IE41777B1 - Fungicidal agents - Google Patents

Abstract

1498199 Heterocyclic amides CIBA-GEIGY AG 1 April 1975 [2 April 1974 10 Feb 1975] 13349/75 Heading C2C Novel compounds of Formula (I) wherein R 1 represents a halogen atom or an alkyl or alkoxy group of 1 to 4 carbon atoms, R 2 represents a hydrogen or halogen atom, an alkyl group of 1 to 3 carbon atoms or an alkoxy group of 1 to 4 carbon atoms, R 5 represents a hydrogen or halogen atom or an alkyl group of 1 to 3 carbon atoms, and R 6 represents a hydrogen atom or a methyl group and the total number of carbon atoms in the substituent groups R 1 , R 2 , R 5 and R 6 on the phenyl ring does not exceed 8; X represents the group R 3 represents the group (wherein each of R1, R11 and R111 represents a hydrogen atom or a methyl or ethyl group); and R 4 represents an unsubstituted or halosubstituted furyl, tetrahydrofuryl, pyridyl, or pyrimidyl group; but excluding the compounds N - (11 - methoxycarbonylethyl) - N - (furan- (211) - carbonyl) - 2,6 - dimethylaniline and N - (11 - methoxycarbonylethyl) - N - (furan- (211) - carbonyl) - 2,3,6 - trimethylaniline) are used in fungicidal compositions. They may be prepared either by (a) acylating a compound of Formula (II) with a compound of formula or an acid halide, or anhydride thereof or by (b) reacting a compound of Formula IV with butyl lithium or sodium hydride to give the corresponding alkali metal salt and then reacting this salt with a compound of formula where Hal is a halogen atom. The enantiomeric D-form of the compounds of Formula (I) in which X = -CH(CH 3 )- may be prepared by reacting the racemic compound of Formula (VI) with a nitrogen-containing, optically active base to give the corresponding salt, followed by fractional crystallization and liberation of the acid of Formula VI 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 VI. The D-form of the amide of Formula II may be prepared by reacting the D-form of the acid with the amine of formula HN(R11)(R111). The D-form of the compound of Formula (I) may then be prepared as in step (a) above. The D-form of the compound of Formula VI may also be prepared by replacing the hydroxy group in the naturally occurring L(+) lactic acid by halogen and reacting this product further with the aniline of Formula VII with reversal of the configuration.

Description

This invention relates to fungicidal agents.

According to the present invention there are provided compounds of the formula I (X) wherein R^ represents a halogen atom.or an alkyl or alkoxy group of 1 to 4 carbon atoms, R2 represents a hydrogen or halogen atom, an alkyl group of 1 to 3 carbon atoms or an alkoxy group of 1 to 4 carbon atoms, Rg represents a hydrogen or halogen atom or an alkyl group of to 3 carbon atoms, and R, represents a hydrogen atom or a methyl group and the total Q number of carbon atoms in the substituent groups R,, R_, R_ and R, X Ζ Ο D on the phenyl ring does not exceed 8? - 2 417 7 7 X represents the group —'CH2— or —CH— ; represents the group R z —COOR' or —CON \ Rl (wherein each of R', R and R1 represents a hydrogen atom or a methyl or ethyl group); and R^ represents an unsubstituted or halo-substituted furyl, tetrahydrofuryl, pyridyl or pyrimidinyl group; but excluding the compounds N-(11-methoxycarbonyl-ethyl)-N-(furan-(2)-carbdnyl)-2,6dimethylaniline and N-(1'-methoxycarbonyl-ethyl)-N-(furan-(2)carbonyl)-2,3,6-trimethylaniline.

The compounds N-(i'-methoxycarbonyl-ethyl)-N-(furan-(2)carbonyl)-2,6-dimethylaniline and N-(1'-methoxycarbonyl-ethyl)-N(furan-(2)-carbonyl)-2,3,6-trimethylaniline are described and claimed in Patent Specification No. 41140.

By alkyl and alkyl moiety of an alkoxy group are meant the following groups, depending on the number of carbon atoms specified: methyl, ethyl, n-propyl, isopropyl or η-, iso-, sec.- or tert.butyl. Halogen is fluorine, chlorine, bromine or iodine.

