DK159551B - 1H-1,2,4-TRIAZOLD DERIVATIVES WITH ANTIFUNGAL AND PLANT GROWTH REGULATORY EFFECTS AND FUNGI PREPARATION PRODUCTS - Google Patents

Description

1 DK 159551B

The present invention relates to novel 1H-1,2,4-triazole derivatives having antifungal and plant growth regulating effect as well as a fungicidal composition comprising as an active component an effective antifungal amount of such derivative.

The aforementioned novel IH-1,2,4-triazolderates have the general formula:

i - N

V

CH2-CH-R (i)

Ar wherein Ar represents phenyl, mono-, di- or trihalophenyl, lower alkylphenyl, lower alkoxyphenyl, nitrophenyl, cyanophenyl or trifluoromethyl phenyl, and R represents all alkyl having from 1 to 10 carbon atoms, cycloalkyl, cycloalkyl, lower alkyl, lower alkenyl, aryl-lower alkyl or aryloxy-lower alkyl, where aryl represents phenyl, naphthalenyl or substituted phenyl, wherein the substituted phenyl group is phenyl having from 1 to 3 substituents, independently selected from halogen, lower alkyl, lower alkyloxy, cyano, nitro and phenyl, with the proviso that only one of the substituents can be cyano, nitro or phenyl when more than one substituent is present.

Also, the physiologically acceptable acid addition salts of the compounds of general formula (I) are encompassed by the present invention.

From Danish patent application no. 2935/75 (DK filing no.

138,601) are related to fungicidal compounds. The compounds of the invention are distinguished by the more powerful fungicidal activity in relation to the compounds thus known, as can be seen in the comparative tests which have been described later.

By the term "alkyl" used in the definition of R, it is intended to include straight-chain and branched aliphatic hydrocarbon radicals containing from 1 to 10 carbon atoms, such as e.g. methyl, ethyl, 1-methylethyl, 1,1-dimethylethyl, propyl, 1-methylpropyl, 2-methylpropyl, butyl, pentyl, hexyl, heptyl, octyl, decyl and the like; the term "lower alkyl" as used herein refers to straight or branched chain alkyl radicals having from 1 to about 6 carbon atoms such as, for example: methyl, ethyl, 1-methylethyl, propyl, 1-methylpropyl, 2-methylpropyl, 2

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butyl, pentyl, hexyl and the like; the term "lower alkenyl" refers to straight or branched unsaturated alkenyl radicals having from 3 to 6 carbon atoms, such as e.g. 2-propenyl, 1-methyl-2-propenyl, 2-butenyl, 3-butenyl, 2-hexenyl and the like; the term "cycloalkyl" refers to 5 cyclic hydrocarbon radicals having from 3 to 6 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; and the term "halogen" is generic for halogens having an atomic weight of less than 127, i.e. chlorine, bromine, fluorine and iodine.

A preferred group of compounds of the general formula (I) can be illustrated by the general formula (Γ):

__N

ΓΊ T. (I1) 15 CH.-CH-R '• Ar * wherein

Ar7 represents phenyl, mono- or di-halophenyl or methylphenyl, and 20 R 'represents alkyl having from 1 to 10 carbon atoms, cycloalkyl, lower alkenyl, arylmethyl and aryl ethyl, wherein the aryl group is preferably phenyl, halogenophenyl, methylphenyl or methoxyphenyl .

Particularly preferred compounds of the general formula (Γ) are those compounds wherein Ar7 represents phenyl, chlorophenyl, fluorophenyl, bromophenyl, dichlorophenyl, dibromophenyl or methylphenyl, the most preferred being dichloro and dibromophenyl; and wherein R7 is alkyl having from 1 to 8 carbon atoms, cycloalkyl or 2-propenyl, the most preferred being alkyl having from 1 to 6 carbon atoms and 2-propenyl.

Typical examples of preferred compounds of the general formula (Γ) are the following: 1- [2- (2,4-di chlorophenyl) propyl] -1H-1,2,4-triazole; 1- [2- (2,4-dichlorophenyl) butyl] -LH-l, 2,4-triazole; L- [2- (2,4-dichlorophenyl) pentyl] -LH-l, 2,4-tiMazol; 1- [2- (2,4-dichlorophenyl) -3-methylbutyl] -1H-1,2,4-triazole; 1- [2- (2,4-dichlorophenyl) -4-pentenyl] -1H-1,2,4-triazole; L- [2- (2,4-dichlorophenyl) hexyl] -LH-l, 2,4-triazole; 1- [2- (2,4-dichlorophenyl) -4-methylpentyl] -1H-1,2,4-triazole; 1- [2- (2,4-di-chlorophenyl} -3-methyl-pentyl] -1H-1,2,4-triazole;

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1- [2- (2,4-di-chlorophenyl) heptyl] -1H-1,2,4-triazole; L- [2-cyclopentyl-2- (2,4-dichlorophenyl) ethyl] -LH-l, 2,4-triazole; 1- [2-cyclohexyl-2- (2,4-dichlorophenyl) ethyl] -LH-l, 2,4-triazole; L- [3- (4-chlorophenyl) -2- (2,4-dichlorophenyl) propyl] -LH-l, 2,4-triazole; 1- [2- (2,4-di bromophenyl) hexyl] -1H-1,2,4-triazole; 1- [2- (2,4-di bromophenyl) -4-methylpentyl] -1H-1,2,4-triazole;

1- [2- (2,4-di bromophenyl) -3-methylbutyl] -1H-1,2,4-triazole; 1- [2- (2,4-dibromophenyl) -3-methylpentyl] -1H-1,2,4-triazole; 1- [2- (4-fluorophenyl) -4- (4-methylphenyl) butyl] -1H-1,2,4-tri azole, and 1- [4- (4-chlorophenyl) -2- (4- fluorophenyl) -butyl1-1H-1,2,4-triazole.

The group of compounds of the general formula (I) which can be illustrated by the general formula (Ia) ij 1 2 (I "a) CH, -CH-ir c I Ar wherein Ar has the previously defined meaning and R2 represents alkyl, cycloalkyl, cycloalcyl-lower alkyl, lower alkenyl, aryl-lower alkyl or aryloxy-lower alkyl can be conveniently prepared by N-alkylation of 1H-1,2,4-triazole (II) with a suitable reactive ester of formula (III) wherein Ar and R 2 have the previously defined meanings and X represents a reactive ester function such as, for example, halogen, methyl sulfonyloxy, (4-methylphenyl) sulfonyloxy and the like.

In carrying out the reaction of (II) and (III), it is convenient to first convert (II) to an all potassium metal salt, preferably the sodium salt, by reacting (II) with a suitable strong metal base such as e.g. sodium hydride, sodium methanolate, sodium amide and the like and then stir and heat the metal salt with (III) in a suitable polar organic solvent. Suitable solvents for this purpose include amides such as e.g. Ν, Ν-dimethylformamide and N, N-dimethylacetamide, and nitriles such as e.g. acetonitrile, benzonitrile and the like.

Alternatively, (II) and (III) may be reacted directly with each other without prior salt formation, in which case the reaction is preferably carried out in a suitable polar organic solvent as defined above, in the presence of a suitable base to collect it during reaction. the acid released acid. Appropriate bases which can advantageously be used

DK 159551 B

4 comprises inorganic bases such as e.g. sodium and potassium carbonate and hydrogen carbonate and the like, and organic bases such as e.g. N, N-diethylethanamine, pyridine and the like. It is convenient to use some elevated temperature to increase the reaction rate, and the reaction is particularly preferred at the reflux temperature of the reaction mixture.

The foregoing reactions can be illustrated as follows: 10O NaOCH3 r (II) Ί + X_CH -CH.R2

7 sodium salt. 2 I

H L —1 Ar (Η) (ΙΠ)

15 _N

-> N ^ JI

Ah.-CH-B2 2 I Ar 20 (I-a) base (II) + (IH) ..................> (I-a) 25 solvent

It will be appreciated that the compounds of general formula (I) obtained by following the procedures described above are isolated from the reaction mixture and, if necessary, further purified using methods known in the art.

