AP446A

AP446A - Fungicidal derivatives of 2-alkoxy-2-imidazolin-5-ones.

Info

Publication number: AP446A
Application number: APAP/P/1993/000591A
Authority: AP
Inventors: Jean-Philippe Bascou
Original assignee: Rhone Poulenc Agrochimie
Priority date: 1992-11-25
Filing date: 1993-11-18
Publication date: 1996-01-17
Also published as: BG98239A; IL107706A0; ZW15993A1; JPH06211804A; PL301187A1; NZ250216A; CZ253393A3; MY109069A; SI9300611A; FR2698359B1; SK130793A3; HRP931431A2; KR940011450A; MA23032A1; HUT65906A; AU5188093A; HU9303342D0; TR28264A; FI935228A0; BR9304573A

Abstract

The invention relates to derivatives of

Description

Fungicidal derivatives of 2-alkoxy-2-imidazolin-5-ones

The present invention relates to novel 2alkoxy-2-imidazolin-5-one compounds for plant protection use. It likewise relates to the processes for preparation of the said compounds and the products which can optionally be used as intermediates in the preparation processes. It then relates to the use as fungicides of these compounds, the fungicidal compositions based on these compounds and the processes • · for combating fungal diseases of crops using these — · compounds.

One object of the present invention is to propose compounds showing improved properties in the treatment of fungal diseases.

Another object of the present invention is to propose compounds showing a spectrum of use in the field of fungal diseases which is likewise improved.

It has now been found that these objects could be achieved in whole or in part as a result of the products of the invention, which are derivatives of 2alkoxy-2-imidazolin-5-ones of general formula (I):

in which:

- R¹ represents an aryl radical including

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AP Ο Ο Ο 4 4 6 phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl or methylenedioxyphenyl, each of these radicals being optionally substituted by 1 to 3 groups chosen from amongst the meanings of R‘;

- R² represents an alkyl or haloalkyl radical with from 1 to 3 carbon atoms,

- R¹ and R² being additionally able to form, with the carbon to which they are bonded to the ring, a carbocycle or a heterocycle having from 5 to 7 atoms, it being possible for these rings to be fused with a phenyl, each of these radicals being optionally substituted by 1 to 3 groups chosen from amongst the meanings of R*;

- R³ represents an alkyl or haloalkyl group with from 1 to 3 carbon atoms,

- R* represents an aryl radical, including phenyl, naphthyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl, or methylenedioxyphenyl, each of these radicals being optionally substituted by 1 to 3 groups chosen from amongst the meanings of R‘;

- R^s represents a hydrogen atom or a formyl or acyl radical with from 2 to 6 carbon atoms, aroyl, alkoxycarbonyl with from 2 to 6 carbon atoms, aryloxycarbony1, alkylsulphonyl or arylsulphonyl;

- R‘ represents:

- a halogen atom or

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- an alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, cyanoalkoxy, alkylthio, haloalkylthio, cyanoalkylthio or alkylsulphonyl radical with from 1 to 6 carbon atoms or

- a cycloalkyl, halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio radical with from 3 to 6 carbon atoms or

- the nitro or cyano or thiocyanate group or

- an amino radical optionally mono- or disubstituted by an alkyl or acyl radical with from 1 to 6 carbon atoms or alkoxycarbonyl with from 2 to 6 carbon atoms

- a phenyl, phenoxy, phenylthio, phenyl15 sulphonyl or pyridyloxy radical, these radicals being optionally substituted by one or more of the following groups:

- a halogen atom or

- an alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulphonyl radical with from 1 to 6 carbon atoms or

- a cycloalkyl, halocycloalkyl, alkenyl, alkynyl, alkenyloxy,______ alkynyloxy, alkenylthio or alkynylthio radical with from 3 to 6 carbon atoms or

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- the nitro or cyano or thiocyanato group or

- an amino radical optionally monoor disubstituted by an alkyl or acyl radical with from l to 6 carbon atoms or alkoxycarbonyl with from 2 to 6 carbon atoms

- a phenyl, phenoxy, phenylthio, phenylsulphonyl or pyridyloxy radical, and their salt forms.

The compounds of formula II below represent preferred compounds:

in which R^r to R⁶ have the same meanings as above.

R⁴ preferably represents phenyl, substituted phenyl, pyridyl or substituted pyridyl. R⁵ preferably represents hydrogen or acyl (eg acetyl).