It has surprisingly been found that the compounds of formula I have fungicidal activity. The invention thus also provides a method of combating phytopathogenic fungi which method comprises applying to a locus infested with or liable to be infested with the fungi a compound of formula I.

With the compounds of the formula I it is possible to inhibit or destroy phytopathogenic fungi which occur in plants, particularly cultivated plants, or on parts (fruit, blossoms, leaves, stems, tubers, roots) of cultivated plants and related cultures of useful plants and also to protect from such fungi parts Of plants which grow later. Examples of such cultivated plants are: cereals, maize, rice, vegetables, sugar beet, soya, ground nuts, fruit trees, ornamental plants, but primarily vines, hops, cucumber plants (cucumbers, marrows, melons), Solanaceae. such as potatoes, tobacco and tomatoes, as well as bananas, cocoa and natural rubber plants.

The compounds of formula I act against the phytopathogenic fungi which belong to the following classes'.' Ascomycetes (e.g. Erysiphaceae)? Basidiomvcetes, above all rust fungi; Fungi Imperfecti; 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. Accordingly the invention also provides harvested seeds, fruits and tubers treated With a compound, of formula I, In the compounds of formula I, R2 may represent a halogen atom or an alkyl group of 1 to 3 carbon atoms and Rg and R^ both represent hydrogen atoms and R^ represents an unsubstituted 2-furyl or 2-tetrahydrofuryl group.

Preferred fungicides are compounds of the formula I wherein R represents a methyl group, R is ortho with respect to the amino group and represents a chlorine atom or a methyl or ethyl group, and the group —X—R^ represents the group - 4 417 7 7 —CH—COOR' ; R^, R,., Rg and R' being as defined above. These cornpouunds will be referred to as group Ia. Preeminent among these compounds Ia are those wherein R^ represents a 2-furyl radical which is preferably unsubstituted.

Within this last mentioned group, especial importance attaches to fungicidal compounds wherein —X—represents a 1'-methoxy carbonylethyl group and wherein the total number of carbon atoms of the substituents R., E., R_ and R does not exceed 4, for example 1 J □ 0 the .2, 3,5,6-tetramethylaniline, 2,6-dimethyl-3-ethylaniline or 2,6dimethylaniline derivatives as well as those 2,6-dimethylaniline derivatives which contain in addition a third substituent R^ or R. 0 in the phenyl nucleus.

The compounds of the formula I may be manufactured according to the invention by acylating a compound of the formula II with a carboxylic acid of the formula III HO—CO—R4 (III) or with an acid halide or acid anhydride thereof.

According to another method of the invention, it is also possible to manufacture the compounds of the formula I by converting an acyl anilide of the formula IV with butyl lithium or sodium hydride into the corresponding alkali metal salt, which is then reacted with a compound o£ the formula V Hal-X—R3 (V) to give the desired end product, or else to react the acyl anilide of the formula IV with the compound of the formula V in the presence of an alkali metal carbonate (e.g. Na^CO^ or KjCO^) as proton acceptor, preferably with the addition of catalytic amounts of alkali metal iodide (e.g. potassium iodide).

In the formulae II, III, IV and V, the symbols R^ to R0 and X have the meanings assigned to them in formula I and Hal represents a halogen atom, preferably chlorine or bromine, or another readily replaceable radical. The acid halide used is preferably an acid chloride or acid bromide.

The reactions can be carried out in the presence or absence of solvents or diluents which are inert to the reactants. Examples of such 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 such as dialkyl ethers, dioxan, tetrahydrofuran; nitriles like acetonitrile; N,Ndialkylated amides like dimethyl formamide; anhydrous acetic acid, dimethyl sulphoxide; ketones like methyl ethyl ketone and mixtures of such solvents. The reaction temperatures are generally between 0° and 180°C, preferably between 20° and 120°C. In many cases it - 6 4 17 7 7 is advantageous to use acceptors or condensation agents. Suitable examples are: tertiary amines, e.g. trialkylamines (e.g. triethyl amino), pyridine and pyridine bases, e.g. the oxides and hydroxides, hydrogen carbonates and carbonates of alkali metals and alkaline earth metals, as well as sodium acetate. Furthermore, it is also possible to use a surplus of the compound of the formula II as acid acceptor in the first method. The process of manufacture which proceeds from compounds 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 hydrogen halide that has formed. In other instances, it is very advantageous to use dimethyl formamide as reaction catalyst.

