GB2216798A

GB2216798A - Fungicidal compositions containing tetrachloroisophthalonitrile and an N-phenyl-carboxamide

Info

Publication number: GB2216798A
Application number: GB8905713A
Authority: GB
Inventors: Kazuhiro Kojima; Kenji Morioka; Matsutaro Yamaguchi; Mamoru Yoshida
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1988-03-16
Filing date: 1989-03-13
Publication date: 1989-10-18
Anticipated expiration: 2009-03-13
Also published as: KR890013986A; DE3908460C2; PH26831A; IT1232821B; FR2628604A1; GB8905713D0; NL194985C; FR2628604B1; IT8947739A0; GB2216798B; DE3908460A1; NL194985B; NL8900641A; JPH01238504A; JP2568099B2; KR920002221B1; ES2013120A6

Description

21 - 4 116798 Case 130-4037 IMPROVEMENTS IN OR RELATING TO ORGANIC

COMPOUNDS This invention relates to a fungicidal composition and more particularly to an agricultural and horticultural fungicidal composition with improved plant disease controlling effect on plants.

Fungicidal compositions containing tetrachloroisophthalonitrile (hereinafter called 11TPN11) as an active ingredient are known. They are i.a. used for preventing and controlling fungal diseases of fruitbearing trees and vegetables, and in general are applied as a foliar spray or by admixture.

Compounds of the formula [I] 0 CH 3 X 2 Il - R-C-N [il 1 ïj H_ 3 1 wherein R is methoxymethyl, benzyl, chloromethyl, 2-tetrahydrofuryl or 2- furyl, is 2-oxo-1,3-oxazolidin-3-yl, 1-(methoxycarbonyl)ethyl, 2-oxothiolan-3-yl or tetrahydro-2-oxo-3-furanyl, X, is H or Cl and X2 is H or Cl, are known to have an excellent preventive, curative systemic fungicidal effect particularly in controlling downy mildew and epidemic diseases, which bring serious damages upon fruit-bearing trees and vegetables.

Various mixtures of TPN or of a compound of formula [I] with other fungicides have been suggested and used to extend the spectrum of activity, to enhance the activity or to improve the fungicidal effect against resistant strains.

130-4037 While the use of a mixture composed of TPN and 2-methoxy-N-(2-oxo-1, 3oxazolidine-3-yl)-aceto-21,61-xylidine (common name: oxadixyl) is reported in Trans. Br. Mycol. Soc. 85, 299-306 (1985), this reference does not suggest that a mixture of TPN and oxadixyl shows a more than additive (i.e. synergistic) fungicidal effect. Furthermore, the TPN used in the cited case is employed as wettable powder, and the only example cited of the mixture ratio for oxadixyl and TPN is 1:3.

The present invention provides a flowable formulation (i.e. an aqueous suspension concentrate) containing a phenylamide compound of formula I and TPN in the weight ratio range of from 1:2 to 1:15, and a surfactant wherein the solid components have a particle size in the range of from 0. 5 to 5.0 pm (micron) at the 50% volume accumulation point. The latter volume medium diameter is hereinafter designated VMD.

It has been found that the formulations of the invention have a fungicidal effect which is substantially superior over the additive effect that would be expected by admixture of the active Ingredients.

The synergistic effect is especially pronounced with formulations comprising a compound of formula I wherein R is methoxymethyl, benzyl, chloromethyl or 2-furyl, Z is 2-oxo-1,3-oxazolidin-3-yl, 1-(methoxylcarbonyl)ethyl or tetrahydro-2-oxo-3-furanyl, X, is H or Cl, and X2 is E (hereinafter compounds of formula [Iaj- Preferred compounds of formula I for use in the formulation of the invention include the compound of formula [Ial wherein a) R is methoxymethyl, Z is 1-(methoxycarbonyl)ethyl and X, is H (metalaxyl) i i i i i 1 i j i 130-4037 b) R is methoxymethyl, Z is 2-oxo-1,3-oxazolidin-3-yl and X, is H (oxadixyl) c) R is benzyl, Z is 1-(methoxycarbonyl)ethyl and X, is H (benalaxyl) d) R is chloromethyl, Z is tetrahydro2-oxo-3-furanyl and X, is H (ofurace) e) R is 2-furyl, Z is 1-(methoxycarbonyl)ethyl and X, is H (furalaxyl) and f) R is methoxymethyl, Z is 2-oxo-1,3-oxazolidin-3-yl and X, is Cl.

