IL46988A - N-(1'-methoxycarbonylethyl)-n-furan-2-ylcarbonyl aniline derivatives their manufacture and microbicidal and fungicidal compositions containing them - Google Patents
N-(1'-methoxycarbonylethyl)-n-furan-2-ylcarbonyl aniline derivatives their manufacture and microbicidal and fungicidal compositions containing themInfo
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
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- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
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- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- C07—ORGANIC CHEMISTRY
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- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
- C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
- C07D327/06—Six-membered rings
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- C—CHEMISTRY; METALLURGY
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- Furan Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Pyridine Compounds (AREA)
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
1448810 Furan derivatives CIBA-GEIGY AG 1 April 1975 [2 April 1974 10 Feb 1975] 13332/75 Heading C2C The invention comprises compounds of the Formula (I) in which R is H or methyl. They may be prepared by (a) acylating a compound of Formula (II) with furan (2)-carboxylic acid or an acid halide, anhydride or ester thereof, or (b) reacting a compound of Formula (III) with either an α-halopropionic acid methyl ester in the presence of an alkali metal carbonate, or with butyl lithium or sodium hydride to give the corresponding alkali metal salt, followed by reaction with an α-halopropionic acid methyl ester. The enantiomeric D-form of the compound of Formula (I) may be prepared by reacting the racemic compound of Formula (IV) in known manner with a nitrogen-containing optically active base to give the corresponding salt followed by fractional crystallization and liberation of the acid of Formula IV which is enriched with the optical D-antipode. The D- form of the ester of Formula (II) may then be prepared in conventional manner from the D form of the acid of Formula (IV), followed by acylation as in step (a) above, to give the D- form of the compound of Formula (I). The D- form of the acid of Formula (IV) may also be prepared by replacing the hydroxy group in L(+) lactic acid by halogen and reacting this product with 2,6-dimethylaniline or 2,3,6-trimethylaniline with reversal of the configuration. The compounds of Formula (II) may be prepared by reacting 2,6-dimethylaniline or 2,3,6- trimethylaniline with 2-bromopropionic acid methyl ester. The compounds of Formula (I) are used in fungicidal compositions.
[GB1448810A]
Description
46988/3 jianp »K-2- iDr| ( *nR *3ianp*opiKna-1 nn^m o» »aan ni»iOBi o»pn »n * ei o»n*t ni jnaan ,|» »JK N-(1·-methoxycarbonylethyl)-N-furan-2-ylcarbonyl aniline derivatives, their manufacture and microbicidal and fungicidal compositions containing them CIBA-GEIGT AG.
C. 44807 The present invention provides compounds of the formula I s wherein R for the manufacture of these compounds, also microbicidal compositions which contain these compounds as active substance, as well as a method of using these compounds as microbicides , preferably for combating phytopathogenic fungi.
Bacterial diseases and mycoses in useful plants are helped by two factors. On the one hand, in plant hybridizing it is a primary objective to attain an increase in yield and an improvement in quality. But in this process the plants frequently lose some of their natural resistance to parasites. On the other hand, experience has shown that bacteria and harmful fungi have developed over the years a substantial resistance to the known pesticides. There is therefore an urgent need for microbicides that are compatible with the cultivated plants and destroy their direct parasites.
Cultivated plants within the scope of the present invention are, for example, cereals, maize, rice, vegetables, sugar beet, soya, ground nuts, fruit trees, ornamental plants, but principally vines, hops, cucumber plants (cucumbers, marrows, melons), solanaceae, such as potatoes, tobacco tomatoes, as well as bananas, cocoa and rubber plants.
The present invention is based on the surprising observation that it is possible to inhibit or destroy with the compounds of the formula I the fungi which occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of these and related cultures or useful plants and also to protect from such fungi which grow later.
The active suostances are effective against phytophathogenic fungi which belong to the following classes: a.scomycetes (e.g. e'rysiphacea )* Uasidiomycetes, above all rust fungi; fungi imperfecta; but especially against oomycetes which belong to the class of phycomycetes , e.g. phytophthora, peronospora,pseudoperonospora, pythium or plasmopara. In addition, the compounds of the formula I have a systemic action. They can also be used as seed-dressing agents for protecting seeds (fruit, tubers, kernels) and plant cuttings from fungus infections as well as from phytopathogenic fungi which occur in the soil.
The N- (substituted phenyl)-N-furanoyl-analinine-methyl esters of the formula I constitute a hitherto unknown class of new microbicidal active substances which are markedly superior in their field of use to the conventional commercial preparations .
Compounds of the formula I are manufactured by a method according to the invention, for example by acylation of a compound of the formula II with furan- (2)-carboxylic acid, the acid halide, acid anhydride or ester thereof, in isolated instances also with a furan- (2)- carboxy amide (transamidation) .