The starting materials of formula II can be prepared by processes analogous to those which are generally indicated for the manufacture of anilino-alkane acid ester in the following publications: J. Org. Chem. 30,4101 (1965). Tetrahedron 1967, 487, Tetrahedron 1967, 493.

The compounds of the formula I in which CH I χ = —*ch— possess an asymmetrical carbon atom(*) and can be resolved into the optical antipodes in the customary manner. In this connection, the enantiomeric D-form has the more pronounced fungicidal action.

Within the scope of the invention, those compounds, their compositions and their use which refer to the D-configuration of the formula I are accordingly preferred. In ethanol or acetone theee D-forms have, as a rule a negative angle of rotation.

The pure, optical D-antipodes may be obtained by manufacturing the racemic compound of the formula VI wherein R,, R_, R_ and R. have the meanings assigned to them in X Ζ 5 Ό formula I, and then reacting this in known manner with a nitrogencontaining, 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 VI which is enriched with the optical D-antipode and, if appropriate, repeating (also several times) the salt formation, crystallisation and liberation of the α-anilinopropionic acid of the formula VI.

From this D-form it is then possible, if desired, to manufacture the optical D-configuration of the ester of the formula II in conventional manner, e.g. in the presence of HCl or H2S°4 > with methanol Or ethanol,or to manufacture the amide of the formula II with the corresponding amine of the formula HN(R)(R'). A suitable optically active organic base is, for example, a-phenylethy1amine.

Instead of fractional crystallisation, it is also possible to obtain the enantiomeric D-form of the formula VI by replacing the hydroxy group in the naturally occurring L(+) lactic acid by halogen and reacting this product further with the desired aniline of the formula Vii (VII) - 8 41777 with reversal of the configuration.

In addition to optical isomerism, an atropisomerism is normally observed about the phenyl —nZ axis in those cases where the phenyl ring is substituted at least in the 2,6-positions and at the same time unsymmetrically to this axis (i.e. also by the presence of additional substituents as the case may be). This feature is caused by the steric hindrance of the radicals —X—R^ and —CO—R^. Provided no synthesis is carried out with the aim of isolating pure isomers, a produce is normally obtained as a mixture of two optical isomers or of two atropisomers or as a mixture of these four possible isomers. The basically better fungicidal action of the enantiomeric D-form (in comparison to the D,L-form or to the L-form) is retained however and is not noticeably affected by the atropisomerism.

The following Examples illustrate the invention in more detail. Unless otherwise stated, an active substance of the formula I, which can occur in optically active forms, is always the racemic mixture.

Manufacture of Example 1 CH - C00CHII λ/ CH„ (compound 2) N - (1' - methoxycarbonyl - ethyl) - N - (furan - (2) - carbonyl)· 2,3 - dimethyl - δ - ethylaniline. a) 100 g of 2,3-dimethyl-6-ethylaniline, 223 g of 2-bromopropionic acid methyl ester and 84 g of NaHCO3 were stirred for 17 hours at 140°C. The mixture was then cooled, diluted with 300 ml of water and extraction was performed with diethyl ether. The extract was washed with a small amount of water, dried over sodium sulphate, filtered, and the ether evaporated off. After the surplus 2-bromopropionic acid methylester had been distilled off, the crude product was distilled in a high vacuum; b.p. 88°_ 90°C/0.04 Torr. b) 13 g of furan-2-carboxylic acid chloride were added drop10 wise with stirring to 17 g of the ester obtained in a), 2 ml Of dimethyl formamide and 150 ml of absolute toluene and the mixture was refluxed for 1 hour. The solvent was evaporated off and the crude product was then crystallised by trituration with petroleum ether; m.p. 110.5°—126°C (ethyl acetate/petroleum ether). Compound 2 is the mixture of two pairs of diastereoisomers.

The D-forms of both atropisomers (compounds 2a and 2b) are obtained by acylating the D-form of a-(2,3-dimethyl-6-ethylanilino) propionic acid methyl ester with furan-(2)-carboxylic acid or one of the reactive derivatives thereof.