Most preferred compounds of formula I for use of the invention are metalaxyl and oxadixyl.

There is no particular restriction to the process for producing the fungicidal composition proposed in this invention. The composition of the invention can be produced in conventional manner, e.g. by a process comprising the steps of mixing the components and grinding its solid particles in an appropriate mill to the desired particle size.

Examples of mills suitable for use in the process of the invention include ball mills, impact-type crushers, air mills, wet-type mills, and so forth.

1 r".) The VMD has been measured with the Coulter Counter(" model TA-II (by Kabushiki Kaisha Nikkaki). Preferably, the VMD should be within the range of from 0.8 pm to 2.5 pm, and it is more preferable to keep the VMD in the range from 0.8 pm to 1.8 p and particularly in the range of from 0.5 to 1.5 pm.

While the contents of TPN and the phenylamide compound of formula I in the composition of this invention are not particularly limited, the composition should desirably comprise from 1% to 98% by weight more preferably of from 1% to 70% by weight of active ingredients. The weight ratios of TPN and the phenylamide compound of formula I should 130-4037 preferably be in the range of from 1:3 to 1:13, more preferably in the range from 1:4 to 1:12, particularly in the range of from 1:4 to 1:11 e.g. in the range of from 1:5 to 1:11. Though the amount of surfactant to be applied is not critical, preferred formulations will comprise from 1 to 10% weight by weight and more preferably from 2 to 5% weight by weight of surfactant. Examples of suitable surfactants are any agrculturally acceptable surfactant appropriate for use in a flowable, in particular liquid surfactants such as Nonypole 100 and Demole N.

In addition to the active ingredients, surfactant(s) and diluent (water), the formulation may contain other components such as for example agriculturally acceptable thickening agents.

Typical examples of such formulations comprise e.g. from 0.1 to 1% by weight of thickening agent.

Although there is not necessarily any restriction to the sprayed amount of the chemical, it is usually appropriate to use it approximately in the amount of 1-500 g110 ares (hereinafter designated 'tall) as active ingredient compound (A.I.) for its spraying application over a farm field where crops are grown and approximately in the amount of 0.1-5.0 kg (A.I.)/10a. in case it is used in the soil.

Of course, these are general standards, which are to be subject to adjustment as necessary in consideration of the varieties of crops, the types of diseases, and the degrees of damages, the period or the season, the weather, the forms of the chemical formulation, and so forth.

Next, the reference formulations and forms of manufactured formulations in embodiment of the composition proposed in this invention are described below, but it goes without saying that the forms of such formulations are not limited to these.

1 1 Q 130-4037 Example 1

Metalaxyl suspension concentrate having the following composition was prepared by mixing, followed by milling with the wet-type mill (Eiger motormill made by Eiger Engineering Limited), in order to make particle size 1.5 jim in VMD while controlling the total amount of milling time:

Metalaxyl 25 parts Nonypole 100 1 part (supplied by Sanyo Kasei Kogyo Co. Lt.) Demole N 2 parts (supplied by Kao Co. Ltd.) Water 72 parts Example 2 Oxadixyl suspension concentrate having the following composition was also prepared similar to the above (particle size is 1.5 pm in VMD):

Oxadixyl 25 parts Nonypole 100 1 part Demole N 2 parts Water 72 parts Example 3-6 (Reference Example) TPN suspension concentrate was prepared by uniformly mixing the following ingredients and milled with the wet-type mill in order to make particle of various size in VMD while controlling the total amount of milling time:

TPN 50 parts Nonypole 100 1.5 parts Demole N 3 parts 45.5 parts Water In Reference Examples 3-6, particle size in VMD are as follows:

Example 3 0.5 pm Example 4

Example 5

Example 6

1. 0 Jim 1. 5 jim 5. 0 pm 130-4037 Example 7

TPN with Oxadixyl suspension concentrate having the following composition was prepared according to the same procedure as used in Example 1 (particle size is 1.0 pm in VMD):

TPN 32.0 parts Oxadixyl 6.4 parts Nonypole 100 1.5 parts Demole N 3 parts Water 57.1 parts Example 8 TPN with Methalaxyl suspension concentrate having the following composition was prepared according to the same procedure as used in Example 1 (particle size is 1.5 pm in VMD):

