AMINOINDANES AMIDES HAVING A HIGH FUNGICIDAL ACTIVITY AND THEIR PHYTOSANITARY COMPOSITIONS

Abstract

New aminoindanes amides are described, having general formula (I)

##STR00001##

the relative phytosanitary compositions and their use for the control of phytopathogenic fungi.

Claims

1-15. (canceled)

16. A fungicidal composition comprising: (i) one or more aminoindane amides having structural formula (I) ##STR00006## wherein: R.sub.1, R.sub.2 and R.sub.4, equal to or different from each other, represent a C.sub.1-C.sub.3 alkyl group, a C.sub.1-C.sub.3 haloalkyl group, a C.sub.3-C.sub.6 cycloalkyl group, a C.sub.3-C.sub.6 halocycloalkyl group, the groups R.sub.1 and R.sub.2 can possibly also be joined to form a C.sub.3-C.sub.6 cycloalkyl group spiro-condensed with indanyl; R.sub.3 represents a hydrogen atom, a C.sub.1-C.sub.3 alkyl group, a C.sub.1-C.sub.3 haloalkyl group, a C.sub.3-C.sub.6 cycloalkyl group, a C.sub.3-C.sub.6 halocycloalkyl group; R.sub.5 represents a halogen atom, a C.sub.1-C.sub.4 alkyl group, a C.sub.1-C.sub.4 haloalkyl group, a C.sub.1-C.sub.4 alkoxy group, a C.sub.1-C.sub.4 haloalkoxy group, an SH group, a C.sub.1-C.sub.4 alkylthio group, a C.sub.1-C.sub.4 haloalkylthio group; n represents an integer ranging from 1 to 3; A represents the following heterocycle A.sub.1 ##STR00007## R.sub.6 is a C.sub.1-C.sub.3 alkyl group, a C.sub.1-C.sub.3 haloalkyl group, a C.sub.3-C.sub.6 cycloalkyl group, a C.sub.3-C.sub.6 halocycloalkyl group, a C.sub.1-C.sub.4 alkoxy group, a C.sub.1-C.sub.4 haloalkoxy group, an SH group, a C.sub.1-C.sub.4 alkylthio group, a C.sub.1-C.sub.4 haloalkylthio group; (ii) at least one from: a solvent, a solid support or a liquid diluent.

17. The fungicidal composition according to claim 16 further comprising a surfactant.

18. The fungicidal composition according to claim 16, characterized in that it is in a form selected from: dry powders, wettable powders, emulsifiable concentrate, emulsion, micro-emulsion, paste, granulate, water dispersible granules, solution, or suspension.

19. The fungicidal composition according to claim 16, wherein the solid support is selected from: silica, kaolin, bentonite, talc, diatomaceous earth, dolomite, calcium carbonate, magnesia, gypsum, clays, synthetic silicates, attapulgite, sepiolite and mixture thereof.

20. The fungicidal composition according to claim 16, wherein the solvent or liquid diluent is selected from: water, aromatic organic solvents, paraffins, alcohols, esters, vegetable oils, ketones, amides, sulfoxides, sulfones and mixtures thereof.

21. The fungicidal composition according to claim 16, wherein the surfactant is selected from: sodium salts, calcium salts, potassium salts, salts of triethylamine or triethanolamine of alkyl-naphthalenesulfonates, polynaphthalenesulfonates, alkyl sulfonates, aryl sulfonates, alkylaryl sulfonates, polycarboxylates, sulfosuccinates, alkyl sulfo-succinates, lignin sulfonates, alkyl sulfates, polyethoxylated fatty alcohols, polyethoxylated alkylphenols, polyethoxylated esters of sorbitol, polypropoxy polyethoxylates and mixtures thereof.

22. The fungicidal composition according to claim 16 further comprising at least one additive selected from: antifreeze agents, adhesion agents and mixture thereof.

23. The fungicidal compositions according to claim 16 further comprising one or more active principles compatible with the aminoindane amides having structural formula (I), selected from: fungicides different from the compounds having structural formula (I), phytoregulators, antibiotics, herbicides, insecticides, fertilizers or mixtures thereof.

