AU9036282A - 1-phenyl-3-triazol-1-yl vinyl ethers - Google Patents

Description

AUSTRALIA f CONVENTION J ison Ferguson COMMONWEALTH OF AUSTRALIA STANDARD. PATENT THE PATENTS ACT 1952 APPLICATION. FORM, SFP2

CONVENTIO'N APPLICATION FOR STANDARD PATENT OR A STANDARD PATENT OF ADDITION PATENT OFFICE

FL~

362182 DECL-ARA: Full name(s) of f/We CIBA-GEIGY AG Applicant(s) In suppor. patent fa Xlybeckstraase 141, 4002 Basle, Microb: Address( Is) of Switzerland Applicant(&)

hereby apply for the grant of astnadpet We, Arnol Ernst for an invention entitled do solemn]

"MICROBICID-AL COMPOSITIONS" 0 Titelf 009

which is described in the accompanying complete specification. DETAILS OF BASIC APPLICATION(-&-) Number(s) of Basic Application(s) 727 3/81-5 Name(s) of Convention Country(4es) in which Basic Application(s) was/were filed

Switzerland (re-ip WY) Date(s-) of Basic Application(s+

12th November, 1981 (fesieeti4yei-Y)

is (aiFee) t which the The said My/ Our address for service is: CQ- Spruson Ferguson PATENT ATTORNEYS CBA CENTRE, 60 MARGARET ST. SYDNEY, NEW SOUTH WALES AUSTRALIA Dated this TWENTY S IXTH day of OCTOBER, 19 82 DECLARED CIBA-GEIGY AG October 2

To: The Commissio~ier of Patents Registered Pate Attovney, o0: The C 11/81

COMVMONWEALTH OF AUSTRALIA PATENTS ACT 1952 Form

COMPLETE SPECIFICATION (ORIGINAL)

FOKP 8 1' fi I COMMONWEALTH OF AUSTRALIA

Patents Act 1952 1969

DECLARATION IN SUPPORT OF A CONVENTION APPLICATION FOR A PATENT 9036 2/82 1. g; In support of the Convention Application made by CIBA-GEIGY AG for a i'

patent for an inention entitled: Microbicidal Compositions

We, Arnold Seller and of CIBA-GEIGY AG, Klybeckstrasse 141, Ernst Altherr 4002 Basle, Switzerland do solemnly and sincerely declare as follows:

We are authorised by the applicant for the patent to make This declaration on its behalf.

The basic application(s) as defined by Section 141 of the Act was(wee-) made in Switzerland on November 12, 1981

by CIBA-GEIGY AG, 4002 Basle, Switzerland

Elmar Sturm, Klusstrasse 66, 4147 Aesch, Switzerland

is(are) the actual inventor(s-) of the invention and the facts upon which the applicant is entitled to make the application are as follows: y^ i: The said applicant is the assignee of the actual inventor(s).

4. The basic application(s) referred to in paragraph 2 of this De- claration was(we-se-) the first application(-s) made in a Conven- tion country in respect of tbh invention the subject of the application.

DECLARED at Basle, Switzerland on i October 21, 1982 C1BA-GEIGY AG

A. Seiler Altherr 7o: The Commissioner of Patents 9.79 521

(12) "1 AUSTRALIAN PATENT ABSTRACT (Ig) AU (11) AU-A-90362/82 (11) Au- 7. A pri defined

A) react:

(54) 1-PHENYL-3-TRIAZOL-1-YL VINYL ETHERS (71) CIBA-GEIGY AG (21) 90362/82 (22) 11.11.82 (24) 12.11.81 (31) 7273/81 (32) 12.11.81 (33) CH wherein (43) 19.5.83 the font (51,)3 C07D 249/08 C07D 405/12 A0iN 43/64 AO1N 43/82 (72) ELMAR STURM (74) SF wherein

(57) Claim selectee? 1. A compound of the general formula I R1 is al vantagec /X R aqueous R-C=C-N tional r OR 1 P) subje wherein X is hydrogen'or halogen, Y is hydrogen, halogen, phenyl or phenyl which is substituted by one or two halogen atoms,

R1 is C Calkyl, C C alkenyl, C -lkynyl, a lower alkoxyalkyl wherein radical containing at most 8 carbon atoms or one of the groups solvent

0-0 -CH 2-<C or -CH 2-< 8. A pE microor~

in which each of R3 and R4 independently of the other is hydrogen of the f

or methyl; and R2is hydrogen, C 1-C4 alky, C 3 alkenyl, C3 alkynyl, phenyl or phenyl which is substituted by one or two halogen atoms or by one or two C1-C alkyl or C -C alkoxy groups, or an acid addition salt, quaternary azolium salt or metal complex thereof. /2

4 36

105/4 ;105/43/14

12

The invention furthermore relates to a method of treating plants,

(11) AU-A-90362/82 2 7. A process for the preparation of a compound of the formula I as defined in claim 1, which process comprises

A) reacting an a-lH-l, 2 4 -triazolylphenone of the formula

7oR 2

Y- -C-CH-N (II), wherein X, Y and R2 are as defined for formula I, with a compound of the formula III

R -Z (III)

wherein R1 is as defined for formula I and Z is a leaving group selected from chlorine, bromine, R 1 S4 or (R 0)2(O)P=0, in which R is also defined for formula I, in the presence of a base and ad- vantageously in the presence of a polar aprotic solvent or of an aqueous organic two-phase medium and in the presence of a conven- tional phase transfer catalyst; or, where R2 is hydrogen,

B) subjecting an open acetal df the formula IV

(IV), Y- C2 RO OR1 N=

wherein X, Y and R1 are as defined for formula I, in a high boiling solvent in the temperature range from 1000 to 220 0 C, to thermolysis.

8. A pesticidal composition for controlling or preventing attack by microorganisms, which composition comprises at least one compound of the formula I as claimed in claim 1.

;105/43/15 L

By X To:, The Commissioner of Patents Registered Pate Attcy~l:-ey 11/81

COMMONWEALTH OF AUSTRALIA Form PATENTS ACT 1952

COMPLETE SPECI1FCATION (ORIGINAL)-

FOR OFFICE USE:

Class Int. Class Application Number: ?034a2,2 Lodged

Complete Specification Lodged Accepted Published "1drort

000

00 V. 0

Jolted Art

Name of Applicant ts): CIBA-GEIGY AG

,,,Address of Applicant(. Klybeckstrasse 141, 4002 Basle, Switzerland

Actual Inventor (s4: ELMAR STURM

Address for Service Spruson Ferguson, Patent Attorneys, CBA Centre Margaret Street, Sydney, New South Wales, 2000 Australia

Complete Specification for the invention entitled

"MICROBICIDAL COMPOSITIONS"

The following statement is a full description of this invention, including the best method of, performing it known to mne/us

10/8 2 U

Case 5-13656/=

Microbicidal Compositions

The present invention relates to novel substituted l-phenyl-3-triazol-

ylvinyl ethers and to the acid addition salts, quaternary azolium

salts and metal complexes thereof. The invention also relates to the

preparation of these compounds and to microbicidal compositions which

contain at least one of said compounds as active ingredient. The

invention further relates to the preparation of said compositions

and to the use of the aforementioned compounds or compositions for

controlling harmful microorganisms.