By another method according to the invention it is also possible to manufacture the compounds of the formula I by - converting the acy.1 anilide of the formula III with butyl lithium or sodium hydride into the corresponding alkal salt, which is then reacted with the cc-halogenopropionic acid methyl ester to give the desired end product, or else! to react the anilide of the formula III with the cc-halogenopropionic acid methyl ester in the presence of an alkali carbonate, e.g. ΙΟ,ΟΟ^, as proton acceptor, preferably with the addition of catalytic amounts of an alkali iodide, e.g. potassium iodide.
In the formulae II and III, R represents hydrogen or methyl, the term "acid halide" denotes preferably acid chloride or acid bromide and the halogen atom in cc-halogeno-propionic acid methyl ester is preferalby chlorine or bromine. The reactions can be carried out in. the presence or absence of solvents or diluents which are inert to the reactants .
Examples of suitable solvents or diluents are: aliphatic or aromatic hydrocarbons, e.g. benzene, toluene, xylene, petroleum ether; halogenated hydrocarbons, e.g. chlorobenzene, methylene chloride, ethylene chloride, chloroform; ethers and ethereal compounds, e.g. dialkyl ethers, dioxan, tetrahydro-furan; nitriles, e.g. acetonitrile; N,N-dialkylated amides, e.g. dimethyl formamide; anhydrous acetic acid, dimethyl sulphoxide, ketones, e.g. methyl ethyl ketone, and mixtures of such solvents.
The reaction temperatures are between 0° and 180°C, preferably between 20°C and 120°C. It is often advantageous to use acid acceptors or condensation agents. Suitable examples are: tertiary amines, e.g. trialkylamines (e.g. triethylamines) , pyridine and pyridine bases, or inorganic bases, e.g. the oxides and hydroxides, hydrogen carbonates and carbonates of alkali metals and alkaline earth metals, as well as sodium acetate. In the above first manufacturing method it is also possible to use a surplus of the respective aniline derivative of the formula II as acid acceptor.
The process of manufacture which proceeds from of the formula II can also be carried out without acid acceptors; in some instances it is expedient to pass in nitrogen in order to expel the hydrogen halide that has formed. In other instances it is very advantageous to use dimethyl formamide as reaction catalyst.
Particulars on the manufacture of the intermediates of the formula II can be inferred from the methods which are generally indicated for the manufacture of aniline-alkane acid esters in the following publications: J. Org. Chem.30, 4101 (1965); Tetrahedron 1967, 487; Tetrahedron 1967, 493.
The compounds of the formula I contain an asymmetrical carbon atom in the propionic acid ester chain and can be resolved into the optical antipodes in the customary manner. In this connection, the enantiomeric D-form has the more pronounced microbicidal action.
Within the scope of the invention, those compounds, their compositions and their use which refer to the D-configu-ration of the formula I are accordingly preferrred. These D- forms have in ethanol or acetone a negative angle of rotation.
The pure, optical D-antipodes are manufactured, for example, by preparing the racemic compound of the formula IV (R = H or CH¾) and then reacting this in known manner with a nitrogen- containing, optically active base to give the corresponding salt. The pure D-form is obtained stepwise by fractional crystallisation of the salt and subsequent liberation of the acid of the formula IV which is enriched with the optical D-antipode and, if appropriate, by repetition (also repetition several times) of the salt formation, crystallisation and liberation of the a-anilinopropionic acid of the formula IV. From this pure D-form it is then possible to obtain the optical D-configuration of the ester of the formula II in conventional manner, for example in the presence of HCl or ^SO^, with methanol. A suitable optically active organic base is, for example, oc-phenylethyl amine.
Instead of fractional recrystallization also possible to obtain the enantiomeric D-form of the formula IV by replacing the hydroxy group in the naturally occurring L(+) lactic acid by halogen and reacting this product further with 2, 6-dimethylaniline or 2,3 , 6- trimethylaniline with, reversal of the configura ion.
Besides the optical isomerism, when R = CH^* there occurs in the furanoylation of the compound II (or in the reaction of the compound III with a-halogenopropionic acid methyl ester) an atropisomerism about the phenyl—N< xis , as a consequence of the steric hindrance of the two radicals additionally introduced at the nitrogen atom of the trimethyl-aniline. Provided no synthesis is carried out with the aim of isolating pure isomers, compound 2 (the manufacture of which is described hereinafter) occurs in the manufacture as a mixture of 4 isomers. However, the better fungicidal action of. the enantiomeric D-form (in comparison to the D,L-form or the L-form) is retained, and is not noticeably affected by the atropisomerism.
The manufacture of the active substances of the formula I is illustrated by the following Examples 1 and.2.
Example 1 Manufacture (compound 1) N- (1 '-methoxycarbonylethyl)-N- (furan- (2M)-carbonyl)-2 , 6-dimethylaniline.
