Title of Invention

A FUNGICIDAL MIXTURE COMPRISING A CARBAMATE AND A MORPHOLINE OR PIPERIDINE DERIVATIVES

Abstract The present invention relates to a fungicidal mixture which comprises a) a carbamate of the formula II Where T is CH or N, is 0, 1 or 2 and R is halogen, C<sub>1</sub>-C<sub>4</sub>-alkyl or C<sub>1</sub>-C<sub>4</sub>-haloalkyl, it being possible for the radicals R to be different if n is 2, and b) a morpholine or piperidine derivative III selected form the group of the compounds IIIa, IIIb and IIIc [n= 10, 11, 12 (60 – 70%) or 13] in a synergistically active weight ratio of 20:1 to 0.1:2.
Full Text

Fungicidal mixtures
The present invention relates to a fungicidal mixture which comprises
a) an oxime ether of the formula I

where the substituents have the following meanings;
X is oxygen or amino (NH);
Y . is CH or N;
Z is oxygen, sulfur, amino (NH) or C1-C4--alkylamino (N-Ci R' is Ci-Ce—alJcyl, Ci-C$-haloalkyl, C3~C6-alkenyl,
C2~C6-haloalkeny 1, C3-C6-alkynyl, C3~C6-haloalkyny1, C3*Ce—cycloalkylmethyl, or is benzyl which can be par¬tially or fully halogenated and/or can have attached to it one to three of the following radicals: cyano, C1-C4—alkyl, Ci-C4-haloalkyl/ C1-C4—alkoxy, C1-C4—halo~ alkoxy and C1-C4—alkylthio;
and/or
b) a carbamate of the formula II
10
where T is CH or N, n is 0, 1 or 2 and R is halogen, Ci~C4-al-kyl or Ci-C4^haloalkyl, it being possible for the radicals R to be different if n is 2,

c) a morpholine or piperidine derivative III selected from the group of the compounds Ilia, Illb and IIlc

[n= 10,11,12 (60 - 70%) or 13] in a synergistically active amount.
Moreover, the invention relates to methods of controlling harmful fungi with mixtures of the compounds I and/or II and III and to the use of the compounds I and/or II and the compounds III for the preparation of such mixtures.
The compounds of the formula I, their preparation and their action against harmful fungi have been disclosed in the litera¬ture (WO-A 95/21,153, WO-A 95/21,154, DE-A 195 28 651.0).
Compounds of the formula II, their preparation and their action against harmful fungi have been described in WO-A 96/01,256 and WO-A 96/01,258,
The morpholine or piperidine derivatives III (Ilia: common name; fenpropimorph, US-A 4,202,894; Illb: common name: fenpropidin, US-A 4,202,894; IIlc: common name; tridemorph, DE-A 11 64 152),

their preparation and their action against harmful fungi has also been disclosed.
It was an object of the present invention to provide mixtures which have an improved activity gainst harmful fungi combined with a reduced total amount of active ingredients applied (syner¬gistic mixtures) with a view to reducing the rates of application and to improving the spectrum of action of the known compounds.
Accordingly, we have found that this object is achieved by the mixture defined at the outset. Moreover, we have found that better control of the harmful fungi is possible by applying the compounds I and/or II and the compounds III simultaneously to¬gether or separately or by applying the compounds I and/or II and the compounds III in succession than when the individual com¬pounds are used.
In particular, the general formula I represents oxime ethers in which X is oxygen and Y is CH or X is amino and Y is N.
Moreover, preferred compounds I are those where Z is oxygen.
Equally, preferred compounds I are those where R' is alkyl or benzyl.
Especially preferred with a view to their use in the synergistic mixtures according to the invention are the compounds I compiled in the tables which follow;
Table 1.
Compounds of the formula IA where ZR'#for each compound
corresponds to one line of Table A

Table 2.
Compounds of the formula IB where ZR' for each compound
corresponds to one line of Table A