Accordingly, there are provided compounds of the general formula I

/X R2 Y-0 OR

wherein X is hydrogen or halogen, Y is hydrogen, halogen, phenyl or phenyl which is substituted by one or two halogen atoms,

R 1 is C1-C8alkyl, C3 -C5 alkenyl, C3 alkynyl, a lower alkoxyalkyl radical containing at most 8 carbon atoms or one of the groups

o i~i 0 R /j -CH2 or -CH 2 -Cb 4

in which each of R and R independently of the other is hydrogen or methyl; and

2'-

R 2 is hydrogen, C 1 -C 4 alkyl, C3alkenyl, C3alkynyl, phenyl or phenyl

which is substituted by one or two halogen atoms or by one or two

C1-C3alkyl or C -C3alkoxy groups, and the acid addition salts, quaternary azolium salts and metal

complexes thereof.

Depending on the indicated number of carbon atoms, alkyl by itself or

as moiety of another substituent comprises e.g. the following groups:

methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl etc. and

the isomers thereof, e.g. isopropyl, isobutyl, tert-butyl, sec-butyl,

isopentyl etc. Throughout this specification, halogen denotes fluorine,

chlorine, bromine or iodine, with fluorine, chlorine or bromine

being preferred. Alkenyl is e.g. propen-l-yl, allyl, buten-l-yl,

buten-2-yl, buten-3-yl or penten-2-yl. Alkynyl is in particular

propargyl.

Lower alkoxyalkyl comprises e.g. the folluoing substituents:

-CH2OCH3, -CH2-CH2-OCH 3 -CH2-OC2H 5 -CH2-OC3H 7 -CH2-OC7H15' -CH2-CH2-OC2H5, -CH2-CH2-CH2-OC3H7, -CH2-CH2-CH2-OC4H 9 etc.

Accordingly, the present invention relates to the free compounds of

the formula I and to the acid addition salts, quaternary azolium alts

o and metal complexes thereof. The free compounds are preferred.

Examples of salt-forming acids are inorganic acids, e.g. hydrohalic

acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid

or hydriodic acid, and also sulfuric acid, phosphoric acid, phos-

phorous acid, nitric acid; and organic acids such as acetic acid,

trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic

acid, thiocyanic acid, lactic acid, succinic acid, citric acid,

benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfonic

acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid,

p-aminosalicylic acid, 2-phenoxybenzoic acid or 2-acetoxybenzoic acid.

16

Further suitable non-ionic surfactants are the tiater-soluble adducts

of. polyethylene oxide with'polypropylene glycol, ethylenediamine

propylene glycol and alkylpolypropylene glycol containing 1 to

Metal complexes of the formula I consist of the basic organic mole- cule and an inorganic or organic metal salt, for example the halides, nitrates, sulfates, phosphates, acetates, trifluoroacetates, tri-

chloroacetates, propionates, tartrates, sulfonates, salicylates, benzoates etc. of the elements of the third and fourth main group of the Periodic Table such as aluminium, tin or lead, and of the first to eighth auxiliary group such as zirconium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, mercury etc. Preferred elements are those of the auxiliary groups of the fourth period. The (0 metals may exist in different valency states. The metal complexes of the formula I may be mononuclear or polynuclear, i.e. they may con- tain one or more parts of the organic molecule as ligands. Complexes with copper, zinc, manganese, zirconium and tin are preferred.

The compounds of formula I are oils, resins or mainly solids which are stable at room temperature and have very valuable microbicidal properties. They can be used in agriculture or related fields preven- tively and curatively for controlling phytopathological microorganisms. The compounds of the formula I have excellent microbicidal activity in broad concentration ranges and their use -s unproblematical.

;o On account of their pronounced microbicidal activity, preferred com- pounds of the formula I are those compounds which contain the follow- ing sbstituents or combirnations thereof with one another:

for X: a) H, F, Cl, Br, I b) H, F, Cl, Br, c) H, Cl d) Cl fEor Y: a) H, F, 01, Br, C6H5 C, C6 H4Hal(2), C6 H4Hal(Y), C6H 3Hal C6 HR 3 Hal 2 in which Hal Cl, Br, I b) H, F, Cl, C6H5 C6H4 Cl(2), C6H4Cl(4), C6H3 Cl 2 C H Cl (3,4) 6 3 2 c) H, F, Cl, C06H15 d) F, Ci

.forR a)C 1 -C5 alkyl, CH 2 C=H2CH 2 C CH, CH2 OH3CH2 C2 CH2 0C3 H7' CH 2 CH 2 OH3'C 2CH2 0C2 CH-CH- CH CH 2 -CH-O CH2 -CH-CH, 0 O\O2i O\ >O

C 3 \CH3

b) CI-c4 alkyl, CH2CH=CH 21CH2C-CH, CH 2OCR 3 CHO CH OH2OCH3 c) CH3 C2 H5 2 C3 H7 C3 H7 C4 H9 C4 H9 C4 H9 CH2 OCH3 2 CH2 0C2 H5,C 2CH2 OH3 d) CH3 O2 H5 C3 H7 CO4 H9 (n)

for R2:a) H, C1 -C4 alkyl, CH 2 CH=CH9 CH2 C=CH, C6 H3 C12 b) H, C -C 4akl c) H, OH 3 C2 H5 C3 H7 C3 C4 H9 C4 H9 (S) d) H

Accordingly, preferred compounds of the formula I are e.g. those of the groups a) to d) set forth 'below:

a) compounds of the formula I, wherein X is hydrogen, fluorine, chlorine, bromine or iodine; Y is hydrogen, fluorine, chlorine,

broineioine C6H5' C6 H4 Hal(2), C6 H4 Ral(4), C6 RH 3 Hal 2 or O H3Hal 2 where Hal is fluorine, chlorine, bromine or iodine;

R1is C I 5aklCH2 HH 2 CH2 CCH, OH2 0C CH 2 0C2 H55,C 2 0C3 H7' CH OH2OCR

-18-

carbonate and water and freed from volatile constituents under vacuum.

CH 2 CHR2 OC2 H5 $CH 2 -YH--YH 2 CH2 H-c or CHR2 -H-YHR2 andR2 is

rydogenC1-C4 alkyl, CH CH=CH VCHR2C-CR C6H3 Cl2 or C6H4 Cl(4);

b) compounds of the formula I, wherein X is hydrogen, fluorine, chlorine or bromine; Y is hydrogen, fluorine, chlorine, C R C6H 4Cl(2), C6H4Cl(4), C6H3C1l or C6H3Cl R1 is C1-C4 alkyl1, CR CH=CR2tCR2C=CH, CR OCRVCR OC2H5 or CHJ2 CR OCR3 and R2 is hydrogen or C1-C 4akl

c) compounds of the formula I, wherein X is hydrogen or chlorine; is hydrogen, fluorine, chlorine or C6H5;R1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert--butyl, CUI OCH3' CR OC2H5 or CR2CR OCR and R2 is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butYl or sec-butyl;

d) compounds of the formula I, wherein X is chlorine; Y is fluorine or chlorine;R1 is methyl, ethyl, n-propyl or n-butyl; andR2 is hydrogen.