With stirring, "12.6 g of furan-2-carboxylic acid chloride are added dropwise to 18.2 g of N- (1-methoxycarbonyl-ethyl)-2, 6-dimethylaniline in 10 ml of anhydrous toluene and 0.2 ml of dimethyl formamide. After the weakly exothermic reaction has subsided, the reaction mixture is refluxed for 5 hours and the hydrogen chloride which has formed is completely removed by passing in nitrogen. The solvent is removed and the residue is distilled in vacuo; b.p. 166°-168°C/0.06 Torr.
The congealed end product melts between S1°-84°C after recry-stallisation from toluene/petroleum ether. X-ray powder patterns show that the product is polymorphous. One of the two modifications melts at 85°C. The enantiomeric D-configuration and its primary products have the following physical data: 10,7 + 0,3°;C=1,56 % g in ethanol 9 , 8 + 0 , 5°;C=l, 527o g/v in methanol (compound la) Example 2 Manufacture of (compound 2 ) N (1 '-methoxycarbonyl-ethyl)-N- (furan- (2")-carbony]}-2,3,6- tr^ methylaniline . a) A suspension of 51.5 g (0.382 mole) of 2,3,6-trimethyl-aniline, 35.3 g of aHC03 and 126 ml (1.15 moles) of 2-bromo- . propionic acid methyl ester is stirred for 6 hours at a bath temperature of 130°C, then coaled, filtered from NaBr-salt and distilled. Yield: 67.3 g of a- (2,3, 6-trimethylanilino)-propionic acid methyl ester (b.p. 144°-146°C/9 Torr.) b) A suspension of 33.5 g (0.152 mole) of the ester obtained according to a) and 18 g (0.17 mole) of sodium carbonate in 200 ml of absolute benzene is treated dropwise with 16.7 ml (0.17 mole) of furan-2-carboxylic acid chloride at 60°-70°C and kept thereat for 4 hours. The reaction mixture is cooled and filtered and the filtrate concentrated. The end product crystallises from isopropyl ether (m.p. 98°-102°C).
The D-form of compound 2 is obtained as a mixture of atropisomers (^compound 2a) by acylating the D-form of the a- (2,3,6- trimethylanilino)-propionic acid methyl ester with furan— (2)-carboxylic acid or one of its reactive derivatives. The percentage amount of each of these isomers obtained depends on the respective manufacturing conditions .
The compounds of the formula I can be used with other suitable pesticidal or active substances which promote plant growth in order to improve their activity spectrum.
The compounds of the formula I can be used by themselves or together with suitable carriers and/or other additives. W Suitable carriers and additives can be solid or liquid and corres pond to the customary substances used in formulation technology, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, stickers, thickeners, binders or fertilisers. The amount of active substance in commercially useful compositions is between 0.1 and 90 %.
The compounds of the formula I can be applied in the following process forms (the percentages by weight in brackets denote advantageous amounts of active substance) .* solid forms: dusts and tracking agents (up to 10 %) ; granules, coated granules, impregnated granules and homogenous granules (1 to 80 %) ; liquid forms: a) active substance concentrates which are dis- persible in water: wettable powders and pastes (25-907o in the commercial pack, 0.01 to 15 % in ready for use solution) ; emulsion concentrates and concentrated solutions (10 to 50 70; 0.01 to 15 % in ready for use solution) ; b) solutions (0.1 to 20 ¾,) .
The active substances of the formula I can be formulated, for example, as follows: Dusts: The following substances are used to manufacture a) a 50 % and b) a 2 % dust: a) 5 parts of active substance 2 95 parts of talcum; b) 2 parts of active substance 1 1 part of highly disperse silicic acid 97 parts of talcum.
The active substances are mixed with the carriers and ground and in this form can be processed to dusts for application .
Granules : The following substances are used to manufacture 5 % granules : 5 parts of active substance 1 0.25 parts of epichlorohydrin 0.25 parts of cetyl polyglycol ether 3.50 parts of polyethylene glycol 91 parts of kaolin (particle size 0.3-0.8 mm).
The active substance is mixed with epichlorohydrin and the mixture is dissolved in 6 parts of acetone. Then polyethylene glycol and cetyl polyglycol ether are added. The resultant solution is sprayed on kaolin and the acetone is evaporated in vacuo. Such microgranules are advantageously used for co' bating soil fungi.
