AU656836B2

AU656836B2 - Synergistic combinations of cyproconazole

Info

Publication number: AU656836B2
Application number: AU32821/93A
Authority: AU
Inventors: Cor J. Klaver; Gerbrand Rustenburg
Original assignee: HOECHST HOLLAND NV
Current assignee: Syngenta Participations AG
Priority date: 1992-02-04
Filing date: 1993-02-03
Publication date: 1995-02-16
Anticipated expiration: 2013-02-03
Also published as: ATE186625T1; CA2088714C; JP3693355B2; NO930379D0; DK0554833T3; FI930452L; DE59309869D1; NO930379L; FI930452A0; DE4203090A1; NO321134B1; NO303043B1; ZA93732B; JPH06256115A; NO980307L; EP0554833A1; NZ245824A; MY116458A; FI107013B; CA2088714A1

Abstract

The invention relates to novel fungicidal compositions based on cyproconazole and quaternary ammonium salts, which display surprisingly powerful synergistic activities in the control and prevention of wood-destroying fungi.

Description

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AUSTRALIA

Patents Act 1990 o f

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT Application Number: Lodged: Invention Title: SYNERGIS11C COMBIN'ATIONS OF CYPROCONAZOLE The following statement Is a full description of this Invention, including the best method of performing it known to :-US i f .i .i L~lnllr ~ii bR HOECHST HOLLAND N.V. HOE 92/F 027 Dr.AB/St Synergistic combinations of cyproconazole The cyproconazole-type fungicides found in recent years have good fungicidal activity (cf. US Patent 4,849,439) and have an activity against human and animal dermatophytes and against phytopathogenic fungi.

Novel fungicidal agents based on cyproconazole and quaternary ammonium salts which have surprisingly powerful synergistic activities in the control and prevention of wood-destroying fungi have now been found.

The use of mixtures which entail synergistic effects has considerable economic but also ecological advantages.

"Synergism is to be understood as meaning the mutually enhancing activity of two or more substances. In the present case, the combined application of two fungicides allows the application rate of the fungicides to be reduced while still maintaining an equally good fungicidal activity, or that identical application rates of the fungicides result in a greater activity than the activity to be expected from the individually employed 20 active substances.

The utilization of such synergistic effects allow the application rates of the components to be considerably reduced, and it is possible to control a broad range of wood-destroying fungi. The reduced application rates relate to the quaternary ammonium salts, but also to cyproconazole.

In the present case, cyproconazole is combined with compounds which considerably enhance the activity of the fungicide, which allows the identical activity to be obtained by uoing a lower concentration of the fungicide.

In addition, the combinations according to the invention 2 are active even when used at low application rates. They are therefore outstandingly suitable for controlling wood fungi in wood and masonry.

The present invention therefore relates to fungicidal compositions which comprise A) cyproconazole (Formula I) I -N N OH

CH

2 -C Cl

*H

in combination with B) inorganic or organic ammonium salts of the formula 10 II .oR 0 3 (II) R2- 4 X n- R 2 N +R 1 n n in which R 1 -R are identical or different and are an organic substituent which has up to 18 carbon atoms and which is bonded by a carbon-nitrogen bond, or three of the radicals R 1

-R

4 together with the nitrogen atom form a heteroaromatic system, for example pyridinium, is the anion of an inorganic or organic n-basic acid, and n is 1, 2 or 3.

3 The compounds of type B are preferably ammonium salts i which R 1

-R

4 are identical or different and are (C 1 8 alkyl, (C 7

-C

13 )-aralkyl, such as benzyl, (C-C.)-alkyoxy- (Ci-C 12 )-alkyl, [-CH 2

-CH

2 -O1]-H or [-CH(CH 3

)-CH

2 and x is 1, 2 or 3. Particularly preferred salts are those in which R 1 and R 2 are in each case (C-C 4 )-alkyl, in particular methyl, R 3 and R 4 are in each case (Cs-C 12 )-alkyl, in particular decyl. Preferred anions X" n are Cl1, Br-, S0 4 2, HS0 4 P0 4 HP0 4 2

H

2 P4O, CH 3 COO" C00 2 2 SCN-, in particular C1-.

Most of the wood-destroying fungi are Basidiomycetes, but Ascomycetes and Deuteromycetes can also be found. The compositions according to the invention are preferably used against Basidiomycetes, for example against 15 Coniophora, Gloephyllum, Poria, Serpula and Coriolus. The following fields of application are of particular interest: preventive and curative treatment of wood, and curative treatment of wood and masonry.

The compounds of type B can be combined with cyprocon- 20 azole to give a range of combinations. Cyproconazole and quaternary ammonium salts are commercially available.

mixing ratios of the individual components in the combinations according to the invention can vary within wide limits. However, quantitative ratios of between 25 and 1:25, preferably between 1:4 and 1:6, are selected for practical reasons.

The mixtures according to the invention can be in the form of water-dilutable concentrations which are then applied in a customary manner in the form of a dilution with water, or in the form of so-called tank mixes which are prepared by concomitant dilution of the separately formulated components with water immediately prior to application. They can also be applied in the form of aqueous ready-for-use solutions.

1 1 1r 1 1 4 The application rates of the fungicides of type A in the active substance mixtures are generally between 1 g/l and 100 g/l, the application rates of B are between 5 g/l and 500 g/l; the total amount of product combination to be applied is 15 1/m 3 to 600 1/m 3 of wood.

The compositions according to the invention can be marketed in the form of the conventional preparations whirh are known to a person skilled in the art. They are preferably marketed in the form of water-dilutable concentrates or ready-for-use solutions. The formulated compositions contain for example 0.1 to 50% by weight of the active substance combinations according to the invention.