The following individual compounds are particularly preferred:

l-(2,4-dichlorophenyl)-l--n-propoxy-2-(lR--l,2,4-triazol-1-yl)ethene, 1- 4-dichlorophenyl) -l-n-butoxy-2- (lH-l, 2,4-triazol-l- yl) -etheffe, 1-(2,4-dichlorophenyl)-l-(l'-methylbutoxy)-2-(lH-1,2,4-triazol-1-yl)- ethene, l-(2,4-dichlorophenyl)-l-n.-butoxy-2-(lH-1,2,4-triazol-l-yl)-butene, 1-(2,4-dichlorophenyl)-l-n-butoxy-2-(lH-1,2,4-triazol-1-yl)-hexene.

The compounds of the formula I may be prepared by the following process by reacting an a-lR-l,2,4-triazolylphenone of the formula II

-19-

Example 2: Preparation of

To I

0 R2 acti 1 (II) suc CH-NIsuc hydi bror wherein X, Y and R 2 2 are as defined for formula I, with a compound of or or I the formula III Phoi R -Z (III)

The wherein R is as defined for formula I and Z is a leaving group

selected from chlorine, bromine, R SO or (R10)2(O)P=O in which E 4r icde R1 is also as defined for formula I, in the presence of a base'and ali alii advantageously in the presence of a polar aprotic solvent or of an e.g aqueous organic two-phase medium, in the presence of a conventional amii I, phase transfer catalyst and, if desired, converting the free com- pounds of the formula I by conventional methods into their acid The addition salts, quaternary azolium salts or metal complexes. non

It Examples of suitable polar aprotic solvents are dimethylsulfoxide, for dimethylformamide, hexamethylphosphoric triamide, dimethylacetamide,

N-methylpyrrolidine, 2-pyrrolidinone and other strongly polar aprotic In solvents. Mixtures of these solvents with other inert conventional als solvents such as benzene, toluene, xylenes etc. may also be used. In 90 rat some cases the compound of the formula III may itself be used as met solvent. of

2o The following solvents, for example, are suitable for the organic In water-immiscible phase: aliphatic and aromatic hydrocarbons such as oth pentane,hexane, cyclohexane, petroleum ether, ligroin, benzene, tai toluene, xylenes etc., halogenated hydrocarbons such as dichloro- hyd methane, chloroform, carbon tetrachloride, ethylene dichloride, Acc 1,2-dichloroethane, tetrachloroethylene etc., or aliphatic ethers sub such as dietyl ether, diisopropyl ether, tert-butylmethyl ether etc.

n i

20 m;

0 -60 0 C. The dark brown suspension is poured into water and extracted

3 times with n-hexane and cyclohexane. The combined extracts are 1- A-A fi 1-p-rpd nrl concen-

To hasten the rate of reaction it is necessary to carry out this re- action in the presence of a phase transfer catalyst. Examples of such catalysts are: tetraalkylammonium halides, hydrogen sulfates or hydroxides such as tetrabutylammonium chloride, tetrabutylammonium bromide or tetrabutylammonium iodide; triethylbenzylammonium chloride or bromide; tetrapropylammonium chloride, bromide or iodide etc. Phosphonium salts are also suitable for use as phase transfer catalysts.

The reaction is carried out in the presence of a suitable base. Examples of such bases are inorganic bases such as the oxides, hydrox- ides, hydrides, carbonates and bicarbonates of alkali metals and alk- aline earth metals, as well as organic bases such as tertiary amines, e.g. triethylamine,triethylenediamine, piperidine, pyridine, 4-dimethyl- aminopyridine, 4-pyrrolidylpyridine etc.

The reaction temperatures for the above described reaction are normally in the range from 0° to 120 0 C, preferably from 200 to 800 C. It is preferred to react 1 mole of a-lH-l,2,4-triazolylphenone of the formula III with 1 to 2 moles of the compound of.the formula III,

In addition to the desired vinyl ethers of the formula I, there may also be obtained compounds in which the substituent R 1 does not mig- y rate to the ketone-oxygen but replaces a hydrogen atom at the vicinal methylene group. These by-products can be separated from the compounds of the formula I in simple manner, e.g. by column chromatography.

In addition to the general preparatory methods described above, an- other special process variant may conveniently be employed for ob- taining comnounds of the formula I in which the substituent R2 is hydrogen and which are designated hereinafter as subgroup I'. Accordingly, the compounds of the formula I' may also be prepared by subjecting an open acetal of the formula IV

Y- CH2 -N (IV), R OR1

wherein X, Y and R1 are as defined for formula I, to thermolysis and, if desired, converting the free compounds of the formula I by con- ventional methods into their acid addition salts, quaternary azolium salts or metal complexes. This thermolysis is preferably carried out in high-boiling inert solvents in the temperature range from 1000 to 220 0 C. Examples of suitable solvents are silicone oil, mineral oil, "Dowtherm" (eutectic mixture of biphenyl and dibenzofuran), diphenyl ether etc.

'0o The a-lH-l,2,4-triazolylphenones of the formula II may be prepared by halogenation of the starting ketones V

0 R2 0 -C-CH 2

to give haloketones of the formula VI

/X R2 H-Hal (VI),

and further reaction of VI with a triazole of the formula VII

=N Me-N. (VII), N=*

in which formulae above the substituents X, Y and R2 are as defined for formula I, Hal is halogen, preferably chlorine or bromine, and Me is hydrogen or preferably a metal atom, in particular an alkali metal atom, preferably sodium or potassium. The starting compounds V and VII are generally known or they may be obtained by methods which are known per se.

The reaction of the haloketone VI with the triazole VII is preferably

carried out in a relatively polar, but inert, organic solvent, e.g.

N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide,

acetonitrile, benzonitrile and other solvents. Such solvents may be

used in combination with other inert solvents such as aliphatic or

aromatic hydrocarbons, e.g. benzene, toluene, xylene, hexane, petro-

leum ether, chlorobenzene, nitrobenzene etc.

If Hal in formula VII is chlorine or bromine,'then an alkali metal

iodide (such as Nal or KI) may conveniently be added to hasten the 0 reaction. Elevated temperatures in the range from 00 to 220 C, pre-

ferably from 800 to 170 0 C, are advantageous. It is expedient to

heat the reation mixture under reflux.

Where Me is hydrogen in formula VII, the process is carried out in

the presence of a base. Examples of such bases are inorganic bases

such as the oxides, hydroxides, hydrides, carbonates and bicarbonates

of alkali metals and'alkaline earth metals, as well as e.g. tertiary

amines such as triethylamine, triethylenediamine, piperidine, pyridine,

4-dimethylaminopyridine, 4-pyrrolidylpyridine etc.