We table powders: The following constituents are. used to manufacture a) a 70 , b) a 40 %, c) and d) a 25 % and e) a 10 % wettable powder: a) 70 parts of N- (1 '-methoxycarbonyl-ethyl)-N- [furan- (2M)· carbonyl]-2, 6-dimethylaniline (active substance la (D-form) according to the present invention) 5 parts of sodium dibutyl naptthylsulphonate 3 parts of naphthalenesulphonic acid/phenolsulphonic acid/formaldehyde condensate (3:2:1) 1Q parts of kaolin 12 parts of Champagne chalk. b) 40 parts of active substance 2 5 parts of the sodium salt of ligninsulphonic acid 1 part of the sodium salt of dibutylnaphthalenesul- phonic acid 54 parts of silicic acid. c) 25 parts of active substance 2a (D-form) 4.5 parts of calcium ligninsulphonate 1.9 parts of a Champagne chalk/hydroxyethyl cellulose mixture (1:1) 1.5 parts of sodium dibutylnaphthalene sulphonat^- 19.5 parts of silicic acid 19.5 parts of Champagne chalk 28.1 parts of kaolin. d) 25 parts of active substance 2 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol 177 parts of a Champagne chalk/hydroxyethyl cellulose mixture (1:1) 8.3 parts of sodium aluminium silicate 16.3 parts of kieselguhr 46 parts of kaolin. e) 10 parts of active substance la (D-form) 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates 5 parts of naphthalenesulphonic acid/formaldehyde condensate 82 parts of kaolin.
The active substances are intimately mixed in suitable mixers with the additives and ground in appropriate mills and rollers. Wettable powders of excellent wettability and suspension power are obtained. These wettable powders can be diluted with water to give suspensions of every desired concentration and can be used in particular for application to leaves.
Emulslfiable concentrates: The following substances are useFto to manufacture a 25 % emulsifiable concentrate: 25 parts of active substance 1 2.5 parts of epoxidised vegetable oil 10 parts of an alkylarylsulphonate/fatty alcohol polyglycol ether mixture 5 parts of dimethyl formamide 57.5 parts of xylene.
By diluting such concentration with water it is possible to manufacture emulsions of every desired concentration which are especially suitable for application to leaves.
Example 3 Action against Phytophthora infestans on Solanum lyccpersicum (tomatoes) la) Residual preventive action Solanum lycopersicum plants of the "Roter Gnom" variety are infected when 3 weeks old with a zoospore suspension of Phytophthora infestans after they have been sprayed with a broth prepared from the active substance processed to a wettable powder and containing 0.05 % of active substance, and dried. They are then kept for 6 days in a climatic chamber at 18° to 20°C and high humidity, which is produced with: n artificial wet fog. After this time typical leaf specks appear. Their number and size are the criterion for evaluating the tested substance.
Ib) Curative action > "Roter Gnom"tomato plants are sprayed when 3 weeks old with a zoospore suspension of the fungus and incubated in a climatic chamber at 18° to 20°C and saturated humidity. The humidifying is interrupted after 24 hours. After the plants have been dried, they are sprayed with a broth which contains the active substance formulated as wettable powder in a concentration of 0.05 7o. After the spray coating has dried, the plants are again kept in the humid chamber for 4 days. Size and number of the typical leaf specks which, have occurred during this time are the criterion for evaluating the effectiveness of the tested substances.
II) Preventive- systemic action The active substance is applied as wettable powder in a concentration of 0.05 °L (referred to the volume of the soil) to the surface of the soil of 3 week old "Roter Gnom" tomatoes in pots. Three days later the underside of the leaves of the plants are sprayed with a zoospore suspension of Phytophthora infestans. The plants are then kept for 5 days in a spray chamber at 18° to 20°C and saturated humidit , after which time typical leaf specks form.The number size of the specks serve the criterion for evaluating the effectiveness of the tested substances .
In these three tests, the compounds of the formula '9t have a pronounced leaf- fungicidal action, i.e. the fungus infection is below 5 %. When the D- forms of the compunds are applied, i.e. active substances la and 2a, the fungus infection is below 5 % in all three tests even at rates of application of 0.02 %.
Example 4 Action against PLasmoporara viticola (Bert, et Curt.) (Berl . et De Toni) on vines a) Residual preventive action Vine cuttings of the variety "Chasselas" were reared in a greenhouse. Three plants in the 10 leaf stage were sprayed with a broth prepared from the active substance and formulated as a wettable powder. After the coating layer had dried, the plants were infected on the underside of the leaves with the spore suspension of the fungus. The plants were subsequently kept for 8 days in a humid chamber,after which time symptoms of the disease were visible on the control plants. The number and size of the infected areas on the tested plants served as criterion for evaluating the effectiveness of the tested active substances. b) Curative action Vine cuttings of the variety "Chasselas" were reared in a greenhouse and infected in the 10 leaf stage with a sp e suspension of Plasmopara viticola on the underside of the leaves. After they had been kept for 24 hours in a humid chamber, the plants were sprayed with an active substance broth prepared from a wettable powder of the active substance. The plants were then kept for a further 7 days in a humid chamber, after which time the symptoms of the disease were visible on the control plants. The number and size of the infected areas on the treated plants served as criterion for evaluating the effectiveness of the tested substances.