TPN 20 parts Methalaxyl 2 parts Nonypole 100 1 part Demole N 2 parts Water 75 parts Example 9 TPN with Oxadixyl suspension concentrate having the following composition was prepared according to the same procedure as used in Example 1 (particle size is 0.5 pm in VMD):

TPN 42 parts Oxadixyl Nonypole 100 Demole N Water 6 parts 1.5 parts 3 parts 47.5 parts (3) Effect of the Invention 130-4037 The composition revealed by this invention is effective for controlling a wide variety of diseases of various agricultural and horticultural crops. Examples of such diseases are as follows:

Rice: Blast, Helminthosporium leaf spot, Sheath blight, "Bakanae" disease, Seedling blight Wheat: Leaf rust., Stripe rust, Loose smut, Speckled leaf blotch, Spot blotch, Powdery mildew, Typhula snow blight Potato: Late blight, Early blight, Black scurf Soybean: Downy mildew, Cercospora leaf spot, Septoria brown spot, Sclerotinia rot, Rust, Purple stain Adzukibean: Leaf spot, Rust, Leaf spot, Powdery mildew Peanut: Brown leaf spot, Leaf spot, Sclerotinia rot Tobacco: Brown spot, Black shank, Sclerotinia stem-rot, Sore shin, Damping-off, Bed rot, Frog-eye, Powdery mildew Sugar beet: Downy mildew, Cercospora leaf spot, Damping-off Tomato: Gray mold, Leaf mold, Late blight, Stem rot, Early blight, Cercospora leaf mold, Fusarium wilt, Damping-off Eggplant: Gray mold, Verticillium. wilt, Brown rot, Black rot, Powdery mildew, Leaf mold Ch Cucurbit: Downy mildew, Phytophthora rot, Gray mold, Sclerotinia rot, Scab, Anthracnose, Gummy stem blight, Fusarium wilt, Powdery mildew, Damping-off inese cabbage: Downy mildew, Leaf spot, Sclerotinia rot, Clubroot Onion: Downy mildew, Gray-mold neck rot, Phytophthora rot Lettuce:

Strawberry:

Downy mildew, Gray mold, Leaf spot, Stem rot Gray mold, Powdery mildew, Leaf blight Chrysanthemum: Rust, Powdery mildew Cyclamen: Gray mold Rose:

Citrus:

Blackspot, Powdery mildew Penicillium. rot, Gray mold, Melanose, Scab Apple:

Pear:

Peach:

Grape:

130-4037 Rust, Blight, Silver leaf, Alternaria leaf spot, Scab, Powdery mildew, Blossom blight Rust, Black spot, Scab Brown rot, Scab, Phomopsis rot, Leaf curl Downy mildew, Gray mold, Leaf spot, Anthracnose, Ripe rot, Pestalotia disease, Rust, Dead arm, Powdery mildew i 1 i i 130-4037 Also, the composition revealed by this invention, which is a flowable formulation, makes the following points conceivable.

Since th composition is already dispersed in liquid, it is little liable to cohesion in diluting water, and hence it is possible for the chemical to maintain the optimized particle size as it is.

As it is not necessary to add any solid matter as a diluent, it is possible to avoid the decomposing action by the solid matter.

Owing to these features, the active ingredients can work with remarkable efficiency, achieving an enhanced preventive effect. For its actual application, its excellent dispersion in water enables it to mix well with water, so that it is easy to formule its solution for spraying. As the composition also has excellent suspending feature, the chemical solution can maintain a uniform state of suspension for a long time after its formulation, so that it is possible to spray the solution at the predetermined concentration throughout the duration from the start of spraying to its finish and also that the spraying work will not be hampered with any clogging of the sprayer with the chemical. After the wettable powder formulation is sprayed, there remain some stains (traces of sprayed solution) on the fruits and leaves, but the composition of this invention makes it possible to harvest farm products with an extremely small amount of stain since it does not contain any mineral substance which works as the cause of this stain. Furthermore, this composition, not being powdery, permits its safer application.

Typical test procedure and reults are described below in order specifically to explain the effect of the composition proposed in this invention.

Yet, these are mere examples, and the applications of this invention are, of course, not limited to these alone.