N - (dimethylaminocarbonylmethyl) - N - (furan - (2) - carbonyl)2,6 - dimethylaniline. 28 g of the N-(ll-methoxycarbonyl-methyl)-N-(furan-(2)10 41777 carbonyl)-2,6-dimethylanlline manufactured analogously to Example 1 (m.p. 98°—99°C) are stirred for 1 day at room temperature with 150 ml of 40% aqueous dimethylamine solution and 0.5 g of triethylenediamine.

Unreacted starting material is removed by performing extraction twice with ether and the aqueous phase is then concentrated by rotary evaporation. The residual viscous oil is crystallised by trituration with hexane.

The end product has a melting point of 142°—145°C after 10 reerystallisation from, hexane/tetrahydrofuran.

Example 3 Manufacture of N - (1' - methoxycarbonylethyl) - N - (2,4 - dichloropyrimidine(5) - carbonyl) - 2,6-dimethylaniline With stirring, 25.4 g of 2,4-dichloropyrimidine-5-carboxylic acid chloride in 50 ml of chlorobenzene were added dropwise within minutes to a mixture of 20.7 g of N-(1'-methoxycarbonylethyl) 2,6-dimethylaniline, 2 ml of dimethyl formamide and 150 ml of chlorobenzene, in the process of which the temperature rose by 20 10°C. The reaction mixture was then heated to 110°C and the hydrogen chloride which had formed was removed by passing in nitrogen. The solvent was evaporated off by rotary evaporation and the crude product was then crystallised by trituration with petroleum ether. The end product which was purified by recrystal11 - 41777 lisation from isopropanol had a melting point of 136°—137°C. The following compounds of the formula lb (R^ = 2-position) which are tri- or tetra-substituted in the phenyl nucleus are manufactured, in this manner or by one of the methods indicated hereinabove.

S, ‘9 R. '7 R. ‘1 R, '8 (lb) Ο 0 X α Φ υ 0 CN 0 (Ν r4 $4 υ r-4 | 0 r—1 1 Η 0 kO I 0 φ 1 ιη 1 Γ 0 • 0 ιη σι Ο . νο Ο 0 Ο γ-4 r- . ΓΊ ι-1 r-l r-4 ο ω a ά ά ά έ g Λ g r4 •Η Ο \ '\ a a a a 8 8 8 8 ο υ ο ο o P o y 1 σ, 1 CO L cn 1 a a a a a a a £ U ι m (Continued) (Continued) 417 7 7 (Continued) 417 7 7 The compounds listed hereinafter are mono- or disuhstituted in the phenyl 4J G flj 4-> Ul G u J4 Eh co «if r-i r-4 0 kO O Λ o CM • 0 στ r-4 o •H ω • « >« £X 0» Λ • 1 tx e rQ 0. Λ ir o o o ffi o r „ r K ® ® ru r Ό G G (X £ a ι—I J σ\ co ex £ o ID H <4* r—I r4 (X £ E ω a > a I 1 «3* in ffl U CO E U in in OJ OJ ^1777 (ΰ ο •Η g to Gl fi υ o u 3 0 0 co o CM ι-4 ro p-4 i-4 I r-4 | ,1 0 0 CM 03 o i-4 CM 1—4 r-4 i—4 i-4 ά a a co cm ο co Μ r* μ Η Ο Ε* > 0 o o CM CM r-- β r-4 σ» H o ά ά a fi fi λ Γ CM co Μ1 Η <ί< »—4 l£> co (Continued) co E u o o a n I « L & 8 I ? . p1 L a fca aaaaaaaaa p p — 8 jj—8 jj —u p - jj—o p — o E a □ I kD i—{ □ J kD (O E u n a o P in 1 E ro 0 r- r-4 CM r-4 E ω E υ o u a •H ro i υ kD 1 in kD I kD a in in E co □N s I o ί σι Ε α Ε co ϋ Ο ϋι •Η TJ C Ο ί ο r· CM GO CM Ο ΓΟ ι—4 CO CO co co m co - 18 < 417 7 7 -ρ c: nJ 4J (0 β ο ϋ β Q •Η (0 >1 Λ & Μ Ρ δ ΓΠ Ο ό ο ιη Ρ Μ g («1 Ο Ο ο ΙΛ ο ο ΙΛ ΙΛ CU Λ5 γπ Γ~ι «-4 ά ε η Μ g CM ό \ υ ο tn Qt Λ Επ υ α 0 ΙΛ 0 ΙΛ Ο υ ιη 0 φ γ-4 ό σι γ-4 I Φ j 1 ϋ 1 I 0 3 1 0 CM ΙΛ 0 Μ* 'ζΡ ω φ Η ι-4 r4 ,t ά a Οι a CJ λ ε ε C (Continued) Κ Ο υ Ε υ ο ο ε tc υ Γ" r Ε Ε Μ tc — υ υ —υ ο ΓΠ Ε □ γ4 Ό I φ Ε Ο I φ ΓΠ I φ ϋ I ο ω •Η ι—t Ο ι—I U η γπ Ε Ε U Ο -ύ c β ο Οι ε ο υ σ\ ΓΠ γ4 Ν Π Sf ^Ρ *3' (Continued) ω β ο υ r-l ο •Η η >1 Λ & Μ Μ g Γ* Ο Ο Ο ω ιο Οι Χϊ nJ ci o £ o υ ιη Ο ο Γ*· Οι Λ σ» ιη Ο U Ο Ο οο > οο ιη Η 00 Η • · r Ο* Οι Οι • k « g g fi ° a — ω a a te S I § I r r r r „ r .......

