FR2499079A1 - OXAZOLIDINE DERIVATIVES, THEIR PREPARATION AND FUNGICIDE COMPOSITIONS CONTAINING - Google Patents

Abstract

OXAZOLIDINE DERIVATIVES, THEIR PREPARATION AND FUNGICIDAL COMPOSITIONS IN CONTAINER. THESE COMPOUNDS MEET FORMULA I (CF DRAWING IN BOPI) IN WHICH R REPRESENTS (CF DRAWING IN BOPI) IN WHICH R AND R ALKYL IN C-C, HALOGEN OR ALCOXY IN C-C; R H, C-C ALKYL OR HALOGEN; R IS COR; RH, ALKYL IN CC, ALKYL IN CC POSSIBLY HALOGEN, ALCYNYL IN CC, CYCLOALKYL IN CC, (CYCLOALKYL IN CC) -ALKYL IN CC, EPOXY-ALKYL EN CC, PHENYL, PHENYL- (ALKYL EN CC-) OR PHENYL- (ALKYL EN CC-) OR PHENYL- (ALKYL EN CC-) OR PHENYL- (ALKYL EN CC-) OR PHENYL- (ALKYL EN CC-) IN CC) POSSIBLE SUBSTITUTE; R, R, R AND R H OR ALKYL IN C-C. THESE COMPOUNDS HAVE FUNGICIDAL PROPERTIES THAT CAN BE USED IN AGRICULTURE.

Description

The present invention relates to new doxozolidine drives, their preparation and fungicidal compositions containing them as active substances, and which can be used with advantage to combat phytopathogenic fungi.

dans laquelle R1 représente

The compounds according to the invention rependent in formula I

in which R1 represents

R7 and R8 each represent, independently of one another, a
C1-C4 alkyl group, a halogen or a C1-C4 alkoxy group
C1-C4, and
R9 represents hydrogen, a C1-G4 alkyl group or a
halogen,
R2 represents the COR10 group
in which R10 represents hydrogen, an alkyl group in
C1-C6; an unsubstituted C2-C6 alkenyl group
killed or substituted by a halogen; a group
C2-C6 alkynyl; C3-C7 cycloalkyl;
(C3-C7 cycloalkyl) -C1-C3alkyl;
C2-C6 epoxyalkyl; phenyl, phenyl- (alkyl
C1-C3 or phenyl- (C1-C3 alkenyl) in
which the aromatic part is unsubstituted
or carries 1 to 3 substituents chosen by the
C1-C4 alkyl groups, C1-C4 alkoxy and
halogens, NO2, phenyl or phenoxy groups, R3>R4> R5 and R6 each independently represent
others, hydrogen or a C1-C4 alkyl group.

When one of the symbols R3, R4, R5, R6, R7, R8 or Rg is an allyl group or comprises an alkyl group (in the form for example of an alkoxy group), it is preferably an C1-C3 alkyl group, i.e. methyl, ethyl, n-propyl or isopropyl.

When one or the other of the symbols R7 and R8 represents a halogen, this halogen is F, C1, Br or I, preferably F, C1 or Br, more especially C1 or Br, and better still C1.

When any one of the symbols Rg and R10 is a halogen or contains a halogen, this halogen is F, C1, Br or I, preferably F, -Cl or Br, more especially C1 or Br.

When R10 represents a C1-C6 alkyl group, it is more especially a C2-C4 alkyl group and better still a C3 alkyl group.

When R10 represents a C2-C6 alkenyl group, it is preferably a C2-C4 alkenyl group and more especially a C3 alkenyl group.

When R10 represents a C3-C7 cycloalkyl group, it is preferably a C3-C6 cycloalkyl group and more especially a C3-C4 cycloalkyl group.

When one of the symbols R3 and R4 represents a C1-C4 alkyl group, the other preferably represents hydrogen.

When one of the symbols R5 and R6 represents a C1-C4 alkyl group, the other preferably represents hydrogen.

Thus, a preferred group of compounds are those compounds of formula Ia

in which
R7 'and R8' each represent, independently of one another,
CH3, C1 or Br,
R9 'represents H, Cl> Br or a methyl group and Rlo' represents a C3 alkyl, C3 alkenyl or cyclo-
C3-C4 alkyl, R7 'and R8' are preferably the same.

Most preferred meanings for R10 'are unbranched C3 alkyl or unbranched C3 alkenyl, for example n-propyl or 2-propenyl.

dans laquelle R1, R3, R4 > R5, R6 et R10 ont les significations
indiquées ci-dessus et Y représente un halogène.In accordance with the invention, the compounds of formula I are prepared by intramolecular condensation of a compound of formula II.

in which R1, R3, R4> R5, R6 and R10 have the meanings
indicated above and Y represents a halogen.

