AU666783B2

AU666783B2 - Fungicidal derivatives of 2-alkoxy-2-imidazolin-5-ones

Info

Publication number: AU666783B2
Application number: AU51880/93A
Authority: AU
Inventors: Jean-Philippe Bascou; Gilbert Emeric; Guy Lacroix; Joseph Perez; Fabrice Pinard
Original assignee: Rhone Poulenc Agrochimie SA
Current assignee: Bayer CropScience SA
Priority date: 1992-11-25
Filing date: 1993-11-24
Publication date: 1996-02-22
Anticipated expiration: 2013-11-24
Also published as: BG98239A; MX9307271A; HU9303342D0; NZ250216A; FR2698359B1; KR940011450A; PL301187A1; JPH06211804A; MA23032A1; IL107706A0; FR2698359A1; EP0599749A1; CN1111240A; AU5188093A; AP9300591A0; MY109069A; HUT65906A; HRP931431A2; AP446A; CA2103192A1

Description

OWN~~4 666783f a

AUSTRALIA

PATENTS ACT 1990 COMPLETE SPECIFICATION NAME OF APPLICANT(S): Rhone-Poulenc Agrochlmnle ADDRESS FOR SERVICE: DAVIES COLLISON CAVE Patent Attorneys I Little Collins Street, Melbourne, 3000.

INVENTION TITLE: Fungicidal derivatives of 2 -alkoxy -2 -imidazolin-5 -ones 4

VI

V 4 *4

IV

#4 9*IV I'~

V

41

I

S. *V V I 4 *u4c It VI V itt t 4 AVIV 41 V VI The following statement is a full description of performing it known to me/usof this invention, including +he best method 1IT 1A The present invention relates to novel 2compounds for plant protection use. It likewise relates to the processes 5 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 uoc as fungicides of these compounds, the fungicidal compocitiona based on these compounds and Lhe processes for combating fungal diseases of crops using these cumpounds.

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

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

t t elrrsy4 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 2of general formula O 1R R'

N-^

0

RS

1.I ;in which: R' represents i L-_-II1_I-L~ -2phenyl, thienyl or benzothienyl, each of these radicals being optionally substituted by 1 to 3 groups chosen from amongst the meanings of R 6

R

2 represents an alkyl or haloalkyl radical with from 1 to 3 carbon atoms, R' and R 2 being additionally able to form, with the carbon to which they are bonded to the ring, a carbocycle 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 6

R

3 represents an alkyl or haloalkyl grou wvith from 1 to 3 carbon atoms,

R

4 represents phenyl or pyridyl, each of these radicals being optionally substituted by 1 to 3 groups chosen from amongst the meanings of R 6

R

s represents a hydrogen atom or a formyl or alkanoyl radical with from 2 to 6 carbon atoms, aroyl, alkoxycarbonyl with from 2 to 6 carbon atoms, aryloxycarbonyl, alkylsulphonyl or arylsulphonyl;

R

6 represents: a halogen atom or 4 c tC StC t Ci C t t t C t C c.c.

C 4 1; tC> 951218,pAoperb,51 880,SPE,2 3 -an alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, cyanoalkoxy, alkylthio, haloalkylthio, cyanoalkyithia, or alkylsuiphonyl radical with from i to 6 carbon atoms or4 a cycloalkyl, halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio radical with from to 6 carbon atoms or -the nitro or cyano or thiocyanato, group or -an amino radical optionally ~or~otA'-A-JcIkcivwXyI ezsubtibt..t:- by an alkyl orpacy4 radical with from 1 to 6 carbon atoms or alkoxycarbonyl with from 2 to 6 carbon atoms -a phenyl, phenoxy, phenylthio, phenylsuiphonyl or pyridyloxy radical, these radicals being optionally substituted by one or more of the following groups:

C

a halogen atom or an alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, alkylthio, tat rhaloalkylthio 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 4 -the nitro or cyano or thiecyanato group or an amino radical. optionally woo S4A!tVAeck by an alkyl or UOPAdical with from I to 6 car-bon atoms or alkoxycarbonyl with from 2 to 6 carbon atoms a phenyl, phenoxy, phenyithio, phenylauiphonyl or pyridyloxy ra~dical, and their salt formis.