B_g s_s p |s m nj cm cm u o qj σι m Ui ι 54« u U I O I ID O I ID ffl ϋ in in ffi Ul Cl Cl υ u r- co σι si* s? ii* 417 7 7 -P c fO ϋ •rl 0) os :< rd tf o o rH kD o ID ffi U a -u X a σ υ a u u υ OJ 0 0 0 0 co Ρ ω m Ol in 0 rd Ρ OJ k0 rH O 00 | 0 rH rH H o 1 Η T rd 0 U u 1 | in Η 0 0 0 0 0 0 1 r- 4 ο Ol o Ol CO rd 0 rH Ο co OJ Ol k0 O o ά rH rH rH «—1 rH rH o rd ft a a a ft a a Λ • • ε s 6 ε ε ε rH o k0 K -o OJ oi m ffi M m W io g w κ u m O O — ol I ο o a y o o o o o r r r r OJ OJ OJ OJ | St-H tr« h-ι M U-l |Η μΜ iH r r r r r CO « ffi •u K o r υ I kO W Q kO OJ O I kO I kO W o I kO I in tf υ tf iii u ffi u o o tf υ CO LO Continued P ΰ o a tq 0 0 +3 CN o w σ% r—J c r-l T4 0 1 □ 0 0 cn σ% ta co o o i—! ι-1 •H (0 « • >1 Qt a Λ t • cu e s CM CO a υ CO tn ffl Ά z Q o υ o o r 1 CN r cn a r ffl a Γ u tn a co CN a CN υ a « VO I VO tn rM a co K CN ffl υ 0 Ό d □ 0 σ» o 04 m to ε 0 u i M ΨΙ ri KJ M Φ ΰ 0) tn 0) Χί 4J m o (0 Ό C ί o □ Φ Λ P o (0 r-l d ti I CO-R 417 7 7 (Continued) (Continued) (Continued) 417 7 7 (Continued) (Continued) 417 7 7 The compounds of the formula I can be used by themselves or in fungicidal composition form together with a solid extender and a surface active agent, or a liquid diluent and a surface active agent. The compositions can be solid or liquid and can contain substances used in formulation technology, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, stickers, thickeners, binders or fertilisers. Suitable liquid compositions can contain a surface active agent and a hydrocarbon which boils at a temperature above 130°C.

Liquid compositions may comprise an aerosol propellant e.g. a polyhalogenated hydrocarbon. The amount of active substance in commercially useful compositions is generally between 0.1 and 90%.

The compounds of the formula I can be applied in the following process forms (the percentages hy weight in brackets denote the advantageous amounts of active substance): solid forms: dusts and tracking agents (up to 10%); granules, coated granules, pellets, coated pellets, impregnated granules and homogeneous granules (1 to 80%), impregnated pellets, liquid forms; a) active substance concentrates which are dispersible in water: wettable powders and pastes (25—90% in the commercial pack, 0.01 to 15% in ready for use solution); emulsion concentrates and concentrated solutions (10 to 50%; 0.01 to 15% in ready for use solution); b) solutions (0.1 to 20%).