Y preferably represents chlorine or bromine, more particularly chlorine.

The intramolecular condensation in question can additionally be carried out in the usual manner. The reaction is exothermic.

One can operate for example in an anhydrous medium using as solvent an ether such as dimethoxyethane> a hydrocarbon such as toluene or another inert solvent under the conditions of the reaction. The reaction temperature is not a critical factor and can be between the neighborhood of 0 and 1000C. As the reaction is exothermic, it is preferably started at room temperature and the reaction temperature is allowed to rise gradually.

The reaction is advantageously carried out in the presence of an acid-binding agent such as sodium hydride, sodium amide or a sodium alcoholate, for example sodium ethoxide,
The intramolecular condensation can also be carried out in an aqueous-organic two-phase system in the presence of an inorganic base, for example sodium hydroxide and optionally a catalytic amount of a phase transfer catalyst. The organic phase can consist of any suitable inert, water-immiscible solvent, for example a halogenated hydrocarbon or hydrocabide, inter alia xylene, toluene, lto-dichlorobenzane or dichloromethane. Suitable are quaternary ammonium compounds such as benzyltrimethylammonium bromide, quaternary phosphonium compounds such as benzyltriphenylphosphonium chloride and crown ethers such as 18-crown-6.

The compounds corresponding to formula I in which
R10 represents an epoxyalkyl group can also be prepared from the corresponding compound of formula I, in which R10 represents an alkenyl group, by epoxidation. The epoxidation is advantageously carried out using an organic peroxyacid such as m-chloroperbenzolque acid, or using a mixture of hydrogen peroxide and an inorganic base such as sodium hydroxide.

R R P et Y ont les s1gnifications indiqudes dans laquelle R1 > R3,R4, R5 > R1 et Y ont les significations indiquées cl-dessus, à l'aide d'un composé de formule IV

dans laquelle R10 a les signification indiquée ci-dessus, et
Z représente un halogène, particulierement Cl > ou
un groupe O-COR10 dans lequel R10 a les significa
tions indiquées ci-dessus.The compounds of formula II are new. They can be obtained by acylation of compounds of formula III

RRP and Y have the meanings given in which R1> R3, R4, R5> R1 and Y have the meanings given above, using a compound of formula IV

in which R10 has the meanings given above, and
Z represents a halogen, in particular Cl> or
an O-COR10 group in which R10 has the meanings
mentioned above.

Solvents which are suitable for this acylation reaction are hydrocarbons such as toluene or halogenated hydrocarbons such as chlorobenzene. The reaction is advantageously carried out at a temperature ranging from about 50 to 1200C, for example at 80 C, optionally in the presence of a base such as triethylamine or pyridine, for example.

dans laquelle R3, R4, R5, R6 et Y ont les significations indiquée
ci-dessus, et
X représente un halogène, en particulier C1.Compounds of formula III can be obtained by converting compounds of formula V
al - NH - NH2 V in which R1 has the meanings given above, with a compound of formula VI

in which R3, R4, R5, R6 and Y have the meanings indicated
above, and
X represents a halogen, in particular C1.

This conversion can be carried out at a temperature ranging from 0 10 C approximately in water or in an organic solvent inert under the reaction conditions, preferably in the presence of a base, for example an amine or sodium bicarbonate.

The starting materials and reagents used in the methods described above are known or, when they are not known, can be prepared by methods analogous to those described above or by known methods.

The compounds of formula I have an exploitable fungicidal activity, in particular on the phytopathogenic mgcetes, especially on the fungi of the class Oomycetes, as shown by the net effect observed in the tests below.
Trial A :: Buffet fonaicide on Phvtophthora infestans
Young potted potato plants (at the 3 to 5 leaf stage) are sprayed with an aqueous suspension in aerosol containing 0.003% (weight volume) of a compound of formula I, for example N- (2,6-dimethylphenyl). ) -N- (2-oxo-3-oxazolidinyl) -2-butenamide (in the form described in Formulation Example I below). Two hours later, the treated plants are inoculated with a suspension of Phytophthora infestans spores and then the plants are transferred to a 100% relative humidity cabin, at room temperature of 160 ° C., for a daytime duration of 16 hours. The results obtained on the disease 4 to 5 days later are assessed by comparing the plants treated with plants not treated but inoculated in a similar manner. With the compound tested and identified above, a substantial limitation of the fungal infestation was observed without any sign of phytotoxicity on the host plants.