The compounds of formula I are obtained by 20 reacting 2-alkylthio-2-imidazolin-5-ones of Formula (III) with an alcohol R³OH in the presence of strong base, according to the scheme:

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APO 00 <4 6

ELI

ROH

Base

Solvent

I

R’, R^J, R³ and R⁴ having the same meaning as for 5 the formula I and R^,J representing an alkyl group with from 1 to 3 carbon atoms.

As the strong base, an alkali metal alkoxide R’oiC, an alkali metal hydroxide or a strong organic base can be used. The reaction is preferably carried out in the alcohol R³OH as solvent using the corresponding sodium alkoxide R’cNa* as base. The reaction is carried out at a temperature of between 20 and 80^eC. The 2-alkylthio-2imidazolin-5-ones of formula (III) are obtained according to one of the processes described in the European Patent

Application EP 0 551 048. The acylation of the compounds of formula I, in which R^s is a hydrogen atom, takes place according to classical methods.

Salts of the compounds of formula I may be prepared by known methods.

The examples below are given by way of illustration of the compounds according to the invention, of their preparation processes and of their antifungal properties.

The structures of all the products have been established by at least 1 of the following spectral techniques: proton NMR spectrometry, carbon 13 NMR spectrometry, infrared spectrometry and mass

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AP Ο Ο Ο 4 4 6 spectrometry.

In the table below, the methyl, ethyl, propyl, pyridyl, acetyl and phenyl radicals are respectively represented by Me, Et, Pr, Py, Ac and Ph, and M.p. means melting point.

Example 1: Preparation of compound No. 2.

1.4 g (1.74 mmol) of sodium in 60 ml of c

C c

c

C

C ethanol is reacted, under a dry nitrogen atmosphere, in a 100 ml 3-necked flask. 4 g (1.28 mmol) of 4-metfcyl-2methylthio-4-phenyl-l-phenylamino-2-imidazolin-5-one are then added. The mixture is refluxed for 6 h. It is cooled to ambient temperature and acidified with 0.4 ml of acetic acid. The mixture is diluted with 300 ml of ethyl acetate. The organic solution is washed with water, then dried over magnesium sulphate and concentrated under reduced pressure: a brownish red syrup is obtained. The product is purified by chromatography on a silica column. 1.25 g (31 % yield) of compound No. 2 is obtained in the form of a slightly pinkish powder melting at 106*C.

In the same manner, we have prepared the compounds described below:

No.	R6	R3	R4	R5	M.p. (*C)
1	-	Me	Ph	H	149
2	-	Et	Ph	R	106
3	-	nPr	Ph	H	80
4	4-C1	Me	Ph	B	140
5	-	Me	2-Me-Ph	H	118
6	4-C1	Me	2-pyridyl	B	150
8	-	Me	2-Cl-Ph	B	94
9	-	Me	4-Cl-Ph	H	124
11	3,4-di(MeO)	Me	Ph	B	150
12	4-C1	Me	4-Cl-Ph	H	176
13	4-C1	Me	4-F-Ph	H	147
14	4-C1	Me	2-Cl-Ph	B	syrup
15	4-C1	Me	3-Cl-Ph	H	147
16	4-Cl	Me	4-Me-Ph	H	162
17	4-Cl	Me	3-Me-Ph	B	116
18	4-Me	Me	Ph	B	110
19	4-F	Me	Ph	B	104
20	4-Cl	Me	2-Me-Ph	B	syrup
21	4-F	Me	3-Me-Ph	B	114
23	4-F	Me	2-Me-Ph	H	88
24	4-Me	Me	4-Cl-Ph	H	166
25	4-Me	Me	3-Cl-Ph	B	155
27	4-Me	Me	2-Cl-Ph	B	86
28	4-Me	Me	4-F-Ph	B	124
29	4-F	Me	3-Cl-Ph	B	160
30	4-Me	Me	4-Me-Ph	B	155
31	4-F	Me	4-Me-Ph	B	149
32	4-Me	Me	2-Me-Ph	B	128
33	-	Me	3-F-Ph	B	121
34	4-Me	Me	3-Me-Ph	B	138
35	4-PhO	Me	2-Me-Ph	R	120