A sample solution diluted to a predetermined concentration (20, 10, 5, 2, 1 and 0.5ppm a.i.) was uniformly sprayed on the leaves of 5-true-leafstage on tomatoes (variety: Redcherry) with an amount of 2001/10a, which were dried in a greenhouse for 2 hours. After air drying, zoospores of Phytophthora infestans were inoculated on the leaves by spraying. The incubation was carried out at a temperature of 21'C and a relative humidity (R.H.) of 100% for 2 days. At 5 days after inoculation, the infected areas of 3, 4, and 5 leaf stage were eveluated, and disease intensity was assessed. The disease control was estimated by the expression:

treated disease intensity untreared disease intensity X 100 EC90 values were calculated. Results of Test Example 1 are shown in Table 1 - Table 7.

Test Example 2 A sample solution diluted to a predetermined concentration (20, 10, 5, 2, 1 and 0.5ppm a.i.) was uniformly sprayed on the leaves of 2-true-leaf- stage on cucumbers (variety: Tokiwahikari 3gou Pgata) with an amount of 2001110a, which were dried in a greenhouse for 2 hours. After air drying, zoosporangia of Pseudoperonospora cubensis were inoculated on the leaves by. spraying. The incubation was carried out at a temperature of 21C and- a relative humidity. (R.H.) of 100% for 2 days. At 5 days after inoculation, the infected areas of 1 and 2 leaf stage were ' evaluated, and disease intensity was assessid. The disease control was estimated by the expression:

treated disease intensity --------------------------------------untreared disease intensity _) X 100 EC90 values were calculated. Results of Test Example 2 are shown in Table 1 and Table 8 - Table 13.

Test Example 3 By the same test method of Test Example 1, a sample solution was uniformly sprayed on the leaves of tomatoes, which were dried in a greenhouse for 24 hours. After air drying, the test plants was treated with artificial rain stress of 40mI for 1 hour. At 3 hours after artificial rain stress, zoospores of Phytophthora infestans were inoculated on the leaves. The incubation and evaluation were carried out as mentioned above.

Results of Test Example 3 are shown in Table14 - Table 20.

EC90(th) = --------- SF=EC90(th)/EC90(ob) 1 i X + Y X EC(a)90 ECM90 130-4037 Table 1. Fungicidal activity (EC90) against late blight (Phytophthora infestans) and downy mildew (Pseudoperonospora cubensis) No.

1 2 3 4 5 6 7 8 EC90 (ppm a.i.) Formulation Particle Size Late blight Downy (pm) mildew Metalaxyl 25w/w%FL 1.5 3.8 3.3 Oxadixyl 25w/w%FL 1.5 11.4 10.7 Chlorothalonil 5Ow/w%FL 0.5 19.9 17.4 Chlorothalonil 5Ow/w%FL 1.0 8.4 8.9 Chlorothalonil 5Ow/w%FL 1.5 9.9 10.2 Chlorothalonil 5Ow/w%FL 5.0 17.2 17.1 Oxadixyl 6.4w/w%FL 1.0 2.8 2.9 Chlorothalonil 32.Ow/w%FL Chlorothalonil 75w/w%WP 20.5 21.3 130-4037 Table 2. Theoretical EC90 for various mixture of TPN and Metalaxyl against late blight in tomato (ppm a.i.) 5.0 pm lungicides TPN FL 1 i 0.5 Pm 1.0 Pm 1.5 Pm Ratios 1 6.4 5.2 5.5 2 8.3 6.0 6.5 3 9.7 6.5 7.0 4 10.8 6.8 7.5 11.7 7.0 7.8 6 12.4 7.2 8.1 7 13.0 7.3 8.3 8 13.5 7.4 8.4 9 14.0 7.5 8.5 14.4 7.6 8.6 il 14.7 7.6 8.7 12 15.0 7.7 8.8 13 15.3 7.7 8.9 14 15.5 1 7.8 1 8.9 15.7 1 7.8 1 9.