The compounds of formula 11 below represent preferred compounds:

O-R

3 R2 N- R6~D 0 Rs Sin which R 1 to R6 have the same mnaiiings as above.

R4 preferably represents phenyl, substituted phenyl, pyridyl or substituted pyridyl. RS preferably represents hydrogen or acyl (eq acetyl).

tillThe compounds of formula I are obtained by reacting 2-a lkylthio-2-iniidazolin-5-ones of formula 4: (111) with an alcohol R 3 O in the presence or strong base, according to the scheme: t 0 4 7,

LUA

Sq R3- Nzz... R2-W'R -N rN N1 R4Q Base N /R Solvent R1, R1, R 3 and RI having the same meaning as f or the formula I and R11 1 representing an alkyl group with from I. to 3 carbon. atoms.

As the strong base, an alkali metal alkoxide WWan alkali metal hydroxide or a stronig organic bass can be used. The reaction in preferably carried out in the alcohol R 3 OH as solvent using the corresponding sodium alkoxide WO'Nal as base. The reaction is carried out at a temperature of between 20 and G0CC. The 2-alkylthic-2of formula (III) are obtained according to one of the processes described in the European Patent Application E? 0 551 048. Th-e acylation of the compounds of fo rmula 1, in which R5 is a hydrogen atom, takes place according to classical methods.

Salts of the compounds aC 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 o'f their antifungal propertiesi.

structures or all the products have been eutablished by at least I. of the following spectral tachriiques: proton NMR spectrometry, carbon 13 1NMR spectrometry, infrared spectrometry and mass 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 ethanol is reacted, under a dry nitrogen atmosphere, in a 100 ml 3-necked flask. 4 a (1.28 mmol) of 4-methvl-2methylthio-4-phenyl-l-phenylamino-2-imidazolin-5-one are then added. The mixture is refluxed for 6 h. It is cooled to ambient temerature 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..5 g (31 yield) of compound No. 2 is obtained in the form of a slightly 20 pinkish powder melting at 106 0

C.

In the same manner, we have prepared the compounds described below: rrtr r trrr r d ii L (i 1 L- I

I

(r I

CC

j L

C

I'

(IIC(C

(CLCC(

d CH 3 -O-R3

N,

N-R

4 R6 0 R3 f C c r C r I No. R6 R3 R4 R5 M.p. (OC) 1 Me Ph H 149 2 Et Ph H 106 3 nPr Ph H 4 4-C1 Me Ph H 140 Me 2-Me-Ph H 118 6 4-C1 Me 2-pyridyl H 150 8 Me 2-Cl-Ph H 94 9 Me 4-Cl-Ph H 124 11 3,4-di(MeO) Me Ph H 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 H syrup 4-C1 Me 3-Cl-Ph H 147 16 4-C1 Me 4-Me-Ph H 162 17 4-C1 Me 3-Me-Ph H 116 18 4-Me Me Ph E 110 19 4-F Me Ph H 104 4-Cl Me 2-Me-Ph H syrup 21 4-F Me 3-Me-Ph H 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 H 155 27 4-Me Me 2-Cl-Ph H 86 28 4-Me Me 4-F-Ph H 124, 29 4-F Me 3-Cl-Ph H 160 30 4-Me Me 4-Me-Ph H 155 31 4-F Me 4-Me-Ph H 149 32 4-Me Me 2-Me-Ph H 128 33 Me 3-F-Ph H 121 34 4-Me Me 3-Me-Ph H 138 4-PhO Me 2-Me-Ph H 120 tr tICr I C I tC III C

CC

(r c( c C Ir I Ct t t t 4 t 8 U; 8 No. R6 R3 R4 RS M.p. (OC) 36 4-F Me 4-Cl-Ph H 142 37 Me 4-F-Ph H 157 38 Me 2,4-di(F)-Ph H 166 39 Me 4-Me-Ph H 116 4-F Me 2-F-Ph H syrup 41 4-Me Me 2-F-Ph H 42 4-c1 Me 2-F-Ph H syrup 43 4-F Me 2-C1-Ph H syrup 44 Me 2,3-di(Me)-Ph H 140 Me 3-Cl-2-pyridyl H 140 46 Me 3-Me-Ph H 54 47 Me 2-F-Ph H 136 48 Me 3-Cl-Ph H 93 49 4-F Me 3-Me-2-pyridyl H 126 4-F Me 3-F-Ph H 120 51 4'-Cl Me 3-F-Ph H 125 52 3-Cl Me Ph H 155 53 3-Cl Me 3-Me-Ph H 100 54 3-Cl Me 3-Cl-Ph H 105 55 3-Cl Me 3-F-Ph H 135 56 3-C1 Me 2-Me-Ph H 116 57 3-F Me Ph H 134 58 3-F Me 3-F-Ph H 115 59 Me Ph Ac 121 3-F Me 3-C1-Ph H 90 61 3-Me Me Ph H 98 62 3-Me Me 3-F-Ph H 118 63 4-PhO Me 2-pyridyl H 146 64 2,4-diF Me Ph H 163 2,4-diF Me 3-F-Ph H 162 66 4-PhO Me Ph H 114 4 1 4r 4* 4 A rir rour i i No. R6 R3 R4 R5 M.p. (OC) 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- H 142 ~~~pyridyl 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 2 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-PhQ Me Ph H 76 85 4-F-4-pho Me Ph H 91