In relation to the C=Y double bond, the compounds of the for¬mula I can be in the E or the Z configuration (in relation to the carboxylic acid function)* Accordingly, they can be used in the mixture according to the invention in each case either in the form of the pure E or Z isomers or else in the form of an E/Z isomer mixture• The E/Z isomer mixture or the E isomer are pre¬ferably used, the E isomer being especially preferred.
The C=N double bonds of the oxime ether groups in the side chain of the compounds I can be in each case in the form of pure E or z isomers or in the form of E/Z isomer mixtures. The compounds I can be used in the mixtures according to the invention as isomer mixtures Or else as pure isomers. With a view to their use, com¬pounds I which are particularly preferred are those where the terminal oxime ether group of the side chain is in the cis con¬figuration (OCH3 group relative to ZR')»

In particular, the formula II represents carbamates in which the combination of the substituents corresponds to one line of the table which follows:
Table 3;



The compounds 11.12, 11.23, 11.32 and 11.38 are especially pre¬ferred.
Due to the basic character of the nitro groups, the compounds I and II are capable of forming adducts or salts with inorganic or organic acids or with metal ions.
Examples of inorganic acids are hydrohalic acids such as hydro¬fluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid, sulfuric acid, phosphoric acid and nitric acid.
Suitable organic acids are, for example, formic acid, carbonic acid and alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids having straight-chain or branched alkyl radicals having from 1 to 20 carbon atoms), arylsulfonic acids or -disul-fonic acids (aromatic radicals such as phenyl and naphthyl which have attached to them one or two sulfo groups), alkylphosphonic acids (phosphonic acids having straight-chain or branched alkyl radicals of from 1 to 20 carbon atoms), arylphosphonic acids or -diphosphonic acids (aromatic radicals such as phenyl and naphthyl which have attached to them one or two phosphoric acid

radicals), it being possible for the alkyl or aryl radicals to have attached to them further substituents, eg. p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid etc.
Suitable metal ions are, in particular, the ions of the elements of the second main group, in particular calcium and magnesium, and of the third and fourth main group, in particular aluminum, tin and lead, and of the first to eighth sub—group, in particular chromium, manganese, iron, cobalt, nickel, copper, zinc and others. Especially preferred are the metal ions of the elements of the sub-groups of the fourth period* The metals can in this case be in the various valences which they can assume.
When preparing the mixtures, it is preferred to employ the pure active ingredients I and/or II and III, with which further active ingredients against harmful fungi or other pests such as insects, arachnids or nematodes, or else herbicidal or growth-regulating active ingredients or fertilizers can be admixed, if so desired.
The mixtures of the compounds I and/or II and III, or the simul¬taneous joint or separate use of the compounds I and/or II and III, are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomy-cetes. Some of them act systemically and can therefore be employed as foliar— and soil—acting fungicides.
They are especially important for controlling a large number of fungi in a variety of crop plants such as cotton, vegetable species (eg. cucumbers, beans and curcubits), barley, grass, oats, coffee, maize, fruit species, rice, rye, soybeans, grape¬vine, wheat, ornamentals, sugar cane, and a variety of seeds.
They are particularly suitable for controlling the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) on ce¬reals, Erysiphe cichoracearum and Sphaerotheca fuliginea on curcubits, Podosphaera leucotricha on apples, Uncinula necator on grapevines, Puccinia species on cereals, Rhizoctonia species on
i cotton, rice and lawn, Ustilago species on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helminthosporium species on cereals, Rhynchosporium secalis, Septoria nodorum on wheat, Botrytis cinerea (gray mold) on strawberries, vegetables, ornamentals and grapevines, Cercospora arachidicola on peanuts,
> Pseudocercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on grapevines, Alternaria

