CA1156665A - Fungicidally active furancarboxylic acid anilides - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
The present invention provides fungicidally active furancarboxylic acid anilides of the general formula I

Description

The present invention is concerned with new fungicidal-ly active furancarboxylic acid anilides, with the use of these compounds for controlling phytopathogenic fungi and also with a process for the manufacture of the new active compounds.
Agents that act against phytopathogenic fungi have already been known. Agents of this type known in practice are r for example, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole (United States Patent Specification Nos. 3,260,725 and 3,260,588) and tetramethylthiuram disulphide (German Patent Specification No.
642,532). However, these agents do not always have a satis-factory action against leaf and soil fungi.
The problem upon which the present invention is based has been to provide an agent having a superior action against leaf and soil fungi. This problem is now solved in accordance with the present invention by the compounds of the general formula I, as defined below.
The present invention provides compounds of the general formula I

R ~ N - C ~ ~I) in which Rl represents a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, R2 represents an unsubstituted phenyl group or a phenyl group substituted by one or more substituents selected from alkyl groups containing 1 to 4 carbon atoms~ alkoxy groups 3Q containing 1 to 4 carbon atoms, alkylthio groups containing 1 to 4 carbon atoms, halogen atoms, trifl~oromethyl groups, nitro groups, alkoxycarbonyl groups containing 1 to 4 carbon ~, . .

:atoms in the alkoxy parts, alkylcarbonyl groups containing 1 to 4 carbon atoms in the alkyl parts, phenyl and cyano groups, and n represents 1 or 2.
When the substituted phenyl groups represented by R2 contains two or more substituents these substituents may be the same or different.
The action of the compounds of the present invention against leaf and soil fungi is surprisingly superior to that of known agents having the same direction of action and these compounds are also distinguished by a good plant tolerance and a sufficient duration of action. In addition, since they do not act phytotoxicall~ when applied in the quantities suitable in practice, they may accordingly be used advantageously in agriculture and horticulture for the control of leaf and soil fungi.
The compounds of the present inven~ion have outstand-ing fungicidal properties against harmful fungi.
In contrast to known fungicidal agents having on~y a preventive action, such as, for example, N-trichloromethyl thiophthalimide (United States Patent Specification ~o. 2,553,770) and manganese ethylene bisdithiocarbamate (United ~tates Patent Specification No. 2,504,404) the compounds of the present invention surprisingly also have the additional advantage of a curat~ye and systemic action which, therefore, makes it possible also to control pathogenic agents which have already penetrated into the plants.
The present invention accordingly also provides a fungicidal preparation which comprises a compound of the general 3Q formula I, in admixture or conjunction with a suitable carrier.
The preparation may of course contain one or more compounds of the general formula I.

8 ~
The present invention further provides a method of protecting a living plant against phytopathogenic fungi, wherein `~
the living plant is treated with a compound of the general formula I.
The present invention further provides a method o~
protecting a crop~larea against phythopathogenic fungi, wherein the crop area is treated with a compound of the general formula I.
The present invention further provides a method of dressing seeds, wherein the seeds are treated with a compound of the general formula I.
The present invention further provides a pack which comprises a compound of the general formula I together with instructions for its use for controlling phytopathogenic fungi.
The compounds of the present invention that are es-pecially distinguished by a superior fungicidal action are those of the general formula I in which Rl represents a hydrogen atom or a methyl or ethyl group and R2 represents a phenyl, methyl-phenyl, dimet~ylphenyl, ethylphenyl, isopropylphenyl, methoxy-phenyl, ethoxyphenyl, methylthiophenyl, fluorophenyl, chloro-phenyl, bromophenyl, dichlorophenyl, trifluoromethylphenyl, nitrophenyl, cyanophenyl, methoxycarbonylphenyl, acetylphenyl or biphenylyl group.
The new active compounds may be applied singly or, alternatively, mixtures of at least two constitutionally different compounds of the general formula I may be applied.
If desired, other fungicides, nematocides, herbicides or other types of pest-controlling agents may be added depending on the purpose. The active substances are advantageously applied in the 3Q form of fungicidal preparations, for example powders, strewable pxeparations, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid vehicles or diluents and, .~. . ~, 11,7~5 if desired, of wetting, adhesive, emulsifying and/or dispersing agents.
Suitable liquid carriers are, for example, water, mineral oils or other organic solvents, for example xylene, chlorobenzene, cyclohexanol, cyclohexanone, dioxan, acetonitrile, ethyl acetate, dimethylformamide, isophorone and dimethyl sul-phoxide.
Suitable solid carriers are, for example, li'me,kaolin, chalk, talcum, attaclay and other clays as well as natural or synthetic silicic acid.
As surface-active agents there may be mentioned, for example, salts or lignin sulphonic acid, salts or alkylated benzenesulphonic acids, sulphonated acid amides and salts !, thereof, polyethoxylated amines and alcohols.
When the active substances are to be used for dressing seeds, they may also be admixed with dyestuffs in order to give the dressed seeds a clearly visible colour.
The proportion of active substance(s) in the fungi-cidal preparations may vary within wide limits, ~he exact con centration of the active substances used for the preparations depending primarily on the quantity in which the preparations inter alia are to be used for treating soil or seeds or for treating parts of plants above the soil. The preparations may contain, for example, approximately 1 to 80% by weight, prefer-ably between 20 and 50% by weight, of active compound(s), appxoximately 99 to 20% ~y weight of liquid or solid carrier and also, if desired, up to 20% ~y weight of surface-active agent(s).
The new compounds of the general formula ~I) may be produced by the process of the present invention~ as defined below.
The present invention further provides a process for the manufacture of a compound of the general formula ~, wherein , a compound of the general formula II