Test B: Fungicidal effect on Plasmopara viticola
Young potted vine plants (at the 3 to 6 leaf stage) are sprayed with an aqueous suspension in aerosol containing 0.0008X (w / v) of a compound of formula I, for example N- (2> 6- dimethylphenyl) -N- (2-oxo-oxazolidinyl) -2-butenamide (in the form described in formulation example I below) .Two hours later, the treated plants are inoculated with a suspension of spores due Plasmopara viticola then the plants are transferred to a cabin at 100% relative humidity, at an ambient temperature of 15 to 22 "C (fluctuating over a period of 24 hours) and for a period of daylight of 16 hours. The effects on disease 6 days after inoculation by comparing the treated plants with plants not treated but inoculated in a similar manner. With the test compound, a substantial limitation of the fungal infection is observed without appreciable evidence of phytotoxicity on the host plants. .

Test C: Curative fungicidal effect on Plasmopara viticola
Young vines are inoculated in pots (at the 3-6 leaf stage) as described in test B, but the compound, for example, N- (2> 6-dimethylphenyl) -N- (2-oxo) is applied. -3-oxazolidinyl) -2-butenamide (in the form described in Formulation Example I below) only three days after inoculation; the incubation conditions are the same as in test B. The results obtained on the disease are evaluated as described in test B. With the compound tested, a substantial limitation of the fungal infection is observed.

Test D: Fungicidal effect with eradication on Plasmopara viticola
The procedure for assessing this type of activity is the same as that of test C but the exception is that the treatment is carried out only 6 days after inoculation, while sporulation already appears on the lower leaf surface. The effect on the disease begins 7 days after the application of 0.0129, for example N- (2,6-dimethyl-phenyl) -N- (2-oxo-3-oxazolidinyl) -2-butdnamide (under the form described in formulation example I below), reveals a total stopping effect on the areas already sporulating.

Test E: Translocation in treated sheets of meat
Isolated vine leaves are treated with an aqueous suspension in aerosol containing 0.012 hours of a compound of formula I, for example N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolinyl) -2-butenamide (in the form described in formulation example I below, taking care to treat only the lower half of these leaves. Two days after treatment, the entire leaf is inoculated with a suspension of Plasmopara viticola spore. then the leaves are incubated in a booth at 100% atmospheric humidity under the conditions described in test B.

Although, as stated above, the lower half of the leaves had been treated, substantial control of disease was observed with the test compound throughout the inoculated leaf.

The same effect is observed when treating only the upper half of the leaves. This test therefore shows that N- (2,6-dim8thyl-phenyl) -N- (2-oxo-3-oxazolidinyl) -2-butenamide (in the form described in example of formulation I below) is distributed in a sheet & both in the acropetal part and in the basipetal part.

Test F: Soil treatment.

In vivo, with Pvthium aphanidenmatum. The fungus is grown in a sterile mixture of sand and corn flour (97: 3 by volume); the culture lasts 4 days at 250 C. The fungus is then mixed with a semi-sterile mixture of peat and sand which is then treated with a suspension containing the active component in an amount corresponding to a final concentration of 10 to 160 ppm ( for example 10, 40 and 160 ppm) on the volume of the substrate. The substrate is transferred to pots 5 cm in diameter in which cucumber seeds are sown. The seed pots are incubated at 240C and 60 to 70% relative humidity in an incubation chamber for 7 days, after which the extent of the disease attack is determined by comparing the number of healthy plants released. of soil with that of the holy plants raised from the ground in the untreated control pots but inoculated in a similar way. The compound of Example 1 below, in the wettable powder form indicated above, constitutes an effective remedy against the disease.

Tests similar to test F carried out on peas and sugar beets give similar results.

Each of the compounds listed in the examples below has fungicidal properties which can be used in practice.

A particularly effective fungicidal activity is observed in the above tests with the compounds corresponding to formula Ia in which R7 and R8 ′ both represent
CH3; Rgl represents H and -R10 'represents n-C3H7, CH3-CH = CH-> a cyclopropyl or cyclobutyl group.

The compounds according to the invention therefore make it possible to combat phytopathogenic myctkes, especially those belonging to the class of oomycetes, on plants, seeds or the soil, by application to these plants, these seeds or this soil of an effective fungicidal amount. of a compound of formula I.