24. The fungicidal composition according to claim 16, wherein the concentration of the aminoindane amides having structural formula (I) ranges from 1 to 90% by weight with respect to the total weight of the composition.

25. The fungicidal composition according to claim 24, wherein the concentration of the aminoindane amides having structural formula (I) ranges from 5 to 50% by weight with respect to the total weight of the composition.

26. The fungicidal composition according to claim 16, characterized in that the aminoindane amide having structural formula (I) is in the form of racemic mixtures, diastereoisomeric mixtures, partially separated mixtures, single optical isomers and/or single diastereoisomers.

27. A method of controlling phytopathogenic fungi of agricultural crops comprising applying an effective amount to said agricultural crops of a fungicidal composition according to claim 16.

28. The method of controlling phytopathogenic fungi of agricultural crops according to the preceding claim wherein the fungicidal composition according to claim 16 is applied to said agricultural crops in amounts ranging from 10 g to 5 kg of compound aminoindane amide having structural formula (I) per hectare of agricultural crop.

29. The method of controlling phytopathogenic fungi of agricultural crops comprising applying an effective amount to said agricultural crops of a fungicidal composition according to claim 16 for the control of phytopathogenic fungi belonging to the group of Basidiomycetes, Ascomycetes, Deuteromycetes or fungi imperfecti, Oomycetes: Puccinia spp., Ustilago spp., Tilletia spp., Uromyces spp., Phakopsora spp., Rhizoctonia spp., Erysiphe spp., Sphaerotheca spp., Podosphaera spp., Uncinula spp., Helminthosporium spp., Rhynchosporium spp., Pyrenophora spp., Monilinia spp., Sclerotinia spp., Septoria spp. (Mycosphaerella spp.), Venturia spp., Botrytis spp., Alternaria spp., Fusarium spp., Cercospora spp., Cercosporella herpotrichoides, Colletotrichum spp., Pyricularia oryzae, Sclerotium spp., Phytophtora spp., Pythium spp., Plasmopara viticola, Peronospora spp., Pseudoperonospora cubensis, Bremia lactucae.

30. The method of controlling phytopathogenic fungi of agricultural crops comprising applying an effective amount to said agricultural crops of a fungicidal composition according to claim 16, wherein the agricultural crops are cereals, fruit trees, citrus fruits, legumes, horticultural crops, cucurbits, oleaginous plants, tobacco, coffee, tea, cocoa, sugar beet, sugar cane, cotton.

31. The method of controlling phytopathogenic fungi of agricultural crops comprising applying an effective amount to said agricultural crops of a fungicidal composition according to claim 16 for the control of Plasmopara viticola on vines, Phytophtora infestans and Botrytis Cinerea on tomatoes, Puccinia recondita, Erisiphae graminis, Helminthosporium teres, Septoria nodorum and Fusarium spp. on cereals; Phakopsora pachyrhizi on soya; Uromyces appendiculatus on beans; Venturia inaequalis on apples, Sphaeroteca fuliginea on cucumbers.

32. The method of controlling phytopathogenic fungi of agricultural crops comprising applying an effective amount to said agricultural crops of a fungicidal composition according to claim 16 for the control of phytopathogenic bacteria or viruses.

Description

EXAMPLE 1

Preparation of 3-difluoromethyl-N-(7-fluoro-1,1,3-trimethyl-4-indanyl)-1-methyl-4-pyrazolecarboxamide (Compound N. 1)

[0075] 0.4 ml of triethylamine were dropped into a solution of 7-fluoro-1,1,3-trimethyl-4-aminoindane (0.45 g) and 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonyl chloride (0.44 g) in 8 ml of dichloromethane.

[0076] After being kept under stirring for 8 hours at room temperature, diluted hydrochloric acid was added to the reaction mixture, the phases were separated and the aqueous phase was extracted with dichloromethane.

[0077] The organic phases were then joined, anhydrified with sodium sulfate and concentrated at reduced pressure.

[0078] The raw product obtained was subsequently purified on a silica gel column (eluent hexane/ethyl acetate 8/2) to give 0.45 g of the desired product, a white solid with a melting point of 147° C.