(fH2)n - fH - NH 2 H ~ ~ (II), Rl in which Rl, R2 and n have the meanings given above, is reacted in the presence of an acid-binding agent and, if desired, a sol-vent with a furancarboxylic acid chloride of the formula III
'' Cl - CO - ~ ~
~ (III).

The amounts used of the compound of the general formula II and the compound of the formula III are preferably in equi- ~;
molar proportions.
As acid-binding agents there ~ay be used, for example, organic bases, for example pyridine, triethylamine or N,N-dimethylaniline, or inorganic bases, for example hydroxides,oxides and car~onates of alkali metals and alkaline earth metals, for example sodium, potassium or calcium.
As a solvent that may optionally be used, there may be mentioned, for example, other, tetrahydrofuran, benzene or ethyl acetate. Liquid acid-binding agents, for example pyridine, may serve simultaneously as solvents.
The reaction is advantageously carried out at a tem-perature within the range of from -10C to 120C.

rrhe products of the process of the present invention 3Q may be isolated in a manner known per se.
Some specific compounds of the pr~sent invention are listed in the following Table.

Name __ Physical constant _ _ Furan-2-carboxylic acid [N-(2-oxoperhydro-3-furyl)-2,6-dimethylanilide] M.p.: 135-138C
Furan-2-carboxylic acid [2-chloro-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 98-100C
Furan~2-carboxylic acid [N-(2-oxo-perhydro-3-furyl)-anilide~ M.p.: 140-141C
Furan-2-carboxylic acid [2,6-dîethyl-N-(2-oxoperhydro-3-furyl)-anilide~ M.p.: 12~-125C
Furan-2-carboxylic acid ~2-ethyl-6-methyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 127-129C
Furan-2-carboxylic acid [2-methoxy-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 139-140C
Furan-2-carboxylic acid [2,6-dimethyl-N-(5-methyl-2-oxoperhydro-3-furyl)-anilide] M.p.: 190-191C
Furan-2-carboxylic acid [3,4-dichloro-N~(2-oxoperhydro-3-furyl)-anilide] M.p.: 139-141C
Furan~2-carboxylic acid [2-methyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 132C
Furan-2-carboxylic acid [2,4-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 123-124C
Furan-2-carboxylic acid [3,4-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 122C
Furan-2-carboxylic acid [2,3-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 129-130C
Furan-2-carboxylic acid [3,5-dimethyl-N-(2-oxoperhydro-3-furyl) anilideJ M.p.: 161-162C
Furan-2-carboxylic acid [2,4j6-trimethyl-N-~2-oxoperhydro-3-furyl)-anilide] M.p.: 142 143C
Furan-2-carboxylic acid [3-methyl-N-(2-oxoperhydro-3-furyl)-anilide M.p.: 121C
Furan-2-carboxylic acid C4-methyl-N-(2-oxoperh~dro-3-furyl~-anilide] M.p.: 118-119C
Furan-2-carboxylic acid [3-chloro-N-(2-oxoperhydro-3-furyl)-anilide~ M.p.: 134-135C
Furan-2-carboxylic acid ~4-chloro-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 157-158C
3Q Furan-2-car~oxylic acid ~2-ethyl N-C2-oxoperhydro~3-furyl~-anilide] M.p.: 122-123C

Furan-2-carboxylic acid [N-(2-oxo-perhydro 3-furyl~-3-trifluoromethyl-anilide] M.p.: 130-131C

