IE45462B1 - Novel1-(2-r-ethyl)-1h-1,2,4-triazoles - Google Patents

Novel1-(2-r-ethyl)-1h-1,2,4-triazoles

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Publication number
IE45462B1
IE45462B1 IE1664/77A IE166477A IE45462B1 IE 45462 B1 IE45462 B1 IE 45462B1 IE 1664/77 A IE1664/77 A IE 1664/77A IE 166477 A IE166477 A IE 166477A IE 45462 B1 IE45462 B1 IE 45462B1
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triazole
acceptable acid
acid addition
physiologically acceptable
addition salt
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IE1664/77A
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IE45462L (en
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Janssen Pharmaceutica Nv
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
    • C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • C07C309/66—Methanesulfonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/40—Halogenated unsaturated alcohols
    • C07C33/50—Halogenated unsaturated alcohols containing six-membered aromatic rings and other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

A fungicidal composition contains, as active ingredient, novel 1H-1,2,4-triazole derivatives of the formula in which the substituents are as defined in Claim 1, and physiologically acceptable acid addition salts of compounds of the formula I. The fungicidal composition is prepared according to the invention either by N-alkylating 1H-1,2,4-triazole with an ester derivative or by O-alkylating a corresponding 1H-1,2,4-triazole, in which the N atom has the substituent -CH2-CH(Ar)OH, and mixing the reaction products with formulation auxiliaries. The above-described fungicidal composition can be used for controlling methane in various plant species.

Description

Price 12fp The present invention relates to certain 1-(2-aryl2-R-ethyl)-1H-1,2,4-triasoles which demonstrate fungicidal and plant-growth regulating properties.
A number of fungicidal and plant-growth regulating 5 imidazole and triazole derivatives are known. She compound of the present invention differ from the known triazole derivatives in respect of the nature of the substituted ethyl side chain present in the 1-position of the triazole nucleus and from the imidazole derivatives essentially by the replacement of the imidazole group with a 1H-1,2,4triazole group. The prior art is represented by United States Patents Nos. 3,717,655; 3,658,813; 3,927,017; 3,821,394;' 3,897,438 and 3,647,814.
The 1-(2-aryl-2-R-ethyl)-1H-1,2,4-triazoles of the present invention may structurally be represented by the general formulas tT · --¾ (Ii CH_-CH-R 2 S Ar wherein s Ar is a phenyl, mono-, di- or tri-halophenyl, lower 20 alkylphenyl, lower alkyloxyphenyl, nitrophenyl, cyanophenvl or trifluoromethylphenyl group; R is an alkyl group having from 1 to 10 carbon atoms, a cycloalkyl, cycloalkyl-lower alkyl, lower alkenyl, aryllower alkyl or aryloxy-lower alkyl group, said aryl being a phenyl, naphthalenyl or substituted phenyl group, * ·1 b Λ having from 1 to 3 substituents which are each independently halogen, lower alkyl., lower alkyloxy, cyano, nitro or phenyl, provided that when more than one substituent is present only one thereof may oe cyano, nitro or phenyl.
By the term alkyl as used in the definition of R is meant straight and branched chain aliphatic hydrocarbon groups containing from 1 to 10 carbons, such as, methyl, ethyl, 1-methylethyl, 1,1-dimethylethvl, propyl, 1-methylpropyl, 2-methylpropyl, butyl, pentyl, hexyl, heptyl, octyl and decyl; by the term ’lower alkyl as used herein is meant a straight or branched chain alkyl group containing from 1 to 6 carbon atoms, such as methyl, ethy. :-methylethyl, propyl, 1-methylpropyl, 2-methylpropyl, butyl, pentyl and hexyl; by the term lower alkenyl is meant straight and branched chain alkenyl groups having from I to 6 carbon atoms, such as 2-prcoenyi, 1-methyl-2 propenyl, 2-butenyl, 3-butenyl and 2-nexenyi; ay the term cycloalkyl is meant a cyclic hydrocarbon group having from 3 to 6 carbon atoms, such as cvciopropyl, cyc.obutyi, cyclopentyl and cyclohexyl; and by tee term halo is meant halogens of atomic weight j.ess that 127, i.e. chloro, bromo, fluoro and iodo.
The physiologically acceptable acid addition salts cf the foregoing compounds (I) are also included within the scope of this invention. '4 54 S& Τ %/r One prefessed group of compounds within the scope of formula (X) may be represented by the formulas Ar· whsreia As1 io selected from the group consisting of phenyl, monoaad di-halopheayl, and methylpheayl; snd S S' is selected fesm the group consisting of alkyl having from to 10 carbon atoms, cycloalkyl, lower alkenyl, arylmethyl and aryleihyl, wherein said aryl ie preferably phenyl, halophenyl, methylpheayl or methoxyphenyl.
Especially preferred within the scope of formula (X1) are compounds wherein Ar* ia phenyl, ehlarophesyl, Snerophenyl, bromophenyl, dichloropheayl, dibromcghcayl ss* methylpheayl, the moat preferred being dishlsrs- sad dibremopheayi; rad, wherein R ’ is alkyl having from 1 to 8 carbon atoms, cycloalkyl, or 2-propenyl, the moat preferred being aHsyl having feoSi 1 to 6 carbon atoms and 2-propenyl.
IS . Typical ssamgleo ef preferred compounds within the scope of formula (I1) arc the following: 1-22-(2,4-d2ehlorepheayl)pEOpyX7-IH-l, 2,4-triaaole; -^=(2,4«diehlorophsayl)buty^’-lK-l, 2,4-triazole; - ^-(2,4-diehlorophenyl)peaty^7-lX4-l, 2,4—triazole; .1-^-(2,4-dieklor©pheayl}-3-E3ffithylbutyl7-lS"l, 2,4-triazole; *«* fl 1-/5-(2,4-dichlorophenyl)-4-pentenyl7-lH-l, 2,4-triazole; -£-(2, 4-dichlorophenyl)hexyj7-IH-I,2,4-triazole; -/2-(2,4-dicbloropheayl)-4-iaethylpentyi7-IK-1,2,4-triazole; 1-/5-(2,4-dicfclorephenyl)-3-methylpenty£7-lH-l, 2, *3—triazole; X -/2f-(2,4-diehlorophenyl)heptyl7-lH-l, 2,4-triazole; -/5-cydopentyl-2-(2,4-dichloropheayl)ethy£7-lH-l, 2,4-triazole; l-/5-cydohexyl-2-(2,4-dichloropheayl)ethyl7«lH-l, 2,4-triazole; -/3-(4-ehlorophenyl)-2-{2,4»dicbloropbenyl)propy^-lH-l, 2,4triazole; 1-^-(2,4-dibromopheayl)hexyl7-lH-l, 2,4-triazole; 1-/5-(2,4-dibromophenyl)-4-methylpentyl7-lH-l, 2,4-triazole; - /5-(2,4-dibronaophenyl}-3-methylbutyl7-IH-I, 2,4-triazole; - /5-(2,4-dibromophenyl)-3-methylpentyl7-lH-l, 2,4-triazole; -/5-(4-fluoropheayl)-4-(4-Haetbyipheayl)butyj7"lH-l, 2,4-triazole; and 1 -/3-(4-ehlorophenyl)-2-(4-£luorophenyl)butyl7-lH-l, 2,4-triazole. ,4S46£ Tha compounds s£ fecauls. (I) which may he represented b’ the formula: rf1 r 2CHg-CH-ST Ar (I-a) wherein Ar is a previously defined and S2 is selected from the group consisting of alkyl, cyeloalkyl, cyeloalkyl-lower alkyl, lower alkenyl, aryl-lower alkyl and aryloxy «lover alkyl, may conveniently be prepared by K-all^rlating 1H-1,2,4-triaaole (ll) with an appropriate reac· tive eater of formula (ΠΧ' wherein Ar and R are as previously define: and, X is a reactive eater function such as, for example, halo, methyl· sulfonyloxy, (4-methylphenyl)sulfonyloxy, Xn carrying out the reaction of (ll) and (IE) it is appropriati to first convert (ΪΣ) into an alkali metal salt, preferably the sodium salt, by the reaction ©£ (Ώ.) with an appropriate strong metal base, such as, for essample, sodium hydride, sodium methanalate, sodium amide - and thereafter stirring and heating said metal salt with (Hl) ia aa appropriate polar organic solvent. Suitable solvents fox this purpose include amides such as, N,N-dimethylformamids aadl'TiN-dte’ethylacetaKade, and nitriles such as, for example acetonitrile, bensanitsile,. .
Alternatively (H) and (Hl) may be reacted directly with each other without previous salt formation, in which ease the reaction is preferably carried out in an appropriate polar organic solvent as defined hereabov®, ia the presence of an appropriate base to pick up the acid which ia liberated during the course of the reaction. Suitable bases which ‘may advantageously fee employed include inorganic bases - such as, for example, sodium and potassium carbonate and hydrogen carbonate and organic bases such as, for example, N,N diethylethanamin e, pyridine, Somewhat elevated temperatures are appropriate to enhance the rate of the reaction and most preferably the reaction is carried out at the reflux temperature of the reaction mixture.