In this and in the subsequent process variants, the intermediates

and final products may be isolated from the reaction medium and, if

desired, purified by one of the conventional methods generally em-

ployed, e.g. by extraction, crystallisation, chromatography, distilla-

tion etc.

The open starting ketals of the formula IV may be obtained e.g. by

ketalising a 1H-l,2,4-triazolylmethylphenone of the formula II, in

the presence of an acid, with an alcohol of the formula VIII

R1OH (VIII)

wherein R, is as defined for formula I. Similar ketalisation reactions L are known from US patent specification 4 079 062, and the procedure

I

Surprisin

to be followed may correspond to the methods described therein. the compos

useful mi In the preferred embodiment of the ketalisation, both reactants are bacteria. heated under reflux for several hours together with an azeotrope propertie former in a conventional organic solvent. Examples of suitable azeo- compounds trope formers are benzene, toluene, xylene, chloroform or carbon organisms tetrachloride, while the addition of a strong acid, e.g. p-toluene- leaves, s sulfonic acid, may be advantageous for speeding up the reaction. while at Suitable organic solvents in this case are e.g. aromatic hydrocarbons protected such as benzene, toluene, xylene etc., and saturated hydrocarbons

such as n-hexane. The compo fungi bel In the synthesis of the compounds of formula I, these latter may be Podosphae obtainer in two different geometrical forms, viz. as E- or Z-isomers genera He Botrytis, Alternari Rio action. T or C seeds (fr RI \R yI V/ fections

E-Form Z-Form occur in well tole Generally, mixtures of both forms are obtained. The individual geometrical isomers are isolated by conventional methods, e.g. on the Accordingl basis of their differing solubility, by salt formation, by Craig and to the distribution or by chromatographic separating methods or by a com- phytophatc bination of these methods. An unequivocal clarification of structure preventive is made on the basis of the H -NMR data, in particular using dis- microoLgan placement reagents. The greater the signal displacements caused by these reagents, the smaller the distance between the complexed central The invent atom of the displacement reagent and the observed proton. compositic with one o Unless otherwise specially indicated, mention of a compound of the formula I always refers to a mixture of both geometrical isomers. Both isomers exhibit different microbicidal activity.

24

The a 6. Granulates mixtu a compounL of table 1 powde kaolin 1 -2-11-2 desir ii;

11

Surprisingly, it has been found that the compounds ot formula I qnd the compositions containing them have for practical purposes a very

useful microbicidal spectrum against phytopathogenic fungi and

bacteria. They have very useful curative, preventive and systemic

properties and can be used for protecting cultivated plants. With the

compounds of formula I it is possible to inhibit or destroy the micro-

organisms which occur in plants or parts of plants (fruit, blossoms,

leaves, stems, tubers, roots) in different crops of useful plants,

while at the same time the parts of plants which grow later are also

C protected from attack by such microorganisms.

The compounds of formula I are effective against the phytopathogenic fungi belonging to the following classes: Ascomycetes Venturia, Podosphaera, Erysiphe, Monilinia, Uncinula); Basidomycetes the genera Hemileia, Rhizoctonia, Puccinia); Fungi imperfecti (e.g.

Botrytis, Helminthosporium, Fusarium, Septoria, Cercospora and

Alternaria). In addition, the compounds of formula I have a systemic

action. They can also be used as seed dressing agents for protecting

seeds (fruit, tubers, grains) and plant cuttings against fungus in-

fections as well as against phytopathogenic microorganisms which

occur in the soil. The compounds of the invention are also especially

well tolerated by plants.

Accordingly, the invention also relates to microbicidal compositions and to the use of compounds of the formula I for controlling

phytophatogenic microcrganisms, especially harmful fungi, and for the

preventive treatment of plants to protect them from attack by such

microoLganisms.

The invention further embraces the preparation of agrochemical

compositions which comprises homogeneously mixing 'he active ingredient with one or more compounds or groups of compounds described herein.

i,

*ar 'i t* :ci I

The invention furthermore relates to a method of treating plants,

which comprises applying thereto the compounds of tbe 'formula I or

the novel compositions.

Target crops to be protected within the scope of the present invention

comprise e.g. the following species of plants:

cereals (wheat, barley, rye, oats, ri'e, sorghum aid related crops), beet (sugar beet and fodder beet), drupes, pomes and soft fruit

(apples, Ysars, plums, peaches, almonds, cherries, strawberries, rasberries and blackberries), leguminous plants (beans, lentils,

to peas, soybeans), oil plants (rape, mustard, poppy, olives, sunflowers, coconuts, castor oil plants, cocoa beans, groundnuts), cucumber plants (cucumber, marrows, melons) fibre plants (cotton, flax, hemp, jute), citrus fruit (oranges, lemons, grapefruit, mandarins), vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika), lauraceae (avocados, cinnamon, camphor), or plants such as maize, tobacco, nuts, coffee, sugar cane, tea, vines, hops, bananas and natural rubber plants, as well as

ornamentals (composites).

The compounds of formula I are normally applied in the form of

2o compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession, with further compounds. These compounds may be boTh fertilisers or micronutrient donors or otn:er preparations that influence plant growth. They may also be selective herbicides, insecticides, fungicides, bactericides, nematicides, mollusicides or mixtures of several of these prepartions, if desired together with further carriers, surfactants or application- promoting adjuvants customarily employed in the art of formulation. Suitable carriers and adjuvants can be solid or liquid and correspond

to the substances ordinarily employed in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, binders or fertilisers.

;105/43/15

13

A preferred method of applying a compound of the formula I or an

agrochemical composition which contain at least one of said compounds,

is leaf application. The number of applications and the rate of

application depend on the intensity of infestation by the corresponding

pathogen (type of fungus). However, the compounds of formula I can

also penetrate the plant through the roots via the soil (systemic

action) by impregnating the locus of the plant with a liquid composi-

Lion, or by applying the compounds in solid form to the'soil, e.g. in

granular form (soil application). The compounds of formula I:may also

to be applied to seeds (coating) by impregnating the seeds either with a liquid formulation containing a compound of the formula I, or

coating them with a solid formulation. In special cases, further

types of application are also possible, e.g. selective treatment of

the plant stems or buds.

The compounds of the formula I are used in unmodified form or, prefer-

ably, together with the adjuvants conventionally employed in the art

of formulation, and are therefore formulated in known manner to

emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble

yo powders, dusts, granulates, and also encapsulations in e.g. polymer

substances. Like the nature of the compositions, the methods of

application, such as spraying, atomising, dusting, scattering or

pouring, are chosen in accordance with the intended objectives and

the prevailing circumstances. Advantageous rates of application are

norma 1 ly from 50 g to 5 kg of active ingredient per hectare,

preferably from 100 g to 2 kg a.i./ha, most preferably from 200 g to

600 g a.i./ha.