Furan-2-carboxylic acid [4 isopropyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 95-96C
Furan-2-carboxylic acid [3-bromo-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 150-153C
Furan-2-carboxylic acid [4-methoxy-N-(2-oxoperhydro-3 furyl)-anilide] M.p.: 149-151C
Furan-2-carboxylic acid [4-ethoxy-N-(2-oxoperhydro-3~furyl)-anilide] M~po 87-88C
Furan-2-carboxylic acid [4-ethyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 120-121C
Furan-2-carboxylic acid ~4-bromo-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 137-140C
Furan-2-car~oxylic acid [3-fluoro-N-(2-oxoperhydro-3-furyl~-anilide] M.p.: 142-144C
Furan-2-carboxylic acid [4-fluoro-N-(2-oxoperhydro-3-furyl)-anilide] ' M.p.: 165~1~6C
Furan-2-carboxylic acid [4-methoxy-2-methyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 133-135C
Furan-2-carboxylic acid r2,5-dimethyl-N-(2-oxoperhydro-3-fu~yl)-anilide] M.p.: 120-121C
Furan-2-carboxylic acid [2-ethoxy-N-(,2-oxoperhydro-3-furyl)-anilide] M.p.: 150C
Furan-2-carboxylic acid [2,6-diisopropyl-N-(2-oxoperhydro-3~furyl)-anilide] M.p.: 149-150C
Furan-2-carboxylic acid [3,5-dichloro-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 143-145C
Furan-2~carboxylic acid r 3-chloro-2-methyl~N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 151C
Furan-2-carboxylic acid [5-chloro-2-methyl-N-(2-oxoperhydro-3-furyl~-anilide] M.p.: 138-139C
Furan--2-carboxylic acid [2-methoxycarbonyl-N~(2-oxoperhydro-3-furyl)-anilide] M.p.: 110~112C ~.i Furan-2-carboxylic acid [3-methoxy-N-(2-oxoperhydro-3-furyl)-anilide~ M.p.: 145-148C
Furan-2-carboxylic acid [3-nitro N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 137-138C
Furan-2-carboxylic acid [3-chloro-N-(5-methyl-2-oxoperhydro-3-furyl)-anilide] M.p~: 105-108C
Furan-2-car~oxylic acid ~3-methylthio~N- -3Q (2-oxoperhydro-3-furyl)-anilide] M.p.: 154~155C
Furan-2-carboxylic acid ~5-chloro-2-methoxy-N-(,2-oxoperhydro-3-furyl~-anilide M.p.- 171-173C

Furan-2-carboxylic acid [3-fluoro-N-(5-methyl-2-oxoperhydro-3-furyl)-anilide] M.p.: 93~94C

Furan-2-carboxylic acid [4-phenyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 186-187C

Furan-2-carboxylic acid [3-acetyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 166-167C

Furan-2-carboxylic acid ~2-chloro-6-methyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 145-148C

Furan-2-carboxylic acid [2-bromo-N-~2-oxoperhydro-3-furyl)-anilide] M.p.: 118C

Furan-2-carboxylic acid [2,3-dichloro-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 126C

lD Furan-2-carboxylic acid [3-chloro-2-methoxy-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: llS/116-117C

Furan-2-ca~rboxylic acid [3-ethyl-N-2-oxoperhydro-3-furyl)-anilide] M.p.: 128-12~C

Furan-2-carboxylic acid [3-cyano-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 131/132-134C
The compounds of the present invention are generally almost colourless, odourless, crystalline substances that are practically insoluble in water and benzine but, on the other hand hand, vary readily soluble in polar organic solvents, for example acetone, dimethylformamide and dimethyl sulphoxide.

2~ The starting compounds for the manufacture of the compounds of the present invention are known per se or may be produced according to processes known per se , The following Examples illustrate the invention.
Examples 1 to 3 illustrate the manufacture of the compounds of the present invention and Examples 4 to 13 illustrate the possibilities of application of the compounds of the present invention.
Example 1 Furan-2-carboxylic a id [N_(2-oxope~ydro-3-furyl)-3a 2,6-dimethyl-anilide]

206.2 g (1.58 mole) of furan-2-carboxylic acid chlor-ide were added dropwise, at room temperature and while stirring, to a solution of 300 g tl.46 mole~ of 3-(2,6-dimethylanilino)-perhydrofuran-2-one in 600 ml of dry pyridine. After the addi-tion was complete a pyridine complex precipitated out with a simultaneous increase in temperature. Heating was effected for

3 hours at 50C and the whole was then concentrated in vacuo to half its volume. The mixture was then poured, while stirring, into 2.5 1 of ice-cold 5% hydrochloric acid and after 30 min-utes filtered with suction. Washing with a large amount ofwater and drying ln vacuo at 70C were then carried out.
Yield: 387 g = 89% of the theoretical yield.
M.p.: 135-138C.
Example 2 Furan-2-carboxylic acid [2-chloro-N-(2-oxoperhydro-3-furyl)-anilide]
13.05 g (0.1 mole) of furan-2-carboxylic acid chloride were added at room temperature to 21.16 g (0.1 mole) of 3-(2-chloranilino)-perhydrofuran-2-one. The reaction mixture was heated slowly to 120C and maintained at this temperature for 1.5 hours until the evolution of hydrogen chloride had been completed. After cooling, 100 ml of ethyl acetate were added ;
and the mixture was washed until neutral with a saturated sodium bicarbonate solution. The ethyl acetate phase was dried with magnesium sulphate, fil~ered and concentrated in vacuo. The resulting oil was crystallized with a little ether and filtered off with suction, and the resulting crystals were washed with diisopropyl ether.
Yield: 21.4 g - 70% of ~he theoretical yield.
M.p.: 98-100C.
Example 3 Furan-2-car~oxylic acid ~N-[2~oxoperhydro-3~furyl)-_ _ . ......... _ ... _ _ anilide]
, 1~5g~
A solution of 14.16 g (0.08 mole) of 3-anilinoper-y hydro furan-2-one in 150 ml of ethyl acetate and a solution of 9.54 g ~0.09 mole) of sodium carbonate in 15 ml of water were mixed by stirring. 11.70 g (0.09 mole) of furan-2-caxbox-ylic acid chloride were then added dropwise while cooling with ice. The mixture was then stirred for an hour, if necessary neutralized with a little soda solution and extracted by shak-ing with ethyl acetate. After drying over magnesium sulphate the ethyl acetate solution was concentxated to dryness in vacuo and the solid residue was treated with a little ether/ethanol.
The whole was filtered with suction, washed with ether and recrystallized from ethanol.
Yield: 10.6 g = 49~ of the theoretical yieldO
M.p.: 140-141C.
Each of the other compounds of the present invention listed in the Table above may be produced in a manner analogous to that described in any one of Examples 1 to 3.
Example 4 Limiting concentration test in the control of Pythium ultimum In a series of tests 20% pulverulent active substance preparations were mixed uniformly with soîl which was severely infected with Pythium ultimum. The treated soil was placed in . . . :
clay dishes each having a capacity of 0.5 litre and, without a waiting period, 20 marrowfat pea seeds of the Kelvedon Wonder variety were sown in each dish. After a cultivation period of 3 weeks at 20 to 24C the numbex of sound peas was de~ermined and a root assessment (1-4 as defined below) was carried out.
The active substances used and their application quantities, and also the results, are given in the following Table.