The il·.-egoing reactions may be illustrated as follows: Αη,-ch-b2 2 I Ar (I-a) (Π) + (Hl) ba*e_> (I-a) solvent »ΰ4δ5It is evident that the compounds of formula (I) obtained following the procedures described herebefore are isolated from the reaction mixture and, if necessary, further purified by the application of methodologies known in the art.
The compounds of formula {I), obtained in base form in the foregoing procedures, may be converted to their pharmaceutically acceptable acid addition salts by reaction with an appropriate acid, for example, an inorganic acid such as hydrohalic acid, i.e., hydrochloric, hydrobromic or hydroiodic acid; sulfuric, nitric or thiocyanic acid, a phosphoric acid? an organic acid such as acetic, propanoic, 3 1 hydroxyacetic, 2-hydroxypropanoic, 2-oxopropanoic, ethanedioic, propanedioic, butanedioic, (Z)-2-butenedioic, (E)-2-butehedioic, 2hydroxyhutanedioie, 2,3-dihydroxybutanedioic, 2-hydroxy-1,2,3propaaetricarboxylic, benzoic, 3-phenyl-2-propenoic, a-hydroxy5 beazeneacetic, methaaesulfoaic, ethanesulfonic, hydroxyethanesulfoaic, 4-methylbenzenesu'fanic, 2-hydxoxybenzoic, 4-amino-2-hydroxyhanzoic, 2-phenox^benzoic or 2-acetyloxybeazoic acid. The salts are ia turn converted to the corresponding free bases in the usual manner, e. g., by reaction with alkali such as sodium or potassium hydroxide.
A number of the reactive.ester intermediates of formula (III) are known compounds and they may all be prepared according to procedures described in the literature for the preparation of those known compounds. Such compounds and methods of preparing the same are described, for example, in U.S. Pat. No. 3,927,017.
IS In general said intermediates of formula (III) are prepared by converting the corresponding alcohol (V) into the desired reactive ester according to methodologies generally known in the art. For example, methaaesulfonates and 4-methylbenzenesulfonates are easily obtained by treating the alcohol with methanesulfonyl chloride or 420 methylbenzeneaulfonyl chloride respectively, in the presence of an appropriate acid acceptor, such as, for example, pyridine. Halides may be obtained by treating the alcohol with an appropriate halogenating agent, such as, for example, phosphor pentachloride, phosphorous tribromide, etc..
HO-CH.-CH-IT L reactive ester formation (m) (V) •4S463.
Ths intermediate alcohols o£ formula (V), a number of which are known compounds, may fee prepared, according to knows procedures, such as, for ejcample, the'following: As appropriately substituted arylacetositrile of formula (VI) S is alkylated with aa appropriate reactive estsr E^X, (VII). Saia alkylation reaction is preferably carried out by contacting first the arylacetonitrile with aa appropriate strong base, sueh as, for example, sodium hydride, and thereafter adding the reactive eater to the reaction mixture. Suitable solvents for this reaction include amides such as N,N10 dimsthylformaiaide^N.N-dimethylacetamide and hexamethylphosphoric triamide, ether common polar solvents such as dim.cthylEulfcjd.de, or mixtures of sueh solvents with, for example, an aromatic hydrocarbon, such as, bens ene.
The substituted arylaestenitrile (VIII) obtained in the fore» going stop is then converted into an alkyl ester (IX) of the corresponding carboxylic acid. This aiteHa-ta-eeter conversion may be achieved in one step, for example, by heating the nitrile is an appropriate alcohol, or a mixture of an alcohol with an appropriate reaction-inert organic solvent, sueh aa, 2,2!-os5ybiaprapanes ia the presence of a strong non20 oxidising mineral acid such as, for example, hydrochloric acid. Alter .natively the nitrile may be Sr at hydrolysed to the corresponding arylssatie acid in the usual manner, e. g., with sodium hydroxide in 1,2ethanedisl, and said acid may thereafter be converted into the desired ester thereof by classical mesas.
The esters (DS) may also be obtained by alkylating an appropriate'alkyl arylacetate (3S) with E^X according to known procedures.
Ths alcohols (V) are then obtained after reduction of (IX) with an appropriate reducing agent sueh as, for example, lithiumaluminium hydride, lithium borohydride, or sodium borohydride ia the presence of a lithium salt, preferably a halide such as, lithium iodide or lithium chloride.
The foregoing reactions are illustrated in the following schematic representation: Ar-CH2-CN R2X (VI) (VII) ,Ar-CH- CN (VIII) 11+ alkanol Ar-CK2-C-O-alkyl + R X (X) (VII) .Ar-CH- C-O-alkyl r2 (ix) (IX) LiBfy ->(V) The starting materials of formula (Vi) and (Vll) g are generally known and may be prepared following known procedures. For example, starting materials of formula 2 (VII) wherein R represents aryloxy-lower alkyl and X represents halo, are easily prepared by O-alkylating an appropriate hydroxyarene with an appropriate dihalo10 lower alkane using, for example, aqueous alkali as a reaction medium.
The ulimate starting materials in each of the foregoing procedures are generally kncwn and they may all be prepared following kncwn procedures.
Due to the presence of an asymmetric carbon in the subject compounds (I), it is evident that their existence in the form of stereochemical optical isctrers (enantianers) is possible. If desired, the resolution and isolation or the production of a particular form can be £ΰ46#· acoeroplished by application of tha general principles Jmcwn in the art. Hhese enanticners are naturally intended to be included within the scope of this invention.
Tiie compounds of formula (I) and the asid addition salts thereof are useful agestc in combatting fungi. They are especially useful as potent agricultural fungicides, being active against a v/ide variety of fungi such as, those responsible for the occurrence of powdery mildew en different plant species, a. g., Srysipa gsamiais, Erysiphe polygon!, Srysiphe cichsracearum, Esysiphe 1° petygkag3·» Podosphaara leucotriehia, Sphaerotheca gannosa. Sphaerotheea. mors-uvae and gneinalla aecatog; and against other phytopathogenic fungi sueh as, septoria- asil and Uromyeas phaseoli. ' The useful antifungal properties of the compounds of this invention are more clearly illustrated by the results obtained in the following'experiments. The compounds for which experimental data are presented hereafter are not given for the purpose of limiting the iavsa&on thereto but only ts esesiplify the useful antifungal properties of all the compounds within the scops of formula (1).
A.· Prophylactic activity against Erysiphe cichoracearum on gherkins upon foliar treatment.
Young g.-erkin plants, about 10 days old, were sprayed with an aqueous solution containing 100, 10 or 1 ppm. (parts per million) of the compound to be tested, while controls were kept untreated.· After drying of the plants, artificial infection with spores of Erysiphe cichoracearum was carried out by slightly rubbing the plants with a heavily infected leaf. At the 15th day alter artificial infection the degree of fungal attack was evaluated by estimating the percent of leaf surface attacked by the fungus. Three plants were used per object and mean values were calculated for these 3 plants. The results are presented inTables I and II according to the following score system: score % of leaf surface attacked 0 15 1 ^.10 11 to 50 >50 TABLE I: Prophylactic activity against Erysiphe cichoracearum on gherkins (foliar treatment).
TABLE I (coat’d) Compound ao. • « · I • R Base or Salt Scores 100 ppm 10 ppm L ppm. 20 (0^-0-0-01^-4-01-0^) hno3 1 3 3 21 (0^-0-0-0^-4-01-(^) hno3 1 0 2 22 (CH^-O-0-Br-4-01^-C^) hno3 0 0 1 23 (Ciy3-O-(2,4-0^-6-0^- W HNO3 2 2 3 24 (OH2)3-O-(2,4,6-B»3- C6S2> hno3 0 0 i 25 (CH2)3-O-(2-Cl-4-C,H,- C6H3> HN03 0 1 2 26 (CH2 )3-0-(2 -naphthalenyl) hno3 0 0 2 TABLE II: Frophylaetie activity agaisst Erysiphe Gishoracearum on gherkins (ioliar treatment).
CH,-CH-35 2 I Ar Sompouad ao. Base or Salt Scores Ar R 100 pprajlO ppm. IpjOT 27 2,4»3r„-C,K„ 2 ο o HN 0 0 0 28 2-Cl»C6H4 (CH2)2-(4-Er-C6H4) HCl 0 1 2 29 4-ei-cA (CH^-U-Cl-C^) HCl 0 1 2 30 4-Br-CfeH4 (GH^^-Cl-C^) base 0 2 ' 5 31 4-Br=C,H, © Q (CH2)2-(2-OCH,- HCl 0 1 2 32 4 B S’*=* C cA) !ch2)2.(4-Bi-cA) HCl 0 3 3 33 •w-e,». 6 .4 iCH2)2-(^Sl-C6H4) HCl - 0 1 34 '^f-c6k4 (CH2)2-(4-CHs- HCl 0 0 1 - · 35 4-G^-G^ w (CH^-^-Cl-C^) HCl 0 2 3 B; Prophylactic action against Erysiphe graminis on barley upon foliar treatment.