The active substances of the formula I can be formulated, for example, as follows: 417 7 7 Dusts: The following substances are used to manufacture a) a 50% and b) a 2% dust: a) 5 parts of active substance parts of talcum; b) 2 parts of active substance part of highly disperse silicic acid parts of talcum.

The active substances are mixed with the extenders and ground and in this form can be processed to dusts for application. Granules: The following substances are used to manufacture 5% granules: parts of active substance 0.25 part of epichlorohydrin 0.25 part of cetyl polyglycol ether 3.50 parts of polyethylene glycol parts of kaolin (particle size 0.3—0.8 mm).

The active substance is mixed with the 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 micro granules are advantageously used for combating soil fungi.

Wettable 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 active substance parts of sodium dibutyl naphthylsulphonate parts of naphthalenesulphonic acid/phenolsulphonic acid/ acid/formaldehyde condensate (3:2:1) - 30 41777 ί I parts of kaolin parts of Champagne chalk b) 40 parts of active substance parts of sodium lignin sulphonate part of sodium dibutylnaphthalenesulphonic acid parts of silicic acid c) 25 parts of active substance 4.5 parts of calcium lignin sulphonate 1.9 parts of a Champagne chalk/hydroxyethyl cellulose mixture (1:1) 1.5 parts of sodium dibutylnaphthalenesulphonate 19.5 parts of silicic acid 19.5 parts of Champagne chalk 28.1 parts of kaolin d) 25 parts of active substance 2.5 parts of isooctylphenoxy-polyethylene-ethanol 1.7 parts of a Champagne chalk/hydroxyethyl cellulose mixture (1:1) 8.3 parts of sodium aluminium silicate 16.3 parts of kieselguhr parts of kaolin e) 10 parts of active substance parts of a mixture of the sodium salts of saturated fatty alcohol sulphates parts of naphthalene sulphonic acid/formaldehyde condensate 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 suspen31 sion power are obtained. These wettable powders can be diluted, with water to give suspensions of desired concentration and can be used in particular for application to leaves.

Emulsifiable concentrates: The following substances are used to manufacture a 25% emulsifiable concentrate: parts of active substance 2.5 parts of epoxidised vegetable oil parts of an alkylarylsulphonate/fatty alcohol polyglycol ether mixture parts of dimethylformamide 57.5 parts of xylene By diluting such concentrates with water it is possible to manufacture emulsions of desired concentration which are especially suitable for application to leaves.

Example 4 Action against Phytophthora infestans on Solanum lycopersicum (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 heen 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 an artificial wet fog. After this time typical leaf specks appear. Their number and size are the criterion for evaluating the tested substance. lb) 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%. 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% (referred to the volume of the soil) to the surface of the soil of 3 weeks 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 humidity, after which time typical leaf specks form. The size and number of the specks serve as criterion for evaluating the effectiveness of the tested substances.

In the test of Example 4 the compounds of formula I exhibit the following strong action against the leaf-fungus (average values).

TABLE Compound Fungus infection in % Compound Fungus infection in % 1 0—5% 51 0—5% 2 <20% 56 <20% 3 <20% 60 0—5% 4 0—5% 61 <20% 6 <20% 62 20—40% 7 <20% 66 <20% 8 0—5% 70 <20% 9 <20% 74 <20% 12 <20% 76 <20% 13 <20% 80 0—5% 14 20—40% 81 <20% 16 <20% 82 <20% 22 0—5% 83 <20% 24 <20% 25 0—5% 26 <20% 28 <20% 29 0—5% 35 <20% 39 <20% Compounds 1, 4, 8, 51, 60 and 80 reduced the fungus infection to <20% in the same tests at application concentrations of only 0.02%.

Example 5 Action against Plasmopara 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 0.05% 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 treated 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 spore 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 (0.05%) 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 size and number of the infected areas served as criterion for evaluating the effectiveness of the tested substances.