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1 ~5~i5 Example 5 Dressing of su~ rbeet seeds In a series of tests gr~ded sugarbeet seeds o~ the Dieckmann-Suprapoly variety were dressed with 20~ pulverulent active substance preparations. Clay dishes each of 2 litres capacity (20 x 20 x 5 cm) were filled with normal compost soil (damping-off) and lO0 of the sugarbeet seeds were sown in each dish. After a cultivation period of 18 days at 19 - 21 C in a greenhouse the number of sound seedlings was determined.
The active substances used and their application quantities, and also the results, are given in the following Table.

Compound accordin~ to the ~ctive substance Number o~
InYention 'n u/kg seed sound seedlings _ lQO~seeds Furan-2-carboxyl~c ac~d~N 0-.-4 g 84 (2-oxoperhydro-3-~uryl)-2,6- 0.8 g 90 dimethylanilide] 1.6 g 91 Furan-2-carboxylic acid [3- 0.4 g 73 chloro-N-(2-oxoperhydro-3- 0.8 g 71 furyl)-anilide] 1.6 g 91 Furan-2-carboxylic acid [3- 0.4 g 75 fluoro-N-(2-oxoperhydro-3- 0.8 g 79 furyl)-anilide] 1.6 g 75 _ Furan-2-carboxylic acid [2,3- 0.4 g 74 dimethyl-N-(2-oxoperhydro-3- 0.8 g 82 furyl)-anilide] 1.6 g 85 Furan-2-carboxylic acid [3-methyl- 0.4 g 72 N-(2-oxoperhydro-3-furyl)- 0.8 g 78 anilide] 1.6 g 79 Furan-2-Ga~rboxylic acid [2,6- 0.4 g 57 dimethyl-N-(5-methyl-2-oxoper~ 0.8 g 70 hydro-3-furyl)-anilide] 1.6 g 92 Furan-2~carboxylic acid ~3- 0.4 g 56 bromo-N-(2-oxoperhydro-3-furyl)- 0.8 g 55 anilide] 1.6 g 75 Agents for comparison 5-Ethoxy-3-trichloromethyl- 0.4 g 26 1,2,4-thiadiazole 0.8 g 44 1.6 g 53 Tetramethylthiuram disulph~de 4.8 g 21 9.6 g 5 .
Control I
(3 repetitions a) 5 Infected soil ~) 7 c~ 6 .
Control Ir (3-re~etition~ a~ 83 Steamed so~ 81 1~ -$ 5 Example 6 Control of Rythi~ splendens in t~e pot cultivation o~ Poinsettia pulcherri~a ~ .. ... :
In a series of tests ~oung poinsettia plants of the Annette Hegg Diva variety which had taken root were potted in clay pots each of 11 cm in diameter. The pot substrate (peat ,-culture substrate + sandy compost soil 1 : 1) was severely infected with Pythium sple-ndens. After potting, 100 ml of the preparation under test and having the concentration indicated in the Table below werepoured once over the plants. There followed a cultivation period of 10 weeks at 20 to 21C in a greenhouse. At the end of the cultivation period the height of each of 10 plants was measured, the fresh weight of the leaves and bracts was determined and a root assessment (1 - 4 as defined below) was carried out.
The active substances used and their application quan-tities, and also the results, are given in the following Tabla.

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Exa~ple 7 Control o~-bulh s~t ~ot and ~bulb root rot in tulip cultivation In a ser~es o~ tests prepaxed tulip bulhs (5C tulips) o~ the Gander variety were peeled and 12 bulbs in each case were planted in wooden boxes each measuring 27 x 27 x 12 cm. The plant su~strate ~sandy compost soil) was severely infected with Pythium ultimum and Pythium sylvaticum. The preparation under test, as a 10% pulverulent preparation, was worked uniformly into the compost ~efore planting. There followed a cultivation period of 47 days at a soil temperature rising slowly from 12 to 17C. The mature flowers were weighed, the plant losses as a result of bulb rot were determined, and a root assessment (1-4 as defined below) was carried out.
The active substance used and its application quanti-ties, and also the results, are given in the following Table.