Among the fungi of the class of oomycetes, on which the compounds according to the invention are particularly active, mention will be made of those of the genus Phytophthora in plants such as potatoes, tomatoes, tobacco, citrus fruits, cocoa and rubber. , apples, strawberries, vegetable and ornamental crops, for example Phytophthora infestans on potatoes and tomatoes; fungi of the genus Plasmopara viticola on vines; of the genus Peronospora on plants such as tobacco, for example Peronosnora tabacina on tobacco; of the genus Pseudoperonospora on plants such as hops and cucumber, for example PseudoPeronosnora humuli on hops; of the genus Bremia on plants such as lettuce; for example
Bremia lactucae on lettuce; of the genus Pvthium causing damping-off of seedlings and roots in a large number of plants such as kitchen gardens, sugar beets, ornamental plants and conifers, for example Pvthium aphanidermatum on sugar beet; of the genus SclerosPora on plants such as sorghum and mats, for example Sclerosuora sorghum on sorghum.

The invention therefore also comprises fungicidal compositions which are characterized in that they contain as active component at least one compound of formula I above, with suitable vehicles.

These fungicidal compositions are used to combat phytopathogenic fungi, in an amount which varies according to factors such as the nature of the fungus to be controlled, the time and the mode of application, the proportion and the nature of the compound of formula I contained in the composition. .

However, in general, satisfactory results are obtained by applying to the site to be treated, for example crops or the soil, doses ranging from 0.05 to 5 kg and preferably 0.1 3 kg of a compound of formula I per hectare of surface treated, application being repeated when necessary. For seed disinfection, satisfactory results are obtained at doses of about 0.05 0.5 and preferably about 0.1 0.3 g of a compound of formula I / kg of seed.

Depending on the circumstances, the compounds of formula I may be used in combination with other pesticides, for example fungicides, bactericides, insecticides, acaricides, herbicides or plant growth regulating agents which improve their activity or broaden their spectrum of activity.

Particularly satisfactory results are obtained in the fight against phytopathogenic fungi by simultaneously applying to the site to be treated effective fungicidal amounts of a component a) containing a compound of formula I and of one or more compounds chosen from cuprous fungicides, capturing it the folpet, the mancozeb or the maneb.

Among the cuprous fungicides suitable for use in combination with a compound of formula I, mention will be made, for example, of copper-II carbonate, calcium and copper-II sulfate, calcium and copper-II oxychloride, 'tetracupric oxychloride, Bordeaux mixture, Burgundy mixture, cuprous oxide, cupric hydroxide, copper-II oxychloride or copper complexes such as cupretriethanolamine hydroxide of formula Cu N (CH2CH20H) 33 - (OH) 2, which is commercially available under the trademark K-Lox, or bis- (ethylenediamine) -copper-II sulfate of the formula (Cu (H2NCH2CH2NH2) 2] S04 which is commercially available under the trademark Komeen, and mixtures thereof, and in particular cuprous oxide, copper-II oxychioride, cupric hydroxide and a mixture of calcium sulfate and copper-II and.

of copper-II oxychloride.

Captan, Folpet, Manoc eb and Maneb are the common names of protective fungicides effective against leaf diseases (Pesticide Manual, Edition, H. Martin and C.R. Worthing> pages 76, 281, 328 and 329 respectively).

The compounds of formula I are commonly used in the form of fungicidal compositions in combination with vehicles or diluents acceptable for agricultural uses. These compositions also constitute an object of the invention. Apart from a compound of formula I which constitutes the active component, these compositions may contain other active agents such as fungicides. They can be used in solid or liquid application forms, for example in powder form. wettable, concentrate for emulsio.de concentrate for suspensions dispersible in water ("pourable"), fine powder, granule8, of delayed release form, containing vehicles, diluents or adjuvants of the conventional type. These compositions can be prepared in the usual manner, for example by mixing the active component with a vehicle and other components.

Compositions in particular which are to be applied by spraying, for example water dispersible concentrates or wettable powders, may contain surfactants such as wetting and dispersing agents4, for example the condensation product of formaldehyde on a naphthalene. sulfornate, an alkylarylsulfonate, a lignin sulfonate, a fatty alcohol sulfate, an alkylphenolethoxylated or an ethoxylated fatty alcohol.

In general, these compositions contain from 0.01 to 90% by weight of the active agent consisting of at least one compound of formula I or a mixture of such a compound with other active agents such as fungicides. In concentrated forms, the compositions generally contain from about 2 to 80%, preferably from about 5 to 70% by weight of active agent. For the application, the compositions may contain, for example, from 0.01 to 20% by weight and preferably from 0.01 to 5% by weight of active agent.