Young barley plants, about 8 cm. high, were sprayed with an aqueous solutio: containing 100, 10 or 1 ppm. of the compound under investigation while controls were kept untreated. After drying of the plants they were artificially infected by dusting them with conidia of Erysiphe graminis. Fungal attack was evaluated 10 days thereafter in the same manner as described in experiment A. The results of this ' experiment are represented in Table III wherein the compound numbers and the score system are the same as in Tables I and II.
TABLE III : Prophylactic action against Erysiphe graminis on barley upon foliar treatment. aS-46& TABLE Π (coat'd) Compound no. Scores 100 ppm. 10 ppm. ι PP® 13 0 0 1 14 1 3 3 15 Ό 1 1 • 16 1 2 3 17 1 2 3 18 Σ 2 3 19 1 3 3 22 1 2 3 24 1 3 3 26 3 2 3 27 0 0 1 281 3 3 29 0 0 1 30 2 • 3 3 31 1 3 3 1 32; I 2 333 1 1 1 34 0 1 1 35 0 .0 1 •j ΰ 4 θ 5· C. Systemic activity against Erysiphe cichoracearum on gherkins.
Young gherkin plants, about 10 days old, where treated by watering of the soil with an aqueous solution of the test compound.
Per plant 100 ml. vcre given and the total amount ox test compound S was 10 or 1 mg. per plant. Controls received the same amount of the solution without active ingredient. 4 Days thereafter the plants were artificially infected with Erysiphe cichoracearum by slightly rubbing the plants with a heavily infected leaf. Evaluation of fungal attack was done 15 days thereafter in the same manner as described in test A.
The results are given in table IV wherein the compound numbers and the score system are the same as in tables I and II.
TABLE IV: Systemic activity against ErvBiphe cichoracearum on gherkins. 4S4G£· TABLS IV (coat'd) Compound no. Scores 10 mg./plant 1 mg./plant 15 2 3 18 2 2 Si 2 2 S. Prophylactic activity against Uromyces phaseoli on beans upon, foliar treatment.
Young bssn. plaate, about 15 ©a. aiga. were sprayed with an aqueous solution eeataiaiag 230, 10G os 10 ppm. of the test compound while controls were kept untreated. After drying,, .the plants were artificially infested by assaying them with a suspension of spores of Uraaayees phaseoli. Subsequently She plants were incubated for 24 hours at 18°C aad at 95-100% relative humidity. Fungal-attack was evaluated 10 days after tae artificial infection ia the same manner as ia test A.
The results are given in table V wherein the same compound numbers aad the same score system as in tobies I and ΪΙ are used. 2.0 TABLE V: Prophylactic activity against ggomve^ on beans upon foliar treatment.
Compound no. Scores 250 ppm. 100 ppm. 10 ppm. 1 1 2 3 2 1 1 3 3 .1 1 2 4 0 1 1 5 0 0 3 6 0 0 1 7 0 0 2 9 0 0 3 10 0 2 . 3 11 2 3 3 Apart from their aatiSengal effect, the compounds of formula (l) possess valuable plant growth, regulating properties. Depending on different factors such as the sgaeies af the plants under investigation and the dose of active ingredient administered, the observed effect may be growth stimulation or growth inhibition.
As such the compounds of this invention are useful as plant growth regulators and this usefal property is naturally intended to be also within the scope af this invention. la view of the aforementioned antifungal and growth-regulating 18 activities this invention provides valuable compositions comprising the subject tsiasoleo {I) or the acid addition salts thereof as the active ingredient in a solvent or a solid, aemi-solid or liquid diluent or carrier and, is addition, it provides aa effective method of combatting fungal growth by use of aa effective antifungal amount of such triaaoles (I) ' or salts thereof. Ths subject compounds can be used in suitable solvents or diluents, ia the form as smuleions, suspensions, dispersions or ointaasta, ©a suitable solid er 3casi=selia carrier substances, in ordinary or eyathctie soaps, detergents or dispersion media, if desired, together with other eompsuadfl having arachnicidal, insecticidal, ovicidal, fuagi26 cifial and/or bactericidal effects, or together with inactive additives.
Solid carrier sufeatansea whish are suitable for the preparation of compositions in powder form include various inert, porous and pulverous distributing ageatG of inorganic or organic nature, such as, I. for example, tsiealeium pho s chat a, calcium carbonate in the form of 25 prepared chalk or ground limestone, kaolin, bole, bentonite, talcum, kieselguhr and boric acid; powdered cork, sawdust, and other fine pulverous materials of vegetable origin are also suitable carrier substances. •i ΰ 4 6 3The active Ingredient is mixed with these carrier substances, for example, by being ground therewith; alternatively, the inert carrier substance is impregnated with a solution of the active component in a readily volatile solvent and the solvent is thereafter eliminated by heating or by filtering with suction at reduced pressure. By adding wetting and/or dispersing ay ants, such pulverous preparations can also be made readily wettable wit? water, so that suspensions are obtained.
Inert solvents used for the production of liquid preparations should preferably not be readily inflammable and should be as far as possible odorless and as far as possible non-toxic to warm-blooded animals or plants in the relevant surroundings. Solvents suitable for this purpose are high-boiling oils, for example, of vegetable origin, and lower-boiling solvents with a flash point of at least 30*C, such as, for example, polyethylene glycol, isopropanol, dimethylsulfoxide, hydrogenated naphthalenes and alkylated naphthalenes. It is, Of course^ also possible to use mixtures cf solvents. Solutions can be prepared in the usual way, if necessary, with assistance of solution promotors. Other liquid forms which can be used consist of emulsions or suspensions of the active compound in water or .suitable inert solvents, or also concentrates for preparing such emulsions, which can be directly adjusted to the required concentration. For this purpose, the active ingredient is, for example, mixed with a dispersing or emulsifying agent. The active component can also be dissolved or dispersed in a suitable inert solvent and mixed simultaneously or subsequently with a dispersing or emulsifying agent.
It is also possible to use semi-solid carrier substances of a cream ointment, paste or waxlike nature, into which the active component can be incorporated, if necessary, with the aid of solution promoters and/or emulsifiers. Vaseline and other cream bases are examples of semi-solid carrier substances. (VASELINE is a Registered Trade Mark). 415462· Furthermore, it ia possible for the active companeat to be used ia the form of aerosols. For this purpose, the active’component is dissolved or dispersed, if necessary, with the aid of suitable inert solvents as carrier liquids, sush aa diSuorodichlorometfcane, which at atmospheric pressure boils.at a temperature lower than room temperature. er in other volatile solvents. .In thia way, solutions under pressure are obtained which, when sprayed, yield aerosols which are particularly suitable fee controlling or combatting feagi, e.g., ia closed chambers and storage rooms, and for application to vegetation for eradicating or for preventing infections by fungi.
The subject compounds and compositions thereof can be applied by conventional methods. For eijample, a fungal growth ar a material to bs treated or to be protected against attack by fungus can be treated with the subject compounds and the compositions thereof by dusting, IS sprialding. spraying, brushing, dipping, smearing·, impregnating’or other suitable means.
When tho subject compounds ars employed in combination with suitable carriers, e.g., in-solution, suspension, dust, powder, ointment, eaaulaisa, and the lihe farms, a high activity aver a very high range of . dilutisn is observed. For easaaaplo, eeaeeatratiess of the active ingredient gaagfeg fesm 0.1 » 10 gcreesS by weight, based os the weight of composition employed, have beau found effective is combatting fungi.
Of sours e, higher eeaeentratieas may ale© be employed as warranted by the particular situation.
The following eisasapleo are intended to illustrate, the scope of the present invention. Unless otherwise stated, all parts are fey weight.
EXAMPLE I To a stirred and refluxing mixture of 122 parts of 4-chloro3-methylphenol, 214.1 parts of 1, 3-dibromopropane and 850 parts of water is added dropwise, during a one hour-period, a solution of 34 parts of sodium bvdr oxide in 213 parts of water. Upon completion, stirring at reflux is continued 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 sodium hydroxide solution 10%, dried, filtered and evaporated. The residue is distilled twice, yielding 114 parts of 4-(3-bromopropoxy)-l-chloro-2-methylbenzene; bp. 119*C at 0.6 mm. pressure.
EXAMPLE II Following the procedure of Example I and using an equivalent amount of an appropriate substituted phenol in place of the 4-chloro-315 methylphenol used therein the following intermediate compounds are prepared: 1- {3-bromopropoxy)-4-chloro-2-methylbenzene;bp. 115-ll6*C at 0.6 mm. pressure; 2- (3-bromopropoxy)-lj 5-dichloro-3-methylbenzeae;bp. 118*C at 0.6 mm. pressure; 4~(3-bromopropoxy)-3-ehloro-/r, 1 '-biphenyl 2-bromo-l-(3-bromopropoxy)-4-methylbenzene;bp. 123-126’C at 0.8 mm. pressure; and 1,3,5-tribromo-2-(3-bromopropoxy)benzene.bp. 160-177* C. 4ΰ46& EXAMPLE HI To a stirred aad cooled (water-bath) suspension of 7 parts of a -sefiium hydride dispersion 78 % in 75 parts of dimethylsulfoxide is ' added dropwise, during a SO minutes -period, a solution of 37 parts of s gj^-dicdjlorephaiylacefceiiiirile in 100 parts of dimethylsulfoxide.