The compounds of general formula (I) obtained in base form by the foregoing processes can be converted to their physiologically acceptable acid addition salts by reaction with a suitable acid, such as e.g. an inorganic acid such as hydrohalogenic acid, i.e. hydrochloric, hydrobromic or iodo; sulfuric acid, nitric acid or thiocyanic acid; a phosphoric acid; an organic acid such as acetic acid, propanoic acid, hydroxyacetic acid, 2-hydroxypropanoic acid, 2-oxopropanoic acid, ethanedicarboxylic acid, propane carboxylic acid, butanedicarboxylic acid (Z) -2-butenedicarboxylic acid, (E) -2-butyric acid

5 DK 15955 1 B

tendi carboxylic acid, 2-hydroxybutanedicarboxylic acid, 2,3-dihydroxybutane-carboxylic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid, benzoic acid, 3-phenyl-2-propenoic acid, α-hydroxybenzeneacetic acid, methanesulfonic acid, ethanesulfonic acid phonic acid, hydroxyethanesulfonic acid, 4-methylbenzenesulfonic acid, 2-hydroxybenzoic acid, 4-amino-2-hydroxybenzoic acid, 2-phenoxybenzoic acid or 2-acetyl yloxybenzoic acid. Similarly, the salts can be converted to the corresponding free bases in the usual manner, e.g. by reaction with alkali, such as sodium or potassium hydroxide.

Some of the reactive ester intermediates of general formula 10 (III) are known compounds and can all be prepared by the methods known in the art as described in the literature for the preparation of these known compounds. Such compounds and processes for their preparation are e.g. disclosed in U.S.A. U.S. Patent No. 3,927,017.

In general, the intermediates of the general formula (III) are prepared by converting the corresponding alcohol (V) into the desired reactive ester according to the methodologies well known in the art. Eg. methanesulfonates and 4-methylbenzenesulfonates are readily obtained by treating the alcohol with methanesulfonyl chloride and 4-methylbenzenesulfonyl chloride, respectively, in the presence of a suitable acid acceptor, such as e.g. pyridine. Halides can be obtained by treating all the carbon with a suitable halogenating agent, such as e.g. phosphorus pentachloride, phosphorus tribromide, etc.

Forming the (III) reactive ester (V) The intermediate product alcohols of the general formula (V), some of which are known, can be prepared by known methods, such as e.g. following:

An appropriately substituted arylacetonitrile of the general formula (VI) is alkylated with an appropriate reactive ester R2X (VII). This alkylation reaction is preferably carried out by first contacting the aryl acetonitrile with a suitably strong base such as e.g. sodium hydride, after which the reactive ester is added to the reaction mixture. Appropriate dissolving. Agents for this reaction include amides such as N, N-dimethyl

DK 159551B

6 formamide, Ν, Ν-dimethylacetamide and hexamethylphosphoric triamide, other common polar solvents such as dimethylsulfoxide, or mixtures of such solvents with e.g. an aromatic hydrocarbon such as benzene.

The substituted arylacetonitrile (VIII) obtained by the preceding step is then converted to an alkyl ester (IX) of the corresponding carboxylic acid. This nitrile-to-ester conversion can be accomplished in one step, e.g. by heating the nitrile in a suitable alcohol or a mixture of alcohol with a suitable reaction inert organic solvent, such as 2,2'-oxybispropane in the presence of a strong non-oxidizing mineral acid such as e.g. hydrochloric acid. Alternatively, the nitrile may first be hydrolyzed to the corresponding arylic acetic acid in a conventional manner, e.g. with sodium hydroxide in 1,2-ethanediol, and this acid can then be converted to the desired ester in a conventional manner.

The esters (IX) can also be obtained by alkylating an appropriate alkyl aryl acetate (X) with R2X in accordance with known methods.

The alcohols (V) are then obtained after reduction of (IX) with a suitable reducing agent such as e.g. lithium aluminum hydride, lithium borohydride or sodium borohydride in the presence of a lithium salt, preferably a halide such as lithium iodide or lithium chloride.

The aforementioned reactions can be illustrated schematically as follows:

Ar-CHO-CN + R2X -> Ar-CH-CN

2 R2 (VI) (VII) (VIII) H + alkanol 30 o

Ar-CEU-C-O-alkyl + R2X -> Ar-CH-C-O-alkyl Z '2 or (X) (VII) (IX) (IX) LiBH. '(V) - ->

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7

The starting materials of the general formulas (VI) and (VII) are well known in the art and can be prepared by methods known in the art. Eg. the starting materials of the general formula (VII) wherein R2 represents aryloxy lower alkyl and X represents halo can be readily prepared by O-alkylation of a suitable hydroxyarene compound having a suitable dihal and lower alkane using e.g. aqueous alkali as a reaction medium.

Because of the presence of an asymmetric carbon atom in the compounds of the present invention (I), it is clear that they may exist in the form of 10 stereochemical optical isomers (enantiomers). If desired, the dissolution and isolation or preparation of a particular mold can be carried out using the usual principles known in the art.

These enantiomers are, of course, encompassed by the present invention.

The compounds of general formula (I) and the acid addition salts thereof are useful agents for controlling fungi. They are particularly useful as potent agricultural fungicides in that they are active against a wide range of fungi, such as e.g. the fungi that are responsible for the occurrence of mold in various plant species, e.g. Erysiphe graminis,

Erysiphe polygony, Erysiphe cichoracearum, Erysiphe polyphaga, Podo-20 sphaera leucotrichia, Sphaerotheca pannosa, Sphaerotheca mors-uvae and Uncinul1a necator and against other phytopathogenic fungi such as e.g. Sep- toria api i and Uromyces phased i.

The useful antifungal properties of the compounds of the invention are more clearly illustrated by the results obtained in the subsequent experiments.

For comparison, results obtained with the compound of Example 5 in DK Patent Specification No. 138,601 are given under the same conditions. This compound has the formula 30 T? H / = \ _ ch2 — ch— £ λ — Cl 35 Cl A. Prophylactic effect of Erysiphe cichoracearum on cucumbers by leaf growth treatment «8

DK 159551 B

Young cucumber plants, ca. 10 days old, was sprayed with an aqueous solution containing 100, 10 or 1 ppm of the compound to be tested while control plants were not treated. After drying the plants, artificial infection was carried out with spores of Erysiphe cichoracearum by rubbing the plants lightly with a heavily infected leaf.

On the 15th day after the artificial infection, the degree of fungus attack was assessed by determining the percentage of leaf area affected by fungus. Three plants were used per day. object, and averages were calculated for these 3 plants. The results are shown in Tables I and II using the following point system: 15 Point% attacked leaf surface 0 0 1 ^ 10 2 11 to 50 20 3> 50 9

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Table I: Prophylactic effect of Erysiphe cichoracearum on cucumbers (leaf growth treatment).

π-N

ISLAND

. "Point

Improve Base ___ ratio r or '100 ppm, 10 ppm 1 ppm.

No. 'salt 1 CHj base 0 "0 0 2 π H_ base 0 0 0 2 5 3 nC3H7 base 0 0 0 4 iC3H? HN03 0 0 0 5 nC4H9 HN03 0 0 0 6' ch2-ch (ch3) 2 hno3 0 0 0 7 ch {ch3) -ch2-ch3 - hno3 0 0 0 8 nC8H17 HN03 0 0 2 9 CH2-CH = CH2 hno3 ooo 10 -Q hno3 ooi 11 ^ base 0 1 2 12 (ch2) 2 -O. Base 0 1 2 13 KNO- 1 3 3

2 W 0. 5 H2C

14 (cn2) 2 {~) ι »ββ 0 0 z '15 CH2- (4-Cl-C6H4) HNOj 0 0. '3 16 CH2 - (Z-Br-C6H4) HNO3 0 0.0 17 CH2- (4-C6H5-C6H4) HCl 0 0 2 18 (CH2) 2-0 ^ 4-Br-C6H4) HNOj 0 0 3 19 (CI ^) 3-0. (3,5-Cl2-C6H3) HNOj 1 2 3 10 DK 1 b 9 b 5

Table I: (continued) ~ Connect - "" _ j "" Ί Base 1 'Point 1 level' R or __ nr> salt 100 ppm. 10 ρριηψ ppm.

