FI63567B - SUBSTITUTES FURAN-2-CARBONSYRA ANILID WITH FUNGICIDIC VERKAN OCH DESS ANVAENDNING - Google Patents

Description

---- ”I Γβ1 .... ANNOUNCEMENT,, c ^ n VÖV [“ 1 ("> UTL * OONINOJSKPUfT 63567 gwLft C Patent granted on 11 07 1933 • S® <45) Patent oeddelat ^ ^ (51) K» .ik.3 / ht.a.3 c 07 D 307/68 FINLAND — FINLAND (21) N ^ wwiM-iwnewift ^ 750920 (22) H «k * ml« ptly »- An * eknlns * 4« «26.03. 75 (Fl) (23) Alkupllvi — GlMghutadag 26.03.75 (41) Tullut lulkMcsI - MMt offmdlf 03.10.75

Date of issue of the patent and of the rakiatarihallitut / 44} Nthtivlkslpanon | - ___

Patant- och ragietarstyralaan '' Amakan utiugd och utUki-Mkun puMtcund 31.03.Ö3 (32) (33) (31) * rr * «* r • tuofk.u * —iuflrd prlorltut 02.0fc. p. 10.02.75 Switzerland-Switzerland (CH) ^ 572/7 ^, 1591/75 (71) Ciba-Geigy AG, CH-U002 Basel, Switzerland-Switzerland (CH) (72) Adolf Hubele, Magden, Switzerland-Switzerland ( This invention relates to the fungicidal activity of fungicidal activity and its use. Substituted furan-2-carboxylic acid anilide having fungicidal activity and its use - Substituted furan-2-carboxylic anilide with fungicidal activity and its use substituted and furan-2-carboxylic acid anilides of the formula -CHo R CH, jL. 1 3 I_1 J ^ CH-C00CH3 CH3 wherein R represents a hydrogen atom or a methyl group The symbol * C represents an asymmetric carbon atom.

Substituted furan-2-carboxylic acid anilides of the formula I are prepared, for example, by acylation in a manner known per se of a compound of the formula 2,63567 R au J-1 CH3 NH-CH-COOCH3 (II) CH3 in which R is a hydrogen atom or a methyl group, furan- (2) - carboxylic acid, its acid halide, acid anhydride or ester, in some cases also its amide, with or without an inert solvent (optionally halogenated hydrocarbons, ether, DMF and others) in the temperature range 0-180 ° C.

Bacterial and fungal diseases of useful plants depend on two factors. In the first place, the primary aim of crop production is to increase yields and improve quality. However, plants often lose some of their natural resistance to parasites. On the other hand, experience has shown that bacteria and fungi have become resistant to known pesticides on a larger scale over the years.

Thus, there is a great need for microbicides that are tolerated by useful plants and that destroy their immediate parasites.

Examples of useful crops are cereals, maize, rice, vegetables, sugar beet, soybeans, peanuts, fruit trees, ornamentals, but above all vines, hops, cucumbers (cucumber, pumpkin, melons), solanacee and also tomato, tobacco and t , cocoa and natural rubber crops.

It has now surprisingly been found that the compounds of the formula I can prevent or eradicate fungi present in plants or parts of plants (fruits, flowers, foliage, stems, tubers, roots) of such and closely related useful crops, so that subsequently growing parts of plants are also protected against such fungi. The active ingredients are effective against phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Erysiphacear); Basidiomycetes, such as, above all, rust fungi;

Fyngi imperfecti; above all, however, Oomycetes, such as Phytophtora, Peronaspora, Pseudo-63567 Peronospora, Pythium or Plasmopara, belong in particular to the Phycomycetes class. In addition, the compounds of the formula I act systemically.

They can also be used as pickling agents to treat seeds (fruits, tubers, grains) and plant cuttings to protect them against fungal infections and against phytopathogenic fungi present in the soil.

The substituted furan-2-carboxylic acid anilides of the formula I are microbicidal active ingredients which are considerably superior in use compared with customary commercial preparations and known analogs for the same use, as is apparent from the comparative experiments set out below.

2,5-Dimethylfuran-3-carboxylic acid anilide and its corresponding 2'-toluidide known from DE 1 768 686 are such plant fungicides. However, the limits of action of this type of compound are at relatively high dosage levels, as shown by comparative experiments.