The formulations, i.e. the compositions containing the compound (active ingredient) of the formula I and, where appropriate, a solid or liquid

adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents,

The following statement is a full description of this invention, including the best method of performing it known to meus:

10/82

14

solid carriers and, where appropriate, surface-active compounds

(surfactants). Phospholipids are also very useful formulation assis-

cants.

Suitable solvents are: aromatic hydrocarbons, preferably the fractions

containing 8 to 12 carbon atoms, e.g. ,.ylene mixtures or 'substituted

nrghthalenes, phthalates such as dibutyl phthalate or dioctyl

phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins,

alcohols and glycols and their ethers and esters, such as ethanol,

ethylene glycol monomethyl or monoethyl ether, ketones such as cyclo-

(0 hexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide, as well as epoxidised vege--

table oils such as epoxidised coconut oil or soybean oil; or water.

The solid carriers u.ed e.g. for dusts and dispersible powders, are

normally natural mineral fillers such as calcite, talcum, kaolin,

montmorillonite or attapulgite. In order to improve the physical

properties it is also possible to add highly dispersed silicic acid

or highly dispersed absorbent polymers. Suitable granulated adsorptive

carriers are porous types, for example pumice, broken brick,

sepiolite or bentonite; and suitable nonsorbent carriers are materials $a such as calcite or sand. In addition, a great number of pregranulated

materials of inorganic or organic nature can be used. e.g. especially

dolomite or pulverised plant residues.

Depending on the nature of the compound of the formula I to be formu-

lated, suitable surface-active compounds are nonionic, cationic and/

or anionic surfactants having good emulsifying, dispersing and

wetting properties. The term "surfactants" will also be understood

as comprising mixtures of surfactants.

Suitable anionic surfactants can be both water-soluble soaps and

water-soluble synthetic surface-active compounds.

28

b) Systemic action

Wheat plants are treated 5 days after sowing with a spray mixture

Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C0-C22), e.g. the sodium or potassium Falts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty. acid methylt, :in salts.

More frequently, however, so-called synthetic surfactants are used, especially fatt. sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

7 The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substi- tuted ammoniums salts and contain a C8 C2 2 alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignonsulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These

compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benz- imidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensation product. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide.

Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

29

11 days later. Compared with untreated and infected controls (number

I M

16

Further suitable non-ionic surfactants are the water-soluble adducts of, polyethylene oxide with polypropylene glycol, ethylenediamine propylene glycol and alkylpolypropylene glycol containing 1 to carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of non-ionic surfactants are nonylphenol- polyethoxyethanols, castor oil polyglycol ethers, polypropylene/poly- t0 ethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxyethoxyethanol. Fatty acid esters of polyoxy- ethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C -C22alkyl radical and as further substituents, lower unsubstituted or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethyl- ammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in the art of formulation are described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp. Ringwood, New Jersey, 1979, and Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc. New York. 1980.

T a mical composition usually contain 0.1 to 99 preferably V 95 of a compound of the formula I, 1 to 99.9 preferably 99.8 to 5 of a solid or liquid adjuvant, and 0 to 25 preferably 0.1 to 25 of a surfactant.

30

Compounds of the formula I are very effective against Erysiphe fungi. Erysiphe attack is 100% on untreated and infected control plants. ^m,nmrc nf TnailP 1 rnmnnim rl 1 -1 tn 1 1.6- 1.8.

Whereas commercial products are preferably formulated as concentrates,

the end user will normally employ dilute formulations.

The compositions may also contain further ingredients, such as stabi-

lisers, antifoams, viscosity regulators, binders, tackifiers as well

as fertilisers or other active ingredients in order to obtain special

effects.

Such agrochemical compositions also constitute an object of the present

invention.

The invention is illustrated in more detail by the following Examples,

without implying any restriction to what is described therein. Parts

and percentages are by weight.

Preparatory Examples

Example 1: Preparation of

Cl H Cl-* (1.2) N=* OC H OC2H

1-(2,4-dichlorophenyl)-l-ethoxy-2-(1H-l,2,4-triazol-l-yl)-ethene

a) Preparation of the starting material Cl

Cl-* *-C-CH Br

C2 H5 0 C2 H

2,4-dichlorophenacylbromide diethyl acetal

112 g of 2,4-dichlorophenacylbromide, 120 g of triethyl orthoformate

o and 8 g of p-toluenesulfonic acid are heated in 1 litre of absolute

ethanol for 40 hours under reflux. The solvent is stripped off under

vacuum and the pale yellow oily residue is washed with sodium bi-

31

very strongly inhibit fungus attack. For example, at a concentration

of 0.002%, compounds 1.9 and 1.22 are fully effective (0 to

attack). Compounds 1.8 and 1.28 are also fully effective (0 to carbonate and water and freed from volatile constituents under vacuum. Yield: 140 g of a yellow oil which is further processed without purification.

b) Preparation of a further intermediate

/Cl 11 Cl-- -C-CH -N 2 N=

1-(2,4-dichlorophenyl)-1,l-djethoxy-2-(1H-1,2,4-triazol-l-yl)-ethane With stirring, a solution of 140 g of 2,4-dichlorophenacylbromide diethyl al in 100 ml of dimethylformamide is added dropwise to a suspension of 88 g of 1H-l,2,4-triazole potassium salt in 500 ml of absolute dimethyl formamide. The reaction mixture is then stirred 0 0 for 12 hours at a temperature of 120 -130 C. About two-thirds of the dimethylformamide are distilled off under vacuum and ice-water is added to the residual suspension. The precipitated oil is extracted with methylene chloride and, after stripping off the solvent, the extract is distilled in a high vacuum. Yield: 51 g of an almost 0 0 colourless oil with a boiling point of 155 -160 C/0.04 mbar.

c) Preparation of a final product: 4 g of the l-(2,4-dichlorophenyl)-l,l-diethoxy-2-(lH-1,2, -triazol- l-yl)-ethane obtained in b) are mixed with 30 ml of Dowtherm (eutectic 0 0 mixture of biphenyl and dibenzofuran, m.p. 12 -14 C) and 1 g of p-toluenesulfonic acid and the mixture is kept for 5 hours at a bath temperature of 220 0-230 0 C, while ethanol condenses in a descending cooler. The Dowtherm is distilled off under vacuum and the residual brown oil is taken up in toluene "and washed with sodium bicarbonate solution and with water. Excess toluene is removed by evaporation and the residual oil is crystallised by addition of petroleum ether/ diethyl ether. Yield: 7 g of l-(2,4-dichlorophenyl)-l-ethoxy-(1H- 0 0 1,2,4-triazol-l-yl)-ethene with a melting point of 92 -94 C.