In both these tests of Example 4, the compounds of the formula I exhibit a pronounced fungicidal action in the following concentrations: Active -Substance Concentration Fungus infection in a) and b) 1 0,05 % 0 - 5 % 0,02 % 0 - 5 % la 0,02 % 0 - 5 % 2 0,05 % 0 - 5 % 0,02 % 0 - 5 % *a 0,02 % 0 - 5 % Control 100 % Example 5 Action against Fythium debaryanum in Beta vulgaris (sugar beet) a) Action after soil application The fungus is cultivated on sterile oat kernels and added to a mixture of earth and sand. Flower pots are filled with the infected soil in which sugar beet seeds are then sown. Immediately after sowing, the tests preparations formulated as wettable powders are poured Ln the form of aqueous suspensions over the soil (0.002 % active substance referred to the volume of the soil). The pots are then-stood for 2-3 weeks in a greenhouse at 20°-24°C. The soil is kept uniformly moist by gently spraying it with water. The emergence of the sugar beet plants as well as the number of healthy and sick plants are ascertained in evaluating the tests. b) Action after seed treatment application The fungus is cultivated on sterile oat kernels and added to a mixture of earth and sand. Flower pots are filled with the infected soil and sugar beet seeds which have been treated with the test preparations formulated as seed dressing powders are sown therein (0.1 % active substance referred to the weight of the seeds). The pots are then stood in a greenhouse for 2-3 weeks at 20°-24°C. The soil is kept unifornly moist by gently spraying it with water. The emergence of the sugar beet plants as well as the number of healthy and sicl- plants are ascertained.
Under the conditions of both test a) and test b) , 8! of the sugar beet plants emerged after treatment with one of the active substances 1, la, 2 or 2a and had a healthy appearance. Less than 20 % of the untreated control plants emerged and their appearance was in part sickly.
Claims (12)
1. Anilides of the formula I wherein R represents hydrogen or methyl,? in the form of racemates or optical antipodes .
2. N- (1 '-methoxycarbonyl-ethyl)-N- (furan- (2")-carbonyl)- 2, 6-dimethylaniline of the formula according to claim 1.
3. N- (l'-methoxycarbonyl-ethyl)-N- (furan- (2")-carbonyl)-2,3,6- trimethylaniline .
4. The enantiomeric D-configurations of the compounds according to any one of claims 1 to 3.
5. A process for the manufacture of compounds of the formula I wherein R represents hydrogen or methyl, wherein a compound of the formula II in which R has the meaning assigned to it, is acylated -with furan(2)-carboxylic acid, the acid halide, acid anhydride or one of the esters or amides thereof.
6. A process according to claim 5, wherein furan(2)-carboxy-lic acid chloride or furan- (2)-carboxylic acid bromide is used for the acylation.
7. A process for the manufacture of compounds of the formula I wherein R represents hydrogen or methyl .wherein the furan- (2)-carboxanilide of the formula III in which R has the meaning already assigned to it, is reacted initially with butyl lithium or sodium anhydride to give the corresponding alkali salt, which is then reacted with oc-halo-genopropionic acid methyl ester, or wherein the anilide of the formula III is reacted with oc-halogenopropionic acid methyl ester in the presence on alkali carbonate as proton acceptor.
8. A process according to claim 7, wherein the reaction with 'cc-chloro or oc-bromopropionic acid methyl ester is carried out in the presence of an alkali carbonate with the addition of catalytic amounts of alkali iodide.
9. A microbicidal composition which contains as active substance a compound of the formula I 46988/2 wherein R represents hydroge or methyl, together with suita . carriers and/or additives which promote the application.
10. A microbicidal composition according to claim 9 which contains as active substance N- (11 -methoxycarbonyl-ethyl )-N- (furan- (2")-carbonyl)-2,6-dimethylaniline.
11. A microbicidal composition according to claim 9 which contains as active substance N- (11 -methoxycarbonyl- ethyl )-N- (furan- (2")-carbonyl)-2,3, 6- trimethy1aniline.