The examples which follow illustrate the invention without, however, limiting its scope; in these examples, the parts and percentage indications are understood to be by weight unless otherwise specified.

Example of formulation I: wettable powder
50 parts of N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) -2-butenamide are ground with 2 parts of lauryl sulphate, 3 parts of sodium lignin sulphonate and 45 parts of kaolinite in the state of fine division until the average particle size is less than 5 microns. A wettable powder is thus obtained which is diluted with water for use, to a concentration of 0.01 to 5% of active agent. The spray liquor can be applied by spraying the leaves or by dipping the roots.

Example of formulation II: granules
On 94.5 parts of quartz sand placed in a tilting mixer, 0.5 part of a binder (nonionic surfactant) is sprayed and mixed carefully. Then 5 parts of N- (2,6-timethylphenyl) -N- (2-oxo-3-oxazolidinyl) -2-butJnamide powder are added and the mixing is continued carefully; a granulated product is obtained having a particle size in the range of 0.3 to 0.7 mm. The granules can be applied by incorporation into the soil in the vicinity of the plants to be treated.

Example of formulation II1: concentrate for emulsions
25 parts of a compound of formula I, for example the compound of Example 1 below, 65 parts of xylene, 10 parts of a mixture of the reaction product of ethylene oxide with an alkylphenol and calcium dodecylbenzenesulfonate. A concentrate for emulsions is obtained which is diluted with water before use.

Example 1: N- (2 6-dimethviphenyi) -N- (2-oxo-3-oxazolidinvl-2-bu-
tenamide
Slowly add 15.0 g (0.048 mole) of 2- (2-butenoyl) -2- (2, 6-dimethylphenyU-hydrazine-carboxylate of 2-chorethyl in 100 ml of dry methanol to a cooled solution of 2 , 7 g (0.05 mole) of sodium methoxide in 50 ml of dry methanol.

After stirring for one hour at room temperature, the solution is concentrated in vacuo, the residue is taken up in dichloromethane and washed carefully with water. The organic phase is dried over anhydrous magnesium sulfate, the solvent is removed and the residue is recrystallized from ethyl ether; the desired compound is obtained in the form of colorless crystals, melting at 123-1240C.

Example 2
The procedure of Example 1 is followed, but the appropriate compounds corresponding to formula II in which R3, R4, R5 and R6 represent H and Y represent C1, a are used and the compounds of formula I.ci- are obtained. after in which R3> R4, R5 and R6 represent H.

<tb> Example <SEP> R7 <SEP> R8 <SEP> 9 <SEP> R10 <SEP> - <SEP> - <SEP> Point <SEP> of
<tb><SEP> I <SEP> o
<tb> 2-1 <SEP> CH3 <SEP> CH3 <SEP> H <SEP> 2-1 <SEP> CH3 <SEP> CX3 <SEP> 1O4-W6C
<tb> 2-2 <SEP> Ch '<SEP> Cllj <SEP> H <SEP> 112- <SEP> 119C
<tb> 2-3 <SEP> CH3 <SEP> CH3 <SEP> 3-C1 <SEP> CH-ÇHCH3 <SEP> - <SEP> oil
<tb> 2-4- <SEP> CH3 <SEP> CH3 <SEP> 3-Br <SEP> CH-CHCH3 <SEP>. <SEP>
<tb> 2-5 <SEP> CH3 <SEP> CH3 <SEP> H <SEP> wO <SEP> îlG-i180C
<tb> 2-6 <SEP> I <SEP> CH2CH3 <SEP> 120- <SEP>: 22C
<tb> 2-7 <SEP> - <SEP> CH <CH3) 2 <SEP> 141- <SEP>143'C
<tb> 2-8 <SEP> (CH2) 3CH3 <SEP> 69- <SEP> 700C
<tb> 2-9 <SEP> - <SEP> CH2CH (CH3> 2 <SEP> 119- <SEP>120'C
<tb> 2-10 <SEP> C (CH3) 3 <SEP> 162- <SEP>163'C
<tb> 2-11 <SEP>. <SEP> CHCH2 <SEP> 141- <SEP> 143iC
<tb> 2-12 <SEP> (CH2) 4CH3 <SEP>59-61'C
<tb> 2-13 <SEP>. <SEP> CH2C (CH3) 3 <SEP> CH2Ç <SEP><CH3> 3 <SEP>114-'liC
<tb> 2-14 <SEP> (CH2) 6CH3 <SEP> oil
<tb> 2-15 <SEP> (CH2) 8CH3 <SEP>. <SEP> 48-51e <SEP> C
<tb> 2-16 <SEP> CH-C <SEP> (CH3) <SEP> 2 <SEP> 123- <SEP> 1250C
<tb> 2-17 <SEP> - <SEP> CH3 <SEP> 135-136eC
<tb> 2-18 <SEP> - <SEP> C, <SEP> -CH2 <SEP> 141-1420C
<tb><SEP> CH3
<tb> 2-19 <SEP> CH3 <SEP> C1 <SEP> H <SEP> 4 <SEP> 123-124iC
<tb> 2-20 <SEP> CH3 <SEP> Cl <SEP> CH "CHCH3
<tb> 2-21 <SEP> C133 <SEP> CH3 <SEP> ua <SEP> 162-164eC
<tb> 2-22 <SEP> CH3 <SEP> CH3 <SEP> 200-201iC
<tb>