DE-A-20 06 471 discloses a large number of furan-3-carbonamides as fungicides and insecticides. Particular emphasis has been placed on their effect on rust fungi. The structurally closest or most potent compounds have been used for comparison. Homologous preparations are also described in DE-A-20 19 535 and 23 23 197 as fungicides.

4,63567

Test 1

Effect against Phytophtora infestans in tomatoes

The following known compounds ch3 were used as reference compounds

Comp. A (DE-hak.

/ QVnH-CO-j | - published 2006471 '- / H3C-4sJ) s · 13 and 18> öh3

Comp. B _94 (DE-hak.

/ TT \ Publication 2006471 94 (DE-Hak.

Still. C / ΊΓ \ published 2006471, <£> "·“> / \ (DE

VM. D (Oy-m-C * -JJ — JL: ext. 1768686, 3 Example 1) f-v (DE-hak.

Comp. E / H \ _ NH -CO —-- jp- CH3 published 2006471 '-' h3cch3 s> 19 '4' one,) 5 63567

Fungal infection of more than 50% means that the the active substance used is ineffective for practical purposes. No other rating scale is used.

(a) Healing effect

After three weeks of cultivation, tomato seedlings of the species "Roter Gnom" are sprayed with a fungal sprouting suspension and incubated in a chamber at 18-20 ° C and saturated humidity. Irrigation is stopped after 24 hours. After the seedlings have dried, these are sprayed with porridge containing the compound formulated as a spray powder at the concentrations mentioned below. After drying the sprayed material, the seedlings are again placed in a humid chamber for four days. The number and size of typical leaf spots occurring after this time are considered a basis for judging the efficacy of the substances tested. Infected but untreated control seedlings are used as a reference.

Total compound_Test concentration_ Fungal infection 1 0.06% active substance 5-10% 0.02 5-10 2 0.06 5-10 0.02 5-20 A 0.06 20-40% 0.02 over 50% B 0, 06 20-40% 0.02 20-40% C 0.06 over 50% 0.02 over 50% D 0.06 over 50% 0.02 over 50% E 0.06 over 50% 0.02 over 50 % b) Preyentative-systemic effect

The compound formulated as a spray powder is applied as a spray porridge to the surface of the soil of tomato seedlings "Roter Gnom" planted in pots 3 weeks old, so that the concentration at the roots is 0.006% resp. 0.002% active substance (based on soil volume). Care must be taken to ensure that the spray porridge 6 63567 does not come into contact with parts of the plant above the ground. After 48 hours, the treated plants are infected with a spore suspension of the fungus. Fungal infection is evaluated after incubation of infected plants for 5 days at 20 ° C and saturated humidity. The number and size of leaf spots present after this time are considered a measure of the efficacy of the test substances compared to infected but untreated control plants.

Total compound_Test concentration_ Fungal infection 1 0.006% 5-10% 0.002 5-10% 2 0.006 5-10% 0.002 5-10% A 0.006 20-40% x) 0.002 20-40% x) B 0.006 20-40% 0.002 over 50% C 0.006 more than 50% xx) 0.002 more than 50% x) D 0.006 20-40% 0.002 more than 50% E 0.006 more than 50% 0.002 more than 50% x) slightly phytotoxic xx) intolerable phytotoxicity

Koe II

Effect against Plasmopara viticola (Bert. Et Curt.) (Berl. Et DeToni) in the vine a) Residual inhibitory effect

In the greenhouse are grown wine cuttings, species "Chasselas".

In the 10-leaf step, three taines are sprayed with porridge made from a compound formulated as a spray powder. After drying the sprayed material, the seedlings are evenly infected from the underside of the leaves with a spore suspension of the fungi. The seedlings are then kept for 8 days in a humid chamber. After this time, there are clear symptoms of the disease in the control seedlings. The number and size of sites of infection in the treated seedlings were used as a basis for evaluating the efficacy of the test substances. The prior art compounds mentioned in Experiment I were used for comparison.

