of 21-24 ° C. After 6-8 days, the extent of the disease, which is manifested by the presence of rust deposits on the leaf surface, is determined.

The test for efficacy on grass rust (Puccinia graminis f. Sp. Tritici) is to be carried out 24 hours before the chemical treatment of a seven-day wheat plant (var. Mononj is cut to a height of about 6 cm). were allowed to dry and then inoculated by spraying (to runoff] suspension containing at least 2.5 x 10 ⁵ spores / ml of the above fungus. After inoculation, the plants are returned to the humid environment of a temperature of about 20 ° C and the temperature was controlled so as to not exceed 29 [deg.] C. After 2 weeks, the extent of the disease is evaluated and compared with the presence of irregular powdery mildew in the presence of irregular piles of brick-red spores on the leaves and stalks of wheat plants.

The results of the above tests carried out with the arylcyanalkyl- and diarylcyanalkylimidazoles of the invention, with their acid addition salts and metal salt complexes, are summarized in Table VII below. The trial fungi are indicated in the table by symbols with the following meaning:

BC = Botrytis cinerea (Gray mold),

EP = Erysiphe polygoni, PI = Phytophthora infestans,

PO = Piricularia oryzae

PV = Plasmopara viticola (vine peronospora),

HT = Helminthosporium teres (brown spots of barley),

PR = Puccinia recondita, PG = Puccinia graminis f. Sp. tritici (grass rust).

The results of the fungicidal activity are reported on the scale A - E, where the individual values have the following meanings:

A = 90-100% disease control,

B = 90-96% disease control,

C = 70-89% disease control,

D = 50-69% disease control,

E = disease control less than 50 ¹ %.

TABLE VII

Disease control with 300 ppm of active ingredient compound HT BC EP PV PO PI PR of Example No.

PG

105

106

107

108

109

110 111 112

113

114

115

116

117

118

119

120 121 122

123

124

125

126

127

128

129

130

AND

E

AND

AND

AND

E

E

E

AND

E

AND

AND

AND

AND

AND

E

E

E

E

AND

E

AND

AND

AND

C

E

(B)

E

D

C

E

C

(B)

C

E

E

AND

(B)

(B)

E

E

C

C

(B)

E

C

E

AND

E

AND

AND

AND

AND

AND

AND

AND

AND

E

AND

AND

AND

AND

AND

AND

AND

AND

AND

E

AND

AND

E

AND

AND

AND

E

AND

E

(B)

(B)

(B)

(B)

E

E

E

E

E

(B)

E

E

(B)

(B)

(B)

(B)

E

E

E

C

E

E

(B)

E

E

E

(B)

AND

E

E

E

E

AND

AND

(B)

E

E

E

E

(B)

(B)

Έ

E

E

E

E

E

C

E

E

(B)

E

E

E

E

E

AND

E

E

E

E

(B)

AND

AND

AND

AND

AND

E

AND

AND

C

E

AND

AND

AND

E

AND

AND

E

C

C

(B)

E

E

PV PO

PI PR PG Compound HT BC EP of Example No.

131 AND E AND 132 E E AND 133 AND C AND 134 E E E 135 C AND AND 136 E AND E 137 AND AND AND 138 AND E AND 139 (B) (B) AND 140 C E AND 141 AND E AND 142 AND E E 143 E C AND 144 (B) (B) AND 145 AND AND AND 146 E AND AND 147 E (B) AND 148 E E AND 149 E E E 150 E E E 151 E E E 152 E E E 153 E E AND 154 C E AND 155 C (B) AND 156 E E E 157 E E E 158 AND (B) AND 159 AND AND AND 160 AND (B) AND 161 E E E As standard comparative preparations

(B)

(B)

(B)

E

E

E

E

C

E

E

E

(B)

AND

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(B)

C

C

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E, the commercial preparation triadimefon (1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone), which is a systemic fungicide At a concentration of 2.5 to 6.2 g / 100 l, this composition combines various types of rust and powdery mildew attacking vegetables, cereals, coffee, stone fruit, grapevine and ornamental plants Acute toxicity to rats (LDsoj of this substance) is 568 mg / kg.