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No.	R6	R3	R4	R5	M.p. CC)
36	4-F	Me	4-Cl-Ph	S	142
37	-	Me	4-F-Ph	B	157
38	-	Me	2,4-di(F)-Ph	H	166
39	-	Me	4-Me-Ph	H	116
40	4-F	Me	2-F-Ph	B	syrup
41	4-Me	Me	2-F-Ph	B	90
42	4-C1	Me	2-F-Ph	B	syrup
43	4-F	Me	2-Cl-Ph	B	syrup
44	-	Me	2,3-di(Me)-Ph	H	140
45	-	Me	3-Cl-2-pyridyl	B	140
46	-	Me	3-Me-Ph	B	54
47	-	Me	2-F-Ph	B	136
48	-	Me	3-Cl-Ph	B	93
49	4-F	Me	3-Me-2-pyridyl	B	126
50	4-F	Me	3-F-Ph	B	120
51	4-C1	Me	3-F-Ph	B	125
52	3-C1	Me	Ph	B	155
53	3-C1	Me	3-Me-Ph	H	100
54	3-C1	Me	3-Cl-Ph	H	105
55	3-C1	Me	3-F-Ph	B	135
56	3-C1	Me	2-Me-Ph	H	116
57	3-F	Me	Ph	B	134
58	3-F	Me	3-F-Ph	B	115
59	-	Me	Ph	Ac	121
60	3-F	Me	3-Cl-Ph	B	90
61	3-Me	Me	Ph	B	98
62	3-Me	Me	3-F-Ph	B	118
63	4-PhO	Me	2-pyridyl	B	146
64	2,4-diF	Me	Ph	B	163
65	2,4-diF	Me	3-F-Ph	B	162
66	4-PhO	Me	Ph	B	114

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C ²⁰ ο

C

No.	R6	R3	R4	R5	M.p. (·Ο)
67	4-PhO	Me	3-F-Ph	H	56
68	2-Cl	Me	Ph	H	214
69	-	Me	4-phO-Ph	H	118
70	2-Cl	Me	3-F-Ph	H	201
71	2-F	Me	Ph	H	172
72	2-F	Me	3-F-Ph	H	151
73	2,4-diF	Me	3-Cl-Ph	H	130
74	2-F	Me	3-Cl-Ph	H	151
75	4-iPr	Me	Ph	H	132
76	4-PhO	Me	3-Me-2- pyridyl	H	142
77	4-iPr	Me	3-F-Ph	H	128
78	3-Me	Me	3-Cl-Ph	H	115
79	4-iPr	Me	3-Cl-Ph	H	139
80	4-Br	Me	Ph	H	138
81	4-NO,	Me	Ph	H	143
82	3-PhO	Me	Ph	H	syrup
83	2,4-di(F)-4-PhO	Me	3-F-Ph	H	71
84	2,4-di(F)-4-PhO	Me	Ph	H	76
85	4-F-4-PhO	Me	Ph	H	91

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Compound No. 7:

Compound No. 22:

Cl

M.p. - 71*C

Compound No. 86:

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AP000446

Example 2: In vivo test on Plasmopara viticola (grape downy mildew):

An aqueous suspension is prepared, by fine grinding, of the active substance to be tested, having the following composition:

- active substance: 60 mg

Tween 80 surface-active agent (oleate of polyoxyethylene derivative of sorbitan), diluted to 10 % in water: 0.3 ml

- make up to 60 ml with water.

This aqueous suspension is then diluted with water to obtain the desired concentration of active substance.

Vine cuttings (Vitis vinifera), Chardonnay 15 variety, are grown in pots. When these plants are 2 months old (8 to 10 leaf stage, height from 10 to 15 cm), they are treated by spraying by means of the aqueous suspension below.

Some plants, used as controls, are treated 20 with an aqueous solution which does not contain the active substance.

After drying for 24 hours, each plant is contaminated by spraying an aqueous suspension of spores of Plasmopara viticola obtained starting from a culture of 4-5 days, then suspended at the rate of 100,000 units per cm’.

The contaminated plants are then incubated for two days at approximately 18‘C in a

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AP Ο Ο Ο 4 4 6 moisture-saturated atmosphere and then for 5 days at approximately 20-22°C at 90-100 % relative humidity.

Reading takes place 7 days after contamination, in comparison with the control plants.