species on vegetables and fruit, and Fusarium and Verticillium species*
Furthermore, they can be used in the protection of materials (eg. in the protection of wood), for example against Paecilomyces variotii.
The compounds I and/or II and III can be applied simultaneously together or separately or in succession, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.
The compounds I and/or II and III are normally used in a weight ratio of from 20:1 to 0.1:2, preferably 10:1 to 0.2:1, in partic¬ular 5:1 to 0*5:1.
The application rates of the compounds I in the mixtures accord¬ing to the invention are generally from 0.01 to 0.5 kg/ha, pre¬ferably 0.05 to 0.5 kg/ha, in particular 0.05 to 0.3 kg/ha, de¬pending on the nature of the desired effect.
Correspondingly, in the case of the compounds III, the applica¬tion rates are normally from 0.05 to 1 kg/ha, preferably 0.1 to 1 kg/ha, in particular 0*1 to 0.8 kg/ha.
For seed treatment, the application rates of the mixture are generally from 0.001 to 50 g/kg seed, preferably 0.01 to 10 g/kg, in particular 0.01 to 5 g/kg.
If phytopathogenic harmful fungi are to be controlled, the sepa¬rate or joint application of the compounds I and/or II and III or of the mixtures of the compounds I and/or II and III is effected by spraying or dusting the seeds, the plants or the soils before or after sowing of the plants, or before or after plant emer¬gence .
The fungicidal synergistic mixtures according to the invention, or the compounds I and/or II and III, can be formulated for exam¬ple in the form of ready-to-spray solutions, powders and suspen¬sions or in the form of highly concentrated aqueous, oily or oth¬er suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading or granules, and applied by spray¬ing, atomizing, dusting, spreading or pouring. The use form de¬pends on the intended purpose; in any case, it should guarantee as fine and uniform as possible a distribution of the mixture ac-

The formulations are prepared in a manner known per se, eg. by adding solvents and/or carriers. It is usual to admix inert addi¬tives, such as emulsifiers or dispersants, with the formulations.
Suitable surfactants are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, eg. ligno-, phenol—, naphthalene— and dibutylnaphthalenesulfonic acid, and of fatty acids, of alkyl- and alkylarylsulfonates, of alkyl, lauryl ether and fatty alcohol sulfates, and salts of sul¬fated hexa—, hepta— and octadecanols or fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene, or of the naphtha-lenesulfonic acids, with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctyl—, octyl— or nonylphenol, alkylphenyl polyglycol ethers or tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ Ethylene oxide condensates, ethoxylated castor oil, polyoxy¬ethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquors or methylcellulose.
Powders, materials for spreading and dusts can be prepared by mixing or jointly grinding the compounds I and/or II or III or the mixture of the compounds I and/or II and III with a solid carrier.
Granules (eg. coated granules, impregnated granules or homo¬geneous granules) are normally prepared by binding the active ingredient, or active ingredients, to a solid carrier.
Fillers or solid carriers are, for example, mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, and fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders or other solid carriers.
The formulations generally comprise from 0.1 to 95% by weight, preferably 0.5 to 90% by weight, of one of the compounds I and/or II and III, or of the mixture of the compounds I and/or II and III. The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum or HPLC).

The compounds I and/or II or III, or the mixtures, or the corre¬sponding formulations, are applied by treating the harmful fungi or the plants, seeds, soils, areas, materials or spaces to be kept free from them with a fungicidally active amount of the mix¬ture, or of the compounds I and/or II or III in the case of sepa¬rate application- Application can be effected before or after in¬fection by the harmful fungi.
The fungicidal activity of the compounds and of the mixtures is demonstrated by the following experiments:
The active ingredients, separately or together, are formulated as a 10% emulsion in a mixture of 70% by weight of cyclohexanone, 20% by weight of Nekanil® LN (Lutensol® AP6, wetting agent having emulsifying and dispersing action based on ethoxylated alkylphe-nols) and 10% by weight of Emulphor® EL (Emulan® EL, emulsifier based on ethoxylated fatty alcohols) and diluted with water to give the desired concentration.
Evaluation is carried out by determining the infected leaf areas in percent. These percentages are converted into efficacies. The expected efficacies of the mixtures of the active ingredients are determined using Colby's formula [R.S. Colby, Weeds 15, 20-22 (1967)] and compared with the observed efficacies.
Colby's formula:
E = x + y - X'y/100
E expected efficacy, expressed in % of the untreated control, when using the mixture of the active ingredients A and B at concentrations of a and b
x efficacy, expressed in % of the untreated control, when using active ingredient A at a concentration of a
y efficacy, expressed in % of the untreated control, when using active ingredient B at a concentration of b
The efficacy (H) is calculated as follows using Abbot's formula:
W m (i - ct)»100/p
a is the fungal infection of the treated plants in % and