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Total compound _Test concentration_Slene infection 1 0.02 0-5% 0.006 0-5% 2 0.02 0-5% 0.006 0-5% A 0.02 20-40% 0.006 over 50% B 0.02 20-40% 0.006 over 50% C 0.02 over 50% 0.006 over 50% D 0.02 over 50% 0.006 over 50% E 0.02 over 50% 0.006 over 50% b) Healing effect

Wine cuttings, species “Chasselas”, were grown in a greenhouse and infected in a 10-leaf stage with a spore suspension of Plasmopara viticola from the underside of the leaves, kept for 24 hours in a humid chamber, after which the seedlings were sprayed with active ingredient porridge prepared from further spray powder. 7 days in a humid chamber, after which time symptoms were observed in control seedlings, and the number and size of sites of infection in the treated seedlings were used as a basis for evaluating the efficacy of the test substances.

Total compound Concentration Fungal infection test- _ '....... sa a) and b) _ 1 0.05% 0-5% 0.02% 0-5% 1a 0.02% 0-5% 2 0.05% 0-5% 0.02% 0-5%

Test III

Effect against Pythium debaryanum in Beta vulgaris (sugar beet) a) Effect after soil treatment

The fungus is implanted in sterile oat grains and added to the soil 63567 sand mixture. The soil thus infected is filled into flower pots in which sugar beet seeds are planted. Immediately after sowing, the test preparations formulated as a spray powder are applied as an aqueous suspension to the soil (0.002% of the compound based on the volume of the soil).

The pots are then placed for 2-3 weeks in a greenhouse at 20-24 ° C. The soil is then kept evenly moist by spraying lightly with water. The test is evaluated by determining the growth of sugar beet seedlings and the number of healthy and diseased seedlings, b) Effect after pickling treatment

The fungus is implanted in sterile oat grains and added to the soil-sand mixture. The soil thus infected is filled into flower pots sown with sugar beet seeds pickled with test preparations formulated as a pickling powder (0.1% of the compound by weight of the seed). The sown pots are then kept for 2-3 weeks in a greenhouse at 20-24 ° C. The soil is thus kept evenly moist by spraying lightly with water. Evaluate by determining the growth of sugar beet tadin and the number of healthy and diseased seedlings.

After treatment with active ingredient 1, 1a or 2, more than 85% of the sugar beet seedlings germinated under both experimental conditions a) and b) and had a uniformly healthy appearance. Of the untreated controls, less than 20% sprouted and some had a diseased appearance.

The starting compounds of formula III used to prepare the compounds of formula I can be prepared according to the methods described in Journal of Organic Chemistry, 30, p. 4101 (1965), Tetrahedron 1967, p. 487 or p. 493.

The compounds of general formula I have an asymmetric carbon atom * C in their propionic acid barrier chain and can be divided into optical antipodes by conventional methods. The enantiomeric D-form has a stronger microbicidal effect, so compounds having the D-configuration are preferred as active ingredients. Form D has a negative rotation angle in ethanol or acetone.

To prepare pure D-antipodes of the compounds of general formula I, the optical 9 63567 D-configuration of the ester of formula II is furanoylated as described above.

In addition to optical isomerism, there is an atrial isomer of R = CH 2 with respect to the phenyl axis due to the presence of a di-ortho substitution and both space-consuming side chains in the aniline nitrogen preventing rotation around the phenyl-N-single bond. This particular substituent system prevents free rotation about the molecular axis as well as the planar system and always results in the formation of atropic isanes with substituents, phenyl ring and nitrogen side chains located vertically relative to each other.

If no synthesis is performed to isolate the pure isomers, the following compound 2 is obtained as a mixture of four isomers. However, the more favorable fungicidal effect of the enantiomeric Form D (compared to the D, L form and L form) remains unchanged and is not significantly affected by the atropian isaner.

The starting D-form of the ether of formula II is prepared, for example, by reacting a racemic compound of the formula R CH-) -VP * 3 NH -CH -COOH (III) (R-H or CH3) in a manner known per se with an N-containing optically with an active base such as α-phenylethylamine to the corresponding salt and fractionally crystallizing the salt and then liberating the acid of formula III enriched with an optical D-antipode and optionally repeating (also multiplying) the salt formation, first crystallizing and liberating the α-anilinopropionic acid of formula III pure Form D, from which the desired ester can then be prepared in a conventional manner, e.g. in the presence of HCl or H 2 SO 4 with methanol.

10 63567

The compounds of the formula I can be mixed with other suitable pesticides or plant growth promoters in order to broaden their spectrum of action.