The "hole is stirred for 20 minutes while cooling in a water-bath.
Then there is added dropwise, during a 30 minutes-pariod, a solution of 56 parts ef l-bremo-4-(2-bromoethoxy)beneeae in 125 parts-of dimethylsulfoxide and stirring is continued for another 30 minutes. The reaction mixture is poured onto water and the product is extracted twice with 2, Z’-esrybisprspane. The combined extracts are washed twice with water, dried, filtered and evaporated. The residue is triturated in petreleuaa ethsc. The product is filtered off and crystallised from ethanol, yielding 38 parts of K-^=(4-bromopheno3:y)ethyl7-2,4-di15 chlsrophsnylacEfcanitrile; sap· 73.9°G· EXAMPLE..IV A mixture ef 18.5 parts ef 2,4-diehlorophenylacetonitrile and ISS parts of K,N-djmefeylformamide is stirred and cooled ia an iee-fehtfe while nitrogen gas is introduced. 3.2 Farts of a sodium hydride 20 solution 78 % ars added portionwise and the whole is stirred for oso hour. Then there are added dropwise, during a one hour-period, 17.8 parts of (bromomethyljeyclehexaae while still sealing and while nitrogen gas is still introduced. Upas completion, 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 msthanol and water. The product is filtered off and dried, yielding 25.5 parts of 'a-(cyclchsjqSsiafiiyl) 2,4-dichlorqphenylaoetonitrile mp. 58.8°C. 2q*·* S 3 6 £.
EXAMPLE V By repeating the procedure of Example IV and using equivalent amounts of the appropriate starting materials, there are prepared: a-(3-butenyl)-2,4· iichloropher^laortcnitrile,· bp. 104-108'C at 5 0.1 mm. pressure; and 2,4-dichloro-a-(2-cyclopentylethyl)phenylaoetonitxile; bp. 130-135’C at 0.05 mm. pressure.
EXAMPLE VI To a stirred and cooled (ice-bath) mixture of 27.5 parts of 10 2,4-dibromophenylacetriiitrile, , 135 parts of Ν,Ν-dimethylformamide and 67.5 parts of benzene are added portionwise 3.2 parts of sodium hydride dispersion* 78% while nitrogen gas is introduced. After stirring for one hour, 14 parts of 1-bromobutane are added dropwise. Upon completion, stirring is continued for 2 hours at room temperature. The reaction mixture is poured onto 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, yielding . 22 parts of 2,4-dibromo-a-butylphenylacetonitrile; bp. 124’C at 0.05 mm. pressure.
EXAMPLE VII By repeating the procedure of Example VI and using an equivalent amount of respectively an appropriate bromide and an appropriate arylacetonitrile in place of the 1-bromobutane and the 2,4dibromophanylacetonitrile used therein the following compounds are prepared: ll 464692.4- dichloro=E-/3-{4-shlero-3-methylphenoxy)p*epyl/^fcjgnylacetonitrile; bp. 216-219°C at 0.05 mm. pressure; 2„ 4-eiehiorO"S"^-(3,5"diGhlarepheaoxy)propyf7 chsnylacetonitrile; bp. 210-215*C at 0.05 zvsa. pressure; 2,4-di«^oro-e-/3-(2~naphthalenylexy)propyl73^£nylaastOfiitrile; mp. 100Ό; ί^·/5-(2-6»θ®ορ&βηοκχ·)ρϊ0ρχί7»2,4«diGhlore^i2nylaaetcnitKlls,· mp. 61.2*0; 2,4«dichloro<-e-/^*-(4-ehloro-2-methylphen0xy)propyl/pbsnylaceto^ nitrile; mp. 73°C; 2.4- diehloro»e-^=(2,4»djeHosQ-6-methylpheaoxy)propy,$di£nyl aeetonitsile; bp. 212~2I6°G at 0.05 mm. pressure; 2,.4-diehlQro-e-^-(3-ehiero-^’i I '-bipheayl7-4-ylojsy3propyl7" ^isnyiacstonitelle; ng>. 7O„3°C; 1§ @»/s»{2°ferora3°4-mathylphf2ao3iy)pi?OByi7"z» 4«diehlorapiisnylacetoBitrUe; bp. 215-2’9°G at β,Θ5 ram, pressure; and 2.4- dicHoro-K- /3-(2,4S c-tribreaaQphcmejiyJprepyl/phaylaestoaifirUe; sip. 85.2°6, EgAMPLS„VIH, 0- To a stirred misters ef 18.5 parts of 2,4-diehlorojfcaayl acetonitrile, 90'parts oi N,N»dimothylformaraide and 87.5 parts of bensene are added portionwise 3.2 parts of a sodium hydride dispersion 78 % while nitrogen gas is introduced. After stirsing for 1 hour at room temperature, 14.5 parts of (2-chloroethyl)cyclsheJsaae are added.
The whole is stirred, first for 5 hours at 40-50*C and further overnight at room temperature... The reaction mixture is poured onto 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, yielding 16 parts (54%) of 2,4 '-dichloro-ee(2-cyclohexylethyl5i3isnylacstaiitrile; bp. 145-148‘C at 0.05 mm. pressure.
EXAMPLE IX Following the procedure of Example VH1 and using equivalent amounts of the appropriate starting materials, there are prepared: a-(2,4-dichlorophenyl)-^, l'-bipheny^-4-propanenitrile; bp. 215230*C at 0. 05 mm, pressure; 2,4-dichloro-«-(2,4-diijhlorophenyl)‘plienyIbutanenitrile as an oily residue; 4-chloro-«-(4-chlorophenyl)phenylbutanenitrile 'as an oily residue; 4-chloro-a-(4-methylphenyl^hanyIbutanenitrile; ; bp. 175-178*C at 0.1 mm. pressure; «-(4-bromophenyl)-2-methoxyfhenylbutanenitrile as an oily residue; a-(4-bromophenyl)-4-chlerophenylbutanenitrile; as an oily residue; 4-chloro-«-(4-fluorophenyl) phenyUxitanenitrile; bp. 165-168*C at 0,1 mm, pressure; «-(4-flLuorophenyl)-4»methylphenylbutanenitrile; 'bp. 160-165’C at 0,3 mm. pressure; 4-bromo-a-(2»cMorepheayl) j&snylbutansalfcrilfi? . fep. 176-140*C at 0.1 asm. pressure; and 4"bromo-«"(4-bromophenyl)jfo6nylbutai!saitrile as aa oily residue.
EXAMPLE X § 120 Parts of methanol are saturated with gaseous hydrogen chloride while cooling in an ice-bath. Then there are added 22 parts of 2,4=dibromo=«-butyiphsiylacetcnitrils and the whole is stirred and refimssd overnight. The reaetiaa mte&ore is cooled and poured onto wafer. The product is extracted with 2,2'-oxybispropane. The extract is washed with water, dried, filtered and evaporated. The residue is distilled, yielding 16.5 parts (&£%) of methyl 2,4-dibromo-«-butylphenylacetate bp. 125*G af 8.1 mm, pressure. ..f, Following the procedure of Example X, the following esters are prepared starting feoa the appropriate nitriles; aaethyl K"(3»feuteayX)-2,4«d£ehlar0£toiylaeefcate > aa a residue; methyl 254-dichlora«.ta/cyclohaxyJmethyl^>henylacstate; aa a residue; methyl 2,4-dichloro-«-(2-eyelopentylethylfchenylacetate as a residue; aaethyl 2,4-dieaioro-a-(2»cyelahexylethyl)phenylaeefcate as a residue; methyl s-{2,4~diehl©rQpheByl)-J/ri,l*-biphenyl7"4"propaaoate as an oily residue; methyl 2,4»diehloro««t«>(2,4«diehlorephaayl) pheny3butanoate .· as an oily residue; ϊ C 4 S Λ methyl 4-chloro-«-(4-chlorophenyl)chenylbutanoate; bp. 175-178 °C at 0.1 mm. pressure; methyl 2,4-dichloro»«-/3-(2-naphthalenyloxy)propyl^iienylacetate; mp. 69.7’C; methyl 4-chloro-K-(4-methylphenyl)'jtienyL’jutanoate as an oily residue; methyl a-(4-bromophenyl)-2-methoxyphenylbutanoate; . bp. 178-185*C at 0.1 mm. pressure; methyl «-(4-bromophenyi)-4-ahj.aroEhenylbufcanoate; · bp. 177-180’C at 0.1 mm. pressure; methyl 4-chloro-a-(4-fluoropheayl)Ehenylbutanoate as an oily residue; methyl a-(4-fluorophenyl)-4-methylphenylbutanoate as a residue; methyl 4-bromo-«-(2-chloropheayl}ihenylbutanoate as an oily residue; methyl 4-bromo-a-(4-bromophenyl)phenyIbutanoate as an oily residue; methyl a-^-(4-bromophesoxy)ethyl7-2,4-dichlorophenylaoetate as a residue; methyl 2,4-dichloro-a-/3-(3,5-dichlorophenoxy)propyl7phenylacetate as a residue; methyl 2,4-dichloro-«-^-(4-chloro-3-methylphenoxy)propyl7jiienylacetate as a residue; methyl a-^-(2-bromophenoxy)propyi7-2,4-dichlorotiienylacetate aa a residue; methyl 2,4-dichloro-a-/J-(4-chloro-2-methylphenoxy)propyl7phenylacetate as an oily residue; *546*· methyl Ζ, 4-dichloro-a-23"(2,^-dichlaro-o-methylphenox^propyl/phenylacetate as a residue? methyl «-/3-{2-bromo-4-methylpheaoxy)psopyl7-2,4-dichlorophenylacetate aa a residue; methyl 2,4-ciehloro-ffi-. Χ·(3-εΕΙθϊθ-^, 1 *-biphenyj7-4-ylo;iy)propjd7phenylacetate; and , methyl 2,4-dichl©r ο-«-/3-(2,4,6-tribromopheaoxy)propy£?phenyl" acetate as aa oily residue.