Under these conditions, good (at least 75 %) or total protection is seen at a dose of 1 g/1 with the following compounds: 1, 3 to 21, 23 to 25, 27 to 81,

83, 84 and 86.

r

Example 3: In vivo test on Puccinia recondita 10 (brown rust of wheat):

An aqueous suspension of the active substance to be tested is prepared, by fine grinding, having the following composition:

active substance: 60 mg

- Tween 80 surface-active agent (oleate of

Γ polyoxyethylene derivative of sorbitan), diluted to % in water: 0.3 ml o

make up to 60 ml with water.

This aqueous suspension is then diluted with 20 water to obtain the desired concentration of active substance.

Wheat, in pots, sown on a 50:50 peatpozzuolana soil substrate, is treated at the 10 cm height stage by spraying with the aqueous suspension above.

After 24 hours, an aqueous suspension of spores (100,000 spores/cm³) is sprayed onto the wheat;

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AP Ο Ο Ο 44 6 this suspension has been obtained starting from contaminated plants. The wheat is then placed for 24 hours in an incubation chamber at approximately 20^eC and at 100 % relative humidity, then for 7 to 14 days at 60 % relative humidity.

Checking of the state of the plants takes place between the 8th and the 15th day after contamination, by comparison with a non-treated control.

Under these conditions, good (at least 75 %) or total protection is seen, at a dose of 1 g/1, with the following compounds: 1, 4 to 10, 14, 15, 19 to 21, 23, 25, 27 to 29, 31 to 33, 36, 37, 39, 40 to 48, 50 to 55, 57, 58, 60, 61, 63 to 67, 69, 71 to 80, 82 to 84 and 86.

Example 4: In vivo test on Phytophthora infestans (tomato blight):

- active substance: 60 mg

- Tween 80 surface-active agent (oleate of polyoxyethylene derivative of sorbitan), diluted to % in water: 0.3 ml

- make up to 60 ml with water.

This aqueous suspension is then diluted with water to obtain the desired concentration of active

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AR000446 substance.

Tomato plants (Marmande variety) are grown in pots. When these plants are one month old (5 to 6 leaf stage, height 12 to 15 cm), they are treated by spraying with the aqueous suspension above and with various concentrations of the compound to be tested.

After 24 hours, each plant is contaminated by spraying by means of an aqueous suspension of spores (30,000 spores/cm^J) of Phytophthora infestans.

After this contamination, the toeato plants are incubated for 7 days at approximately 20°C in a moisture-saturated atmosphere.

Seven days after contamination, the results obtained in the case of the plants treated with the active substance to be tested are compared with those obtained in the case of the plants used as controls. Under these conditions, good (at least 75 t) or total protection is seen, at a dose of 1 g/1, with the following compounds: 1, 4 to 10, 15, 18 to 21, 23, 28,

29, 31 to 33, 36, 37, 39, 42 to 44, 46 to 55, 57, 58, to 67, 72 to 74, 81, 84 and 86.

Example 5: In vivo test on Pyricularia oryzae (blast disease of rice):

An aqueous suspension is prepared, by fine grinding, of the active substance to be tested having the following composition:

active substance: 60 mg

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AP 0 0 0 4 4 6 surface-active agent (oleate of polyoxyethylene derivative of sorbitan) diluted to 10 % in water: 0.3 ml make up to 60 ml with water.

Rice, sown in pots in a 50:50 mixture of enriched peat and pozzuolana, is treated at the approximately 10 cm height stage (which corresponds to the 2-3 leaf stage) by spraying with the aqueous suspension above.

After 24 hours, an aqueous suspension of spores of Pvricularia orvzae. obtained from a culture of 15 days and then suspended at a rate of 100,000 units per cm³, is applied to the leaves.

The rice plants are incubated for 24 hours (25°C, 100 % relative humidity), then put in an observation chamber, under the same conditions, for 5 days.

Reading takes place 6 days after contamination.

Under these conditions, good (at least 75 %) or total protection is seen, at a dose of 1 g/1, with the following compounds: 1, 4 to 7, 17, 19, 20, 23, 25, 29, 31 to 33, 35, 40 to 43, 46, 47, 50, 52, 54, 55, 57, 59, 61, 63 to 67, 71, 72, 74, 78, 82, 84 and 85.