20 (01 ^ -0- (3-01 ^ -4-01-0 ^) HN03 1 3 3 21 (CH ^ -O-fc-CHj-4-Cl-CgEy HN03 1 0 2 22 (01 ^ -0 - (2-Br-4-01 ^ -O ^) HNO3 0 0 1 23 (CH2) 3-0- (2,4-Cl2-6-CH3-HNO3 2 2 3 C6H2 ^ 24 (CH2) 3-0 - (2,4,6-Br3-HNO3 0 0 1 C6H2> 25 (CH2) 3-0- (2-Cl-4-C6H5-HNO3 0 1 2 C6H3> 26 (CH2) 3 - O - (2 - naphthalenyl) HNO 3 0 0 2 -1-_ 1 1-11

Table II: Prophylactic effect of Erysiphe cichoracearum on cucumbers (toladyaks t treatment).

DK 159551 B π

, _N

ISLAND

CH.-CH-R “1 Ar

Connect Bf? E Point 1 score - ^ r ^ - “nr> total 100 ppm. 10 ppm 1 graph 36 2,4-Br2-C6H3 nC ^ HNO3 0 0 0 37 2-Cl-C6H4 (CH2) 2- (4-Br-C6H4) HCl 0 1 2 38 4-Cl-C6H4 (CH2) 2 - (4-Cl-C6H4) HCl 0 12 39 4-Br-C6H4 (CH2) 2- (4-Cl-C6 H4) base 0 2 3 40 4-Br-C6H4 (CH2) 2- (2-OCH3 - HCl 0 1 2 c6k4) 41 4-Br-C6H4 (CH2) 2- (4-Br-C6H4) HCl 0 3 3 42 4-F-C6H4 (CH2) 2- (4-Cl-C6H4) HCl - 0 1 43 4-F-C6H4 (CH2) j- (4-CH3-HC1 0 0 1 ^ H4> 44 4-CHj-C6H4 (CH2) 2- (4-Cl-C6H4) HCl 0 2 3 I Ι · | ..... 11- - ........... I 1 -------- - - - ·· - "11

Conn.

according to 0 13

example 5 in DK

138.601 DK 159551 B. Prophylactic effect on Erysiphe granri nis on barley by leaf growth treatment.

12

Young barley plants, approx. 8 cm high, was sprayed with an aqueous solution 5 containing 100, 10 or 1 ppm of the compound to be tested while control pianos were not treated. After drying the plants, they were artificially infected by powdering with conidia of Erysiphe graminis. Fungus attacks were then evaluated for 10 days in the same manner as described in Experiment A. The results of this experiment are shown in Table III, where the numbers of the for-10 binders and the scoring system are as in Tables I and II.

Table III: Prophylactic effect of Erysiphe graminis on barley by leaf growth treatment ________Point

Compound No. 100 ppm 10 ppm 1 ppm 1 2 3 4 5 6 7 8 9 10 11 12 1 1 3 2 0 0 2 3 0-1 2 4 O 1 2 5 0.1 2 6 0 0 1 7 0 1 1 8. 0 1 2 9 0 13 10 0 12 11 .1 2 2 12 13 3 13

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Table III: (continued)

Point

Compound No. 100 ppm, 10 ppm, 1 ppm 'Ϊ3 0 0 1 14 13 3 15' 0 11-

16 1 2 V

17 12 3 18 12 3 19 13 3 22 1 2 3 24 1 1 3 26 2 2 3.

36 0 0 1 37 .1 3 3 38 0 0 1.

39 2 3 3 40 1 3 3 41 1 2 3 42 .1 2 43 0 1 1 44 0 0 1

Conn. according to example 5 in 0 33 DK 138.601_J ____—.

2

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14 C. Systemic activity against Erysiphe cichoracearum on cucumbers.

Young cucumber plants, ca. 10 days old, treated with aqueous solution of the soil with an aqueous solution of the test compound. 5 100 ml per ml were added. The total amount of test compound was 10 or 1 mg per plant. plant. Control samples were treated with the same amount of solution but without active component. Four days later, the plants were artificially infected with Erysiphe cichoracearum by rubbing the plants lightly with a heavily infected leaf. Assessment of fungal infestation was done 10 days thereafter in the same manner as described in Experiment A. The results are given in Table IV, where the numbers of the compounds and the points system are as in Tables I and II.

Table IV: Systemic activity against Erysiphe cichoracearum on cucumbers.

15

Point

Compound No. 10 mg / plant 1 mg / plant 1 0 0 2 0 0 3 0 1 4 0 1 5 2 3 6 0 3 7 0 3 9 1 2 10 2 2 11 2 2 12 2 3 15 2 3 18 2 2 36 '2 2

Conn. according to example n 2 5 of DK 138.601 _ _ (_____

DK 159551B

D. Prophylactic activity against Uromyces phaseoli on beans in leaf growth treatment.

Young bean plants, approx. 15 cm high, was sprayed with an aqueous solution containing 250, 100 or 10 ppm of test compound, while control samples were not treated. After drying, the plants were artificially infected by spraying with a suspension of spores of Uromyces phaseoli. Then, the plants were incubated for 24 hours at 18 ° C and a relative humidity of 95-100%. Fungus attacks were assessed 10 days after the artificial 10 infection in the same way as in Experiment A. The results are listed in Table V, where the same numbers were used on the compounds and the same scoring system as in Tables I and II.

Table V: Prophylactic activity against Uromyces phaseoli on beans in leaf growth treatment

Point

Compound No., rn -771- Z50 ppm. 100 ppm 10 ppm 1 1 2 3 2 1 13 3 .1 1. 2 4 Oli 5 O 0 3 6 0 0 1 7 0 0 2 9 0 0 3 10 0 2 3 • 11. 2 33

Conn. according to Ex.

5 in DK 138,601 3 33

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16

In addition to the antifungal effect, the compounds of general formula (I) have valuable plant growth regulating properties. Depending on various factors, such as the nature of the plants being studied for the administered dose of active component, the observed effect 5 may be growth stimulation or growth inhibition. As such, the compounds of the invention are useful as plant growth regulators, and this useful property is, of course, also encompassed by the scope of the present invention.

By virtue of the aforementioned anti fungal and growth regulating effects 10, the present invention provides valuable compositions containing the present triazoles of the general formula (I) or the acid addition salts thereof as the active component of a solvent or solid, semi-solid or liquid diluent or carrier. and it further provides an effective method of controlling fungal growth using an effective antifungal amount of such triazoles (I) or salts thereof. The present compounds can be used in suitable solvents or diluents, in the form of emulsions, suspensions, dispersions or ointments, on suitable solid or semi-solid carriers, in conventional or synthetic soaps, detergents or dispersion media, if desired with other compounds. with arachnid, insecticide, ovicide, fungicide and / or bactericidal action or together with inactive additives.

Solid carriers suitable for the preparation of powder form preparations include various inert, porous and powdery distribution agents of inorganic or organic nature such as e.g. tricalcium phosphate, calcium carbonate in the form of prepared chalk or ground limestone, kaolin, bolus, bentonite, talc, diatomaceous earth and boric acid; powdered cork, sawdust and other fine powdery materials of vegetable origin are also suitable support materials.

The active component is mixed with these carriers, e.g. by being ground therewith. Alternatively, the inert support material is impregnated with a solution of the active component in a slightly volatile solvent, and the solvent is then removed by heating or by filtration with suction at reduced pressure. By the addition of wetting and / or dispersing agents, such powdered compositions can also be made slightly wettable with water to obtain suspensions.

Preferably, inert solvents used in the preparation of liquid preparations should not be readily flammable and should be as far as possible.

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may be odorless and, as far as possible, non-toxic to warm-blooded animals and humans or plants in the environment concerned. Solvents suitable for this purpose are high boiling oils, e.g. of vegetable origin and non-boiling solvents with flash point 5 of at least 30 ° C, such as e.g. polyethylene glycol, isopropanol, dimethyl sulfoxide, hydrogenated naphthalenes and alkylated naphthalenes. Of course, it is also possible to use mixtures of solvents. Solutions may be prepared in the usual manner, if necessary by means of solution-promoting agents. Other liquid forms which may be used are 10 emulsions or suspensions of the active compound in water or suitably inert solvents or concentrates to prepare such emulsions which can be directly adjusted to the required concentration. For this purpose, the active component is mixed e.g. with a dispersant or emulsifier. The active component may also be dissolved or dispersed in a suitable inert solvent and mixed simultaneously or later with a dispersant or emulsifier.

It is also possible to use semi-solid carriers of cream, ointment, paste or wax-like nature in which the active component can be incorporated, if necessary by means of solvents and / or emulsifiers. Vaseline and other cream bases are examples of semi-solid carriers.