Example 2: Preparation of

*=N -C=CH-N (1.7)

OC4 H 9 n)

l-(4-chlorophenyl)-l-n-butoxy-2-(1H-1,2,4-triazol-l-yl)-ethene To a solution of 17.7 g of a-(lH-l,2,4-triazol-l-yl)-4-chloroaceto- pheno in 100 ml of hexamethylphosphoric triamide are added, with exclusion of moisture, 4.2 g of a 50% dispersion of sodium hydride in mineral oil. After the evolution of hydrogen has ceased, 24 ml of tri-(n)-butylphosphate are added dropwise to the mixture. With further stirring, the temperature in the reaction mixture is raised CO to 75°-80°C and stirring is continued for another 10 hours. The reaction mixture is then cooled to room temperature and poured onto ice-water. After extraction with ethyl acetate and removal of the solvent under vacuum, the residual crude oily product is purified by o o column chromatography (silica.gel/methylene chloride 5% methanol).

Recrystallisation from n-hexane yields 6 g of colourless crystals of the above compound 1.7 with a melting point of 750 -760 C.

Example 3: Preparation of

C H9(n)

SCl- Nl (1.26)

0C4 H9 (n)

1-(2,4-dichlorophenyl)-l-(n)-butoxy-2-(IH-1,2,4-triazol-l-yl)-hex- o0 1-ene To a solution of 15 g of a-(lH-1,2,4-triazol-l-yl)-2,4-dichloro- acetophenone in 50 ml of dimethylformamide are added, in portions, 6.1 g of a 50% dispersion of sodium hydride in mineral oil. After the evolution of hydrogen has ceased, 14 ml of n-butyl bromide are added dropwise and the reaction mixture is stirred for 8 hours at

32

What. iz claimd -i:

The claims defining the invention are as follows: 1. A compound of the general formula I i

20 T m. 0 -600 C. The dark brown suspension is poured into water and extracted T 3 times with n-hexane and cyclohexane. The combined extracts are washed with water, dried over sodium sulfate, filtered and concen- trated in vacuo, yielding 18 g of an oil which consists of two reac- tion products. Preparative separation of the products is effected by column chromatography (silica gel/methylene chloride). The first fraction yields 6 g of a colourless oil whose analytical and NMR spectroscopic data confirm the structure of an E/Z mixture of 1-(2,4- dichlorophenyl)-l-(n)-butoxy-2-(IH-1,2,4-triazol-l-yl)-hex-l-ene.

J( A second fraction yields 6 g of crystalline l-(2,4-dichlorophenyl)- l-(n)-butoxy-2-(lH-l,2,4-triazol-l-yl)-ethene (compound 1.4) with a melting point of 680 -710 C.

Examples 3a: Preparation of

OC3H 7 (n) I Cl-* *-C=-NI(1.32)

l-(4-chlorophenyl)-l-n-propoxy-2-(iH-1,2,4-triazoi-l-yl)-2-(4-chloro- phenyl)-ethene To a solution of 16 g of a-(4-chlorophenyl -a-(1H-1,2,4-triazol-l-yl)- 4-chloroacetophenone in 150 ml of absolute dimethylformamide are added 4.7 g of potassium tert-butoxide and the mixture is heated to (O 70C. Then 3.3 g of n-propyl bromide are added and the reaction mixture is stirred for 15 hours at 700 -900 C. The brown suspension, which has been cooled to room temperature, is diluted with water and extracted 3 times with methylene chloride/n-hexane The o combined extracts are dried over sodium sulfate, filtered and con- centrated. The residue is purified over silica gel, affording 7 g of compound 1.32 in the form of yellowish crystals with a melting point of 140 0-1430 C.

i I

33

R2 is hydrogen, C1 -C4 alkyl, CH2CH=CH 2 CH2 C-CH, C6 H3 C12 or w C6H 6 44C1(4). t

-3 1-

Y-0Y0\--C=C-NI OR 1

Com- x Physical data (00C pound I i i

1.1 CHR3 m.p. 98-1O0o

1.2 m.p. 92-94'

1.3 C3 H7 (n) M.P. 104-1050

1.4 C4 H 9 (n) m.p. 68-71-

(CH(CH 3 2 95-~960 ~M P. tp. 75-76o 1.6 C4 9 (n)

1.7 C3H 7(n) H Cl M.p. 82-84*

1.8 CR (C Cl Cl viscous oil 3 )C C2 H5

1.9 CR (C C3 H7 Wn Cl Cl viscous oil 3 )C

1.10 CH2 CH(CH 3 Cl Cl Im.p. 75-80' 2

1.11 Cl Cl Ip.60-62' CH2C 2 CRH 3 2

1.12 C 6 H1 3 Cl Cl viscous oil

CH 2 HOC 2IHI Cl Cl M.P. 56-60' 1.13 CR 2 21- 2 1.14 Cl Cl

34

wherein X, Y and R2are as defined for formula 1, with a compound of

the formula III

R1-

Tabelle 1 (continuation)

Cor- I j( Pyscl0 c)Data pound RR2__IxI__

C3\/CH3

1.15 CH 2 H~ 2 H Cl Ic

1.16 CH2 H Cl M.P. 128-1290

1.17 CR-C H H F m.p. 53-600 1 25 CR3

1.18 CH2 CH2 CR(CR3 H F 2

c8H17 H F

1.20 CR3 H m.p. 104-1060

1.21 c4H 9 (n) H

1.22 viscous oil Cl 1.23 CH3 C4 H9(n) Cl 1.24 CR3 viscous oil Cl 1.25 Cl 1.26 C4 H 9 (n) c4 H 9 (n) viscous Cl 1.27 CH2CR=CH viscous CH 2 C= CH2 C2 C 2C Cl 1.28 viscous CR C=-CH Cl 1.29 CH 2C=CR viscous Cl 1.30 CR3 CH 2CH=CH2 Cl 1.31 c4 H9 (n) 4 C1 (4) c6 RH m.p. 85-870 Cl 1.32 c3 H 7 (n) c 6 H4 C1(4) in-P. 140-1430

L- I I I I 1,

35

11, wqhich com- composition according to any one of claims 8 to 12. A of a solid of formula 1, 99.9 to 1% priseS 0.1 to 99% of a compound u o27 fasr actant. or liquid adjuvant and

Formulation Examples

Formulation Examples for liquid active ingredients of the formula I (throughout, percentages are by weight)

4. Emulsifiable concentrates a) b) c) a compound of table 1 25% 40% calcium dodecylbenzenesulfonate 5% 8% 6%

castor oil polyethylene glycol ether 5% (36 moles of ethylene oxide)

tributylphenol polyethylene glycol ether S 12% 4% moles of ethylene oxide)

cyclohexanone 15%

xylene mixture 65% 25%

Emulsions of any required concentration can be produced from such

concentrates by dilution with water.

Solutions a compound of table 1 ethylene glycol monomethyl ether

polyethylene glycol 400

N-methyl-2-pyrrolidone 20 epoxidised coconut oil 1% petroleum distillate (boiling range 94% 160-1900)

These solutions are suitable for application in the form of microdrops.

6. Granulates a compound of table 1 kaolin highly dispersed silicic acid 1%

attapulgite 94%

The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evapora- ted off in vacuo.

7. Dusts a compound of table 1 highly dispersed silicic acid talcum kaolin

Ready-for-use dusts are obtained by intimately mixing the carriers with t-Le active ingredient.