<SEP> xeinple <SEP> R7 <SEP> R8 <SEP> R9 <SEP> R10 <SEP> Have <SEP> e
<tb><SEP> R, <SEP> 8 <SEP> Rg <SEP> R10fusion
<tb><SEP> 2-23 <SEP> .CH3 <SEP> CH3 <SEP> 3-C1 <SEP> CH <SEP> CH <SEP> CH3 <SEP> - <SEP> 84-880c
<tb><SEP> 2-24 <SEP> CH3 <SEP> CH3 <SEP> 3-Br <SEP> CH2CH2CH3 <SEP> 98-10bo
<tb><SEP> 2-25 <SEP> CH3 <SEP>'<SEP> CH3 <SEP> 3-CH3 <SEP> ClI = CHCH3
<tb><SEP> 2-26 <SEP> CH3 <SEP> - <SEP> CH3 <SEP> 147- <SEP> 1490C
<tb><SEP> 2-27 <SEP> CH3 <SEP> CH3 <SEP> 3-Br <SEP> 4 <SEP> 147- <SEP> 1480C
<tb><SEP> 2-28 <SEP> CH3 <SEP> CH3 <SEP> 3-CH3 <SEP><
<tb> 2-29 <SEP> CH3 <SEP> CH <SEP> H <SEP> -CH2 <SEP> 132-1330c
<tb><SEP> oil
<tb><SEP> 2-30 <SEP>. <SEP>. <SEP> CH2 <SEP> 6 <SEP> oil
<tb><SEP> 2-31 <SEP> -CH2CH2 <SEP> 137- <SEP> 1390C
<tb><SEP> 2-32 <SEP> -CH = CH <SEP> 233-235eC
<tb><SEP> 2-33 <SEP> - <SEP> CH2CH2CH = CH2 <SEP> -97-100
<tb><SEP> 2-34 <SEP> C-CH <SEP> 135- <SEP> 1370C
<tb><SEP> 2-35 <SEP> - <SEP> CH = CH-CH2CH3 <SEP> 100- <SEP> 1090C
<tb><SEP> 2-36 <SEP> - <SEP> C = CH-CH3 <SEP>
<tb><SEP> - <SEP>C'H3<SEP>
<tb><SEP> 2-37 <SEP> C <SEP> Ws <SEP> CH3 <SEP> H <SEP> H <SEP> 9c-980C
<tb><SEP> oCH3
<tb><SEP> 2-38 <SEP> CH3 <SEP> CH-3 <SEP> H <SEP> CH2 <SEP> 4 <SEP> 177-178 C
<tb><SEP> 2-39 <SEP> CH3 <SEP> CH3 <SEP> H <SEP> 204- <SEP> 207 "C
<tb><SEP> 2-40 <SEP> CH3 <SEP> CH3 <SEP> H <SEP> C1 <SEP> 17-7- <SEP> 1790C
<tb><SEP> Cl
<tb><SEP> 2-41 <SEP> CH3 <SEP> CH3 <SEP> H <SEP> 6 <SEP> -NO2 <SEP> 166- <SEP> 1680C
<tb><SEP> 2-42 <SEP> CH3 <SEP> CH3 <SEP> lI <SEP> 6 <SEP> -C1 <SEP> 2q4- <SEP> 2050C
<tb><SEP> 2-43 <SEP> CH3 <SEP> CH1 <SEP> H <SEP><SEP> 236-2380C
<tb>