Another comparative preparation is the commercial triamophos [5-amino-3-phenyl-1,2,4-triazol-1-yl-N, N, N ', N'-tetramethylphosphondiamide], a fungicide for controlling powdery mildew, showing some systemic efficiency. To combat apple powdery mildew, this preparation is applied at a concentration of 25 g / 100 L. The preparation is relatively toxic since it is 20 mg / kg as an acute oral toxicity to rats (LDOO value).

On the other hand, the compounds of the present invention, in addition to their high potency and broad spectrum of activity, are very safe to use because, for example, the compound of Example 1 has an LD50 when administered orally to rats (acute toxicity 1250 mg / kg). even higher at 1590 mg / kg.

The aralkylimidazoles and their metal salt complexes of the invention are useful as fungicides for use in agriculture and as such can be applied in various ways, such as to seed, soil or plant leaves. For this purpose, the compounds can be used as prepared in the technical or pure state, in the form of solutions or fungicides. The compounds of the present invention are usually combined with a carrier or formulated to enable subsequent application as a fungicide. For example, these aralkylimidazoles or metal salt complexes thereof may be formulated as wettable powders, emulsifiable concentrates, dusts, granules, aerosol formulations or liquid emulsion concentrates. In these compositions, the compounds of the invention are included together with a solid or liquid carrier, and optionally with suitable surfactants.

It is generally desirable, especially in the case of foliar spray formulations, that such formulations contain excipients such as wetting agents, distribution aids, dispersants, binders, adhesives and the like, in accordance with the practice of the art. Such commonly used excipients are described, for example, in &quot; Detergents

68 and Emulsifiers Annual ', John W. McCutcheon, Inc.

In general, the compounds of the invention may be dissolved in certain solvents such as acetone, methanol, ethanol, dimethylformamide, pyridine or dimethylsulfoxide and diluted with water. The concentration of active ingredient in the solution may range from 1% to 90%, preferably from 5 to 50%.

To prepare emulsifiable concentrates, the compound of the invention may be dissolved in a suitable organic solvent or solvent mixture, together with an emulsifier to disperse the fungicide in water. The concentration of the active ingredient in the emulsifiable concentrates is usually from 10 to 90% and in the liquid emulsion concentrates may be up to 75%.

Wettable powders suitable for spray application can be prepared by mixing a compound of the invention with a finely divided solid, such as one selected from the group consisting of clays, inorganic silicates and carbonates, and various modifications of silica, and wetting agents are added to the mixture. , binders and / or dispersants. The concentrations of the active compounds in such compositions are usually in the range from 20 to 98%, preferably from 40 to 75%. A typical wettable powder is made by mixing 50 parts of 1- [β- (2,4-dichlorophenyl) hexyl] imidazole, 45 parts of synthetic precipitated hydrated silica and 5 parts of sodium lignosulfonate. In another of these compositions, kaolin-type clay is used in place of the silica described above, and in another such formulation, 25% of the silica described above is replaced with synthetic sodium aluminosilicate.

Dusts are prepared by mixing aralkylimidazole or a complex thereof with a metal salt with finely divided inert solids of organic or inorganic origin. Materials suitable for this purpose include vegetable flours, various modifications of silica, silicates, carbonates and clays. One suitable method of preparing the dust is to dilute the wettable powder with a finely divided carrier. Dusts in the form of concentrates are generally formulated to contain 20 to 80% active ingredient and diluted to a concentration of 1 to 10 percent for application.

Aralkylimidazoles or metal salt complexes thereof can be applied as fungicides by conventional methods, such as conventional high-volume and low-volume pressure spraying, blower spraying, spraying and spraying from aircraft. The dilution of the composition to be applied and the dose to be applied depend on the type of device used, the mode of application and the diseases to be controlled, but the preferred effective dose is usually from about 0.11 to 55 kg of active ingredient per hectare.