Suitable carriers or additives in the preparations may be solid or liquid and correspond to those commonly used in the art, e.g. they may be natural or regenerated minerals, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. substances.

The active ingredient content is 0.1-90% in commercial substances.

Suitable forms of treatment (wherein the weight percentages in parentheses refer to the preferred amounts of active ingredient) are, for example:

Solid applications: Dusts and dispersants (up to 10%), granules, coating granules, impregnation granules and homogeneous granules (1-80%);

Liquid forms of treatment: a) Water-dispersible power concentrates: Wet-table powders and pastes (25-90% in commercial packaging, 0.01-15% in ready-to-use solution); emulsion and solvent concentrates (10-50%; 0.01-15% in ready-to-use solution); b) Solutions (0.1-20%).

Example 1: N- (1'-Methoxycarbonylethyl) -N- (furan- (2 ') carbonyl) -2,6-dimethylaniline CH-CH * 3 _p CH-C00CH3 / (Compound No. 1 )

\ CO-U

ch3 63567 11 To 18.2 g of N- (1'-methoxycarbonylethyl) -2,6-dimethylaniline in 10 ml of anhydrous toluene and 0.2 ml of dimethylformamide was added dropwise with stirring 12.6 g of furan -2-karbonihappokloridia. When the weakly exothermic reaction was complete, it was heated at reflux for 5 hours and the hydrogen chloride formed was completely removed by passing nitrogen through the mixture. After removal of the solvent, it was distilled in vacuo. Bp At 166-168 ° C / 0.06 torr the distilled product solidified on standing.

X-ray powder diagrams showed that the compound was polymorphic. After recrystallization from ethyl acetate / petroleum ether, a uniformly crystalline product was obtained, m.p. 85-86 ° C. Yield 72.2% of theory.

If the D-configuration of N- (1'-methoxycarbonylethyl) -2,6-dimethylaniline is used as the starting material, CH-.-1 CH3 (D) -form NH- * CH-C00CH3 [(a) * 0 to +29, 8 + 0.5 °; 01.52% w / v in methanol] ch3 is obtained in a similar manner as N- (1'-methoxycarbonylethyl) -N- (furan- (2 ") -carbonyl) -2,6-dimethylaniline D-form CH GH- I 3

J J ^ ^ * CH-C00CH3 m.p. 102-103 ° C

(OVn <T π («> D ° · - ^ 7.0 + 0.7 ° ^ -CO-LJ 01.73 7. w / v in acetone (compound 1a) LH3

Example 2; N- (1'-methoxycarbonyl-ethyl) -N- (furan- (2 ") -carbonyl) -2,3,6-trimethylaniline CH3 CH3 ^ 3 and 1 CH-C00CH3 / V * II-J | (Compound n: o 2) \ - /

II

CH3 o

Claims (3)

12,63567 A suspension of 51.5 g / 0.382 mol) of 2,3,6-trimethylaniline, 35.3 g of NaHCO 3 and 126 ml (1.15 mol) of 2-bromopropionic acid methyl ester is stirred. hours at a bath temperature of 130 ° C, the cooled salt is filtered off and distilled. 67.3 g of α- (2,3,6-trimethylanilino) -propionic acid methyl ester are obtained, m.p. 144-146 ° C (9 torr). To a suspension of 33-5 g (0.152 moles of α- (2,3,6-trimethylanilino) -propionic acid methyl ester and 18 g (0.17 moles) of soda in 200 ml of absolute benzene is added dropwise 16.7 ml (0, 17 moles) of furan-2-carboxylic acid chloride at 60-70 [deg.] C. and maintained for a further 4 hours at this temperature After cooling, filtration and evaporation of the filtrate, the final product is crystallized from isopropyl ether in a yield of 86% of N- (1'-methoxycarbonylethyl) -N- (furan- (2 ") -carbonyl) -2,3,6-trimethylaniline, mp 98-102 ° C. Claims; Substituted furan-2-carboxylic acid anilide having fungicidal activity, characterized in that it has the formula CH, R CHn jl <J i_l J ^ CH-C00CH ~ π <.> \ -Γ CO JQ CH3 in which R represents a hydrogen atom or a methyl group. Anilide according to Claim 1, characterized in that it is in the enantiomeric D-configuration. Use of an anilide according to claim 1 in a fungicidal preparation together with suitable carriers or spreading agents.