Example <SEP> R7 <SEP> R8 <SEP> R9 <SEP> R10 <SEP> Point <SEP> of
<tb>Exa; nple <SEP> R7 <SEP> R, <SEP> Point <SEP> of
<tb><SEP> 2-44 <SEP> CH3 <SEP> CH3 <SEP> 3-Br <SEP> 107 <SEP> 163-1650C
<tb><SEP> 2-45 <SEP> CH3 <SEP> CH3 <SEP> 3-C1 <SEP> Cl29) <SEP> 112-115 "C
<tb><SEP> 2-46 <SEP> CH3 <SEP> CH3 <SEP> 3-CH3 <SEP> Cl24)
<tb><SEP> 2-47 <SEP> CH3 <SEP> OCI! 3 <SEP> H
<tb><SEP> 2-48 <SEP> CH3 <SEP> 0CH3 <SEP> H <SEP> CH = CHCH3
<tb><SEP> 2-49 <SEP> C1 <SEP> C1 <SEP> H <SEP> CH = CHCH3
<tb><SEP> 2-50 <SEP> C1 <SEP> C1 <SEP> H
<tb><SEP> 2-51 <SEP> CH3 <SEP> C <SEP> 2115 <SEP> H <SEP> CII = CHCH3
<tb><SEP> 2-52 <SEP> CH3 <SEP> CH3 <SEP> 3-C1 <SEP> CH = CH2 <SEP> 118-121 C
<tb><SEP> 2-53 <SEP> CH3 <SEP> CH3 <SEP> 3-Br <SEP> CH = CH2 <SEP> 87- <SEP> 890C
<tb><SEP> 2-54 <SEP> CH3 <SEP> CH3 <SEP> 3-Br <SEP> CH = C (CH3) 2
<tb><SEP> 2-55 <SEP> CH3 <SEP> CH3 <SEP> 4-CH3 <SEP> CH = CHCH3
<tb><SEP> 2-56 <SEP> CH3 <SEP> CH3 <SEP> 3-C1 <SEP> CH-CH2
<tb><SEP> 2-57 <SEP> CH3 <SEP> CH3 <SEP> 3-CH3 <SEP> CH-CH2
<tb><SEP> 20
<tb><SEP> 2-58 <SEP> CH3 <SEP> CH3 <SEP> H <SEP> (CH2) 5CH3 <SEP> nD w1,5193
<tb><SEP> 2-59 <SEP> CH3 <SEP> CH3 <SEP> H <SEP> CH (CH2CH3? 2 <SEP> 1 <SEP> 5
<tb><SEP> 2-60 <SEP> CH3 <SEP> CH3 <SEP> H <SEP> C, H (CH2) 3-CH3 <SEP> nD D1,5179
<tb><SEP> CH3
<tb><SEP> 2-61 <SEP> CH3 <SEP> CH3 <SEP> H <SEP> CH2CHCH2CH3 <SEP> 89-920
<tb><SEP> CH3
<tb>

Example 3: 2 3-t> oxv-N- (2. 6-dimethyihnvi) -N- (2-oxo-3-oxazoli- dinsl) -butanamide
3.8 g (13.9 mmol) of N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) -2-butenamide in 40 ml of methanol and 3 are cooled to 15 ° C. with stirring. , 5 g of hydrogen peroxide (40% solution in water) and slowly added a solution of 0.26 g (7 mmol) of sodium hydroxide in 12 ml of water. Stirred for 1 hour at 200C then poured into 5 ml of water, extracted with dichloromethane, the organic phase is washed with water, dried over
MgSO4 and the solvent evaporated; the compound is obtained in the form of a colorless oil.

Example 4
By following the procedure of Example 3 but using the appropriate compounds of formula I in which R3> R4, R5 and R6 represent H and R10 represents an alkenyl group, the compounds of formula I below are obtained in which R3 , R4,
R5 and R6 represent H and R10 an epoxyalkyl group.

<tb>

<SEP> Point <SEP> of
<tb> Example <SEP> R7 <SEP> R8 <SEP> R <SEP> R <SEP> R1o <SEP> merge
<tb><SEP> 10
<tb><SEP> 4-1 <SEP> CH3 <SEP> CH3 <SEP> H <SEP> CII-CH, <SEP> 124-1270C
<tb><SEP> 4-2 <SEP> CH3 <SEP> CH3 <SEP> H <SEP> CH-CHCH3
<tb><SEP> o
<tb><SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH-CllCH3
<tb><SEP> o
<tb><SEP> 4-4 <SEP> CH3 <SEP> CH3 <SEP> 3-Br <SEP> C \ HHCH3
<tb><SEP> 4-5 <SEP> CH3 <SEP> CH3 <SEP> 3-C1 <SEP> CH2 <SEP> 136- <SEP> 1400C
<tb><SEP> 4-6 <SEP> CH3 <SEP> CH3 <SEP> 3-CH3 <SEP> CII-CH2
<tb><SEP> 0
<tb><SEP> 4-7 <SEP> CH3 <SEP> CH3 <SEP> 3-CH3 <SEP> CH-CH-C! IS
<tb><SEP> I <SEP> / 3
<tb><SEP> o
<tb><SEP> 4-8 <SEP> CH3 <SEP> Cl <SEP> H <SEP> CH
<tb><SEP> 4-5 <SEP> CH3 <SEP> C1 <SEP> H <SEP> / CHCH3
<tb><SEP> ~
<tb>
Intermediate products
Example A: 2- (2-butenovl) - (2,6-dimethylphenyl) -hydrazine-carboxy-
2-chlorethyl late.