Formulation examples for solid active ingredients of the formula I (throughout, percentages are by weight)

8. Wettable powders a compound of table: 1

sodium lignosulfonate sodium lauryl sulfate sodium diisobutylnaphthalpnesulfonate octyiphenol polyethylene glycol et, er (7-8 moles of ethylene oxiie)

higbly dispersed silicic acid kaolin

The active ingredient is thoroughly mixed with the adjuvants and the mixtures is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.

9. Emulsifiable concentrate a compound of table 1 octylphenol polyethylene glycol ether 3% moles of ethylene oxide)

calcium dodecylbenzenesulfonate 3% O( castor oil polyglycol ether 4% (36 moles of ethylene oxide)

cyclohexanone xylene mixture

Emulsions of any required concentration can be obtained from this concentrate by dilution with water.

a) b) a compound of table 1 5% 8% talcum 95%

kaolin 92%

2c Ready-for-use dusts are obtained by mixing the active ingredient with the carriers, and grinding the mixture in a suitable mill.

11. Extruder granulate a compound of table 1 sodium lignosulfonate 2% carboxymethylcellulose 1% kaolin 87%

ii

The active ingredient is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water. The mixture is extruded and then dried in a stream of air.

12.Coated granulate a compound of table 1 3% polyethylene glycol 200 3% kaolin 94%

The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated rO granulates are obtained in this manner.

13. Suspension concentrate

a compound of table 1 ethylene glycol nonylphenol polyethylene glycol 6% moles of ethylene oxide)

sodium lignosulfonate carboxymethylcellulose 1% 37% aqueous formaldehyde solution 0.2% silicone oil in the form of a 75% 0.8% aqueous emulsion

water 32%

T' fin ly ground active ingredient is intimately mixed with the a. s, giving a suspension concentrate from which suspensions of any desired concentirtion can be obtained by dilution with water.

1.V ~i 'i O

In the following biological tests, the closest comparable compounds A and B known from the literature are also tested for comparison purposes:

From German Offenlegungsschrift 29 31 755:

71

CH I 2 .=N page 27, Example 1; A (CH C-- 3 3 C Z/E mixture OC H 25

From German Offenlegungsschrift 26 10 022:

S. CH B C1- -C-CH- page 5, compound 1

0

Biological Examples

Example 14: Action against Puccinia graminis on wheat

a) Residual-protective action

Wheat plants are treated 6 days after sowing with a spr.y mixture

prepared from a wettable powder formulation of the active ingredient

After 24 hours the treated plants are infected with a

uredospore suspension of the fungus. The infected plants are incubated 0 for 48 hours at 95-100% relative humidity and about 20 C and then

stood in a greenhouse at about 22°C. Evaluation of rust pustule

development is made 12 days after infection.

7r b) Systemic action

Wheat plants are treated 5 days after sowing with a spray mixture

prepared from a wettable powder formulation of the active ingredient

(0,002% based on the volume of the soil). After 48 hours the treat=d

plants are infected with a uredospore suspension of the fungus. The

plants are then incubated for 48 hours at 95-100% relative humidity

and about 200 C and then stood in a greenhouse at about 22C.

Evaluation of rust pustule development is made 12 days after infection.

Compounds of Table 1 are very effective against Puccinia fungi,

O Puccinia attack is 100% on untreated, infected controls. At a test

concentration of 0.002%, compounds 1.3, 1.6, 1.9, 1.22 and 1.26 in-

hibit Puccinia attack completely At a concentration of 0.006%, the other compounds of Table 1 also inhibit attack to At the low test concentration of 0.002%, comparison compound A inhibits attack

to 30-40% and comparison compound B to

Example 15: Action against Cercospora arachidicola in groundnut plants

a) Residual protective action

Groundnut plants 10-15 cm in height are sprayed with aspray mixture

(0.02 prepared from a wettable powder formulation of the active ingrcdient, and infected 48 hours later with a conidia suspension of

the fungus. The infected plants are incubated for 72 hours at about

2100 and high humidity and then stood in a greenhouse until the typical

leaf specks occur. Evaluation of the fungicidal action is made 12 days

after infection and is based on the number and size of the specks.

b) Systemic action

Groundnut plants 10-15 cm in height are sprayed with a spray mixture

prepared from a wettable powder formulation of the active ingredient

(0.006%, based on the volume of the soil). The treated plants are

infected 48 hours later with a conidia suspension of the fungus and

O then incubated for 72 hours at about 210 C and high humidity. The plants

are then stood in a greenhouse and evaluation of fungus attack is made

11 days later. Compared with untreated and infected controls (number and size of the specks 100%) attack by Cercospora on the groundnuit plants treated with compounds of Table 1 is greatly reduced.

In the above tests, compounds 1.1 and 1.4 prevent speck development ,almost comp'-tely (0 to The closest comparable compounds A and

on. BSof the prior art, however, effect no inhibition of attack by

I Cercospora at the above test concentration. Even. by increasing the test concentration to 0.02%, no reduction in attack is observed.

1; Phytotoxic effects are observed in the treatment with comparison tocompound B. ICl .ow Example 16:_ Action against Erysiphe graminis on barley

a) Residual protective action

Barley plants about 8 cm in height are sprayed with a spray mixture its (0.0002%)prepared from the active ingredient formulated as a wettable

powder. The treated plants are dusted with conidia of the fungus after 3-4 hours. The infected barley plants are then stood in a green- house at about 22'C. The extent of the infestation is evaluated after days.

.cal b) Systemic action

Lys Barley plants about 8 cm in height are treated with a spray mixture (0.006%, based on the volume of the soil) prepared from the active ingredient formulated as wettable powder. Care is taken that the spray mixture does not come in contact with the part'n of the plants above the soil. The treated plants are infected 48 houvs later with a conidia suspension of the fungus. The infected barley plants are then stood in a greenhouse at about 22*C and evaluation of infestation is made after 10 days.

nts de

Compounds of the formula I are very effective against Erysiphe fungi.

Erysiphe attack is 100% on untreated and infected control plants.

Among other compounds of Table 1, compounds 1.1 to 1.4, 1.6, 1.8,

1.9, 1.22, 1.31 and 1.32 inhibit fungus attack to Compounds 1.3

and 1.4 in particular inhibit Erysiphe attack completely even at

still lower test concentrations of 0.00002%. A comparably good action

with compounds A and B of the prior art is observed only at an in-

creased test concentration of 0.02%. In addition, compoundBdamages

the test plants noticeably.

Example 17: Residual-protective action against Venturia inaequalis on apple shoots

Apple cuttings with 10-20 cm long fresh shoots are sprayed with a

spray mixture (0.006%) prepared from a wettable powder formulation of

the active ingredient. The plants are infected 24.hours later with a

conidia suspension of the fungus. The plants are then incubated for

days at 90-100% relative humidity and stood in a greenhouse for a

further 10 days at 200 -24°C. Scab infestation is evaluated 15 days

after infection.