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l l ~g~5 Exam~le 8 Control o~ Ph~top~t~or~ paras~tica ~'ar.' ni'coti'a'nae ~n the pot _ult~vation o~ S~nning~a specosa (~loxinia) In a series of tests ~oung Sinningia plants of the Gierth's Blaue variety were potted in clay pots each of ll cm in diameter. The pot substrate was a l : 1 mixture of peat culture substrate and sandy compost soil. After potting, lO0 ml of the preparation under test and having the concentration indicated in the Table below were poured once over the plants. 3 days after-wards the pots were inoculated uniformly with mycelium flocci of a 3-week-old Phytophthora culture. There followed a cultivation period of 7 weeks at 22 to 24C in a greenhouse.
The active substance used and its application quantities, and also the results, are given in the following Table.

C~x~d according Active substance Plant losses Average fre~h to the invention concentrationafter 7 weeks weight of the plants after ' 7 weeks Furan-2-carbcxylic 0.01 % O ~ 217 g acid ~N-(2-oxoperhydro- 0.02 % O ~ 259 g 3- ~ yl)-2,6-dimethyl- 0.04 % 0 % 223 g 20 anilide]

Control I
In~ated sn % 140 g Control II
Not inoculated - 0 ~ 239 g ~ . . _ .. . .
Example 9 Control of Pythium ultimum in the pxvpagation of Pelargonium cuttings - ' ~

In a ~eries of tests cla~- pots each o~ 6 cm in diameter were ~illed with a pxopa~gat,ion sub~trate ~Jhic~ was severely in-fected with Pyth~u~ ulti~um. The su~strate was a mixture of 8~5 3 parts o~ peat culture substrate and 2 parts of sand. 30 ml of t~e acti~e su~stance concentration indicated in the Ta~le below was poured on to the soil surface in each pot. Afterwards, shoots, which had not taken root, of Pelargonium peltatum of the Luisenhof variety were planted in 24 pots per test series.
After a cultivation period of 25 days at 22 to 25C in a propa-gation bed the plant losses were ascertained and the average fresh weight o~ the cuttings which has taken root was determined.
The active substances used and their application quanti-ties, and also the results, are given in the following Table.

Compound according Active substance Plant losses Average fresh to the invention concentration weight of the plants .
Furan-2-ca~boxylic 0.005 % O % 7.3 g acid 13-chloro-N- 0.01 % Q % 7.1 g (2-oxoperhydro,3-~yl)-anilide]
_ .
Furan-2-carboxylic 0.005 % 0 % 6.2 g acid [N-(2-oxoper- ~.01 ~ O ~ 6.8 g hydro-3-~yl)-2,6-dimethylanilide]
-Control I
~0 Infected soil . - 83 % 2.6 g Control II

Steamed soil - 0 % 6.8 g , Exa~ple 10 Effect of prophylactic leaf treatment against Plasmopara viticola on vines in a ~reenhouse In ~ s.er~es of test$ young vines having approximately 5 to 8 leayes were spra~ed unt~l dr~ppin~ wet with the concentra-tion o~ act~Ye substance indicated ~n the Ta~le below and, after the spra~ coatin~ ~ad dried on, an aqueous suspension of sp~ran-gia of the fun~us indicated in the heading above (app.rroxi-mately 20,QOQ per ~1) was ~prayed on th.e undersides o~ the leaves and plants were then immediately incubated in a green-house at 22 to 24C ~n an at~osp~ere as saturated with steam as possible. From the second day on the air humidity was reduced for 3 to 4 days to the normal le~el (30 to 70% saturation) and then maintained for a further day at steam saturation. The per-centage proportion o~ the surface attacked by fungi of each leaf was then noted and the avera~e per treatment was calculated as follows to determine the ~ungicidal effect:

100 - lQ0 x a~tack in treated plants = % effect attack in untreated plants % Effect against Plasmopara viticola in vines +) Compound according to Concentration 0.001 the invention (% active substance) -Furan-2-carboxylic acid ~N- 100 ~2-oxoperhydro-3~furyl)-2,6-dimethylanilide~

Furan-2-carboxylic acid ~2,6-dimethyl-N-(5-methyl-2-oxoperhydro-3-furyll-aniltde] 100 Furan-2-carboxylic acid [3-chloro-N-(2-oxoperhydro 3-furyl~-anilide] 98 Agent for comparison N-Trichloromethyl thio-phthalimide 80 +~ Effect was calculated on lQ0 % attack in the untreated control.