P is the fungal infection of the untreated (control) plants in %
An efficacy of 0 means that the infection level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants are not infected.
Examples 1-7
Activity against mildew of wheat
Leaves of wheat seedlings cv. "Friihgold" in pots were sprayed to run~off with an aqueous preparation of active ingredient made with a stock solution composed of 10% of active ingredient, 63% of cyclohexanone and 27% of emulsifier and, 24 hours after the spray coating had dried on, dusted with spores of mildew of wheat (Erysiphe graminis forma specialis tritici). The test plants were subsequently placed in a greenhouse at from 20 to 22°C and a rela¬tive atmospheric humidity of 75 to 80%. After 7 days, the extent of mildew development was determined visually in % disease of the entire leaf area.
The visually determined values for the percentage of diseased leaf area were converted into efficacies as % of the untreated control. An efficacy of 0 is the same disease level as in the untreated control, an efficacy of 100 is a disease level of 0%. The expected efficacies for combinations of active ingredients were calculated using Colby's formula (Colby, S.R. (Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, 15, p. 20 - 22, 1967) and compared with the observed efficacies.
Table 4:



Examples 8-17
Activity against Puccinia recondita on wheat (leaf rust of wheat)
Leaves of wheat seedlings cv. "Frtthgold" in pots were dusted with leaf rust spores (Puccinia recondita). The plants were then pla¬ced for 24 hours into a chamber of high atmospheric humidity (90 to 95 %) and 20 to 22°C. During this time, the spores germinated, and the germination tubes penetrated the plant tissue. The next day, the inoculated plants were sprayed to run-off with an aqueous preparation of active ingredient made with a stock solu¬tion consisting of 10% of the active ingredient, 63% of cyclohe-xanone and 27% of emulsifier. After the spray coating had dried on, the test plants were grown in the greenhouse for 7 days at from 20 to 22°C and a relative atmospheric humidity of 65 to 70%. The extent of rust development on the leaves was then determined.
The visually determined values for the percentage of diseased leaf area were converted into efficacies as % of the untreated control. An efficacy of 0 is the same disease level as in the untreated control, an efficacy of 100 is a disease level of 0%, The expected efficacies for combinations of active ingredients were calculated using Colby's formula (Colby, 5.R. (Calculating synergistic and antagonistic responses of herbicide

combinations", Weeds, 15, p. 20 - 22, 1967) and compared with the observed efficacies.
Table 6:

* calculated using Colby's formula
Examples 18-28
Activity against mildew of wheat
Leaves of wheat seedlings cv. "Fruhgold" in pots were sprayed to run-off with an aqueous preparation of active ingredient made with a stock solution composed of 10% of active ingredient, 63% of cyclohexanone and 27% of emulsifier and, 24 hours after the





* calculated using Colby's formula Examples 29-39
Activity against Puccinia recondita on wheat (leaf rust of wheat)
Leaves of wheat seedlings cv. "Friihgold" in pots were dusted with leaf rust spores (Puccinia recondita). The plants were then pla¬ced for 24 hours into a chamber of high atmospheric humdity (90 to 95 %) and 20 to 22°C. During this time, the spores germinated, and the germination tubes penetrated the plant tissue. The next day, the inoculated plants were sprayed to run-off with an 'aqueous preparation of active ingredient made with a stock solu¬tion consisting of 10% of the active ingredient, 63% of cyclohe-xanone and 27% of emulsifier. After the spray coating had dried on, the test plants were grown in the greenhouse for 7 days at from 20 to 22°C and a relative atmospheric humidity of 65 to 70%. The extent of rust development on the leaves was then determined.
The visually determined values for the percentage of diseased leaf area were converted into efficacies as % of the untreated control. An efficacy of 0 is the same disease level as in the untreated control, an efficacy of 100 is a disease level of 0%. The expected efficacies for combinations of active ingredients were calculated using Colby's formula (Colby, S.R. (Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, 15, p. 20 - 22, 1967) and compared with the observed efficacies.