EXAMPLE XII Te a stirred mixture et’ 23 parts of methyl Z, 4-dichlorophenylacatate and 135 parts af N, N-dimethylfermamide are added 3.1 parts of sodium hydride dispersion 78 % while nitrogen gas ia introduced. The whole is stirred till foaming has ceased and cooled in an icebath. Then there are added dropwise 16 parts ©f iodomethane. Upon completion, stirring ia continued for 3 hours at room temperature. The reaction mixture is poured oat© water and the product is extracted with 2,2'°exybispropane. Ths extract ia washed with water, dried, filtered aad evaporated, yielding 20 gar€3 (80%) ef methyl 2,4-diehloro-omsthylghmylacafcate as a residue. se mMgLE-XgL To a stirred mixture of 22 parts of methyl 2,4-dichloxophenylscetate and 135 parte ef N, N-dimethylformamide are added 3.1 ' parts of a sodium hydride dispersion 78 % while nitrogen gas is introduced. After stirring till foaming has ceased, there are added 15 parts . of 2-bromopropane and the whole is stirred for 3 hours at room temperature, The reaction mixture is poured onto water and the product is -434 6^. extracted twice with 2,2'-oxybis propane. The combined extracts are washed with water, dried, filtered and evaporated, yielding 24. 5 parts (94%) of methyl a-(1-methylethyl) 2,4-dichlorcfhenylacetate as a residue.
To 140 parts of 1,1'-oxybisethane are added 3 parts of lithium aluminium hydride. Then there is added dropwise a solution of 24.5 parts of methyl 2,4-diehloro-a-(l -methylethyljphenylacetate in 35 parts of 1,1'-oxybis ethane while cooling in a water-hath. Upon completion, stirring is continued overnight at room temperature. There are added dropwise successively 3 parts of a sodium hydroxide solution 50% and 1 part of water, and tha whole is stirred for one hour at room temperature. The mixture is filtered over Hyflo and the filter-cake is washed with 2,2'-oxybispropane. The filtrate is evaporated, yielding .5 parts (93.5%) of β-(1-wsthylethyl) 2,4-dlchlorochenylethanol as a residue, (HYFID is a Eajistered Trade Mark).
EXAMPLE XIV A mixture of 16.5 parts of methyl 2,4-dibromo-a-butylphenyhoetate, 11.5 parts of lithium iodide dihydrate and 180 parts of acetonitrile is stirred till all solid enters solution. Then there are added portionwise 3.6 parts of sodium borohydride. Upon completion, the whole is heated to reflux and stirring is continued overnight at reflux temperature. After cooling, the reaction mixture is acidified with a diluted 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, yielding 15 parts (100.%) of 0~butyl 2,4-dibromo-phenylethanol as a residue. ¢2 462, EXAMPLE XV Following the procedure of Exanple XIV and using an equivalent amount of an appropriate methyl ester as a starting material the following alcohols are obtained as a residues β-(3-butenvl)-2,4-diehlorophenylethanol; β -methyl 2,4-dichlcj.O-phenylethanol ; β- (cyclohexylmethyl) 2,4-dichloro-phenylethanol; β- (2-cyclopentylethyl) 2,4-dichloro-phenylethanol; β-(2-cyclohexyletnyl) 2,4-dichloro-phenylethanol; β- (2,4-dichlorophenyl)~/ϊ,1'-biphenyl/-4-propano1; β-(2,4-dichlorophenyl) 2,4-dichloro-phenylbutanol; β-(4-chlorophenyl) 4-chloro-phenylbutanol; β-(4-methylphenyl) 4-chloro-phenylbutanol; β-(4-bromophenyl)-2-methcxyphenylbutanol; β-(4-bromophenyl)-4-chIorophenylbutanol; β- (4-fluorophenylF4-ohloro-phenylbutanol; S- (4-fluorophenyl)-4-methylphenylbutanol; β- (2-chlorophenyl)4-bromo-phenylbutanoI; β-(4-bromophenyl)-4-bromo-phenylbutanol; - 34 4 ΰ I 63.
P-^-(4-bromophenoxy)ethyl7-2.4-dxrhlorophenyle+hanol ; 0-/3,5-dichlorophenoxy) propyl/ 2,4-aichloro-phenylethanol; - /~3- (2-brcmcphenoxy) piOpyl7_2, l-didilorrbenzeneethanol; g- /3- (4-ciiloro-3-T.iethyij#ienoxy)propyl/ 2,4-dichloro-phenylethanol; /-3-(4-chloro-2-mothylphenaxy) propyl/ 2 ,4-dichloro-phenylethanol; . 3- /-j-(2-narhbhalenyloxy)proryl7 2,1-dicixloro-phenyletixanolj β - /~3- (2-brono-4-iretiiylpiienoxy )prqpyl/-2r4-didilorophenylethanal; β - /" 3- (2,4-aichloro-6methyljhenoKy) propyl/ 2,4-didhlorcrphenylethanol; 0 - /"3- (3-chloro-/ 1,11 -birhenyl7-4-yloxy) propyl/ 2,4-dichloro-thenylethanol; and 6- /3-{2,4,6-tribramopiionoxy) propyl/ 2,4-dichloro-phenylethanol.
EXAMPLE XVI To a stirred and cooled (ice-bath) mixture of 22 parts of [i-(cyclohczylmatbyl) 2,4-didUaro~HiGiiyiethanol and 50 parts of oyridine are added dropwise 8.8 parts of methanesulfonyl chloride. Upon completion, stirring is continued for 3 hours at room temperature. The reaction mixture is poured onto water and the product is extracted twice with trichloromethane. The combined extracts are washed twice with a diluted hydrochloric acid solution and once with water, dried, filtered and evaporated. The residue is crystallized from 2,2'-oxybispropane, yielding 16.5 parts of 3-cydchexyl-2-(2,4-dichlorophenyl)propyl methanesulfonate; 'mp. 105.1*C.
S 4 s5i.
EXAMPLE ΧΤΠ Following tha procedure of Example XVI the following methane sulfonates are prepared starting from the corresponding alcohols s 2-(2,4-dichlorepheayl)=5«bexenyl methanesulfonate as a residue; 2-(2,4-dichloropheayl)propyl methane sulfonate ae a residue; 2=(2,4~dichl©5?opheayX)=3=saethylbutyl methanesulfonate as a residue; 2=(2,4=dibromophenyl)hexyl methanesulfonate as a residue; . 4=eyelopeatyl«2=(2, 4»diehl©regheayl)butyX methanasulfonate; mp. 65.4‘C; • 4-sycloheKy4=2-(2,4=diehloraphenyl)butyl methanesulfonate; mp. 44.4eC; 3=( , 1 * -biphenyl=4--/1)-2 =(2- A=diebloropheayl)propyl methanesulfonate as aa sily raaiduo; · . 2,4-bio(2,4=dichleropheayl)fcutyl methanesulfonate as an oily residue; 2,4=^is(4=efelerophenyl)butyl methanesulfonate as a residue; 4=(4=ehles®phenyl)=2=(4=sffiethylphsnyl)buftyl methanesulfonate as an ©ily residue; 2=(4-bromepheayl)»4-(2-methexypheayl)butyl methanesulfonate as aa oily residue; 2=(4=bromephenyl)=4=(4»ehlordpheayl)butyl methanesulfonate as an oily residue; 4- (4-chlorophenyl)-2-(4-fIuorophui./.’)bc';"I meihancavllc^te ii ·„η oily residue; 2-(4-£Luorophenyl)-4-(4-methylphenyl)butyl methane sulfonate as an oily residue; and 4-(4-bromophenyl)-2-(2-chlorophenyl)butyl methane sulfonate as an oily residue.
EXAMPLE XVIII A mixture of 30.4 parts of p-J/^-(4-bromophenoxy)ethyl72,4-didilorcjhenyl ethanol, 31.5 parts of methanesulfcnyl chloride, 100 parts of pyridine and 70 parts of 2,2'-oxybispropane is stirred overnight at room temperature. The reaction mixture is poured onto water and the product is extracted twice with 2,2'-oxybispropane.