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AP Ο Ο Ο 4 4 6

Example 6: In vivo test on Septoria tritici (leaf spot of wheat):

An aqueous suspension, of concentration 1 g/1, of the active substance tested is obtained by grinding 60 mg of the latter in the following mixture: acetone: 5 ml

- surface-active agent (oleate of polyoxyethylene derivative of sorbitan) diluted to 10 %: 0.3 ml then the volume is adjusted to 60 ml with water.

Wheat plants (Darius variety), sown on a 15 50:50 peat-pozzuolana substrate and grown under glass at a temperature of 10-12*0, are treated at the 1 leaf stage (height of approximately 10 cm) by spraying with the suspension of active substance described above.

Some plants, used as controls, are treated by 20 spraying with an aqueous solution which does not contain the active substance.

hours after treatment, the plants are contaminated by spraying with an aqueous suspension of spores (500,000 spores/ml) collected in a 7 day-old culture. _____

After contamination, the plants are placed in a humid atmosphere at 18°C. Marking is carried out 20 days after contamination in comparison with the control

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plants.

Under these conditions, good (at least 75 %) or total protection is seen, at a dose of 1 g/1, with the compounds: 1, 4 to 6, 9, 19, 20, 23, 32, 33, 35 to

37, 40, 42 to 45, 47, 48, 50, 52, 54, 55, 57, 58, 60, to 64, 66, 67, 71 to 80, 83, 84 and 86.

These results clearly show the good fungicidal properties of the derivatives according to the invention against fungal diseases of plants due to fungi belonging to the most diverse families such as

Phycomycetes, Basidiomycetes, Ascomycetes, Adelomycetes or Fungi imperfecti, in particular grape downy mildew, tomato blight, brown rust and leaf spot of wheat and also blast disease of rice.

For their practical use, the compounds according to the invention are rarely used alone. Most often, these compounds are part of compositions. These compositions, which can be used as fungicidal agents, contain as active substance a compound according to the invention such as described above mixed with solid or liquid supports acceptable in agriculture and/or surface-active agents likewise acceptable in agriculture. In particular, the common inert supports and the common surface-active agents can be used. These compositions are likewise part of the invention.

These compositions can also contain all sorts of other ingredients such as, for example, protective colloids, adhesives, thickeners, thixotropic agents.

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penetrants, stabilizers, sequestering agents, etc....

More generally, the compounds used in the invention can be combined with all the solid or liquid additives corresponding to customary formulation techniques.

Unless otherwise specified percentages in this specification are by weight.

In a general manner, the compositions according to the invention customarily contain from approximately 0.05 to 95 % (by weight) of a compound according to the invention (subsequently called active substance), one or more solid or liquid supports and, optionally, one or more surface-active agents.

The term support” in the present account indicates an organic or inorganic, natural or synthetic substance, with which the compound is combined to facilitate its application to the plant, to seeds or to the soil. This support is thus generally inert and it must be acceptable in agriculture, especially on the plant treated. The support can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc...) or liquid (water; alcohols, especially butanol, etc...).

The surface-active agent can be an emulsifying, dispersing or wetting agent of ionic or25 non-ionic type or a mixture of such surface-active agents. For example, salts of polyacrylic acids, salts of lignosulphonic acids, salts of phenylsulphonic or naphthalenesulphonic acids, polycondensates of ethylene oxide on fatty alcohols or on fatty acids or on fatty amines, substituted phenols (especially alkylphenols or ,

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AP Ο Ο Ο 4 4 6

Ο 10

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arylphenols), salts of esters of sulphosuccinic acids, derivatives of taurine (especially alkyltaurates), phosphoric esters of alcohols or of polyoxyethylated phenols, esters of fatty acids and polyols, and derivatives with sulphate, sulphonate and phosphate functions of the above compounds can be mentioned. The presence of at least one surface-active agent is generally indispensable if the compound and/or the inert support are not soluble in water and if the carrier agent for application is water.

Consequently, therefore, the compositions for agricultural use according to the invention can contain active substances according to the invention within very large limits, ranging from 0.05 % to 95 % (by weight). Their content of surface-active agent is advantageously between 5 % and 40 t by weight.

These compositions according to the invention are themselves in fairly diverse, solid or liquid forms.

As solid composition forms, powders for dusting (with a content of compound which can range up to 100 %) and granules, especially those obtained by extrusion, by compaction, by impregnation of a granulated support, by granulation starting from a powder (the content of compound in these granules being between 0.5 and 80 % for these last cases), pills or effervescent tablets.