~Q

Exa~ple 11 Effect of ~oph~lactic lea~ treatment against Ph~tophthora infestans in tomato plants or potato plants in a greenhouse In a ,eries o~ tests young tomato plants having at least two developed folia~e leaves and potato plants (for example from eye cuttings) at least 10 cm tall were sprayed until dripping wet with the concentration of active substance indicated in the Ta~le below and, after the spray coating had dried on, they were ~pxayed with an aqueous suspension which contained per millilitre 50,0Q0 to 80,0QQ sporangia of the fungus indicated in the heading above and which had been incubated for approxi-mately 2 hours in a refrigerator at 11C. The plan~.s were incubated at a high level of air humidity and approximately 15 to 18C in a greenhouse and after approximately 5 days the percentage proportion of the leaf surface that had been at~acked was assessed. The fungicidal effect was calculated as follows: :
100 - 1_0 x attack in treated plants = % effect .

attack in untreated plants % Effect against_Phytophthora infestans in -,potatoes ~) ;

~ Compound according to Concentration 0.005 0.001 t,ke,,~.nve,ntion ~% active substance) _ Furan-2-carboxylic acid [N-(,2-oxoperh~dro-3-furyl~-anilide] 70 Furan-2-carboxylic acid [N-(2-oxoperhydro-3-furyl)-2,6-dimethyl-anilide~ 100 9 Furan-2-car~ox~lic acid ~2,6-d~methyl-N-(5-methyl-2-oxoperh~dro-3-~ur~ anil~de~ ~5 95 ~gent for comparison Man~anese et~ylene b-isdi-thiocarh~ma,te 50 30 :. .

~ Effect ~gainst Ph~.to.phthora : nfe:s.tans in .tomat~.e.s.~) Co~pound a~ccording to Concentration 0.005 0.001 t~e invent~on- (:~ active substance) :
Furan-2-ca~o~l~c Acid 100 86 ~N-C2-oxoperh~dro-3-furyll-2,6-dlmethyl~
anil~de] 100 86 Furan-2-carboxylic acid L 2, 6-dimethyl-N- (5 methyl-2-oxoperhydro-3-furyl)-anilide~ 100 86 Furan-2-car~ox~lic acid [2,3-dimeth~l-N-~2-oxoperhydro-3-furyl)-anilide~ 71 Furan-2-carboxylic acid 13-chloro-N- t2-oxoper-hydro-3-furyl)-anilide] 100 Furan-2 carboxylic acid [3-fluoro-N-C2-oxoper-hydro-3-furyl~-anilide] 81 Agent for comparison Manganese ethylene ~isdithio-carbamate 67 0 ~) Effect was calculated on 100 % attack in the untreated control.

- Example -12 Systemic effect o~ soil treatment against Phytophthora infestans in tomato plants or in potato plants in a greenhouse In a series of tests the active substances to be tested, ~hich ~ad been weighed out, (weight by volume), were mixed w~th soil which was then placed in plant pots and young to~ato plants having at least two developed foliage leaves and potato plants (f~r example from eye cuttin~s) at least 10 cm tall wexe placed in these pots. After the expiry of the desired pre-dose t~e C~r exa~ple a~ter 3, 4 or 18 days) the plants were ~pxa~ed ~th. an 6 ~

aqueous su~pension ~h~ch. contained per millilitre 50,000 to 8Q,QQQ sp~X,an~i`,a o~ the ~ungus ~nd~cated in the heading above and wh~ch.had been Incubated for approximately 2 hours in a refrigerator at 11C. The plants wére incubated at a high level of air ~umidity and at approximately 15 to 18C in a greenhouse and after approximately 5 days the percentage proportion of lea~
surface that ~ad been attacked was assessed. The fungicidal effect was calculated as follows:
100 - 100 x attack in treat_d plants - % effect attack in untreated plants -.
Systemic effec.t o~..soil treatment against Phytophthora:.infestans in tomato plants ~Weight active substance/volume) .
Compound according ppm active % Effect +) ' o~ treatment to the invention su~stance 4 days before 18 days before inoculationinoculation Furan-2-carboxylic acid lN-(2-oxoperhydro-3- 25 32 75 furyl)-anilide] . 5 10 32 Furan-2-carkoKylic acid [N-(2-oxoperhydro,3 ~yl)- 25 60 92 2,6-dimethylanil~de~ 5 27 66 Furan-2-carbRxyltc acid 12,6-dimethyl-N-(5-methyl-2-oxoperhydro-3-furyll- 25 94 100 anilide] ' 5 57 95 ~) Effect was calculated on 100 ~ attack in untreated control.

Exa~p-le 13 Curatl~ve e~ect o~ lea~ treatment ~ainst Phytophthora infestans . in .tomato plants.''.or.''.p.o.tato plants in a ~reenhouse In a series of tests young tomato plants hav.ing at least 2 de~eloped foliage leaves and potato plant (for example $rom eye cuttings) at least 10 cm tall were sprayed with an aqueous suspension w~ich contained per millilitre 50,000 to 8Q,000 sporangia of the fungus indicated in the heading above and which has been incubated for approximately 2 hours in a refrigerator at 11C. The plants were incubated at a high level of air humidity. After the expiry of the desired pre-dose time the plants were sprayed until dripping wet with the concentra-tion to ~e tested on the fungicide (indicated in the Table below) within the period of latent fungal attack. After the outbreak of fungal attack in the untreated control plants the percentage proportion of leaf sur~ace that had been attacked wa~ assessed.
The fun~icidal e~fect was calculated as follows:
lQ0 - .l.O.O.x .attack in treated plants = % effect attack in untreated plants Ca~x~nd accordin~ to ~ ActiYe % Effect ~) of treatment t~2 invention substance before 1 day after . spraYed inoculation inoculation ... . . . . . . . .
Furan-2-carfioxylic ac~d ~N-~2-oxoperhydro-3-furyl)-2,6~ hyl-anilide~ 0.004 100 75 Furan-2-car~oxylic acid ~,6-dimethyl-N ~5-meth~l 2-oxoperhy~x~3-furyl~-an~lide] 0.Q04 100 47 A~ent'fo~'ce~

M~nganesP ethylene ~isdi-t~iocarEamate Q.004 91 0 Ef~ect w~$ calc~lated on lQQ ~ attack i.n the untreated control.