The combined extracts are washed successively with a diluted hydrochloric acid solution and twice with water, dried, filtered and evapo15 rated, yielding 34 parts of 4-(4-bromophenoxy)-2-(2,4-diehlorophenyl)butyl methanesulfohate as a residue.
EXAMPLE XIX Following the procedure of Example XVIII the following methanesulfonates are prepared starting from the corresponding alcohols: - (3,5-dichloro phenoxy)-2-(2,4-dichlorophenyl)pentyl methane sulfonate as a residue; -(2-bromophenoxy)-2-(2,4-diehlorophenyl)pentyl methanesulfonate as a residue; '57 aS46£ 5-(4-chloro-3-mei-h.ylphenexy)2«(2,4-dichloFsphenyl)pentyl methanesulfonate as a residue; 2-(2,4—dichlorophenyl)-5-(2-naphthalenyloxy)pentyl methaaesulfonate as a residue; -(4-chloro-2-methylphsnoxy)-2-(2,4»dichlorophenyl)pentyl methanesulfonate as a residue; -(2-bromo-4-methylphenoxy)-2-(2,4-dlehlorephenyl)peatyl methanesulfoaate as an oily residue; -(2,4-diehloro-6-methyiphenoxy}»2-(2,4-dichlorophenyl)peatyl 10 methanesulfonate as a residue; S-(2-eh.lo2?o-/T, 1 ’-biphoay^-4—yle5iy)-2-(2,4-dichXorophenyl)p3atyl = methanesulfonate as a residue; 2S 4-bia(4-bromsphenyl)butyl methanesulfoaate as an oily residue; and 2-(2,4-diehXerophsayl)-5-(2,4,δ-trihr omo phenoxy /pentyl methane 15 sulfonate as a residue.
EXAMPLE XX To a stirred mixture of 14 parts of lH-l,2,4-triasole and 225 parts of N,N-dimethylformamide are added 6.2 parts of a sodium hydride dispersion 78%. When foaming has ceased, there are added 19.5 parts of 2-(2, -dichlorophanyi)propyl methanesulfonate and stirring ie continued for ό hours at reflux. The reaction mixture is cooled, poured onto 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 petroleumether. The product is filtered off and dried, yielding 10.2 parts (58%) of 1-/2(2,4-dicixlorophenyl)propjd/-lH-i,2,4-triasole; mp. 79.5*C.
EXAMPLE XXT To a stirred mixture of 16 parts of 1H-1,2,4-triazole in 225 parts of Ν,Ν-dimethylformamide are added 6.8 parts of a sodium hydride dispersion 78% and the -whole is stirred till foaming has ceased.
Then there are added 23.5 parts of 2-(2,4-dichlorophenyi)-3-methylbutyi methanesulfonate and 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'-oxybispropane. The combined ex20 tracts 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 into the nitrate salt in 2,2'-oxybispropane. The salt is filtered off and crystallised from a mixture of 4-methyl-2pentanone and 2,2,-oxybispropane, yielding 18.4 parts (70%) of 1-^-(2,4-dichlorophenyl)-3»methylbutyl/-lH-l, 2,4-triazole nitrate; mp. 147. l’C. 46# EXAMPLE XXUi EoUowing the procedure of Example ΧΧΓ and using an equi• valent amount of an appropriate methanesulfoaate ia place of the 2=(2,4-dichler ophenyl)-3-methylbutyl methanesulfonate used therein, the fallowing triaseles ;;nd teiazole nitrate salts are prepared: 14-dieldorophenyl)bafc^7-lH-l, 2,4-triazole; mp. 70.2’C; 2=/2=(2,4=dichloroghsayl)peat5d7-lH-2,2,4-triazole; mp. 62. 7’C; 1-/2-(2,4"dibsomapheayl)hexyl7=lH»l, 2,4-triazole nitrate; mp. 241.7’C; 1=^=(2,4-diehlorophenyl)-3=methylpentyl7-lK-l,2,4-triazole nitrate; mp. 116.6*C; -/2=(2,4-diehlorophenyl)=4-Eaethylpentyl7-lH-l, 2,4-triazole nitrate; mp. 146.8*C; 1=^=(2, ^-dieMorephesylJhept^-lH-l, 2,'4-triazole nitrate; ap.
IS 144.6*C; 1-^-(2,4-dicidorophenyl)decyl7»lH=l,2,4-triaaole nitrate; mp. 116.6’C; 2=^i=eyelepeatyl»2={2,4«dichles?9pheayl)ethyl7=lB-l, 2,4-triazole nitrate; mp. 149.2*G; »/2-eyelsh®:syl-2»(2,4-dichlorophenyl)ethy£7-l£t-l, 2,4-triazole; mp. 79.2‘C; »^’-cyelahexyl=2-(2,4-dichlorophenyl)propyi7lH-l, 2,4-triazole nitrate hemihydrate; mp. 124.3’G; l-^=cyeloheKyl-2-(2,4=dichlorophenyl)butyl7=2H=l, 2,4-triazole; mp. 96.5°G;, .40 * s 4 as. 1-/2-(2,4-dichlorophenyl)-4-pentenyi7-lH-l, 2,4-triazole nitrate; mp. 139. 7*C; and -/g-(2,4-dichlorophenyl)-5-hexenyj7-IH-l, 2,4-triazole mononitrate; mp. 114.8*0, ’ ‘ EXAMPLE XXIII To a stirred mixture of 3.8 parts of a sodium hydride dispersion 78% and 90 parts of Ν,Ν-dimethylformamide is added dropwise a eolution of 21 parts of 2,4-bis(4-chlorophenyl)butyl methanesulfonate in 45 parts of Ν,Ν-dimethylformamide. After stirring 10 for 15 minutes at room temperature, there is added a solution of 7.6 parts of 1H-1,2,4-triazole in 45 parts of Ν,Ν-dimethylformamide. The whole is heated slowly to 100*C and stirring is continued for 2 hours at 100*C. The reaction mixture is poured onto water and the product is extracted with 1, l'-oxybisethane. The extract is washed with water, dried, filtered and evaporated. The oily residue is purified by column chromatography over silica gel using a mixture of trichloromethane and methanol (97.5:2.5 by volume) as eluent. The pure fractions are collected and the eluent is evaporated. The oily residue is converted into the hydrochloride salt in 2,2'-oxybia propane. The salt is filtered off and crystallized from a mixture of methanol and 2,2'-oxybispropane, yielding 7 parts (32.5%) of 1-/2,4-bis(4-chlorophenyl)butyl7-lH-l,2,4triazole hydrochloride; mp. 173.4* C.
EXAMPLE XXIV Following the procedure of Example ΧΧΠΙ and using an equi25 valent amount of an appropriate methanesulfonate in place of the 2,4bia(4-chlorophenyl)butyl methanesulfonate, the following triazoles and triazole hydrochloride salts are prepared: 4346^· 11 -biphenyl/=4=yl)=2-(2,4-dichlorophenyl)propyj/ -1,2,4triazola hydrochloride; mp. I?S,5*C; -/&"(4"ehleropheayl)-2-(4-snethyXphenyl)butyd/-lH-l, 2,4-triazole hydrochloride; mp. 170*C; S I -^-(4=bromophenyl)-4-(2-methoxyphenyi)but>d/-1H-1,2,4-triazole hydrochloride; mp. 153.2eG; l-^zF»(4"bramoehenyl)-4-(4-ehi©r©phenyl)butyl7-lH-l, 2,4-triasole; mp. 87.6’C; l=/4=(4-ehlorophenyi)-2-(4-£luoropheayl)butyl7~IH-l, 2,4-triazole hydrochloride; mp. 171.8®C; l-/2’-(4=fl«orophenyl)=4-(4-msth\‘lphenyl)butyd7-lli-l, 2,4-triazole hydrochloride; mp. Ί28. δ " C; -^’=(4~bromophsnyl)-2 -(2=cL'lorophsayl)buty^-1H-1,2,4-triazola hydsoehleside; mp. 142.6’G; and 1 -fT, 4-bis(4=bromopheayl)buSy^'=iS=1,2,4-triasole hydrochloride; mp. X63*G.
- .^JSgLE..^ ' A aisture of 8,9 parte af 15-1=1,2,4-triazole, 3,4 parte of a oosHusa hydride dispersion 78% and 90 parts of N,N-dimethyl£orm20 amido is stirred for 10 minutes at room temperature. Then there, is added a solution of 19.9 parts of 5»(2-bromo-4-methylphenoxy)-2-(2,4 dichlor©plieayl)pQntyl methanesulfonate in 45 parts of N,N‘-dimethylformamide. Stirring is continued for 2 hours.at 10Q*C. The reaction mixture is allowed to cool to room temperature and poured onto water.
· The product is extracted twice with 1,I'-oxybisctbaae. The combined extracts are washed with water and acidified with a concentrated nitric ί» J 6 A acid solution. The formed nitrate salt is filtered off and crystallized from a mixture of acetonitrile and 2,2'-oxybispropane, yielding 13.3 parts (64%) of l-^T-(2-bromo-4-methylphenoxy)-2-(2,4-diehlorophenyl) peaty|7-lH-l,2,4-triazole nitrate; mp. 119.6*0.