The compounds of formula (I) can moreover be

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AP Ο Ο Ο 4 4 6 (' used in the form of powders for dusting; a composition containing 50 g of active substance and 950 g of talc can also be used; a composition containing 20 g of active substance, 10 g of finely divided silica and

970 g of talc can also be used; these constituents are mixed and ground and the mixture is applied by dusting.

As forms of compositions which are liquid or intended to form liquid compositions during application, solutions, in particular concentrates soluble in water, emulsifiable concentrates, emulsions, concentrated suspensions, aerosols, wettable powders (or powders to be sprayed), pastes and gels can be mentioned.

The emulsifiable or soluble concentrates most often comprise 10 to 80 % of active substance, the emulsions or solutions ready for application containing, for their part, 0.001 to 20 % of active substance.

In addition to the solvent, when necessary the emulsifiable concentrates can contain 2 to 20 % of appropriate additives such as the stabilizers, surfaceactive agents, penetrants, corrosion inhibitors, colorants or adhesives mentioned above.

Starting from these concentrates, emulsions of any desired concentration, which are particularly suitable for application to the crops, can be obtained by dilution.

By way of example, here is the composition of

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AP000446 some emulsifiable concentrates:

Example EC 1:

- active substance 400 g/1

- alkali metal dodecylbenzene5 sulphonate 24 g/1

- nonylphenol ethoxylated with molecules of ethylene oxide 16 g/1

- cyclohexanone 200 g/1

- aromatic solvent q.s.p. 1 litre

According to another formula of emulsifiable concentrate, the following are used:

Example EC 2;

- active substance 250 g

- epoxidized vegetable oil 25 g

- mixture of alkylaryl sulphonate and polyglycol ether and fatty alcohols 100 g

- dimethylformamide 50 g

- xylene 575 g

The concentrated suspensions, which can likewise be applied by spraying, are prepared so as to obtain a stable fluid product which does not settle, and they usually contain 10 to 75 % of active substance, 0.5 to 15 % of surface-active agents, 0.1 to

10 % of thixotropic agents, 0 to 10 % of appropriate additives, such as antifoams, corrosion inhibitors, stabilizers, penetrants and adhesives and, as support,

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AP Ο Ο Ο 4 4 6 water or an organic liquid in which the active substance is only slightly soluble or insoluble: certain solid organic substances or inorganic salts can be dissolved in the support to help to prevent sedimentation or as antifreezes for the water.

By way of example, here is a concentrated suspension composition:

Example CS 1:

	- active substance	500 g
10	- polyoxyethylated tristyryl-
	phenol phosphate	50 g
	- polyoxyethylated alkylphenol	50 g
	- sodium polycarboxylate	20 g
	- ethylene glycol	50 g
15	- organopolysiloxane oil
	(antifoam)	¹ 9
	- polysaccharide	1.5 g
	- water	316.5 g

The wettable powders (or powders for spraying) are usually prepared such that they contain 20 to 95 % of active substance, and they usually contain, in addition to the solid support, from 0 to 30 % of a wetting agent, from 3 to 20 % of a dispersing agent and, when necessary, from 0.1 to 10 % of one or more stabilizers and/or other additives, such as penetrants, adhesives, anti-agglutinating agents, colorants, etc.... To obtain the powders for spraying or wettable powders, the active substances are mixed

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AP Ο Ο Ο 446 <

intimately in appropriate mixers with the additional substances and the mixture is ground using mills or other appropriate grinders. In this way, powders for spraying are obtained whose wettability and suspension are advantageous; they can be suspended with water at any desired concentration and these suspensions can be used very advantageously, in particular for application to the leaves of the plants. In place of wettable powders, pastes can be prepared. The conditions and details of preparation and of use of these pastes are similar to those of the wettable powders or powders for spraying.

By way of example, here are various wettable powder (or powder for spraying) compositions:

Example WP 1:

- active substance 50 %

- ethoxylated fatty alcohol (wetting agent) 2.5 %

- ethoxylated phenylethylphenol (dispersing agent) 5 %

- chalk (inert support) 42.5 %

Example WP 2:

- active substance 10 %

- synthetic C13 oxo alcohol of branched type, ethoxylated with 8 to 10 ethylene oxide (wetting agent) 0.75 %

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AP Ο Ο Ο 4 4 6 neutral calcium lignosulphonate (dispersing agent) 12 % calcium carbonate (inert filler) g.s.p. 100 %

Example WP 3?