12. A method for coirbatting phytopathogenic fungi in seeds plants or in the soil which comprises applying to the locus infested by such fungi a compound of formula I in Claim 1 alone, or in the form of a composition according to any one of Claims 9 to 11. PC:mz
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH457274A CH590608A5 (en) | 1974-04-02 | 1974-04-02 | N-Furoyl-N-aryl-alanine esters - prepd. e.g. by reacting N-aryl-alanine esters with 2-furoic acid or its derivs. |
| CH159175A CH603041A5 (en) | 1974-04-02 | 1975-02-10 | N-Furoyl-N-aryl-alanine esters |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL46988A0 IL46988A0 (en) | 1975-06-25 |
| IL46988A true IL46988A (en) | 1977-12-30 |
Family
ID=25688094
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL46988A IL46988A (en) | 1974-04-02 | 1975-04-01 | N-(1'-methoxycarbonylethyl)-n-furan-2-ylcarbonyl aniline derivatives their manufacture and microbicidal and fungicidal compositions containing them |
| IL46989A IL46989A (en) | 1974-04-02 | 1975-04-01 | Heteroacylanilides,their manufacture and micrtobiocidal and fungicidal compositions containing them |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL46989A IL46989A (en) | 1974-04-02 | 1975-04-01 | Heteroacylanilides,their manufacture and micrtobiocidal and fungicidal compositions containing them |
Country Status (31)
| Country | Link |
|---|---|
| JP (3) | JPS5345364B2 (en) |
| AR (2) | AR205189A1 (en) |
| AT (2) | AT345614B (en) |
| AU (1) | AU465906B2 (en) |
| BG (2) | BG24651A3 (en) |
| CA (2) | CA1050546A (en) |
| CH (1) | CH603041A5 (en) |
| CS (2) | CS183789B2 (en) |
| DD (3) | DD118785A5 (en) |
| DE (2) | DE2560591C2 (en) |
| DK (2) | DK141995B (en) |
| EG (2) | EG12263A (en) |
| ES (2) | ES436175A1 (en) |
| FI (2) | FI750921A (en) |
| FR (2) | FR2265747B1 (en) |
| GB (2) | GB1498199A (en) |
| HU (2) | HU172935B (en) |
| IE (2) | IE41777B1 (en) |
| IL (2) | IL46988A (en) |
| IT (2) | IT1049394B (en) |
| LU (2) | LU72174A1 (en) |
| NL (2) | NL160821C (en) |
| NO (2) | NO142714C (en) |
| OA (2) | OA04916A (en) |
| PH (2) | PH13072A (en) |
| PL (2) | PL98627B1 (en) |
| RO (3) | RO73181A (en) |
| SE (2) | SE418086B (en) |
| SU (4) | SU743561A3 (en) |
| TR (2) | TR18508A (en) |
| YU (2) | YU39026B (en) |
Families Citing this family (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5845433B2 (en) * | 1975-02-10 | 1983-10-08 | チバ・ガイギ− アクチエンゲゼルシヤフト | 2↓-Production method of furancarboxylic acid anilides |
| US4147792A (en) * | 1977-02-04 | 1979-04-03 | Ciba-Geigy Corporation | Fungicidal compositions |
| CH629939A5 (en) * | 1977-03-29 | 1982-05-28 | Ciba Geigy Ag | MICROBICIDAL AGENT. |
| DE2724785A1 (en) * | 1977-05-27 | 1978-12-14 | Schering Ag | FURANCARBONIC ANILIDES, FUNGICIDALS CONTAINING THESE COMPOUNDS AND THE PROCESS FOR THEIR PREPARATION |
| BG28977A3 (en) * | 1978-02-02 | 1980-08-15 | Montedison Spa | Fungicide means and method for fungus fighting |
| CH637368A5 (en) * | 1978-10-27 | 1983-07-29 | Ciba Geigy Ag | ANILINE DERIVATIVES AND Pesticides Manufactured From Them. |
| EP0010673B1 (en) * | 1978-10-31 | 1982-01-27 | Bayer Ag | Substituted n-propargyl anilines, process for their preparation and their use as fungicides |
| CH641760A5 (en) * | 1978-11-27 | 1984-03-15 | Ciba Geigy Ag | PEST CONTROL. |
| CH639940A5 (en) * | 1978-12-05 | 1983-12-15 | Ciba Geigy Ag | Substituted N-alkoxycarbonylethyl-N-acylanilines, microbicides containing them, and process for the preparation of the compounds |
| DE2948734A1 (en) * | 1978-12-07 | 1980-06-19 | Ciba Geigy Ag | PEST CONTROL |
| DE2940189A1 (en) * | 1979-10-04 | 1981-04-16 | Basf Ag, 6700 Ludwigshafen | ISOXAZOLYLCARBONIC ACID ANILIDE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
| MA19111A1 (en) * | 1979-10-26 | 1981-12-31 | Ciba Geigy Ag | HOMOSERIN DERIVATIVES, PROCESS FOR THEIR PREPARATION AND THEIR USE AS MICROBICIDES |