In seed protection, the amount of active ingredient applied to the seed is usually from about 0.06 g to 12.5 g per kg of seed. As soil fungicide, the active compound according to the invention can be incorporated into the soil or applied to the soil surface in a dose of usually 0.11 to 55 kg per hectare. As a foliar fungicide, the active ingredient is usually applied to mature plants at a rate of 0.27 to 11 kg / ha.

The fungicides which can be combined with the fungicidally active compounds according to the invention include:

(a) dithiocarbamates and their derivatives, such as ferric dimethyldithiocarbamate (ferbamj, zinc dimethyldithiocarbamate (ziramj, manganese ethylene bis-dithiocarbamate) and its zinc ion coordinate product (zineb), sodium propylene bisametithiocarbamate (propylene bisamebithiocarbamate) (metham), tetramethylthiuram disulfide (thiram) and

3,5-dimethyl-1,3,5-2H-tetrahydrothiadiazine-2-thione (dazomet);

bj nitrophenol derivatives such as dinitr o- (1-methylheptyl) phenyl crotonate (dinocapj,

2-sec-butyl-4,6-dinitrophenyl-3,3-dimethyl acrylate (binapacryl), and

2-sec-butyl-4,6-dinitrophenylisopropyl carbonate;

(c) heterocyclic compounds such as N-trichloromethylthiotetrahydrophthalimide (captan);

N-trichloromethylthiophthalimide (olpeptide, 2-heptadecyl-2-imidazoline acetate (glycine), 2-octylisothiazol-3-one,

2,4-dichloro-6- (o-chloroanilino) -s-triazine, diethylphthalimidophosphorothioate,

4-Butyl-1,2,4-triazole,

5-amino-1- [bis (dimethylamino) phosphinyl] -3-phenyl-1,2,4-triazole,

5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole,

2,3-dicyano-1,4-dithiaanthraquinone (dithianone),

2-thio-1,3-dithio [4,5-b] quinoxaline (thioquinox), methyl 1- (butylcarbamoyl) -2-benzimidazolecarbamate (benomyl),

2- (4-thiazolyl) benzimidazole (thiabendazole), 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thiol-1-oxide,

8-hydroxyquinoline sulphate,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine-4,4-dloxide,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin,

197284 α- (phenyl) -α- (2,4-dichlorophenyl) -5-pyrimidinylmethanol (triarimol), η 5 - [(1,1,2,2-tetrachloroethyl) thio] -4-cyclohexane-1,2 -dicarboximide,

3- [2- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxy] glutarimide (cycloheximide), dehydroacetic acid,

N- (1,1,2,2-tetrachloroethylthlo) -3,4,7,7a-tetrahydrophthalimide (captafol),

5-Butyl-2-ethylamino-4-hydroxy-6-methylpyrimidine (ethrimol)

4-cyclodecyl-2,6-dimethylmorpholine acetate (dodemorph) a

6-methyl-2-oxo-1,3-dithiolo [4,5-b] quinoxaline (quinomethionate;

(d) various halogenated fungicides such as tetrachloro-p-benzoquinone (chloranil);

2,3-dichloro-1,4-naphthoquinone (dichlorone),

1,4-dichloro-2,5-dimethoxybenzene (chloroneb),

3.5.6- trichloro-o-anisic acid (tricamba),

2.4.5.6- Tetrachloroisophthalonitrile (TCPN)

2,6-dichloro-4-nitroaniline (dicloran), 2-chloro-1-nitropropane, polychloronitrobenzenes such as pentachloronitrobenzene (PCNBJ and tetrafluordichloroacetone;

ej fungicidally effective antibiotics such as griseofulvin, kasugamycin and streptomycin;

(f) copper-based fungicides such as cuprous oxide, basic copper chloride, basic copper carbonate, copper naphthenate and Bordeaux broth;

(g) various fungicides, such as diphenyl, dodecylguanidine acetate (dodine), phenylmercuriacetate;

N-Ethylmerkuri-1,2,3,6-tetrahydro-3,6-endomethano-3,4,5,6,7,7-hexachlorophthalimide, phenylmercurimonoethanolammonium lactate, p-dimethylaminobenzenediazonium sodium sulfonate, methyl isothiocyanate, 1-thiocyano-2 , 4-dinitrobenzene,

1-phenylthiosemicarbazide, nickel-containing compounds, calcium cyanamide, lime sulfur, sulfur and

1,2-bis (3-methoxycarbonyl-2-thioureido) benzene (thiophanatemethyl).