This wettable powder contains the same ingredients as in the preceding example, in the proportions below:

- active substance 75 %

- wetting agent 1.50 %

- dispersing agent 8 %

- calcium carbonate (inert filler) g.s.p. 100 %

Example WP 4:

- active substance 90 %

- ethoxylated fatty alcohol (wetting agent) 4 %

- ethoxylated phenylethylphenol (dispersing agent) 6 %

Example WP 5:

- active substance

- mixture of anionic and nonionic surfactants (wetting agent) %

2.5 «

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AP Ο Ο Ο 4 4 6

- sodium lignosulphonate (dispersing agent) 5 %

- kaolinic clay (inert support) 42.5 %

The aqueous dispersions and emulsions, for 5 example the compositions obtained by diluting a wettable powder or an emulsifiable concentrate according to the invention with the aid of water, are included within the general scope of the present invention. The emulsions can be of the water-in-oil or oil-in-water type and they can have a thick consistency such as that of a mayonnaise.

The compounds according to the invention can be formulated in the form of water-diepersible granules likewise included within the scope of the invention.

These dispersible granules, of apparent density generally of between approximately 0.3 and 0.6 have a particle size generally of between approximately 150 and 2000 and preferably between 300 and 1500 microns.

The content of active substance of these granules is generally of between approximately 1 % and 90 %, and preferably between 25 % and 90 %.

The remainder of the granules is essentially composed of a solid filler and optionally of surface25 active adjuvants conferring properties of dispersibility in water to the granules. These granules can be essentially of two distinct types depending on

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AP Ο Ο Ο 4 4 6 whether the retained filler is soluble or not in water. When the filler is water-soluble, it can be inorganic or, preferably, organic. Excellent results have been obtained with urea. In the case of an insoluble filler, the latter is preferably inorganic, such as, for example, kaolin or bentonite. It is then advantageously accompanied by surface-active agents (at a rate of 2 to 20 % by weight of the granules) of which more than half is, for example, formed by at least one dispersing agent, essentially anionic, such as an alkali metal or alkaline earth metal polynaphthalenesulphonate or an alkali metal or alkaline earth metal lignosulphonate, the remainder being formed by non-ionic or anionic wetting agents such as an alkali metal or alkaline earth metal alkyl naphthalenesulphonate.

In addition, although this is not indispensable, other adjuvants such as antifoam agents can be added.

The granules according to the invention can be prepared by mixing of the necessary ingredients and then granulation according to several techniques known per se (coating pan, fluidized bed, atomizer, extrusion, etc...). The process is generally ended by crushing followed by sieving to the size of the chosen particle within the limits mentioned above.

Preferably, it is obtained by extrusion, working as indicated in the examples below.

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AP Ο Ο Ο 4 4 6

Example DG 1: Dispersible granules % by weight of active substance and 10 % of urea in the form of beads are mixed in a mixer. The mixture is then crushed in a toothed roll crusher. A 5 powder is obtained which is moistened with approximately 8 % by weight of water. The moist powder is extruded in a perforated roller extruder. Granules are obtained which are dried, then crushed and sieved so as only to retain the granules of a size of between

150 and 2000 microns.

Example DG 2: Dispersible granules

The following constituents are mixed in a mixer:

- active substance 75 %

- wetting agent (sodium alkylnaphthalenesulphonate) 2 %

- dispersing agent (sodium polynaphthalenesulphonate) 8 %

- inert filler insoluble in water (kaolin) 15 %

This mixture is granulated in a fluidized bed, in the presence of water, then dried, crushed and sieved so as to obtain granules of a size of between 0.15 and 0.80 mm.

These granules can be used on their own, or in solution or dispersion in water so as to obtain the required dose. They can also be used to prepare associations with other active substances, especially

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AP Ο Ο Ο A A 6 fungicides, the latter being in the form of wettable powders, or of granules or aqueous suspensions.

As far as the compositions suited for storage and for transport are concerned, they more advantageously contain from 0.5 to 95 % (by weight) of active substance.

The invention likewise has as an object the use of the compounds according to the invention for combating fungal diseases of plants by preventive or curative treatment of the latter or of their place of growth.