Compound 1.4 and other compounds inhibit attack to less than

Venturia attack is 100% on untreated and infected shoots. Comparison compound B has no action against Venturia and compound A acts only

at a test concentration of 0.02%.

Example 18: Action against Botrytis cinerea on bea,.

o Residual protective action Bean plants about 10 cm in height are sprayed with a spray mixture

(0.002% concentration) prepared from the active ingredient for:'ulated as wettable powder. After 48 hours, the treated plants are infected

with a conidia suspension of the ungus. The infected plants are

incubated for 3 days at 95-100% rLlative humidity and 21°C, and evalu-

ation of the fungus attack is then made. Many compounds of Table 1

r.

I

31

very strongly inhibit fungus attack. For example, at a concentration

of 0.002%, compounds 1.9 and 1.22 are fully effective (0 to

attack). Compounds 1.8 and 1.28 are also fully effective (0 to

attack) at a concentration of 0.006%. On the other hand, Botrytis 3 attack on untreated and infected control plants is 100%. The closest

comparable prior art compounds A and B effect no reduction in attack on at all against Botrytis fungi. Compound B causes only visible damage

to the test plants. as

The biological tests (Examples 14 to 18) show quite unequivocally

O the superiority of the compounds of the present invention in the

Son control of fungus infections on cultivated plants as compared with

prior art compounds of similar constitution.

3f

a

alu-

4l

i-.

ri'7, tst Lck

LgC-

-4,

Claims (1)

1. What ic claimPd i

   The claims defining the invention are as follows: 1. A compound of the general formula I

   /X R /2

   OR1

   wherein X is hydrogen or halogen, Y is hydrogen, halogen, phenyl or phenyl which in substituted by one or two halogen atoms, R 1 is C -C8alkyl, C3 -C5 alkenyl, C3 alkynyl, a lower alkoxyalkyl radical containing at most 8 carbon atoms or one of the groups

   0 -R-R -CH 2 -C or -CH2-Cj

   in which each of R3 and R4 independently of the other is hydrogen or methyl; and

   R2 is hydrogen, C1-C alkyl, C3 alkenyl, C3 alkynyl, phenyl or phenyl which is substituted by one or two halogen atoms or by one or two C1-C3alkyl or C1-C3alkoxy groups, or an acid addition salt, quaternary azolium salt or metal complex thereof.

   2. A compound of the formula I, wherein X is hydrogen, fluorine, chlorine, bromine or iodine; Y is hydrogen, fluorine, chlorine, bromine, iodine, C6 H5 C6 H4 Hal(2), C6 H4 Hal(4), C6 H 3Hal2(2,4) or C6H3Hal2(3,4), where Hal is fluorine, chlorine, bromine or iodine; R is C1-C5alkyl, CH2CH=CH2, CHCH, CH2CH3, CH2OC2H5, CH2OC3H7, CH2CH2OCH 3 CH2CH20C2H 5 CH2 H-H2, CH2 or CH2H-H2 and

   C^\H^3

   T

   R2 is hydrogen, C1 -C4 alkyl, CH 2 CH=CH2 CH 2 C-CH, C6 H3 Cl 2 or C6H 4cl(4).

   3. A compound of the formula I, wherein X is hydrogen, fluorine, chlorine or bromine; Y is hydrogen, fluorine, chlorine, C6H C6H CI(2), C6H 4Cl(4), C H3C1 or C6H 3Cl2 R1 is C1-C4akl CH2 CH=CH2 CH 2 CH, CH 2OGH 3 CH OC H or CH CH OH;ad 0H;a R is hydrogen or C1-C4 alkyl.

   4. A compound of the formula I, wherein X is hydrogen or chlorine; Y is hydrogen, fluorine, chlorine or C6H5;R1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, CH 2 OCH 3P

   C2 C2H5 o H2 C 2OCH 3 andR2 is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl or sec-butyl.

   A compound of the formula I, wherein X is chlorine, Y is fluorine or chlorine, R1 is methyl, ethyl, n-propyl or n-butyl ,and R2 is hydrogen.

   6. A compound selected from the group consisting of:

   1-(2,4-dichlorophenyl) -1-n-propoxy-2-lH-1, 2,4-triazol-l-yl) ethene, 1- 4-dichlorophenyl) -l-n-butoxy-2- (11-1, 2,4-triazol-l-yl) -ethene,

   ethene, 1- 4-dichiorophenyl) -l-n-butoxy--2- (11-1,2,4-triazol-l-yl) -butene, 1-(2,4-dichlorophenyl)-l-n-butoxy-2-2-l-,2,4-triazol-l-yl)-hexene.

   7. A process for the preparation of a compound of the formula I as defined in claim 1, which process comprises

   A) reacting an a-lH-l, 2 ,4--triazolylphenone of the formula

   C CH~\ wherein X, Y and R 2 are as defined for formula I, with a compound of the formula III

   R -Z (III)

   wherein R1 is as defined for formula I and Z is a leaving group selected from chlorine, bromine, R I SO 4 or (R 0) (O)P=0 in which

   R is also defined for formula I, in the presence of a base and ad- vantageously in the presence of a polar aprotic solvent or of an aqueous organic two-phase medium and in the presence of a conven- tional phase transfer catalyst; or, where R2 is hydrogen,

   B) subjecting an open acetal of the formula IV

   y--N -C-CH-N (IV), -Rld \OR 1

   wherein X, Y and R are as defined for formula I, in a high boiling 0 solvent in the temperature range from 1000 to 220 C, to thermolysis.

   8. A pesticidal composition for controlling or preventing attack by microorganisms, which composition comprises at least one compound of the formula I as claimed in claim 1.

   9. A composition according to claim 8, which comprises at least one compound of the formula I as claimed in claim 2.

   A composition for controlling microorganisms according to claim 8, which comprises at least one compound of the formula I as claimed in claim 3.

   11. A composition according to claim 8, which comprises at least one compound of the formula I as claimed in any one of claims 4 to 6.

   12. A composition according to any one of claims 8 to 11, which com-

   prises 0.1 to 99% of a compound of formula I, 99.9 to 1% of a solid

   or liquid adjuvant and 0 to 25% of a surfactant.

   13. A composition according to"claim 12, which comprises 0.1 to

   of a compound of formula I, 99.8 to 5% of a solid or liquid adjuvant

   and 0.1 to 25% of a surfactant.

   14. A method of controlling phytopathogenic microorganisms or of

   protecting cultivated plants from attack by said microorganisms,

   which method comprises applying to said plants or the locus thereof

   a microbicidailly effective amount of a compound of the formula I as

   defined in any one of claims 1 to 6.

   A method according to claim 14, wherein the microorganisms to be

   controlled are phytophathogenic fungi.

   16. A method according to claim 15, wherein the fungi belong to the classes Ascomyzetes, Basidiomycetes or Fungi imperfecti.

   DATED this TWENTY SIXTH day of OCTOBER,1982

   CIBA-GEIGY AG

   Patent Attorneys for the Applicant SPRUSON FERGUSON

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