In addition, it is possible that the active component can be used in the form of aerosols. For this purpose, the active component is dissolved or dispersed, if necessary, by suitable inert solvents such as carrier liquids, such as difluorodichloromethane, which boils at atmospheric pressure at a temperature lower than room temperature or in other volatile solvents. In this way, pressurized solutions are obtained which, when sprayed, provide aerosols which are particularly suitable for controlling or controlling fungi, e.g. in confined spaces and storage rooms, and for use on vegetation for eradication or prevention of fungus infections.

The present compounds and compositions thereof may be administered by conventional methods. Eg. For example, a fungus growth or material to be treated or protected against fungal infestation can be treated with the compounds and their compositions by powdering, splashing, spraying, brushing, dipping, lubricating, impregnating or other suitable agents.

When the present compounds are used in combination with appropriate

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18 carriers, e.g. in solution, suspension, powder, powder, ointment, emulsion and similar forms a high activity is observed in a very large dilution range, e.g. For example, concentrations of the active ingredient in the range of from 0.1 to 10% by weight based on the weight of the preparation used have been found to be effective in controlling fungi. Of course, higher concentrations can also be used when the particular situation justifies it.

The following examples are intended to illustrate but not limit the scope of the present invention. Unless otherwise stated, all parts are by weight.

Example 1

To a stirred and reflux mixture of 122 parts of 4-chloro-3-methylphenol, 214.1 parts of 1,3-dibromopropane and 850 parts of water is added dropwise over a period of 1 hour. solution of 34 parts of sodium hydroxide in 213 parts of water. After the addition is complete, stirring is continued at reflux overnight. The reaction mixture is cooled to room temperature and the product is extracted with 765 parts of benzene. The extract is washed with a 10% sodium hydroxide solution, dried, filtered and evaporated. The residue is distilled twice to give 114 parts of 4- (3-bromopropoxy) -1-chloro-2-methylbenzene, boiling point 119 ° C at 0.6 mm pressure.

Example 2

Following the procedure of Example 1 and using an equivalent amount of an appropriately substituted phenol in place of 4-chloro-3-methyl-phenol used therein, the following intermediates are prepared: 1- (3-bromopropoxy) -4-chloro 2-methylbenzene, boiling point 115-116 ° C at 0.6 mm pressure; 2- (3-bromopropoxy) -1,5-dichloro-3-methylbenzene, boiling point 118 ° C at 0.6 mm pressure, 4- (3-bromopropoxy) -3-chloro [1,1'-biphenyl] , 2-bromo-1- (3-bromopropoxy) -4-methylbenzene, boiling point 123-126 ° C at 0.8 mm pressure, and 1,3,5-tribromo-2- (3-bromopropoxy) benzene, boiling point 160 -177 ° C.

Example 3

To a stirred and cooled (water bath) slurry of 7 parts 78% sodium-anhydride dispersion in 75 parts dimethyl sul foxide is added dropwise over the course of 19

DK 159551 B

of a 30 minute period a solution of 37 parts of 2,4-dichlorobenzene-tonitrile in 100 parts of dimethyl sul foxide. Stir for 30 minutes while cooling in water bath. Then, over a 30 minute period, a solution of 56 parts of 1-bromo-4- (2-bromethoxy) benzene 5 in 125 parts of dimethyl sul foxide is added dropwise and stirring is continued for another 30 minutes. The reaction mixture is poured into water and the product is extracted twice with 2,2-oxybispropane. The combined extracts are washed twice with water, dried, filtered and evaporated. The residue is triturated in petro-ether. The product is filtered off and crystallized from ethanol to give 38 parts of α- [2- (4-bromophenoxy) ethyl] -2,4-dichlorobenzene acetone-tri, mp 73.9 ° C.

Example 4

A mixture of 18.5 parts of 2,4-dichlorobenzene acetonitrile and 180 parts of 15 N, N-dimethyl formamide is stirred and cooled in an ice bath with the introduction of nitrogen gas. 3.2 parts of a 78% sodium hydroxide solution is added dropwise and the whole is stirred for 1 hour. Then, 17.8 parts (bromomethyl) cyclohexane is added dropwise over a period of 1 hour while still cooling and with the introduction of nitrogen gas. After completing ten to 20 sentences, stirring is continued for 2 hours at room temperature. The reaction mixture is poured onto water. The precipitated product is filtered off and triturated in a mixture of methanol and water. The product is filtered off and dried to give 25.5 parts of 2,4-dichloro-α- (cyclohexylmethyl) benzene-acetonitrile, mp 58.8 ° C.

25

Example 5

Repeating the procedure of Example 4 and using equimolar amounts of the appropriate starting materials are prepared: N - (3-butenyl) -2,4-dichlorobenzene acetonitrile, bp 104-108 ° C at 0.1 mm pressure, and 2 , 4-dichloro-α- (2-cyclopentylethyl) benzeneacetonitrile 1, boiling point 130-135 ° C at 0.05 mm pressure.

Example 6 To a stirred and cooled (ice bath) mixture of 27.5 parts of 2,4-dibromo-benzeneacetonitrile, 135 parts of N, N-dimethyl formamide and 67.5 parts of benzene is added portionwise 3.2 parts of a 78% sodium hydride dispersion. while introducing nitrogen gas. After stirring for 1 hour, dropwise 14 is added

20 DK 159551 B

parts 1-bromobutane. After the addition is complete, stirring is continued for 2 hours at room temperature. The reaction mixture is poured into water and the product is extracted twice with 2,2'-oxybispropane. The combined extracts are washed twice with water, dried, filtered and evaporated. The residue is distilled off to give 22 parts of 2,4-dibromo-α-butylbenzeneacetonitrile, boiling point 124 ° C at 0.05 mm pressure.

Example 7

By repeating the procedure of Example 6 and using a 10 equivalent amount of a suitable bromide and a suitable aryl-acetonitrile instead of 1-bromobutane and 2,4-dibromobenzene acetonitrile, used therein, the following compounds are prepared: 2.4-dichloro-a - [3- (4-chloro-3-methylphenoxy) propyl] benzeneacetone tri1, boiling point 216-219 ° C at 0.05 mm pressure; 2,4-dichloro-α- [3- (3,5-dichlorophenoxy) propyl] benzeneacetonitrile, bp 210-215 ° C at 0.05 mm pressure; 2,4-di chloro-α- [3- (2-naphthalenyloxy) propyl] benzeneacetoni tri1, m.p. 100 ° C; α- [3- (2-bromophenoxy) propyl] -2,4-di chlorobenzene acetone tri1; melting point 61.2 ° C; 2,4-di chloro-α- [3- (4-chloro-2-methylphenoxy) propyl] benzeneacetonitrile; mp 73 ° C; 2,4-dichloro-α- [3- (2,4-dichloro-6-methylphenoxy) propyl] benzeneacetonitrile, bp 212-216 ° C at 0.05 mm pressure; 2,4-di chloro-α- [3- (3-chloro- [1,1'-biphenyl] -4-yloxy) propyl] benzenacetonitrile, m.p. 70.3 ° C; α- [3- (2-bromo-4-methylphenoxy) propyl] -2,4-di chlorobenzene acetone tri 1, boiling point 215-219 ° C at 0.05 mm pressure, and 2.4-di chloro-α- [3- (2,4,6-tribromophenoxy) propyl] benzeneacetone tri 1, mp 85.2 ° C.

Example 8

To a stirred mixture of 18.5 parts of 2,4-dichlorobenzene acetonitrile, 90 parts of Ν, Ν-dimethylformamide and 67.5 parts of benzene is added dropwise 3.2 parts of a 78% sodium hydride dispersion with introduction of nitrogen gas.

After stirring for 1 hour at room temperature, 14.5 parts (2-chloro-ethylcyclohexane) are added. The whole is first stirred for 5 hours at 40-50 ° C and then overnight at room temperature.

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21 and the product is extracted twice with 2,2'-oxybispropane. The combined extracts are washed twice with water, dried, filtered and evaporated. The residue is distilled to give 16 parts (54%) of 2,2'-dichloro-α- (2-cyclohexylethyl) benzeneacetonitrile, bp 145-148 ° C at 0.05 mm pressure.