EXAMPLE XXVI Following the procedure of Example XXV the following triasole nitrate salts are prepared starting from 1H-1,2,4-triazole and an appropriate methanesulfonate: 1-^-(3,5-dichlorophenoxy)-2-(2,4-dichlorophenyl)pentyfT-lH-l ,2,410 triazole nitrate; mp. 145.3*0: - /T-(4-bromophenoxy)-2 -(2,4-dichloropheayl)butyi7 -1H-1,2,4triazole nitrate; mp. 144.6*0; -2s^*(2-bromophenoxy)-2-(2,4-dichlorophenyl)pentyl7-lH-l ,2,4triasole nitrate; mp. 123.2*0; 1-^-(2,4-dichlorophenyl)-5-(2=naphthalenyloxy)pentyl7-lH«l, 2,4triasole nitrate; mp. 136.8*0; -/5-(4-chloro-3-methylpaenoxy)-2-(2,4-dichlorophenyl)pentyj7-lH1,2,4-triazole nitrate; mp. 140*0; - ^S’-(4-ehloro-2 -methylphenoxy)-2 -(2,4-diehlorophenyl)pentyj7-l H 20 1,2,4-triazole nitrate; mp. 123.1*C; 1-/5^(2,4-dichloro-6-methylphenoxy)-2-(2,4»dichlorophenyl)pentyl71 H-l, 2,4-triazole nitrate; mp. 15.3.4*0; -^T-(3-chloro-^, 1 '-biphenyl7-4-yloxy)-2-(2,4-dichlorophenyl)pentyl71H-1,2,4-triazole nitrate; mp. 135.3*0; and -/2-(2, 4-dichlosephenyl)-5-(2,4,6-tribr©megheBexy)penty(7-lH-l, 2,4triasole nitrate; mp. 166.5*C: EXAMPLE XXVII Te a stirred esdium methoxide solutioa, previously prepared 5 starting feoa 3,9 parts of sodium ia 40 parts of methanol,is added a mixture of 12 parts pf 1H-1,2,4-triazole and 225 parts of N, N-dimethylformamide. The methanol is distilled off tin an internal temperature of 150’C is reached. After cooling to 100’C, there are added 13.5 parts of 2-(2,4-dichloroph.eay?,)hexyl mathaaesulfonate and stirring at 100’C is continued fas 2 hours. The reastioa mixture is cooled, poured onto water and the product is extracted three times with 2,2'-oxybispropane. The combined extracts are washed, with water, dried, filtered and evaporated. Ths residue is purified by ealuEns-shromatsgraphy over silica gel using triehloromethaaa as eluent. The pure fractions are collected and the eluent is evaporated. The residue is converted into the nitrate salt in 2,2!-exybi3prep3ae and petroleumether. The salt is filtered off and crystallised from a mixture of 2-propaaone, 2,2'»oxybispropane and patroleumether, yielding 11.6 parts (56%) of 1-/2-(2,4-diehloropheayl)hexyl7» 1H-1,2,4»triasele nitrate; mp. 128.3* C.
EXAMPLE XXVttl Following the procedure of Example XXVH there axe prepared: . . l-/J-eycl©pe»tyl=2"(2,4-dichloropheayl)butyl7-lH-l, 2,4-triazole; ’ mp. 71 C, by the reaction of 1H-1,2,4-triazole with 4-eyclopentyl-225 (25’4°dishlerephenyl)butyl methanesulfonate; and ά ΰ 3 6,2. l-2?»-4-bie(2,4-dichlorophenyl)buiyl7-IH-I,2,4-triazole hydrochlari-c * mp. 158.7*C, by the reaction of 1H-1,2,4-triazole with 2,4-bis(2,4dichlorophenyl)butyl methanesulfonat.e.
EXAMPLE XXIX To a stirred sodium methoxide solution, prepared starting 5 from 1.6 parts of sodium in 56 parts of methanol, are added 4.8 parts of 1H-1,2, 4-triazole. 40 Parts of methanol are distilled off at normal pressure. After the. addition of 80 parts of 4-methyl-2-pentanone, another 28 parts of solvent are distilled off. Then there are added 22 parts of 3-{4-chlorophenyl)-2-(2,4-dichleropheayl)propyl methaaesulfonate and 90 parts of Ν,Ν-dimethylformamide 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 formed nitrate salt is filtered off and crystallized from 4-methyl2-pentanone, yielding 6.6 parts (27%) of l-/3-(4-chlorophenyl)-2~(2,4dichlorophenyl)propyl7-lK-l,2,4-triazole nitrate; mp. 174.8*C.
EXAMPLE XXX Following the procedure of Example XXIX there is prepared ' 1 -/^-(2-bromophenyl)-2-(2,4-dichlorophenyl)propyf7-lH-l, 2,4-triazole nitrate; mp. 168.4*0, by the reaction of 1H-1,2,4-triazole with 3(2-bromophenyl)-2-(2,4-dichloropheayl)propyl me thane sulfonate.
EXAMPLE XXXI Following the procedure of Example X there is prepared methyl 2,4-dibromoben2eneacetate; bp. 105 110°C at 0.1 mm. pressure, starting from 2,4-dibromobenzene5 acetonitrile.
EXAMPLE XXXII Following the procedure of Example XIII and using equivalent amounts of the appropriate starting materials the following compounds are prepared: S-(2-methylpropyl) 2,4-dibromo-phenylethanol as a residue; ¢5-(1-methylethyl) 2,4-dibromo-phenylethanol as a residue; and p-(1-methylpropyl) 2,4-dibromo-phenylethanol as a residue.
EXAMPLE XXXIII Following the procedure of Example XVI and using 15 equivalent amounts of the appropriate starting materials there are prepared: /2-(2,4-dibromophenyl)-4-msthylpentyl7 methanesulfonate as a residue; /2-(2,4-dibromophenyl)-3-methybutyl7 methanesulfonate as a residue; and /2-(2,4-dibromophenyl)-3-methylpentyl7 methanesulfonate as a residue.

Claims (10)

1. CLAIMS:1. formula: lH-l,2,4-triazole derivative having the general wherein CH, - CH - R 2 I Ar Ar is a phenyl, .tone-, di- or tri-halophenyl, lower alkylphenyl, lower aIkyloxyphenyl, nitroohenyl, cyanophenyl or trifluoromethylphenyl group; and R is an alkyl group having from 1 to 10 carbon atoms, a 10 cyeloalkyl, cyeloalkyl-lower alkyl, lower alkenyl, arvllower alkyl or aryloxy-Tower alkyl group, said aryl being a phenyl, naphthalenyl or substituted phenyl group, having from 1 to 3 substituents which are each independently halogen, lower alkyl, lower alkyloxy, cyano, nitro or 15 phenyl, provided chat when more than one substituent is present only one thereof may be cyano, nitro or phenyl.
2. , A lH-l,2,4-triazole derivative having the general formula: (I') CH, - CH - R' 2 I wherein: & r ' 20 Ar' is a phenyl, mono- or di-halonhenyl, or methylphenyl group; and - 47 ό 5 4 63R’ is an alkyl group having from 1 to 10 carbon atoms, a cycloalkyl, lower alkenyl, aryImethyl or arylethyl group, wherein said aryl is a phenyl, halophenyl, methylphenyl or methoxyphenyl group. 53. A compound as claimed in claim 2 wherein Ar' is a dichloro- or dibromo- phenyl group.
3. * 3 4 6a Ar or a physiologically acceptable acid addition salt thereof, wherein Ar and R are as defined in claim 1 which comprises: heating a compound of the formula: II or an alkali metal salt thereof, with a compound of the formula: X - CE, - CH - R I Ar wherein R’is as defined in claim 1, and X is a reactive 10 ester group, in an appropriate polar organic solvent, and, if desired, preparing physiologically acceptable acid addition salts of the product and further, if desired, resolving and isolating optical iscmers of the ccmpcund of formula I. 17. A process as claimed in claim 16 wherein the group 15 X is a halo, methanesulfonyl or 4-methylbenzene sulfonyl group. 18. A process as claimed in claim 16 or claim 17 wherein the reaction is effected at reflux temperature. 19. A process for preparing l-/2-(2,4-dichlorcphenyl)-320 methylbutyl/-lH-l,2,4-triazole or a physiologically acceptable acid addition salt thereof, which comprises reacting the sodium salt of lH-l,2,4-triazole with 2-(2,4-dichlorophenyl)-3-methyl-butylmethane sulfonate and, lf desired, preparing a physiologically acceptable acid addition salt 4. S 4 6·2. of the product thereof. 20. A process for preparing i-/2-(2,4-di\hlorcphsn.yl)“ 3-methylpentyl/ - IH - 1,2,4-triazole or a physiologically acceptable acid addition salt thereof, which comprises
4. A compound as claimed in claim 2 wherein R' is an alkyl group having from 1 to 6 carbon atoms or a 2-propenyl group. 10 5. 1 - /2-(2,4-Dichlorophenyl)-3-methylbutyl-lH-l,2,4triazole.