The compounds of the invention and their metal salt complexes can be advantageously used in various ways. Since metal salt complexes exhibit systemic activity and a broad spectrum of fungicidal activity, they can be used to protect stored cereals. These complexes can also be used as fungicides for lawn and orchard applications. Other applications of the metal salt complexes of the invention in agriculture and horticulture will be apparent to those skilled in the art.

Claims (2)

SUBJECT A fungicidal composition in the form of a wettable powder, an emulsifiable concentrate, a dust, a granulate, an aerosol or a liquid emulsion concentrate, comprising N Al carrier, characterized in that it contains as active ingredient from 0.000001 to 99% by weight of an imidazole derivative of the general formula I, Ί / = N _of -C- (A) _n -C- (Bk) R * (I) wherein Z represents a phenyl group optionally substituted by one, two or three substituents independently selected from the group consisting of chlorine, bromine and fluorine, C 1 -C 4 alkyl, trifluoromethyl, methoxy, methylthio, methylsulfonyl, nitro and amino, furthermore represents naphthyl, diphenyl, pyridyl, indolyl, thienyl, benzodioxanyl, acenaphthalene or indanyl, R ¹ represents hydrogen or cyano, R ² represents a hydrogen atom, a chlorine atom, a C 1 -C 8 alkyl group, a propenyl group, a propynyl group, a cyclohexyl group, a cyclohexenyl group, a phenyl group, an ethylphenyl group, a chlorine or ethyl substituted phenyl group, benzyl group, naphthyl group or pyridines lovou. group R ³ represents a hydrogen atom, a C 1 -C 10 alkyl group, a C 3 -C 6 alkenyl group, a hexyl group, a phenyl group, an ethylphenyl group, a chlorine, fluorine or methyl-substituted phenyl group, or a benzyl group, R ⁴ represents a hydrogen atom or a methyl group, or Z and R ² together may form a grouping of the formula of the above formula (I) in which: Z, R ² , R ³ , R ⁴ , A, B, (X) _and "nan" are as in point 1, and R ¹ is cyano. 3. A composition according to claim 1, wherein the active ingredient is a compound of formula (I), in which n and n ‘have a value of 0, and Z, R ^1, R ^2, R ^3, R ⁴ and _{(Xj, and} are defined as in point 1. 4. The composition according to claim 2, characterized in that as active substances they comprise compounds of the formula I, wherein all symbols are defined as in point 2, provided that Z and R ² are not grouped together with the formula, mean that when R ^1, R ³ and R ⁴ are hydrogen, then R ² is not H or alkyl having 1-3 carbon atoms; A represents a methylene or 1,2-ethylene group, B represents a methylene, 1,2-ethylene or 1,4-butylene group, X represents a chlorine atom, a nitro group, a methyl group or a butyl group, and is a number of 0 to 2, n is 0 or 1, and n is 0 or 1, or an agronomically acceptable acid addition salt or complex salt thereof a metal salt of the formula MY, wherein M is a metal cation and Y is an anion of the corresponding valency. 2. A composition according to claim 1, wherein the active ingredient is a compound. 3. A process according to claim 1, characterized in that the compound of formula (I) R ¹ R ³ Z — C— (A) _n —C— (B) _n —W, R 2 R ⁴ wherein A, B, R ^1, R ^2, R ^3, R ^4, Z, n and n 'are defined as in point 1, and W is halogen, C1 -C4 alkylsulfonyloxy, benzenesulfonyloxy or toluenesulfonyloxy, reacted with an equimolar amount or an excess of imidazole or an imidazole salt, optionally in the presence of an inert solvent at a temperature of from 50 to 180 ° C.