5

Example 9

Following the procedure of Example 8 and using equivalent amounts of the appropriate starting materials, prepare: α- (2,4-di chlorophenyl) - [1,1-biphenyl] -4-propane nitrile, bp 10 215-230 ° C at 0, 05 mm pressure; 2,4-dichloro-α- (2,4-dichlorophenyl) benzenebutanitrile as an oily residue; 4-chloro-α- (4-chlorophenyl) benzenebutanitrile as an oily residue; 4-chloro-α- (4-methylphenyl) benzenebutanitrile, bp 175-178 ° C at 0.1 mm pressure; α- (4-bromophenyl) -2-methoxybenzenebutanitrile as an oily residue; α- (4-bromophenyl) -4-chlorobenzene butanitrile as an oily residue; 4-chloro-α- (4-fluorophenyl) benzenebutanitrile, boiling point 165-168 ° C at 0.1 mm pressure; α- (4-fluorophenyl) -4-methylbenzenebutanitrile, boiling point 160-165 ° C at 0.3 mm pressure; 4-bromo-α- (2-chlorophenyl) benzenebutanitrile 1, boiling point 176-180 ° C at 0.1 mm pressure, and 4-bromo-α- (4-bromophenyl) benzenebutannitrile as an oily residue. Example 10 30 120 parts of methanol are saturated with gaseous hydrogen chloride while cooling in an ice bath. Then 22 parts of 2,4-dibromo-α-butylbenzenacetonitrile are added and the whole is stirred and refluxed overnight. The reaction mixture is cooled and poured onto water. The product is extracted with 2,2'-oxybispropane. The extract is washed with water, dried, filtered and evaporated. The residue is distilled to give 16.5 parts (68%) of methyl 2,4-dibromo-a-butylbenzeneacetate, boiling point 125 ° C at 0.1 mm pressure.

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Example 11

Following the procedure of Example 10, the following esters are prepared, starting from the appropriate nine triels: methyl α- (3-butenyl) -2,4-dichlorobenzene acetate as a residue; Methyl 2,4-dichloro-α- (cyclohexylmethyl) benzene acetate as a remedy; methyl 2,4-dichloro-α- (2-cyclopentylethyl) benzene acetate as a residue; methyl 2,4-dichloro-α- (2-cyclohexylethyl) benzene acetate as a residue; methyl α- (2,4-dichlorophenyl) - [1,1'-biphenyl] -4-propanoate as an oily residue; methyl 2,4-dichloro-α- (2,4-dichlorophenyl) benzenebutanoate as an oily residue; Methyl 4-chloro-α- (4-chlorophenyl) benzene butanoate, bp 175-178 ° C at 0.1 mm pressure; methyl -2,4-dichloro-α- (3- (2-naphthalenyloxy) propyl] benzeneacetate, m.p. 69.7 ° C; methyl 4-chloro-α- (4-methylphenyl] benzenebutanoate as an oily residue methyl α- (4-bromophenyl) -2-methoxybenzenebutanoate, boiling point 178-185 ° C at 0.1 mm pressure; methyl α- (4-bromophenyl) -4-chlorobenzene butanoate, boiling point 177-180 ° C at 0 , 1 mm pressure; methyl 4-chloro-α- (4-fluorophenyl) benzene butanoate as an oily residue; methyl α- (4-fluorophenyl) -4-methylbenzenebutanoate as a residue; methyl 4-bromo-α (2-chlorophenyl) benzene butanoate as an oily residue; methyl 4-bromo-α- (4-bromophenyl) benzenebutanoate as an oily residue; methyl α- [2- (4-bromophenoxy) ethyl] -2,4 dichlorobenzene acetate as a residue; methyl 2,4-dichloro-α- [3- (3,5-dichlorophenoxy) propyl] benzene acetate as a residue; methyl 2,4-dichloro-α- [3- (4- chloro-3-methylphenoxy) propyl] benzene acetate as a residue; methyl α- [3- (2-bromophenoxy) propyl] -2,4-dichlorobenzene acetate as a residue;

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23 residue; methyl 2,4-dichloro-α- [3- (4-chloro-2-methylphenoxy) propyl] benzeneacetate as an oily residue; methyl 2,4-dichloro-α- [3- (2,4-dichloro-6-methylphenoxy) propyl] benzene acetate as a residue; methyl α- [3- (2-bromo-4-methylphenoxy) propyl] -2,4-dichlorobenzene acetate as a residue; methyl 2,4-dichloro-α- [3- (3-chloro- [1,1'-bi-phenyl] -4-yloxy) propyl] -benzeneacetate, and methyl-2,4-dichloro-alkyl [3- (2,4,6-tribromophenoxy) propyl] benzene acetate as an oily residue.

Example 12

To a stirred mixture of 22 parts of methyl 2,4-dichlorobenzene acetate and 135 parts of Ν, Ν-dimethylformamide is added 3.1 parts of a 78% sodium hydride dispersion with the introduction of nitrogen gas. It is all stirred until foaming has ceased and cooled in an ice bath. Then 16 parts of iodomethane are added.

After the addition is complete, stirring is continued for 3 hours at room temperature. The reaction mixture is poured into water and the product is extracted with 2,2'-oxybispropane. The extract is washed with water, dried, filtered and evaporated to give 20 parts (80%) of methyl 2,4-dichloro-a-methylbenzene acetate as a residue.

Example 13 To a stirred mixture of 22 parts of methyl 2,4-dichlorobenzene acetate and 135 parts of Ν, Ν-dimethylformamide is added 3.1 parts of a 78% sodium hydride dispersion with the introduction of nitrogen gas. After stirring until foaming has ceased, 15 parts of 2-bromopropane are added and the whole is stirred for 3 hours at room temperature. The reaction mixture is poured into water and the product is extracted twice with 2,2'-oxybispropane. The combined extracts are washed with water, dried, filtered and evaporated to give 24.5 parts (94%) of methyl 2,4-dichloro-α- (1-methylethyl) benzene acetate as a residue.

To 140 parts of Ι, Γ-oxybisethane are added 3 parts of lithium aluminum hydride.

Then, a solution of 24.5 parts of methyl 2,4-di-35-chloro-α- (1-methylethyl) benzeneacetate in 35 parts of 1,1'-oxybisethane is added dropwise while cooling in a water bath. After the addition is complete, stirring is continued overnight at room temperature. 3 parts of a 50% sodium hydroxy dopi solution are added successively in ng and 1 part water, and the whole is stirred for 1 hour at room temperature. The mixture is filtered over a "hyflo" filtration aid and the filter cake is washed with 2,2-oxybispropane. The filtrate is evaporated to give 20.5 parts (93.5%) of 2,4-dichloro-β- (1-methylethyl) benzene ethanol as a residue.

5

Example 14

A mixture of 16.5 parts of methyl 2,4-dibromo-a-butylbenzene acetate, 11.5 parts of lithium dihydric dihydrate and 180 parts of acetonitrile is stirred until all the solids are dissolved. Next, 3.6 parts of sodium borohydride are added portionwise. After the addition is complete, the whole is heated to reflux and stirring is continued overnight at reflux temperature. After cooling, the reaction mixture is acidified with dilute hydrochloric acid solution and poured onto water. The product is extracted with 2,2 / oxybispropane. The extract is washed with water, dried, filtered and evaporated to give 15 parts 15 (100%) of 2,4-di bromo - / - - butyl benzene ethanol as a residue.