5. Inert carrier material and as an active ingredient an effective antifungal amount of a 1H-1,2,4-triazole derivative as claimed in any one of claims 1 to 15, or 30. 32. A composition for combatting fungi or for use as a plant growth regulator, comprising an inert carrier 10 material and as an active Ingredient an effective antifungal amount or an effective growth-regulating amount of 1-/2-(2,4-dichlorophenyl)-3-methylbuty]/ - lH - 1,2,4triasole, or a physiologically acceptable acid addition salt thereof. 15 33. A composition for combatting fungi or for use as a plant growth regulator, comprising an inert carrier material and as an active ingredient an effective anti-fungal amount or an effective growth-regulating amount of 1-/2- (2,4dichlorophenyl)hexyl/-lH-l,2,4-triazole or a physiologically 20 acceptable acid addition salt thereof. 34. A composition for combatting fungi or for use as a plant growth-regulator, comprising an inert carrier material and as 2n active ingredient an effective anti-fungal amount or an effective growth-regulating amount of 1-/2 - cyclo25 hexyl-2- (2,4-dichlorophenylJethyl/ - 1H-1,2,4-triazole or a physiologically acceptable acid addition salt thereof. 35. A composition as claimed in any one of claims 31 to 34 wherein the active ingredient is present in an amount of from 0.1 to 10 percent by weight. -J S 1 ti s. 36. A composition for combatting fungi or for use as a plant growth-regulator as claimed in claim 31 substantially as hereinbefore described. 37. A method of treating a fungal growth or protecting 5 a material against fungal attack which comprises applying to the fungal growth or to the material to be treated a composition as claimed in any one of claims 31 to 36. 38. A method of regulating the growth of plants which comprises treating the plants with a composition as claimed 5 reacting the sodium salt of 1H-1,2,4-triazole with 2(2,4-dichlorophenyl)-3-siethylpentyl methanesulphonate and, if desired, preparing a physiologically acceptable acid addition salt of ths product thereof. 21. A process for preparing 1-/2-(2,4-dichlorophenyl)10 4-ffiethylpentyl/- 111-1,2,4-triazole or a physiologically acceptable acid addition salt thereof, which comprises reacting the sodium salt of 1 H-l,2,4-triazole with 2-(2,4dichlorcphenyl)-4-methylpentyi methanesulfonate and, if desired, preparing a physiologically acceptable acid 15 addition salt of the product thereof. 22. A process for preparing 1-/2-(2,4-dichlorophenyl)hexyl/- IH - 1,2,4-triasole or a physiologically acceptable acid addition salt thereof, which comprises reacting the sodium salt of 1H-1,2,4-triazole with 2-(2,4-dichlorophenyl)20 hexyl methanesulfonate and, if desired, preparing a physiologically acceptable acid addition salt of the product thereof. 23. A process for preparing 1-/4 - (4-chlorophenyl) 2 - (4-methylphenyl)butyl/ - IH - 1,2,4-triazole or a 25 physiologically acceptable acid addition salt thereof, which comprises reacting 4 - (4-chlorophenyl)-2-(4-methylphenyl)butyl methanesulfonate with 1H-1,2,4-triazole and, if desired, preparing a physiologically acceptable acid addition salt of the product thereof. 30 24. A process for preparing 1-/4-(4-chlorophenyl)-2(4-fluorophenylJbutyl/ - IH - 1,2,4-triazole or a physiologically acceptable acid addition salt thereof, which comprises reacting 4 - ( 4-chlorophenyl)-2-(4-fluorophenyl)butyl methanesulfonate with 1H-1,2,4-triazole and, if desired, preparing a physiologically acceptable acid addition salt, of the product thereof. 25. A process for preparing 1 - /2-(2,4-dibromophenyDhexyl/- 1H - 1,2,4-triazole or a physiologically acceptable acid addition salt thereof, which comprises reacting the sodium salt of 1H-1,2,4-triazole with 2-(2,4-dibromophenyl)hexyl methanesulfonate and, if desired, preparing a physiologically acceptable acid addition salt of the product thereof. 26. A process for preparing 1-/2-(4-fluorophenyl)-4(4-methylphenyl)butyl/-lH-l,2,4-triazole or a physiologically acceptable acid addition salt thereof which comprises reacting 2- (4-fluorophenyl)-4- (4-methylphenyl)butyl methanesulfonate with 1H-1,2,4-triazole and if desired preparing a physiologically acceptable acid addition salt of the product thereof. 27. A process for preparing 1-/2-(2,4-dichlorophenyl)heptyl/ -1H-1,2,4-triazole or a phydiologically acceptable acid addition salt thereof, which comprises reacting the sodium salt of IH 1,2,4-triazole with 2- (2,4-dichlorophenyl)heptyl methanesulfonate and, if desired, preparing a physiologically acceptable acid addition salt of the product thereof. 28. A process for preparing l-/2-cyclohexyl-2-(2,4dichlorophenyl)ethyl/-lH-l,2,4-triazoIe or a physiologically acceptable acid addition salt thereof, which comprises reacting the sodium salt of 1H-1,2,4-triazole with 2-cyclohexyl2-(2,4-dichlorophenylJethyl methanesulfonate and, if desired, preparing a physiologically acceptable acid addition salt of the product thereof. 29. A process as claimed in claim 16 substantially as hereinbefore described with reference to any one of Examples XX to XXXIII. i 3 4 6 230. A 1H-1,2,4-triazole derivative of formula (I) as defined in claim 1 whenever prepared by a process as claimed in any one of claims 16 to 29. 31. A composition for combatting fungi, comprising an
6. 1 - /2- (2,4-Dichlorophenvl)-3-methylpentyl/-lH1.2.4- triazole.
7. 1 - /2-(2,4-Dichlorophenyl)-4-methylpantyl/-lH15 1,2,4-triazole.
8. 1 - /2-(2,4-Dichlo£ophenyl)hexyl7-lH - 1,2,4tria2ole.
9. l-/4-(4-Chlorcphenyl) - 2 - (4-methylplienyl) butyl/1H~1,2,4-triazole. 20 10. 1 -/4-(4-Chlorophenyl)-2-(4-fluorophenyl)butyl7 _ 1H-1,2,4-triazole. 11. 1 - /2-(2,4-Dibromophenyl)hexyl/ - IH - 1,2,4triazole. 12. 1 - /2-(4-Fluorophenyl) - 4 - (4-methylphenyl)butyl/ 25 IH - 1,2,4-triazole. 13. 1-/2-( 2,'4-Dichlorophenyl)heptyl_/ - IH 1.2.4- tria2ole. 14. 1 - /2-Cyclohexy1-2-(2,4-dichlorophenyl)ethyl/ IH - 1,2,4-triazole. 30 15. A physiologically acceptable acid addition salt of a compound as claimed in any one of the preceding claims. 16. A process for preparing a 1H-1,2,4-triazole derivative having the general formula:
10. In any one of claims 31 to 36.
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US3821394A (en) * 1970-07-29 1974-06-28 H Timmler Antimycotic composition and method employing a substituted benzyl-azoles
US3927017A (en) * 1974-06-27 1975-12-16 Janssen Pharmaceutica Nv 1-({62 -Aryl-{62 -R-ethyl)imidazoles
DE2431407C2 (en) * 1974-06-29 1982-12-02 Bayer Ag, 5090 Leverkusen 1,2,4-Triazol-1-yl-alkanones and alkanols, processes for their preparation and their use as fungicides

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FR2361375B1 (en) 1982-05-28
CY1204A (en) 1983-12-31
DE2735872C2 (en) 1989-10-05
DK159551B (en) 1990-10-29
DE2735872A1 (en) 1978-02-16
NL181431C (en) 1987-08-17
AT361918B (en) 1981-04-10
GB1589852A (en) 1981-05-20
ES461526A1 (en) 1978-12-01
PT66902B (en) 1979-12-17
SG34683G (en) 1984-04-19
ATA581377A (en) 1980-09-15
JPS6129347B2 (en) 1986-07-05
JPS5321168A (en) 1978-02-27
CA1133492A (en) 1982-10-12
BR7705266A (en) 1978-06-06
FR2361375A1 (en) 1978-03-10
IL52692A (en) 1981-11-30
AU2732677A (en) 1979-02-01
KE3299A (en) 1983-08-05
NZ184835A (en) 1980-05-08
AR222142A1 (en) 1981-04-30
DK159551C (en) 1991-04-02
HK60683A (en) 1983-12-02
SE7709016L (en) 1978-02-11
IE45462L (en) 1978-02-10
AU515134B2 (en) 1981-03-19
SE437267B (en) 1985-02-18
IL52692A0 (en) 1977-10-31
DK355477A (en) 1978-02-11
IT1080109B (en) 1985-05-16
NL7708764A (en) 1978-02-14
CH630231A5 (en) 1982-06-15
GR58202B (en) 1977-08-23
MY8500032A (en) 1985-12-31
PT66902A (en) 1977-09-01
NL181431B (en) 1987-03-16

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