In both these tests the compounds of the formula I exhibited a predominantly leaf-fungicidal action. Without exception, the compounds listed in the Table of Example 4 reduced the fungus infection to 20% and in some cases, for example that of compound 1 almost no infection occurred (0—5%).

Example 6 Action against Erysiphe graminis on Hordeum vulgare (barley) Residual protective action Barley plants about 8 cm in height were sprayed with a spray broth (0.05% active substance) prepared from a wettable powder of the active substance. After 48 hours the treated plants were dusted with conidia of the fungus. The infected barley plants were stood in a greenhouse at about 22°C and the fungus infection was evaluated 10 days later.

A number of the compounds of the formula I, e.g. compounds 62 and 63, effect in this test a reduction of the fungus infection to <20%.

Example 7 Action against Pythium 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 test preparations formulated as wettable powders are poured in 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 dressing 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 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 Under the conditions of both test a) and test b), more than 85% of the sugar beet plants emerged after treatment with the active substances of the formula I and had a healthy appearance.

Less than 20% of the untreated control plants emerged and their 15 appearance was in part sickly.

Claims (20)

CLAIMS I. A compound of formula I / 3 Ν (I) or an alkyl or alkoxy group of wherein

1. Substantially as described with reference to Example 1, 2 or 3. 21. Compounds according to claim 1 prepared by the process claimed in any one of claims 17 to 20. 22. A fungicidal composition which contains, as active ingredient, a compound as claimed in any one of claims 1, 3 to 11 and 13 to 16 together with a solid extender; a solid extender and a surface active agent; or a liquid diluent and a surface active agent. 23. A fungicidal composition which contains, as active ingredient, a compound as claimed in claim 2 together with a solid extender; a solid extender and a surface active agent; or a liquid diluent and a surface active agent. 24. A fungicidal composition which contains, as active ingredient, a compound as claimed in claim 12 together with a solid extender; a solid extender and a surface active agent; or a liquid diluent and a surface active agent. 25. A solid composition according to claim 22, 23 or 24. 26. A composition according to claim 25 in the form of a granulate or pellets. 27. A composition according to claim 26 wherein the granules or pellets are coated or impregnated with active ingredient. 28. A liquid composition according to claim 22, 23 or 24. 29. A composition according to claim 28 comprising a surface active agent and a hydrocarbon which boils at a temperature above 130°C. 30. A composition according to claim 28 which contains an aerosol propellant. 31. A composition according to claim 30 wherein the aerosol - 42 41777 propell&nt is a polyhalogenated hydrocarbon. 32. A fungicidal composition which contains a compound as claimed in claim 1 and is in the form of a dust, granulate, wettable powder or emulsifiable concentrate specifically described 1 which comprises reacting a compound of formula IV as defined in claim 18 with a compound of formula V as defined in claim 18 in 20 the presence of an alkali metal carbonate as proton acceptor. 20. A process for preparing a compound as claimed in claim 1, which process comprises reacting a compound of formula IV (IV) (wherein R,, R_, R„, R,. and R are as defined in claim 1) with 1 2 4 5 6 butyl lithium or sodium hydride to give the corresponding alkali metal salt and then reacting this salt with a compound of formula V Hal-X—R 3 (V) 1 to 4 carbon atoms, R 2 represents a hydrogen or halogen atom, an alkyl group Of 1 to 3 carbon atoms or an alkoxy group of 1 to 4 carbon atoms, R_ represents a hydrogen or halogen atom or an alkyl group

2. A compound according to claim 1 wherein R^ represents a halogen atom or an alkyl group of 1 to 3 carbon atoms and R^ and Rg both represent hydrogen atoms and R^ represents an unsubstituted 2-furyl or 2-tetrahydrofuryl group.

3. A compound according to claim 1 or 2 wherein R^ represents a methyl group, R 2 is ortho with respect to the amino group and represents a chlorine atom or a methyl or ethyl group, and the group —X—represents the group —CH—COOR 1 (wherein R' is as defined in claim 1).