| DE3013908A1 (en) * | 1980-04-11 | 1981-10-22 | Basf Ag, 6700 Ludwigshafen | 2- (N-ARYL-, N-ISOXAZOLYLCARBONYL) -AMINOBUTYROLACTONE, METHOD FOR THE PRODUCTION THEREOF AND FUNGICIDES CONTAINING THEM |
| MA19215A1 (en) * | 1980-07-25 | 1982-04-01 | Ciba Geigy Ag | NOVEL ARYLAMINE DERIVATIVES, PROCESS FOR THEIR MANUFACTURE AND USE AS MICROBICIDES. |
| DE3030736A1 (en) | 1980-08-14 | 1982-03-25 | Basf Ag, 6700 Ludwigshafen | N-DISUBSTITUTED ANILINE DERIVATIVES, THEIR PRODUCTION, THEIR USE AS MICROBICIDES AND AGENTS THEREFOR |
| GB2095237B (en) * | 1981-03-19 | 1985-04-03 | Ici Plc | Herbicidal and fungicidal substituted n-furyl or thienyl-methyl amides |
| DE3133418A1 (en) * | 1981-08-24 | 1983-03-10 | Basf Ag, 6700 Ludwigshafen | THIAZOLYL AND ISOTHIAZOLYLCARBONIC ACID ANILIDES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
| JPH0326906U (en) * | 1989-07-26 | 1991-03-19 | ||
| DE4011172A1 (en) * | 1990-04-06 | 1991-10-10 | Degussa | COMPOUNDS FOR CONTROLLING PLANT DISEASES |
| DE4304172A1 (en) | 1993-02-12 | 1994-08-25 | Bayer Ag | Fungicidal active ingredient combinations |
| US5723491A (en) | 1994-07-11 | 1998-03-03 | Novartis Corporation | Fungicidal composition and method of controlling fungus infestation |
| DE4429014A1 (en) | 1994-08-16 | 1996-02-22 | Basf Ag | Process for the preparation of cyclic amines |
| PE32799A1 (en) | 1996-12-25 | 1999-04-09 | Agrogene Ltd | NEW DERIVATIVE OF AMINOBUTIRIC ACID FOR THE PROTECTION OF FUNGAL DISEASES |
| DE10347090A1 (en) | 2003-10-10 | 2005-05-04 | Bayer Cropscience Ag | Synergistic fungicidal drug combinations |
| DE10349501A1 (en) | 2003-10-23 | 2005-05-25 | Bayer Cropscience Ag | Synergistic fungicidal drug combinations |
| DE102004049761A1 (en) | 2004-10-12 | 2006-04-13 | Bayer Cropscience Ag | Fungicidal drug combinations |
| DE102005026482A1 (en) | 2005-06-09 | 2006-12-14 | Bayer Cropscience Ag | Active substance combination, useful e.g. for combating unwanted phytopathogenic fungus, comprises herbicides e.g. glyphosate and active substances e.g. strobilurin, triazoles, valinamide and carboxamide |
| MX2007015376A (en) | 2005-06-09 | 2008-02-14 | Bayer Cropscience Ag | Active substance combinations. |
| DE102006023263A1 (en) | 2006-05-18 | 2007-11-22 | Bayer Cropscience Ag | Synergistic drug combinations |
| JP5424881B2 (en) | 2006-09-18 | 2014-02-26 | ビーエーエスエフ ソシエタス・ヨーロピア | Pesticide mixture |
| BR122019020347B1 (en) | 2007-02-06 | 2020-08-11 | Basf Se | MIXTURES, PESTICIDE COMPOSITION AND METHODS TO CONTROL HARMFUL PHYTOPATHOGENIC FUNGI, TO PROTECT PLANTS FROM ATTACK OR INFESTATION BY INSECTS, ACARIDES OR NEMATODES AND TO PROTECT SEED |
| EP2000028A1 (en) | 2007-06-06 | 2008-12-10 | Bayer CropScience Aktiengesellschaft | Fungicidal active agent compounds |
| EP2000030A1 (en) | 2007-06-06 | 2008-12-10 | Bayer CropScience AG | Fungicidal active agent compounds |
| DE102007045920B4 (en) | 2007-09-26 | 2018-07-05 | Bayer Intellectual Property Gmbh | Synergistic drug combinations |
| MX2012000566A (en) | 2009-07-16 | 2012-03-06 | Bayer Cropscience Ag | Synergistic active substance combinations containing phenyl triazoles. |
| EP2910126A1 (en) | 2015-05-05 | 2015-08-26 | Bayer CropScience AG | Active compound combinations having insecticidal properties |
| CN115557887A (en) * | 2022-11-10 | 2023-01-03 | 南京林业大学 | Synthesis of trifluoromethyl pyridine derivative based on Ugi reaction and biological activity research of trifluoromethyl pyridine derivative |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3959481A (en) * | 1969-02-13 | 1976-05-25 | Uniroyal | Method of protecting plants from fungal diseases using furan-3-carboxamide derivatives |
| JPS5345364A (en) * | 1976-10-06 | 1978-04-24 | Daiahoiru Kk | Device for controlling extrusion molding die bolt |
-
1975
- 1975-01-01 AR AR258203A patent/AR205189A1/en active
- 1975-02-10 CH CH159175A patent/CH603041A5/en not_active IP Right Cessation