They can be advantageously applied at doses of 0.005 to 5 kg/ha, and more specifically of 0.01 to 1 kg/ha.

Claims

1. 2-Alkoxy-2-imidazolin-5-one compounds of general formula (I) in which:

5 - R¹ represents an aryl radical including phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, guinolinyl, isoquinolinyl or methylenedioxyphenyl, each of these radicals being optionally substituted by 1 to 3 groups chosen from

10 amongst the meanings of R‘;

- R² represents an alkyl or haloalkyl radical with from 1 to 3 carbon atoms,

- R^l and R² can additionally form, with the carbon to which they are bonded to the ring, a

15 carbocycle or a heterocycle having from 5 to 7 atoms, it being possible for these rings to be fused with a phenyl, each of these radicals being optionally substituted by 1 to 3 groups chosen from amongst the meanings of R*;

20 - R³ represents an alkyl or haloalkyl group vith from 1 to 3 carbon atoms;

- R⁴ represents an aryl radical, including phenyl, naphthyl, pyridyl, pyrimidyl, pyridazinyl,

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AP 0 0 0 4 4 6 pyrazinyl, benzothienyl, benzofuryl, guinolinyl, isoquinolinyl, or methylene dioxyphenyl, each of these radicals being optionally substituted by 1 to 3 groups chosen from amongst the meanings of R⁴;

- R⁵ represents a hydrogen atom or an formyl or acyl radical with from 2 to 6 carbon atoms, aroyl, alkoxycarbonyl with from 2 to 6 carbon atoms, aryloxycarbonyl, alkylsulphonyl or arylsulphonyl; and

- R⁴ represents:

- halogen atom or

- the nitro or cyano or thiocyanato group or

- a phenyl,_phenoxy, phenylthio, phenylsulphonyl or pyridyloxy radical, these radicals being optionally substituted by one or more of the following group:

- a halogen atom or

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AP Ο Ο Ο 4 4 6

- an alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkcxy, alkylthio, haloalkylthio or alkylsulphonyl radical with from 1 to 6 carbon atoms or

5 - a cycloalkyl, halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio radical with from 3 to 6 carbon atoms or

- the nitro or cyano or thiocyanato

10 group or

- an amino radical optionally mono- or disubstituted by an alkyl or acyl radical with from 1 to 6 carbon atoms or alkoxycarbonyl with from 2 to 6 carbon

15 atoms a phenyl, phenoxy, phenylthio, phenylsulphonyl or pyridyloxy radical, and their salt forms.

2. Compounds according to Claim 1,

20 characterized in that they correspond to the general formula II:

in which R¹ to R* have the same meanings as in the formula I.

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AP Ο Ο Ο 4 4 6

3. Process for the preparation of compounds according to Claim 1, characterized in that 2-alkylthio-2-imidazolin-5-ones of formula (III) are reacted with an alkyl R³OH in the presence of strong

5 base, according to the scheme:

R³OH

Base

Solvent

ΠΙ

R¹, R², R³ and R⁴ having the same meaning as

10 for the formula I and R'³ representing an alkyl group with 1 to 3 carbon atoms.

4. Fungicidal compositions comprising one or more imidazolin-5-ones of general formula I or a salt thereof as defined in claim 1, in association with

15 one or more solid or liquid supports acceptable in agriculture and/or surface-active agents acceptable in agriculture.

5. Fungicidal compositions comprising one or more imidazolin-5-ones of general formula II or a

20 salt thereof as defined in claim 2, in association with one or more solid or liquid supports acceptable in agriculture and/or surface-active agents likewise acceptable in agriculture.

6. Fungicidal compositions according to

25 Claim 4 or 5, characterized in that they contain from

0.5 % to 95 % by weight of compounds according to one

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AP000446 i ί of Claims 1 or 2.

7. Method for the treatment of crops attacked or susceptible to being attacked by fungal diseases, characterized in that an effective quantity

5 of an imidazolin-5-one according to Claim 1 or 2 or a salt thereof or a composition according to any one of Claims 4 to 6 is applied.

8. Method according to Claim 7, characterized in that the effective dose is between

C 10 0.0005 and 5 kg/ha.

9. Method according to Claim 8, characterized in that the effective dose is between 0.01 and 1 kg/ha.