Was heated at 500C for 3 hours with stirring a mixture of 20.0 g (0.082 mol) of 2- (2,6-dimethylphenyl) -hydrazin - 2-chlorethyl carboxylate and 8.6 g (0.082 mol) of chloride. 2-butenoyl in 100 ml of dry toluene. After cooling to room temperature, the organic phase is washed successively with water, an aqueous solution of K2CO3 and water, dried over NgSO4 and evaporated in vacuo; the research compound is obtained in the form of a yellow oil. Crystallization of a sample from ethanol gives colorless crystals melting at l38-1400C.

Example B: 2- (26-dimethylphenyl) -hvdrazine-carboxviate of 2-chlorethYl
A mixture of 17.7 g (0.1 mol) of 2,6-dimethylphenylhydrazine hydrochloride and 21.2 g (0.2 mol) of sodium carbonate is stirred for 30 minutes at room temperature in a mixture of 50 ml of water / 50 ml of xylene then cooled to 50C.

14.3 g (0.1 mol) of the 2-chlorAthyl ester of chioroformic acid are added over 1 hour, while maintaining the temperature at 5 ° C. by external cooling. The mixture is stirred at 50C for a further 1 hour after which 100 ml of water are added; the precipitate is filtered off, washed with water and dried; the desired compound is obtained in the form of a slightly colored solid substance, melting at 69-700C. Recrystallization from ethyl ether / petroleum ether brings the melting point to 74-75 C.

Claims (6)

1. Compounds characterized in that they correspond to formula I

in which R1 represents

others, hydrogen or a C1-C4 allyl group. R3, R4, R5 R5 and R6 each independently represent N02, phenyl or phenoxy groups, C1-C4, C1-C4 alkoxy, halogens, substituents selected from allyl groups aromatic is unsubstituted or carries 1 to 3 (C1-C3 alkenyl) in which the part phenyl, phenyl- (C1-C3 alkyl) or phenyl a C2-C6 epoxyalkyl group; a group (C3-C7 cycloalkyl) -C1-C3alkyl group; in C2-C6; a C3-C7 cycloalkyl group; a substituted with a halogen; an alkynyl group unsubstituted C2-C6 alkenyl group or in which R10 represents H; a C1-C6 allyl group, a R2 represents the COR10 group halogen, Rg represents hydrogen, a C1-C4 alkyl group or a in C1-C4) and C1-C4 alkyl group, halogen or alkoxy group R7 and R8 each independently represent a 2. Process for preparing the compounds according to claim 1, characterized in that a compound of formula II is subjected to intra molecular condensation.

in which R1, R3, R4, R5, R6 and R10 have the meanings indicated in claim 1, and Y represents a halogen. 3. As intermediate compounds for the preparation of the compounds of formula I according to claim 1, the compounds of formula II

in which R1, R3, R4, R5, R6 and R10 have the meanings indicated in claim 1, and Y represents a halogen, 4.A process for preparing the compounds of formula II

in which R1, R3, R4, R5, R6 and R10 have the meanings indicated in claim 1, and Y represents a halogen, characterized in that compounds of formula III are acylated

in which R1, R3, R4, R5, R6 and Y have the meanings indicated listed above, using a compound of formula IV

in which R10 has the meanings indicated above and Z represents a halogen, in particular Cl> or group O-COR10, in which R10 has the meaning indicated above. 5. Fungicidal compositions characterized in that they contain a compound according to claim 1 in combination with a vehicle or diluent acceptable for agricultural uses. 6. Method for combating photopathogenic fungi in plants, seeds or soil, characterized in that one applies to these plants, these seeds or this soil an effective fungicidal amount of a compound according to claim 1 or of a composition according to claim 5.