S* Examples of inert substances which can be used are 15 n-butyl glycolate, polyglycol ether or dipropylene glycol monoethyl ether.

In the case of fungicidal compositions, the concentrations of the active substances in the commercially available formulations can vary. The active substance concentration in emulsifiable concentrates is approx. 1 to ee *eSe If appropriate, the commercial concentrates are diluted in the customary manner for application. The application rate and the concentration required varies depending on the field of application, for example for the treatment of wood without or with contact with the soil or water.

A combination of the active substances means that the fungicidal active substances are applied jointly or a few days one after the other, in the form of a so-called split application.

If required, the compositions according to the invention can be combined with other active substances, preferably 5 with fungicides and insecticides. Unless otherwise indicated, percentages are percent by weight. The invention is illustrated by the example which follows without limiting it thereto: Example Determination of the activity of the cyproconazole in combination with dimethyldidecylammonium chloride against wood-destroyina Basidiomycetes.

The active substances were tested in accordance with European Testing Standards ES 84 (1979) and 113 (1986).

Treatment with the active substances prevents the wood from being destroyed. The effect of the treatment is quantified indirectly via the non-existing weight loss of the wood samples.

15 The wood sample used was pine sapwood, and the test fungi used were Coniophora puteana (cellar fungus), Poria plazenta, Gloeophyllum trabeum and Trametes (Coriolus) versicolor. Markedly smaller amounts of the combination according to the invention of cyproconazole 2-(4chlorophenyl)-3-cyclopropyl-3-methyl-l-(lH,1,2,4-triazol- 1-yl)-butan-2-ol) and dimethyldidecylammonium chloride (Bl) have the same result weight loss) as cyproconazole or B1 alone. Comparably good results were also obtained when beech was used as the wood sample.

-6 Table: Pine sapwood Amount (g/m 3 of active Weight Loss Substance at 0% Fungi A+B1 A Bi Coniophora 121 g 247 g 12,415 g 605 g Gloephyllum 119.5 g 247 g 12,505 g 597.5 g Poria 121 g 243 g 3,175 g 605 g Coriolus 105 g 418 g 2,675 g 525 g

S

S. S S S

S.

*5 S S

S.

S S

S

S.

S. *S S S S

Claims

1. A fungicidal composition which fungicidally effective amounts of A) cyproconazole of the Formula I N N-, CH 2 CH 3 includes as the active agents synergistic OH I H-K H 0 0 a p 00 0 0 in combination with B) inorganic or organic ammonium salts of the Formula II R 3 (II) R 2 N R 4 Xn- I L R 1 in which R1-R4 are identical or different and are an organic substituent which has up to 18 carbon atoms and which is bonded by a carbon- nitrogen bond, or three of the radicals R1-R4 together with the nitrogen atom form a heteroaromatic system, Xn- is the anion of an inorganic or organic n-basic acid, and n is 1, 2 or 3, but excluding cetyltrimethylammonium chloride. 7 HC THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS: 1. A fungicidal composition which comprises A) cyproconazole of the Formula I )E 92/F 027 N N"N 0 H I r CH -C- CH 3 -C 1 a H in combination with B) inorganic or organic aonium salts of the formula II r 1 (II) -N -R R 4* I. S S L_ n in whic R'-R 4 are identical or different and are an orga c substituent which has up to 18 carbon atoms and/which is bonded by a carbon-nitrogen bond, or three of the radicals R'-R together with the nitro- en atom form a heteroaromatic system, X" is the anion of an inorganic or organic n-basic acid, and n is 1, 2 or 3.

2. A fungicidal composition as claimed in claim 1, which comprises the active substances A and B in a ratio by weight of 1:2.5 to 1:25. c:' -8

3. The fungicidal composition as claimed in claim 2, wherein the ratio by weight of A:B is 1:4 to 1:6.

4. The fungicidal composition as claimed in claim 1, 2 or 3, which comprises 0.1 to 50% by weight of active substance mixture and 99.5 50% by weight of conventional formulation auxiliaries for prepara- tions as sprayable solutions. A method of controlling harmful fungal growth on wood, which comprises applying an effective amount of a synergistic mixture composed of the compound cyproconazole in combination with compounds of the formula II to the wood to be treated. u 15 a ratio by weight of 1:2.5 to 1:25.

7. The method as claimed in claim 6, wherein the active substances of the formulae I and II are applied in a ratio by weight of 1:4 to 1:6.

8. The process as claimed in claim 6 or 7, which 20 comprises applying the synergistic mixture in amounts from 15 to 600 1/m 3 of wood.

9. The method as claimed in claim 6, 7 or 8, which comprises using spray mixtures which comprise 1 to 100 g/1 of the compound of the formula I and 5 to 500 g/l of a compound of the formula II. The use of a combination of the compounds of the formulae I and II for controlling wood-destroying fungi, which comprises applying the active substan- ces concomitantly or shortly one after the other. S DATED this 3rd day of February 1993. SHOECHST HOLLAND N.V. WATERMARK PATENT TRADEMARK ATTORNEYS SN"THE ATRIUM" 290 BURWOOD ROAD HAWTHORN. VIC. 3122. HOE 92/F 027 Abstract of the disclosure Synergistic combinations of cyproconazole The invention relates to novel fungicidal compositions based on cyproconazole and quaternary ammonium salts which havas surprisingly powerful synergistic effects in the control and prevention of wood-destroying fungi. 0 *sea