TPN WP 6.2 7.9 9.1 10.1 10.8 11.4 11.9 12.4 12.7 13.0 13.3 13.5 13.7 13.9 14.1 9.8 130-4037 Table 3. Fungicidal activity for various mixture of TPN and Metalaxyl against late blight in tomato (observed EC90) (ppm a.i.) , \ Fungicides TPN FL 0.5 pm 1.0 pm 1.5 pm Ratios 1 3.6 2.9 3.0 2 4.5 2.9 3.1 3 4.9 2.5 2.7 4 5.3 2.5 2.8 5.7 2.5 2.9 6 5.9 2.6 3.0 7 5.9 2.5 3.0 49 8 6.1 2.5 3.0 9 6.4 2.6 3.0 6.9 2.7 3.2 11 6.9 2.7 3.2 12 7.2 2.8 3.2 13 7.2 2.8 3.3 14 7.9 3.3 4.1 8.6 4.1 4.5 TPN WP 5.0 pm 3.6 4.0 - 9.4 4.3 4.5 4.5 48 5.0 5.1 5.6 5.7 5.9 6.4 6.9 7.3 1 130-4037- Table 4. Synergism factor (SF) for various mixture of TPN and Metalaxyl against late blight in tomato ungicides TPN FL TPN WP t i 0.5 pm 1.0 11m 1.5 11m 5.0 pm Ratios 1 1.8 1.8 1.8 1.7 2 1.8 2.1 2.1 2.0 - 3 2.0 2.6 2.6 2.1 1.0 4 2.0 2.7 2.7 2.3 - 2.0 2.8 2.7 2.4 6 2.1 2.8 2.7 2.4 - 7 2.2 2.9 2.8 2.4 - 8 2.2 3.0 2.8 2,5 - 9 2.2 2.9 2.8 2.5 - 2.1 2.8 2.7 2.3 - 11 2.1 2.8 2.7 2.3 - 12 2.1 2.8 2.8 2.3 13 2.1 2.8 2.7 2.1 14 2.0 2.4 2.2 2.0 1 1.81 1.9 2.0 1.9 1 130-4037 Table 5. Theoretical EC90 for various mixture of TPN and Oxadixyl against late blight in tomato (ppm a.i.) XLungicides TPN FL ti. 0.5 pm 1.0 Jim 1.5 pm atios 1 14.5 9.7 10.6 2 16.0 9.2 10.4 3 16.8 9.0 10.2 4 17.3 8.9 10.2 17.8 8.8 10.1 6 18.0 8.7 10.1 7 18.2 8.7 10.1 8 18.4 8.7 10.1 9 18.5 8.6 10.0 18.6 8.6 10.0 11 18.7 8.6 10.0 12 18.8 8.6 10.0 13 18.9 8.6 10.0 14 19.0 8.6 10.0 19.0 8.5 10.0 5.0 pm 13.7 14.7 15.3 15.6 15.9 16.0 16.2 16.3 16.4 16.4 16.5 16.6 16.6 16.6 16.7 TPN WP 130-4037 Table6. Fungicidal activity for various mixture of TPN and Oxadixyl against late blight in tomato (observed EC90) Fungicides TPN FL 0.5 pm 1.0 Jim 1.5 jim RI atios 1 6.7 4.4 5.2 2 6.7 3.6 4.3 3 6.9 3.2 3.6 4 6.8 2.9 3.4 6.9 2.8 3.3 6 7.0 2.7 3.3 7 6.8 2.6 3.2 8 6.9 2.6 3.2 9 6.9 2.6 3.2 7.0 2.6 3.2 11 7.0 2.6 3.2 12 7.1 2.7 3.2 13 7.3 2.8 3.2 14 7.9 3.4 3.7 8.1 3.8 4.0 5.0 11M 1 (ppm a.i.) TPN WP 7.1 7.1 6.6 6.5 6.6 6.6 6.4 6.5 6.5 6.8 12.8 6.8 6.8 7.0 7.6 8.0 130-4037 Table 7. Synergism factor (SF) for various mixture of TPN and Oxadixyl against late blight in tomato , \ "\cides Ratios 1: 1 2 3 4 5 TPN FL 0.5 pm 1.0 pm 1.5 pm 2.2 2.2 2.0 2.4 2.6 2.4 2.4 2.8 2.8 2.5 3.1 3.0 2.6 3.1 3.1 2.6 3.2 3.1 2.7 3.4 3.2 2.7 3.4 3.2 2.7 3.3 3.1 2.7 3.3 3.1 2.7 3.3 3.1 2.7 3.2 3.1 2.6 3.1 3.1 2.4 2.6 2.7 2.4 2.2 2.5 5.0 pm TPN WP 1.9 2.1 2.3 2.4 2.4 6 7 2.4 2.5 8 2.5 2.5 2.4 2.4 2.4 2.4 2.2 9 10 11 12 13 14 15 2.1 1 130-4037 Table 8. Theoretical EC90 for various mixture ofTPN and Metalaxyl against downy mildew in cucumber (ppm a.i.) Tlungicides TPN FL OS Ratios 0.5 11m 1.0 pm 1.5 pm 5.0 pm 1: 1 5.6 4.8 5.0 2 7.2 5.7 6.0 3 8.4 6.3 6.7 4 9.4 6.6 7.2 10.2 6.9 7.6 6 10.8 7.2 7.9 7 11.3 7.3 8.1 8 11.8 7.5 8.3 9 12.2 7.6 8.4 12.5 7.7 8.6 11 12.9 7.8 8.7 12 13.1 7.9 8.8 12.9 13 13.0 7.9 8.9 13.2 14 13.5 8.0 9.0 13.4 13.7 8.1 9.0 13.6 TPNW 5.5 7.1 8.4 9.3 10.1 10.7 11.2 11.7 12.1 12.4 127 130-4037 Table 9. Fungicidal activity for various mixture of TPN and Metalaxyl against downy mildew in cucumber (observed EC90) \ FungicideE TPN FL j.0 Ratios 0.5 pm 1.0 pm 1.5 pm 1 2.9 2.3 2.4 2 3.3 2.3 2.7 3 3.8 2.4 2.8 4 4.0 2.2 2.6 4.4 2.3 2.6 6 4.7 2.4 2.7 7 4.8 2.4 2.8 8 5.0 2.4 2.8 9 5.2 2.5 2.9 5.4 2.6 2.9 11 5.6 2.6 2.9 12 5.6 2.6 3.0 13 5.6 2.9 3.2 14 6.3 3.5 4.1 6.5 4.0 4 5.0 pm (ppm a.i.) TPN WP 2.8 3.3 3.6 3.8 4.1 4.4 4.5 4.7 4.9 5.1 5.2 5.3 5.5 6.4 130-4037 Table 10. Synergism factor (SF) for various mixture of TPN and Metalaxyl against downy mildew in cucumber 5.0 1.1m rungicide.! TPN FL Ratios 0.5 pm 1.0 pm 1.5 pm 1 1.9 2.1 2.1 2 2.2 2.5 2.2 2.2 3 2.2 2.6 2.4 2.3 1.0 4 2.4 3.0 2.8 2.5 - 2.3 3.0 2.9 2.5 6 2.3 3.0 2.9 7 2.4 3.0 2.9 8 2.4 3.1 3.0 9 2.4 3.0 2.9 2.3 3.0 2.9 11 2.3 3.0 3.0 12 2.3 3.0 3.0 13 2.3 2.7 2.8 14 2.1 2.3 2.2 2.1 2.0 2.1 TPNW 2.0 2.4 2.5 2.5 2.5 2.4 2.4 2.4 2.4 2.3 2.1 130-4037 Table 11. Theoretical EC90 for various mixture of TPN and Oxadixyl against downy mildew in cucumber Fungicide., TPN FL Ratios 0.5 11m 1.0 pm 1.5 pm 1 13.3 9.7 10.4 2 14.4 9.4 10.4 3 15.0 9.3 10.3 4 15.5 9.2 10.3 15.8 9.2 10.3 6 16.0 9.1 10.3 7 16.1 9.1 10.3 8 16.3 9.1 10.3 9 16.4 9.1 10.3 16.5 9.0 10.2 11 16.5 9.0 10.2 12 16.6 9.0 10.2 13 16.7 9.0 10.2 14 16.7 9.0 10.2 16.7 9.0 10.2 5.0 pm (ppm a.i.) TPN WP 13.2 14.3 14.9 15.3 15.6 15.8 15.9 16.0 16.1 16.2 16,3 16.4 16.4 16.4 16. 5 130-4037 Table 12. Fungicidal activity for various mixture of TPN and Oxadixyl against downy mildew in cucumber (observed EC90) (ppm a.i.) \Fungicides TPN FL Ratios 0.5 jim. 1.0 pm 1.5 pm.