4. A compound according to claim 3, wherein R^ represents a 2-furyl radical. 5. Herein. 33. A method of combating phytopathogenic fungi which method comprises applying to a locus which is infested or liable to be infested with the fungi a compound as claimed in any one of claims 1, 3 to 11 and 13 to 16. 10 34. A method of combating phytopathogenic fungi which method comprises applying to a locus which is infested or liable to be infested with the fungi a compound as claimed in claim 2. 35. A method of combating phytopathogenic fungi whioh method comprises applying to a locus which is infested or liable 5 (wherein R 4 is as defined in claim 1) or an acid halide or acid anhyride thereof. 5 o 5 b

5. A compound according to claim 3 or 4, wherein the group —X—R 3 represents a 1 1 -methyloxycarbonyl-ethyl group and wherein the total number of carbon atoms in the substituent groups R^, R^, R_ and R,_ does not exceed 4. 5 R^ represents a halogen atom

6. A compound according to claim 5 wherein the phenyl group is 2,3,5,6-tetramethyl or 2,6-dimethyl-3-ethyl substituted or is 2,6-dimethyl-substituted and optionally further substituted by other R_ and/or R. groups.

7. N - (1' - Methoxycarbonyl - ethyl) - N - (furan - (2)~ carbonyl) - 2,3,5,6 - tetramethylaniline of the formula ? H 3 HC - C00CH 3

8. N - (1' - Methoxycarbonyl - ethyl) - N - (furan - (2“)carbonyl) - 2,3 - dimethyl - 6 - chloroaniline.

9. N - (1' - Methoxycarbonyl - ethyl) - N - (furan - (2)carbonyl) - 2,6 - dimethyl - 3 - ethylaniline.

10. N - (1‘ - Methoxycarbonyl - ethyl) - N - furan - (2)carbonyl) - 2,6 - dimethyl - 3 - bromoaniline. 10 of 1 to 3 carbon atoms, and R represents a hydrogen atom or a methyl group and the total number of carbon atoms in the substituent groups R^, R 2 » R^ and R, on the phenyl ring does not exceed 8; X represents the group

11. N - (1' - Methoxycarbonyl - ethyl) - N - (furan - (2) carbonyl) - 2,4,6 - trimethyl - aniline.

12. N - (1' - Methoxycarbonyl - ethyl) - N - (tetrahydrofuryl- (2) - carbonyl) - 2,3,6 - trimethyl - aniline.

13. N - (1' - Methoxycarbonyl - ethyl) - N - (furyl(2) - carbonyl) - 2,6 - dimethyl - 4 - chloroaniline.

14. N - (1' - Methoxycarbonyl - ethyl) - N - (tetrahydrofuryl- (2) - carbonyl) - 2,6 - dimethylaniline. 15. To be infested with the fungi a compound as claimed in claim 12. 36. Harvested seeds, fruits .or tubers, treated with a compound as claimed in any one of claims 1, 3 to 11 and 13 to 16. 37. Harvested seeds, fruits or tubers, treated with a ffimpound as claimed in claim 2. 15 (wherein R^ and X are as defined in claim 1 and Hal represents a halogen atom).

15. N - (1' - Methoxycarbonyl - ethyl) - KT - (5 - bromofuryl- (2) - carbonyl - 2,6 - dimethylaniline. 15 CH I 3 —CH 2 — or —CH— ; R 3 represents the group R z —COOR' or —CON \ Rl . , (wherein each of R‘, R and R' 1 'represents a hydrogen atom or a methyl or ethyl group); and 20 R 4 represents an unsubstituted or halosubstituted furyl, tetrahydrofuryl, pyridyl or pyrimidinyl group; but excluding the compounds N-(1'-methoxycarbonyl-ethyl)-N-(furan-(2)-carbonyl)2,6-dimethylaniline and N-(l'-methoxycarbonyl-ethyl)-N-(furan(2 11 ) -carbonyl) -2,3,6-trimethylaniline.

16. The enantiomeric D-configuration of a compound as claimed in any one of claims 1 to 15 wherein X represents the group —CH—

17. A process for preparing a compound as claimed in claim 1, which process comprises acylating a compound of formula IX 40 41777 (wherein R., R_, R . R r , R. and X are as defined in claim 1) with i 2 3 5 o a compound of formula III HO—CO—R 4 (III)

18. A process for preparing a compound as claimed in claim

19. A process for preparing a compound as claimed in claim

20. 38. Harvested seeds, fruits or tubers, treated with a compound as claimed in claim 12.