- 1975-03-26 FI FI750921A patent/FI750921A/fi not_active Application Discontinuation
- 1975-03-26 SE SE7503518A patent/SE418086B/en not_active IP Right Cessation
- 1975-03-26 NO NO751086A patent/NO142714C/en unknown
- 1975-03-26 FR FR7509484A patent/FR2265747B1/fr not_active Expired
- 1975-03-26 DK DK135975AA patent/DK141995B/en not_active IP Right Cessation
- 1975-03-26 FI FI750920A patent/FI63567C/en not_active IP Right Cessation
- 1975-03-26 FR FR7509485A patent/FR2265748B1/fr not_active Expired
- 1975-03-26 SE SE7503517A patent/SE419218B/en not_active IP Right Cessation
- 1975-03-26 NO NO751084A patent/NO141340C/en unknown
- 1975-03-26 DK DK135875AA patent/DK141168B/en not_active IP Right Cessation
- 1975-03-27 CA CA223,227A patent/CA1050546A/en not_active Expired
- 1975-03-27 CA CA223,222A patent/CA1050558A/en not_active Expired
- 1975-03-27 DE DE2560591A patent/DE2560591C2/de not_active Expired
- 1975-03-27 NL NL7503754.A patent/NL160821C/en not_active IP Right Cessation
- 1975-03-27 AU AU79640/75A patent/AU465906B2/en not_active Expired
- 1975-03-27 DE DE19752513732 patent/DE2513732A1/en active Granted
- 1975-03-27 NL NL7503755A patent/NL7503755A/en not_active Application Discontinuation
- 1975-03-28 IT IT21867/75A patent/IT1049394B/en active
- 1975-03-28 IT IT21855/75A patent/IT1048806B/en active
- 1975-03-31 PH PH16998A patent/PH13072A/en unknown
- 1975-03-31 OA OA55458A patent/OA04916A/en unknown
- 1975-03-31 OA OA55460A patent/OA04918A/en unknown
- 1975-03-31 PH PH16995A patent/PH11792A/en unknown
- 1975-04-01 IL IL46988A patent/IL46988A/en unknown
- 1975-04-01 YU YU00828/75A patent/YU39026B/en unknown
- 1975-04-01 DD DD185147A patent/DD118785A5/xx unknown
- 1975-04-01 ES ES436175A patent/ES436175A1/en not_active Expired
- 1975-04-01 HU HU75CI00001563A patent/HU172935B/en not_active IP Right Cessation
- 1975-04-01 LU LU72174A patent/LU72174A1/xx unknown
- 1975-04-01 DD DD192060A patent/DD124733A5/xx unknown
- 1975-04-01 GB GB13349/75A patent/GB1498199A/en not_active Expired
- 1975-04-01 YU YU827/75A patent/YU40259B/en unknown
- 1975-04-01 DD DD185144A patent/DD118510A5/xx unknown
- 1975-04-01 GB GB1333275A patent/GB1448810A/en not_active Expired
- 1975-04-01 AT AT244675A patent/AT345614B/en not_active IP Right Cessation
- 1975-04-01 BG BG029507A patent/BG24651A3/en unknown
- 1975-04-01 BG BG029508A patent/BG26356A3/en unknown
- 1975-04-01 ES ES436174A patent/ES436174A1/en not_active Expired
- 1975-04-01 RO RO7581867A patent/RO73181A/en unknown
- 1975-04-01 AT AT244875A patent/AT343407B/en not_active IP Right Cessation
- 1975-04-01 LU LU72175A patent/LU72175A1/xx unknown
- 1975-04-01 IL IL46989A patent/IL46989A/en unknown
- 1975-04-01 HU HU75CI1564A patent/HU173317B/en unknown
- 1975-04-01 AR AR258204A patent/AR224602A1/en active
- 1975-04-02 CS CS7500002240A patent/CS183789B2/en unknown
- 1975-04-02 RO RO7581876A patent/RO79677A/en unknown
- 1975-04-02 PL PL1975179265A patent/PL98627B1/en unknown
- 1975-04-02 SU SU752121601A patent/SU743561A3/en active
- 1975-04-02 IE IE709/75A patent/IE41777B1/en unknown
- 1975-04-02 CS CS7500002239A patent/CS183788B2/en unknown
- 1975-04-02 EG EG75195A patent/EG12263A/en active
- 1975-04-02 TR TR18508A patent/TR18508A/en unknown
- 1975-04-02 TR TR18339A patent/TR18339A/en unknown
- 1975-04-02 SU SU752120455A patent/SU682096A3/en active
- 1975-04-02 JP JP4022675A patent/JPS5345364B2/ja not_active Expired
- 1975-04-02 RO RO106426A patent/RO84021B/en unknown
- 1975-04-02 JP JP50040227A patent/JPS6042202B2/en not_active Expired
- 1975-04-02 EG EG194/75A patent/EG11640A/en active
- 1975-04-02 IE IE708/75A patent/IE41140B1/en unknown
- 1975-04-02 PL PL1975179266A patent/PL97786B1/en unknown
- 1975-11-05 SU SU752186207A patent/SU628812A3/en active
-
1976
- 1976-04-05 SU SU762342705A patent/SU626690A3/en active
-
1978
- 1978-01-12 JP JP232778A patent/JPS53135964A/en active Granted
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