1 6.4 4.7 5.0 2 6.6 4.0 4.6 3 6.6 3.5 4.0 4 6.3 3.0 3.4 6.4 2.9 3.4 6 6.5 2.9 3.4 7 6.4 2.8 3.3 8 6.4 2.8 3.3 9 6.4 2.8 3.3 6.6. 2.8 3.4 11 6.7 2.8 3.4 12 6.7 2.9 3.4 13 6.8 2.9 3.4 14 7.3 3.0 3.9 7.9 3.5 4.6 T NWP 5.0 JIM 6.1 6.1 6.2 6.1 6.2 6.3 6.2 6.2 6.3 6.4 6.5 6.6 6.7 7.1 7.6 15.0 130-4037 Table 13. Synergism factor (SF) for various miiture of TPN and OxadixYl against downy mildew in cucumber Fungicide TPN FL Ratios 0.5 pm 1.0 pm 1.5 pm 1 2.1 2.1 2.1 2.2 2 2.2 2.4 2.3 2.3 3 2.3 2.7 2.6 2.4 4 2.5 3. 1 3.0 2.5 - 2.5 3.2 3.0 2.5 - 6 2.5 3.1 3.0 2.5 - 7 2.5 3.3 3.1 2.6 - 8 2.5 3.3 3.1 2.6 - 9 2.6 3.3 3.1 2.6 - 2.5 3.2 3.0 2.5 11 2.5 3.2 3.0 2.5 - 12 2.5 3.1 3.0 2,5 13 2,5 3.1 3.0 2.5 14 2.3 3.0 2.6 2.3 2.1 2.6 2.2 5.0 11m TPN WP 1.1 2.2 130-4037 Table 14. Fungicidal activity (EC90) after artificial rain stress against late blight (Phytophtora infestans) (ppm a.i.) No. Formulation Particle Size Late blight (11m.) 1 Metalaxyl 25w/w%FL 1.5 3.8 2 Oxadixyl 25w/w%FL 1.5 12.2 3 Chlorothalonil 5Ow/w%FL 0.5 49.8 4 Chlorothalonil 5Ow/w%FL 1.0 19.3 Chlorothalonil 5Ow/w%FL 1.5 23.4 6 Chlorothalonil 5Ow/w%FL 5.0 51.6 7 Oxadixyl 6.4w/w%FL 1.0 5.3 Chlorothalonil 32.Ow/w%FL 8 Chlorothalonil 75w.w%WP 55.0 z 130-4037 Table 15. Theoretical EC90 for various mixture of TPN and Metalaxyl against late blight in tomato (ppm a.i.) Fungicides Fungicides TPN FL io 0.5 pm 1.0 Jim 1.5 pm Ratios 2 10.1 8.3 8.8 16.8 11.6 12.8 9 22.9 13.8 15.6 12 26.1 14.8 16.9 26.6 28.7 15.5 17.8 TPN WP 5.0 pm 10.2 23.8 17.0 232 29.2 Table 16. Fungicidal activity after artificial rain stress for various mixture of TPN and Metalaxyl against late blight in tomato (observed EC90) (ppm a.i.) "icides ngicides TPN FL Ratios 0.5 pm 1.0 pm 1.5 pm 2 5.2 3.3 3.7 7.6 3,8 4.3 9 10.6 4.5 5.2 12 12.0 4.9 5.9 14.8 5.0 pm TPN WP 5.3 7.5 22.3 10.3 11.8 1 i 1 130-4037 Table 17 Synergism factor (SF) after artificial rain stress for various mixture of TPN and Metalaxyl against late blight in tomato Fungicides TPN FL Rtio 0.5 pm 1.0 pm 1.5 pm atios 1 2 1.9 2.5 2.4 2.2 3.1 3.0 9 2.2 3.1 3.0 12 2.2 3.0 2.9 1.9 2.1 2.1 5.0 p TPN WP 1.9 2.3 2.3 2.3 1.9 i 1 i i i Table 18. Theoretical EC90 for various mixture of TPN and Oxadixyl against late blight in tomato Fungicides TPN FL X t io.