Claims (65)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound of the general formula I

(I) in which R1 represents a hydrogen atom or an alkyl group contain-ing 1 to 4 carbon atoms, R2 represents an unsubstituted phenyl group or a phenyl group substituted by one or more substitutents selected from alkyl groups containing 1 to 4 carbon atoms, alkoxy groups containing 1 to 4 carbon atoms, alkylthio groups contain-ing 1 to 4 carbon atoms, halogen atoms, trifluoromethyl groups, nitro groups, alkoxycarbonyl groups containing 1 to 4 carbon atoms in the alkoxy parts, alkylcarbonyl groups containing 1 to 4 carbon atoms in the alkyl parts, phenyl, and cyano groups, and ?n represents 1 or 2 provided that when R1 is hydrogen or methyl, and R2 is phenyl substituted in both the ortho positions by C1-C4 alkyl, C1-C4 alkoxy or halogen, and unsubstituted in the re-maining positions or substituted in one of the remaining positions by C1-C3 alkyl, C1-C4 alkoxy or halogen or substituted in one of the remaining positions by methyl and another of the remaining positions by C1-C3 alkyl, C1-C4 alkoxy or halogen n is 2.

2. A compound as claimed in claim 1, wherein Rl repre-sents a hydrogen atom or a methyl or ethyl group and R2 represents a phenyl, methylphenyl, dimethylphenyl, ethylphenyl, isopropyl-phenyl, methoxyphenyl, ethoxyphenyl, methylthiophenyl, fluoro-phenyl, chlorophenyl, bromophenyl, dichlorophenyl, trifluoro-methylphenyl, nitrophenyl, cyanophenyl, methoxycarbonylphenyl, acetylphenyl or biphenylyl group.