[0079] .sup.1H NMR (200 Mhz, CDCl.sub.3) δ a: 1.43 (3H, d), 1.38 (3H, s), 1.44 (3H, s), 1.66 (1H, dd), 2.21 (1H, dd), 3.38 (1H m), 3.98 (3H, s), 6.81 (1H, bs), 6.95 (1H, t), 6.70 (1H, m), 7.81 (1H, bs), 8.03 (1H, bs).

EXAMPLE 2

Preparation of compounds N.2-9

[0080] Analogously to the procedure of Example 1, the compounds of general formula (I) reported in Table 1 have been prepared.

##STR00005##

TABLE-US-00001 TABLE 1 Compound No A R.sub.1 R.sub.2 R.sub.3 R.sub.4 R.sub.5 2 3-difluoromethyl-1-methyl-4- Et Et H Me 7-F pyrazolyl 3 3-difluoromethyl-1-methyl-4- Me Me H Me 7-OMe pyrazolyl 4 4-difluoromethyl-2-methyl-5- Me Me H Me 7-F thiazolyl 5 3-difluoromethyl-1-methyl-4- Me Me H Me 7-Me pyrazolyl 6 3-difluoromethyl-1-methyl-4- Me Me H Me 7-Cl pyrazolyl 7 3-difluoromethyl-1-methyl-4- Me Me H Me 7-OCF.sub.3 pyrazolyl 8 3-difluoromethyl-1-methyl-4- Me Me H Me 7-SMe pyrazolyl

Melting Points:

[0081] N.sup.o 2: 115° C.; N.sup.o 3: 110° C.; N.sup.o 4: 95° C.; N.sup.o 6: 140° C.; N.sup.o 7: 105° C.; N.sup.o 8: 97° C.

EXAMPLE 3

[0082] Determination of the Fungicidal Activity in Preventive Application (5 Days) Against Erysiphe graminis on Wheat.

[0083] Leaves of wheat plants of the Salgemma variety, grown in pots in a conditioned environment kept at 20° C. and 70% of relative humidity (R.H.), were treated by spraying on both sides of the leaves with the compounds under examination, dispersed in hydroacetonic solutions at 20% by volume of acetone.

[0084] After remaining 5 days in a conditioned environment, the plants were infected under dry conditions by shaking over them, in order to distribute the inoculum, plants previously infected by Erysiphe graminis.

[0085] The plants were then maintained in the same cell, in a humidity-saturated environment and at a temperature ranging from 18 to 24° C. for 12 days.

[0086] At the end of this period, the external symptoms of the pathogen appeared and it was therefore possible to proceed with the evaluation of the intensity of the infection, on both the parts treated directly with the products (T), and also on the parts which had developed during the test (NT), by means of a visible percentage evaluation scale of the area of affected leafs; the scale comprises, as extremes, the value 100 (healthy plant) and the value 0 (completely infected plant).

[0087] At the same time, the phytotoxicity was evaluated (percentage of leaf necrosis) induced on the wheat plants by the application of the products: in this case, the evaluation scale varies from 0 (completely healthy plant) to 100 (completely necrotized plant).

[0088] Table 2 shows the results obtained by carrying out the test described with compound N. 1, compared with the following reference products described in prior art: [0089] RC1: 3-difluoromethyl-1-methyl-N-(1,1,3-trimethyl-4-indanyl)-4-pyrazolecarboxamide of U.S. Pat. No. 5,093,347; [0090] RC2: 1,5-dimethyl-3-trifluoro-methyl-N-(1,1-dimethyl-7-fluoro-4-indanyl)-4-pyrazolecarboxamide [EP199822, page 15, lines 19-20]; [0091] RC3: 1,3,5-trimethyl-N-(1,1-dimethyl-5-fluoro-4-indanyl)-4-pyrazolecarboxamide [EP199822, compound (4)].

TABLE-US-00002 TABLE 2 Preventive fungicidal activity (5 days) against Erysiphe graminis on wheat. Dose Activity Compound (ppm) T/NT Phytotoxicity N. 1 125 95/90 0 CR-1 125 70/65 10 CR-2 125 25/15 0 CR-3 125 10/0  0