We claim:
1. A fungicidal mixture comprising
a) an oxime ether of the formula I

where the substituents have the following meanings:
X is oxygen or amino (NH);
Y is CH or N;
Z is oxygen, sulfur, amino (NH) or C1-C4—alkylamino (N-Cx-C4-alkyl);
R' is Ci-C6-alkyl, Ci-C6-haloalkyl, C3-C6-alkenyl,
C2-C6-haloalkenyl, C3-C6-alkynyl, C3-C6-haloalkynyl, C3-C6-cycloalkylmethyl/ or is benzyl which can be partially or fully halogenated and/or can have attached to it one to three of the following radicals: cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and Ci-C4—alkylthio and/or
b) a carbamate of the formula II

where T is CH or N, n is 0, 1 or 2 and R is halogen, Ci-C4-al-kyl or C1-C4-haloalkyl/ it being possible for the radicals R to be different if n is 2,
and

c) a morpholine or piperidine derivative III selected from the group of the compounds Ilia, Illb and IIIc

in a synergistically active amount.
i"
2. A fungicidal mixture as claimed in claim 1 comprising an ox-ime ether of the formula I and/or a carbamate of the formula II as set forth in claim 1 and the morpholine derivative Ilia.
3. A fungicidal mixture as claimed in claim 1 comprising an ox-ime ether of the formula I and/or a carbamate of the formula II as set forth in claim 1 and the piperidine derivative Illb,
4* A fungicidal mixture as claimed in claim 1 comprising an ox-ime ether of the formula I and/or a carbamate of the formula II as set forth in claim 1 and the morpholine derivative IIIc,

5* A fungicidal mixture as claimed in claim 1 wherein the weight ratio of the compound I and/or II to the compound III is 20:1 to 0.1:2,
6* A method of controlling harmful fungi, which comprises treat¬ing the harmful fungi, their environment, or the plants, seeds, soils, areas, materials or spaces to be kept free from them with a compound of the formula I and/or a compound of the formula II as set forth in claim 1 and a compound of the formula III as set forth in claim 1.
7. A method as claimed in claim 6, wherein a compound I and/or a
compound of the formula II as set forth in claim 1 and a com¬
pound III as set forth in claim 1 are applied simultaneously
together or separately or in succession.
8. A method as claimed in claim 6, wherein the harmful fungi,
their environment, or the plants, seeds, soils, areas,
materials or spaces to be kept free from them are treated
with from 0.01 to 0.5 kg/ha of a compound I and/or a compound
of the formula II as set forth in claim 1.
9. A method as claimed in claim 6, wherein the harmful fungi,
their environment, or the plants, seeds, soils, areas,
materials or spaces to be kept free from them are treated
with from 0*05 to 1 kg/ha of a compound III as set forth in
claim 1.
10, A fungicidal mixture, substantially as herein
described, and exempti fied.
11. A method for control 1ing harmful fungi, substantially
as herein described, and exemplified.


Documents:

819-mas-1997 others-1.pdf

819-mas-1997 petition.pdf

819-mas-1997-abstract.pdf

819-mas-1997-claims filed.pdf

819-mas-1997-claims granted.pdf

819-mas-1997-correspondnece-others.pdf

819-mas-1997-correspondnece-po.pdf

819-mas-1997-description(complete)filed.pdf

819-mas-1997-description(complete)granted.pdf

819-mas-1997-form 1.pdf

819-mas-1997-form 19.pdf

819-mas-1997-form 26.pdf

819-mas-1997-form 3.pdf

819-mas-1997-form 4.pdf

819-mas-1997-form 5.pdf

819-mas-1997-other documents.pdf

abs-819-mas-1997.jpg


Patent Number 211761
Indian Patent Application Number 819/MAS/1997
PG Journal Number 52/2007
Publication Date 28-Dec-2007
Grant Date 09-Nov-2007
Date of Filing 22-Apr-1997
Name of Patentee M/S. BASF AKTIENGESELLSCHAFT
Applicant Address 67056 LUDWIGSHAFEN,
Inventors:
# Inventor's Name Inventor's Address
1 RUTH MULLER., ET. AL., VON-WIESER-STR. 1, 67159 FRIEDELSHEIM,
PCT International Classification Number A01N 37/52
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 196 16 724.8 1996-04-26 Germany
2 196 17 232.2 1996-04-30 Germany
3 196 35 511.7 1996-09-02 Germany