s 0.5 Pm 1.0 Jim 1.5 pm rRatios 1 2 24.6 16.2 17.9 32.9 17.6 20.3 9 38.1 18.2 21.4 12 40.3 18.5 21.9 41.8 18.6 22.1 5.0 pm (ppm a.i.) TPN WP 24.9 33.5 39.0 41.3 43.9 40.7 27- 130-4037 Table 19. Fungicidal activity after artificial rain stress for various mixture of TPN and Oxadixyl against late blight in tomato (observed EC90) \"'icides ungicides TPN FL 0.5 pm 1.0 pm 1.5 pm Ratios 1: 2 11.6 6.3 7.2 12.4 5.3 6.4 9 14.2 5.5 6.8 12 15.1 5.6 6.9 19.0 7.6 9.1 5.0 jim TPN WP 11.9 13.3 15.6 16.3 18.7 f Table 20. Synergism factor (SF) after artificial rain stress for various mixture of TPN and Oxadixyl against late blight in tomato (ppm a.i.) N"ngicides Fungicides Ratios TPN FL 0.5 pm 1.0 pm 1.5 pm 2.1 2.6 2.5 2.1 2.7 3.3 3.2 2.5 - 2.7 3.3 3.2 2.5 1.3 2.7 3.3 3.2 2.5 - 1.9 2.1 2.4 2.3 5.0 pm TPN W-P 1: 2 9 12 15 130-4037 The test results presented hereinabove demonstrate that the composition proposed in this invention presents an excellent fungicidal effect and an ample synergistic effect.