Example 15

Following the procedure of Example 14 and using an equivalent amount of a suitable methyl ester as starting material, the following alcohols are obtained as a residue: β- (3-butenyl) -2,4-di chlorobenzene ethanol; 2.4- di chloro or - / - - methyl benzenethanol; 2,4-di chloro-β- (cyclohexylmethyl) benzenethanol; 2,4-dichloro-2 - (2-cyclopentylethyl) benzenethanol; 2,4-di chloro-β- (2-cyclohexyl ethyl) benzenethanol; β- (2,4-di chlorophenyl) - [1,1'-biphenyl] -4-propanol; 2,4-dichloro-β- (2,4-dichlorophenyl) benzenebutanol; 4-chloro or N - (4-chlorophenyl) benzenebutanol; 4- (chloro-β- (4-methylphenyl) benzenebutanol; 30β- (4-bromophenyl) -2-methoxybenzenebutanol; β- (4-bromophenyl) -4-chlorobenzenebutanol; 4-chloro-β- ( 4-fluorophenyl) benzenebutanol; β- (4-fluorophenyl) -4-methylbenzenebutanol; 4-bromo-β- (2-chlorophenyl) benzenebutanol; 4-bromo-β- (4-bromophenyl) benzenebutanol; [2- (4-bromophenoxy) ethyl] -2,4-dichlorobenzenethanol; 2,4-dichloro-3- [3- (3,5-dichlorophenoxy) propyl] benzenethanol; O- [3- (2-bromophenoxy) propyl] -2,4-dichlorbenzenethanol;

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2,4-di chloro-β- [3- (4-chloro-3-methylphenoxy) propyl] benzenethanol; 2,4-dichloro-β- [3- (4-chloro-2-methylphenoxy) propyl] benzenethanol; 2,4-dichloro-M3- (2-naphthalenyloxy) propyl] benzenethanol; β- [3- (2-bromo-4-methylphenoxy) propyl] -2,4-dichlorbenzenethanol; 2,4-dichloro-3- [3- (2,4-dichloro-6-methylphenoxy) propyl] benzenethanol; 2,4-dichloro-β- [3- (3-chloro- [1,1'-biphenyl] -4-yloxy) propyl] -benzenethanol, and 2.4-dichloro-β- [3- (2,4,6-tribromophenoxy) ) propyl] benzene ethanol.

Example 16

To a stirred and cooled (ice bath) mixture of 22 parts of 2,4-dichloro-3- (cyclohexylmethyl) benzenethanol and 50 parts of pyridine is added dropwise 8.8 parts of methanesulfonyl chloride. After the addition is complete, stirring is continued for 3 hours at room temperature. The reaction mixture is poured into water and the product is extracted twice with trichloromethane. The combined extracts are washed twice with a dilute hydrochloric acid solution and once with water, dried, filtered and evaporated. The residue is crystallized from 2,2'-oxybispropane to give 16.5 parts of 3-cyclohexyl-2- (2,4-dichlorophenyl) propylmethanesulfonate, mp 105.1 ° C.

20

Example 17

Following the procedure of Example 16, the following methanesulfonates are prepared, starting from the corresponding alcohols: 2- (2,4-dichlorophenyl) -5-hexenylmethanesulfonate as a residue; 2- (2,4-dichlorophenyl) propylmethanesulfonate as a residue; 2- (2,4-dichlorophenyl) -3-methylbutylmethanesulfonate as a residue; 2- (2,4-dibromophenyl) hexylmethanesulfonate as a residue; 4-cyclopentyl-2- (2,4-dichlorophenyl) butyl methanesulfonate, m.p. 65.4 ° C; 4-cyclohexyl-2- (2,4-dichlorophenyl) butyl methanesulfonate, mp 44.4 ° C; 3- ([1,1-biphenyl] -4-yl) -2- (2,4-dichlorophenyl) propylmethanesulfonate as an oily residue; 2,4-bis (2,4-dichlorophenyl) butyl methanesulfonate as an oily residue; 2,4-bis (4-chlorophenyl) butyl methanesulfonate as a residue; 4- (4-chlorophenyl) -2- (4-methylphenyl) butyl methanesulfonate as an oily residue; 2- (4-bromophenyl) -4- (2-methoxyphenyl) butyl methanesulfonate as an oily residue; 2- (4-bromophenyl) -4- (4-chlorophenyl) butyl methanesulfonate as an oily residue; 4- (4-chlorophenyl) -2- (4-fluorophenyl) butyl methanesulfonate as an oily residue; 2- (4-fluorophenyl) -4- (4-methylphenyl) butyl methanesulfonate as an oily residue, and 4- (4-bromophenyl) -2- (2-chlorophenyl) butyl methanesulfonate as an oily residue.

Example 18

A mixture of 30.4 parts / J- [2- (4-bromophenoxy) ethyl] -2,4-dichlorobenzeneethanol, 11.5 parts methanesulfonyl chloride, 100 parts pyridine and 70 parts 2,2'-oxybispropane is stirred overnight over at room temperature. The reaction mixture is poured into water and the product is extracted twice with 2,2'-oxybispropane. The combined extracts are washed successively with a dilute hydrochloric acid solution and twice with water, dried, filtered and evaporated to give 34 parts of 4- (4-bromophenoxy) -2- (2,4-dichlorophenyl) butyl methanesulfonate as a residue.

Example 19

Following the procedure of Example 18, the following methanesulfonates are prepared, starting from the corresponding alcohols: 5- (3,5-dichlorophenoxy) -2- (2,4-dichlorophenyl) pentylmethanesulfonate as a residue; 5- (2-bromophenoxy) -2- (2,4-dichlorophenyl) pentylmethanesulfonate as a residue; 5- (4-chloro-3-methylphenoxy) -2- (2,4-di chlorophenyl) pentylmethanesulfonate as a residue; 2- (2,4-dichlorophenyl) -5- (2-naphthalenyloxy) pentylmethanesulfonate as a residue; 5- (4-chloro-2-methylphenoxy) -2- (2,4-dichlorophenyl) pentylmethanesulfonate as a residue; 5- (2-bromo-4-methylphenoxy) -2- (2,4-dichlorophenyl) pentylmethanesulfonate as an oily residue; 5- (2,4-di chloro-6-methylphenoxy) -2- (2,4-di chlorophenyl) pentylmethanesulfonate as a residue;

DK 159551 B

5- (2-Chloro [1,1'-bi-phenyl] -4-yloxy) -2- (2,4-dichlorophenylpentyl methanesulfonate as a residue; 2,4-bis (4-bromophenyl) butyl methanesulfonate as a residue oily residue, and 2- (2,4-di chlorophenyl) -5- (2,4,6-tri bromophenoxy) pentylmethanesulfonate as a residue.

Example 20

To a stirred mixture of 14 parts of 1H-1, 2,4-triazole and 225 parts of N, N-10 dimethyl formamide is added 6.2 parts of a 78% sodium hydride dispersion. When foaming has ceased, 19.5 parts of 2- (2,4-dichlorophenyl) propylmethanesulfonate are added and stirring is continued for 6 hours at reflux. The reaction mixture is cooled, poured into water and the product is extracted twice with 2,2-oxybispropane. The combined extracts are washed with water, dried, filtered and evaporated. The residue is crystallized from petroleum eum ether. The product is filtered off and dried to give 10.2 parts (58%) of 1- [2- (2,4-dichlorophenyl) propyl] -1H-1,2,4-triazole, m.p. 79.5 ° C.

Example 21

To a stirred mixture of 16 parts of 1H-1,2,4-triazole in 225 parts of N, N-dimethylformamide is added 6.8 parts of a 78% sodium hydride dispersion and the whole stirred until foamy. Then 23.5 parts of 2- (2,4-dichlorophenyl) -3-methylbutylmethanesulfonate are added and the stirring is continued for 24 hours at reflux temperature. The reaction mixture is cooled and poured onto water. The product is extracted twice with 2,2'-oxybis-propane. The combined extracts are washed with water, dried, filtered and evaporated. The residue is purified by column chromatography over silica gel using a mixture of trichloromethane and methanol (98: 2 by volume) as eluent. The pure fractions are collected and the eluent is evaporated. The residue is converted to the nitrate salt in 2,2'-oxybispropane. The salt is filtered off and crystallized from a mixture of 4-methyl-2-pentanone and 2,2'-oxybispropane to give 18.4 parts (70%) of 1- [2- (2,4-di chlorophenyl) -3-methyl butyl] -1H-1,2,4-tri-azole nitrate, mp 147.1 ° C.