3. A compound which is furan-2-carboxylic acid [2-chloro-N-(2-oxpperhydro-3-furyl)-anilide].

4. A compound which is furan-2-carboxylic acid [N-(2-oxoperhydro-3-furyl)-anilide].

5. A compound which is furan-2-carboxylic acid [2-methoxy-N-(2-oxoperhydro-3-furyl)-anilide].

6. A compound which is furan-2-carboxylic acid [3,4-dichloro-N-(2-oxoperhydro-3-furyl)-anilide].

7. A compound which is furan-2-carboxylic acid [2-methyl-N-(2-oxoperhydro-3-furyl)-anilide].

8. A compound which is furan-2-carboxylic acid [2,4-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide].

9. A compound which is furan-2-carboxylic acid [3,4-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide].

10. A compound which is furan-2-carboxylic acid [2,3-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide].

11. A compound which is furan-2-carboxylic acid [3,5-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide].

12. A compound which is furan-2-carboxylic acid [3-methyl-N-(2-oxoperhydro-3-furyl)-anilide].

13. A compound which is furan-2-carboxylic acid 14-methyl-N-(2-oxoperhydro-3-furyl)-anilide].

14. A compound which is furan-2-carboxylic acid [3-chloro-N-(2-oxoperhydro-3-furyl)-anilide].

15. A compound which is furan-2-carboxylic acid 14-chloro-N-(2-oxoperhydro-3-furyl) anilide].

16. A compound which is furan-2-carboxylic acid [2-ethyl-N-(2-oxoperhydro-3-furyl)-anilide].

17. A compound which is furan-2-carboxylic acid [N-(2-oxoperhydro-3-furyl]-3-trifluoromethyl-anilide].

18. A compound which is furan-2-carboxylic acid [4-isopropyl-N-(2-oxoperhydro-3-furyl)-anilide].

19. A compound which is furan-2-carboxylic acid [3-bromo-N-(2-oxoperhydro-3-furyl)-anilide].

20. A compound which is furan-2-carboxylic acid [4-methoxy-N-(2-oxoperhydro-3-furyl)-anilide].

21. A compound which is furan-2-carboxylic acid [4-ethoxy-N-(2-oxoperhydro-3-furyl)-anilide].

22. A compound which is furan-2-carboxylic acid [4-ethyl-N-(2-oxoperhydro-3-furyl)-anilide].

23. A compound which is furan-2-carboxylic acid [4-bromo-N-(2-oxoperhydro-3-furyl)-anilide].

24. A compound which is furan-2-carboxylic acid [3-fluoro-N-(2-oxoperhydro-3-furyl)-anilide],

25. A compound which is furan-2-carboxylic acid [4-fluoro-N-(2-oxoperhydro-3-furyl)-anilide].

26. A compound which is furan-2-carboxylic acid [4-methoxy-2-methyl-N-(2-oxoperhydro-3-furyl)-anilide].

27. A compound which is furan-2-carboxylic acid [2,5-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide].

28. A compound which is furan-2-carboxylic aaid [2-ethoxy-N-(2-oxoperhydro-3-furyl)-anilide].

29. A compound which is furan-2-carboxylic acid [3,5-dichloro-N-(2-oxoperhydro-3-furyl)-anilide].

30. A compound which is furan-2-carboxylic acid [13-chloro-2-methyl-N-(2-oxoperhydro-3-furyl) anilide].

31. A compound which is furan-2-carboxylic acid [5-chloro-2-methyl-N-(2-oxoperhydro-3-furyl)-anilide].

32. A compound which is furan-2-carboxylic acid [2-methoxycarbonyl-N-(2-oxoperhydro-3-furyl)-anilide].

33. A compound which is furanl)-carboxylic acid [3-methoxy-N-(2-oxoperhydro-3-furyl)-anilide].

34. A compound which is furan-2-carboxylic acid [3-nitro-N-(2-oxoperhydro-3-furyl)-anilide].

35. A compound which is furan-2 carboxylic acid [3-chloro-N-(5-methyl-2-oxoperhydro-3-furyll-anilide].

36. A compound which is furan-2-carboxylic acid [3-methylthio-N-(2-oxoperhydro-3-furyl)-anilide].

37. A compound which is furan-2-carboxylic acid [5-chloro-2-methoxy-N-(2-oxoperhydro-3-furyl)-anilide].

38. A compound which is furan-2-carboxylic acid [3-fluoro-N-(5-methyl-2-oxoperhydro-3-furyl)-anilide].

39. A compound which is furan-2-carboxylic acid [4-phenyl-N-(2-oxoperhydro-3-furyl)-anilide].

40. A compound which is furan-2-carboxylic acid [3-acetyl-N-(2-oxoperhydro-3-furyl)-anilide].

41. A compound which is furan-2-carboxylic acid [2-bromo-N-(2-oxoperhydro-3-furyl)-anilide].

42. A compound which is furan-2-carboxylic acid [2,3 dichloro-N-(2-oxoperhydro-3-furyl)-anilide].

43. A compound which is furan-2-carboxylic acid [3-chloro-2-methoxy-N-(2-oxoperhydro-3-furyl)-anilide].

44. A compound which is furan-2-carboxylic acid [3-ethyl-N-(2-oxoperhydro-3-furyl)-anilide].

45. A compound which is furan-2-carboxylic acid [3 cyano-N-(2-oxoperhydro-3-furyl)-anilide].

46. A process for the manufacture of a compound of the general formula I

(I) in which. R1 represents a hydrogen atom or an alkyl group contain-ing 1 to 4 carbon atoms, R2 represents an unsubstituted phenyl group or a phenyl group substituted by one or more substituents selected from alkyl groups containig 1 to 4 carbon atoms, alkoxy groups containing 1 to 4 carbon atoms, alkylthio groups contain-ing 1 ko 4 carbon atoms, halogen atoms, trifluoromethyl groups, nitro groups, alkoxycarbonyl groups containing 1 to 4 carbon atoms in the alkoxy parts, alkylcarbonyl groups containing 1 to 4 carbon atoms in the alkyl parts, phenyl, and cyano groups, and ?n represents 1 or 2, provided that when R1 is hydrogen or methyl and R2 is phenyl substituted in both the ortho positions by C1-C4 alkyl, C1-C4 alkoxy or halogen, and unsubstituted in the remaining positions or substituted in one of the remaining posi-tions by C1-C3 alkyl, C1-C4 alkoxy or halogen or substituted in one of the remaining positions by methyl and another of the remaining positions by C1-C3 alkyl, C1-C4 alkoxy or halogen ?n is 2 wherein a compound of the general formula II

(II) in which Rl, R2 and ?n have the meanings given above, is reacted in the presence of an acid-binding agent with a furancarboxylic acid chloride of the formula III
(III)

47. A process as claimed in claim 46, wherein the reaction is carried out in the presence of a solvent.

48. A process as claimed in claim 46, or 47, wherein the amounts used of the compound of the general formula II and the compound of the formula III are in equimolar proportions.

49. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of claim 1, 2 or 3.

50. A method of protecting a living plant against phytophathogenic fungi, wherein the living plant is treated with a compound of claim 4, 5 or 6.

51. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of claim 7, 8 or 9.

52. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of claim 10, 11 or 12.

53. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of claim 13, 14 or 15.

54. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of claim 16, 17 or 18.

55. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of claim 19, 20 or 21.

56. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of claim 22, 23 or 24.

57. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of claim 25, 26 or 27.

58. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of claim 28, 29 or 30.

59. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of claim 31. 32 or 33.

60. A method of protecting a living plant against phytopathgenic fungi, wherein the living plant is treated with a compound of claim 34, 35 or 36.

61. A method of protecting A living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of claim 37, 38 or 39.

62. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of claim 40, 41 or 42.

63. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with compound of claim 43, 44 or 45.

64. A method of protecting a crop area against phyto-pathogenic fungi, wherein the crop area is treated with a com-pound of claim 1, 2 or 3.

65. A method of dressing seeds, wherein the seeds are treated with a compound of claim 1, 2 or 3.