5t

Claims

1. A flowable fungicidal composition ingredients, a) a Compound of the formula [I] 0 CH 3 X 2 a 11 - j R-C-N - H P^ 1 Z H 3 X 1 130-4037 comprising the active [I] wherein R is methoxymethyl, benzyl, chloromethyl, 2-tetrahydrofuryl or 2- furyl, Z is 2-oxo-1,3-oxazolidin-3-yl, 1-(methoxycarbonyl)ethyl, 2-oxo-thiolan-3-yl or tetrahydro-2-oxo-3-furanyl, X, is H or Cl and X2 is H or Cl, and b) tetrachlorisophthalonitrile, and a surfactant in water, wherein the weight ratio of the compound of formula I: tetrachloro- isophthalonitrile is within the range of from 1:2 to 1:15, and wherein the solid components have a particle size in the range of from 0.5 to 5 micron at the 50% volume accumulation point.

2. The composition of Claim 1, wherein the weight ratio of compound of formula I: tetraisophthalonitrile is within the range of from 1:3 to 1:13, more preferably in the range of from 1:4 to 1:12, particularly in the range of from 1:4 to 1:11.

3. The composition of Claim 1, wherein the solid components have a particle size in the range of from 0.8 to 2.5 micron, preferably of from 0.8 to 1.8 micron and particularly of from 0.5 to 1.5 micron at the 50% volume accumulation point.

4. The composition of Claim 2, wherein the solid components have a particle size of from 0.8 to 2.5 micron, preferably of from 0.8 to 1.8 micron and particularly offrom 0.5 to 1.5 micron at the 50% volume accumulation point.

5. The composition of Claims 1 to 4 comprising a compound of formula [I] 1 1 1 130-4037 wherein R is methoxymethyl, benzyl, chloromethyl, 2-tetrahydrofuryl or 2- furyl, Z is 2-oxo-1,3-oxazolidin-3-yl, 1-(methoxycarbonyl)ethyl, 2-oxo-thiolan-3-yl or tetrahydro-2-oxo-3-furanyl, X, is H or Cl and X2 is H.

6. The composition of Claim 5, comprising a compound of formula I wherein a) R is methoxymethyl, Z is 1-(methoxycarbonyl)ethyl and X, is H b) R is methoxymethyl, Z is 2-oxo-1,3-oxazolidin-3-yl and X, is H c) R is benzyl, Z is 1-(methoxycarbonyl)ethyl and X, is H d) R is chloromethyl, Z is tetrahydro-2-oxo-3-furanyl and X, is H e) R is 2-furyl, Z is 1-(methoxycarbonyl)ethyl and X, is H or f) R is methoxymethyl, Z is 2-oxo-1,3-oxazolidin-3-yl and X, is Cl.

7. The composition of Claim 1 comprising from 1 to 98% by weight, preferably from 1% to 70% by weight of active ingredients.

8. The process of preparing a composition of Claim 1, comprising the steps of mixing the components and grinding its solid particles to the desired particle size.

Published 1989 at The Patent Offtoe. State House, 66'71 Righ'HOIbOrl:l, I'Ondon'WUR 4TF- Pku'ther Copies maYbe obtained from The Palent Office, Sales Branch. St M&rY Cr&Y, OrPintgton. Itent BR5 3W. Printed by Multiplex twhnlQues ltd. St M&I7 Cray, Kent, Con. 1/87 1 71