Example 22

Following the procedure of Example 21 and using an equivalent amount of an appropriate methanesulfonate instead of 2- (2,4-dichlorophenyl) -3-methylbutylmethanesulfonate used therein, the following triazoles and triazole nitrate salts are prepared: - [2- (2,4-dichlorophenyl) butyl] -1H-1,2,4-triazole, m.p. 70.2 ° C; 1- [2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole, mp 62.7 ° C; 1- [2- (2,4-dibromophenyl) hexyl] -1H-1,2,4-triazole nitrate, mp 141.7 ° C; 1- [2- (2,4-di-chlorophenyl) -3-methylpentyl] -1H-1,2,4-triazanol nitrate, m.p. 116.6 ° C; 1- [2- (2,4-dichlorophenyl) -4-methylpentyl] -1H-1,2,4-triazole nitrate, mp 146.8 ° C; 1- [2- (2,4-dichlorophenyl) heptyl] -1H-1,2,4-triazole nitrate, mp 144.6 ° C; 1- [2- (2,4-di-chlorophenyl) decyl] -1H-1,2,4-triazolinitrate, m.p. 116.6 ° C; 1- [2-cyclopentyl-2- (2,4-dichlorophenyl) ethyl] -1H-1,2,4-tri-azole nitrate, m.p. 149.2 ° C; 1- [2-cyclohexyl-2- (2,4-dichlorophenyl) ethyl] -1H-1,2,4-triazole, m.p. 79.2 ° C; 1- [3-cyclohexyl-2- (2,4-dichlorophenyl] propyl] -1H-1,2,4-triazole nitrate hemihydrate, mp 124.3 ° C; 1- [4-cyclohexyl-2- (2,4-dichlorophenyl ) butyl] -1H-1,2,4-triazole, m.p. 96.5 ° C; 1- [2- (2,4-Dichlorophenyl) -4-pentenyl] -1H-1,2,4 tri-azole nitrate, m.p. 139.7 ° C, and 1- [2- (2,4-dichlorophenyl) -5-hexenyl] -1H-1,2,4-triazole mononitrate, mp 114.8 ° C.

30

Example 23

To a stirred mixture of 3.8 parts of a 78% sodium hydride dispersion and 90 parts of Ν, Ν-dimethylformamide is added dropwise a solution of 21 parts of 2,4-bis (4-chlorophenyl) butyl methanesulfonate in 45 parts of N, N-dimethyl. -35 formamide. After stirring for 15 minutes at room temperature, a solution of 7.6 parts of 1H-1,2,4-triazole in 45 parts of Ν, Ν-dimethylformamide is added. The whole is slowly heated to 100 ° C and stirring is continued for 2 hours at 100 ° C. The reaction mixture is poured onto water and the product

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29 is treated with 1,1'-oxybfsethane. The extract is washed with water, dried, filtered and evaporated. The oily residue is purified by column chromatography over sil icage! using a mixture of trichloromethane and methanol (97.5: 2.5 by volume) as eluant. The pure fractions are collected and the eluent is evaporated. The oily residue is converted to the hydrochloride salt in 2,2'-oxybispropane. The salt is filtered off and crystallized from a mixture of methanol and 2,2'-oxybispropane to give 7 parts (32.5%) of 1- [2,4-bis (4-chlorophenyl) butyl] -1H-1,2,4- triazole hydrochloride, mp 173.4 ° C.

10

Example 24

Following the procedure of Example 23 and using an equivalent amount of a suitable methanesulfonate in place of 2,4-bis (4-chlorophenyl) butyl methanesulfonate, the following triazoles and triazole hydrochloride salts were prepared: 1- [3 - ([1 1'-bi-phenyl] -4-yl) -2- (2,4-dichlorophenyl) propyl] -1,2,4-triazole hydrochloride, m.p. 175.5 ° C; 1- [4- (4-chlorophenyl) -2- (4-methylphenyl) butyl] -1H-1,2,4-triazole hydrochloride, m.p. 170 ° C; 1- [2- (4-bromophenyl) -4- (2-methoxyphenyl) butyl] -1H-1,2,4-tri azole hydrochloride, mp 153.2 ° C; 1- [2- (4-bromophenyl) -4- (4-chlorophenyl) butyl] -1H-1,2,4-triazole, m.p. 87.6 ° C; 1- [4- (4-chlorophenyl) -2- (4-fluorophenyl) butyl] -1H-1,2,4-triazole hydrochloride, m.p. 171.8 ° C; 1- [2- (4-fluorophenyl) -4- (4-methylphenyl) butyl] -1H-1,2,4-triazole hydrochloride, mp 128.6 ° C; 1- [4- (4-bromophenyl) -2- (2-chlorophenyl) butyl] -1H-1,2,4-triazole hydrochloride, m.p. 142.6 ° C, and 1- [2.4- bis (4-bromophenyl) butyl] -1H-1,2,4-triazole hydrochloride, mp 163 ° C.

Example 25

A mixture of 6.9 parts of 1H-1,2,4-triazole, 3.4 parts of a 78% sodium hydride dispersion and 90 parts of N, N-dimethyl formamide is stirred for 10 minutes at room temperature. Then a solution of 19.9 parts of 5- (2-bromo-4-methylphenoxy) -2- (2,4-dichlorophenyl) pentylmethanesulfonate in 45 parts of N, N-dimethyl formamide is added. Stirring is continued for 2 hours at 100 ° C.

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The reaction mixture is allowed to cool to room temperature and poured onto water. The product is extracted twice with Ι, Γ-oxybisethane. The combined extracts are washed with water and acidified with concentrated nitric acid solution. The nitrate salt formed is filtered off and recrystallized from a mixture of acetonitrile and 2,2'-oxybispropane to give 13.3 parts (64%) of 1- [5- (2-bromo-4-methylphenoxy) -2- (2 4-dichlorophenyl) pentyl] -1H-1,2,4-triazole nitrate, mp 119.6 ° C.

Example 26 Following the procedure of Example 25, the following triazolene trace salts are prepared, starting from 1H-1,2,4-triazole and an appropriate methanesulfonate: 1- [5- (3,5-dichlorophenoxy) -2 - (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole nitrate, m.p. 145.3 ° C; 1- [4- (4-bromophenoxy) -2- (2,4-dichlorophenyl) butyl] -1H-1,2,4-triazole nitrate, m.p. 144.6 ° C; 1- [5- (2-bromophenoxy) -2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole nitrate, mp 123.2 ° C; 1- [2- (2,4-dichlorophenyl) -5- (2-naphthalenyloxy) pentyl] -1H-1,2,4-triazole nitrate, mp 136.8 ° C; 1- [5- (4-chloro-3-methylphenoxy) -2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole nitrate, m.p. 140 ° C; 1- [5- (4-chloro-2-methylphenoxy) -2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole nitrate, m.p. 123.1 ° C; 1- [5- (2,4-dichloro-6-methylphenoxy) -2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole nitrate, m.p. 153.4 ° C; 1- [5- (3-Chloro- [1,1'-biphenyl] -4-yloxy) -2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole nitrate, m.p. 135 , 3 ° C, and 1- [2- (2,4-di chlorophenyl) -5- (2,4,6-tri bromophenoxy) pentyl] -1H-1,2,4-30 triazole nitrate, m.p. 166.5 ° C.

Example 27

To a stirred sodium methoxide solution prepared from 3.9 parts of sodium in 40 parts of methanol, a mixture of 12 parts of 35 H-1,2,4-triazole and 225 parts of Ν, Ν-dimethylformamide is added. The methanol is distilled off until an internal temperature of 150 ° C is reached. After cooling to 100 ° C, 18.5 parts of 2- (2,4-dichlorophenyl) hexylmethanesulfonate are added and stirring at 100 ° C is continued for 2 hours. The reaction mixture is cooled, 31

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pour into water and extract the product three times with 2,2'-oxybispropane. The combined extracts are washed with water, dried, filtered and evaporated. The residue is purified by column chromatography over silica gel using trichloromethane as eluant. The pure fractions are collected and the eluent is evaporated. The residue is converted to the nitrate salt in 2,2'-oxybispropane and petroleum ether. The salt is filtered off and recrystallized from a mixture of 2-propanone, 2,2'-oxybispropane and petroleum eum ether to give 11.6 parts (56%) of 1- [2- (2,4-dichlorophenyl) hexyl] -1H-1,2,4-triazole nitrate, mp 128.3 ° C.

10

Example 28

Following the procedure of Example 27, the following compounds are prepared: 1- [4-cyclopentyl-2- (2,4-dichlorophenyl) butyl] -1H-1,2,4-triazole, m.p. 71 ° C, by reacting 1H -1,2,4-triazole with 4-cyclopentyl (2,4-dichlorophenyl) butyl methanesulfonate, and 1- [2,4-bis (2,4-dichlorophenyl) butyl] -1H-1,2,4-triazole hydrochloride , mp 158.7 ° C, by reacting 1H-1,2,4-triazole with 2,4-bis (2,4-di chlorophenyl) butyl methanesulfonate.

20

Example 29

To a stirred sodium methoxide solution prepared from 1.6 parts of sodium in 56 parts of methanol is added 4.8 parts of 1H-1,2,4-triazole. 40 parts of methanol are distilled off under normal pressure. After adding 80 parts of 4-methyl-2-pentanone, an additional 28 parts of the solvent are distilled off.

Then 22 parts of 3- (4-chlorophenyl) -2- (2,4-dichlorophenyl) propylmethanesulfonate and 90 parts of Ν, Ν-dimethylformamide are added and the whole is stirred and refluxed overnight. The reaction mixture is allowed to cool to room temperature and poured onto water. The product is extracted twice with 2,2'-oxybispropane. The combined extracts are washed twice with water and an excess of a concentrated nitric acid solution is added. The nitrate salt formed is filtered off and recrystallized from 4-methyl-2-penta-non to give 6.6 parts (27%) of 1- [3- (4-chlorophenyl) -2- (2,4-dichlorophenyl) propyl ] -1H-1,2,4-triazole nitrate, m.p. 174.8 ° C.

Example 30

Following the procedure of Example 29, 1- [3- (2-bromophenyl) -2- (2,4-dichlorophenyl) propyl] -1H-1,2,4-triazole nitrate, melting point 168 is prepared. , 4 ° C, by reacting 1H-1,2,4-triazole with 3- (2-bromophenyl) -2- (2,4-dichlorophenyl) propylmethanesulfonate.

Example 31 5 Following the procedure of Example 10, methyl 2,4-dibromobenzene acetate, boiling point 105-110 ° C is prepared at 0.1 mm pressure, starting from 2,4-dibromobenzene acetonitrile.

Example 32 Following the procedure of Example 13 and using equivalent amounts of suitable starting materials, the following compounds are prepared: 2.4-dibromo- [1- (2-methylpropyl] benzenethethanol as a residue; 2.4-dibromo-β- (1-methylethyl) benzenethanol as a residue residue, and 2.4-dibromo-0- (1-methylpropylbenzene ethanol) as a residue.

15

Example 33

Following the procedure of Example 16 and using equivalent amounts of suitable starting materials: [2- (2,4-dibromophenyl) -4-methylpentyl] methanesulfonate is prepared as a residue; [2- (2,4-dibromophenyl) -3-methylbutyl] methanesulfonate as a residue, and [2- (2,4-dibromophenyl) -3-methylpentyl] methanesulfonate as a residue.

25

Example 34

Following the procedure of Example 21 and using equivalent amounts of suitable starting materials, the following compounds are obtained: 1- [2- (2,4-dibromophenyl) -4-methylpentyl] -1H-1,2,4-triazole mononitrate, m.p. 153, 6 ° C; 1- [2- (2,4-di bromophenyl) -3-methyl butyl] -1H-1,2,4-triazole mononitrate, mp 142.9 ° C; 1- {2- (4-chlorophenyl) -2- (1-methylethoxyethyl) -1H-1,2,4-triazole mononitrate, m.p. 135.3 ° C; 1- {2- (2,4-dichlorophenyl) ) -2- (1-methylethoxy) ethyl] -1H-1,2,4-triazole mononitrate, mp 146.1 ° C, and 1- [2- (2,4-dibromophenyl) -3-methylpentyl] - 1H-1,2,4-triazole mononitrate, mp 131.8 ° C.

Claims (16)

1. IH-1,2,4-Triazole Derivatives with Antifungal and Plant Growth Regulating Effect, CHARACTERIZED BY THEIR GENERAL FORMULA: 5 ._N'Ό in CH_ -CH-R Chemical compound according to claim 1, characterized in that it is 25- [2- (2,4-dichlorophenyl) -3-methylbutyl] -1H-1,2,4-triazole or a physiologically acceptable acid addition salt thereof. 2. Ar 10 wherein Ar represents phenyl, mono-, di- or trihalophenyl, lower alkyl phenyl, lower alkoxyphenyl, nitrophenyl, cyanophenyl or trifluoromethylphenyl, and R represents all alkyl having from 1 to 10 carbon atoms, cycloalkyl, cycloalkyl all lower alkyl, lower alkenyl, aryl lower alkyl or aryloxy-lower alkyl, aryl representing phenyl, naphthalenyl or substituted phenyl, wherein the substituted phenyl group is phenyl having from 1 to 3 substituents, independently selected from halogen, lower alkyl, lower alkyloxy, cyano, nitro and phenyl, provided that only one of the 20 substituents can be cyano, nitro or phenyl when more than one substituent is present, or physiologically acceptable acid addition salts thereof. Chemical compound according to claim 1, characterized in that it is 1- [2- (2,4-dichlorophenyl) -3-methylpentyl] -1H-1,2,4-triazole or a physiologically acceptable acid addition salt thereof . Chemical compound according to claim 1, characterized in that it is 1- [2- (2,4-dichlorophenyl) -4-methylpentyl] -1H-1,2,4-triazole or a physiologically acceptable acid addition salt thereof. 35 Chemical compound according to claim 1, characterized in that it is 1- [2- (2,4-dichlorophenyl) -hexyl] -1H-1,2,4-triazole or a physiologically acceptable acid addition salt thereof. DK 15955 ' Chemical compound according to claim 1, characterized in that it is 1- [4- (4-chlorophenyl) -2- (4-methylphenyl) butyl] -1H-1,2,4-triazole or 1 is a physiologically acceptable acid addition salt thereof. 5 Chemical compound according to claim 1, characterized in that it is 1- [4- (4-chlorophenyl) -2- (4-fluorophenyl) butyl] -1H-1,2,4-triazole or 1 is a physiologically acceptable acid addition salt thereof. Chemical compound according to claim 1, characterized in that it is 1- [2- (2,4-dibromophenyl) hexyl] -1H-1,2,4-triazole or a physiologically acceptable acid addition salt thereof. Chemical compound according to claim 1, characterized in that it is 15- [2- (4-fluorophenyl) -4- (4-methylphenyl) butyl] -1H-1,2,4-triazole or a physiologically acceptable acid addition salt thereof. The chemical compound of claim 1, characterized in that it is 1- [2- (2,4-dichlorophenyl) heptyl] -1H-1,2,4-triazole or a physiologically acceptable acid addition salt thereof. Chemical compound according to claim 1, characterized in that it is 1- [2-cyclohexyl-2- (2,4-dichlorophenyl) ethyl] -1H-1,2,4-triazole or a physiologically acceptable acid addition salt thereof. 25 Chemical compound according to claim 1, characterized in that it is an IH-1,2,4-triazole derivative of the general formula NO 30 CH 2 - <pH-R 'Ar' or a physiologically acceptable acid addition salt thereof, wherein 35 Ar represents dichlorophenyl or dibromophenyl, and R 'represents any alkyl having from 1 to 8 carbon atoms, cycloalkyl or 2-propenyl. DK 15955 1 B 13. A composition for controlling fungi, characterized in that it comprises an inert carrier material and as an active component an effective antifungal amount of a compound in the form of a 1H-1,2,4-triazole derivative of the general formula tf in CH CH-R • 2L 10 or a physiologically acceptable acid addition salt thereof, wherein Ar represents phenyl, mono-, di- or trihalogenphenyl, lower alkylphenyl, lower alkoxyphenyl, nitrophenyl, cyanophenyl or trifluoromethyl-phenyl, and R represents all alkyl with from 1 to 10 carbon atoms, cycloalkyl, cycloalkyl-lower alkyl, lower alkenyl, aryl-lower alkyl or aryloxy-lower alkyl, where aryl represents phenyl, naphthalenyl or substituted phenyl, wherein the substituted phenyl group is phenyl with from 1 to 3 substituents independently selected from halogen, lower alkyl, lower alkyloxy, cyano, nitro and phenyl, provided that only one of the 20 substituents can be cyano, nitro or phenyl when there is more than one substituent . 14. A composition according to claim 13, characterized in that it contains as an active component 1- [2- (2,4-dichlorophenyl) -3-methylbutyl] -1H-1,2,4-triazole or a physiologically acceptable acid addition salt thereof. . A composition according to claim 13, characterized in that it contains as an active component 1- [2- (2,4-dichlorophenyl) hexyl] -1H-1,2,4-triazole or a physiologically acceptable acid addition salt thereof. 30 Composition according to claim 13, characterized in that it contains as an active component 1- [2-cyclohexyl-2- (2,4-dichlorophenyl) ethyl] -1H-1,2,4-triazole or a physiologically acceptable acid addition salt thereof .