S

C

20 Compound No. 7: 00 NH-0Q M.P. 73*C Compound No. O NH0 M.P. 86*C 5 Compound No. 22:

I

4*

I

,t cit 4 4<4, 4 4< 14 4 441441 4 4<12', I, I 44 M.P. =71*C Compound No. 86: N <0 -CH 3

CH

3 N

NH

0 M.P. 98*c 11 Example 2: In Vivo test on P1asmopara viticola (grape downy mildew): An aqueous suspension is prepared, by fine grinding, of the active substance to be tssted, having the following composition: active substance: 60 mg Tween 80 surface-active agent (cleats of polyoxyethylene derivative of sorbitan), diluted to 0 in water: 0.3 ml make up to 60 ml with water.

This aqueous suspension im than 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

I

15 cm), they are treated by spraying by means of the aqueous susponsion 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 Pla2mopara vlticola obtained starting from a U. 25 culture of 4-5 days, then suspended at the rate of 100,000 units per cm 3 The ontaminated plants are then incubated for two days at approximately 180C in a *4it 11 *.4.2

A

It 44 k *4 12 moicture-saturated atmosphere and then for 5 days at approximately 20-22OC 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 I g/l with the following compounds: 1, 3 to 21, 23 to 25, 27 to 81, 83, 84 and 86.

jxmp in vivo test on Puacinla recondita (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 15 Tween 80 surrace-active agent (oleato of polyoxyethylene derivative of sorbitan), diluted to t 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.

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/c) is sprayed onto the wheat; this suspension has been obtained starting from contaminated plants. The wheat in then placed for 24 hours in an incubation chamber at approximately and at 100 relative humidity, then for 7 to 14 days at 60 t 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 4) or total protection is seen, at a dose of I g/l, 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 57, 58, 60, 61, 63 to 67, 69, 71 to 80, 82 to 84 15 and 86.

4€ Example 4: In vivo test on Phytophthora Snfestans (tomato blight): An aqueous suspension of the active substance to be tested is prepared, by fine grinding, having the 20 following composition; active substance: 60 mg Tween 80 surface-active agent (oleate of polyoxyetnylene derivative of sorbitan), diluted to 10 in water: 0.3 ml make up to 60 ml with water.

This aqueous suupension io thon diluted with water tc obtain the desired concentration of active 1 1 1 1 i

I

14 substance.

Tomato plants (Marmande variety) are grown in pots. When these plants are one month old 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 3 of Phytophthora infestans.

After this contamination, the tomato 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 15 active substance to be tested are compared with those obtained in the case of the plants used as controls.

4 9 4 Under these conditions, good (at least 75 or total t protection is seen, at a dose of 1 g/l, with the following compounds: 1, 4 to 10, 15, 18 to 21, 23, 28, 4 20 29, 31 to 33, 36, 37, 39, 42 to 44, 46 to 55, 57, 58, to 67, 72 to 74, 81, 84 and 86.

t t SExample 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 surface-active agent (oleate of polyoxyethylene derivative of sorbitan) diluted to 10 in watert 0.3 ml make up to 60 ml with water.

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

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

The rice plants are incubated for 24 hours o t 100 relative humidity), then put in an observation chamber, under the same conditions, for '20 days.

Li 20Reading taken place 6 days after contamination.

S i It Under these conditions, good (at least 75 or total protection is seen, at a dose of 1 g/I, with the following compounds: 1, 4 to 7, 17, 19, 20, 23, 2S, 29, 31 to 33, 35, 40 to 43, 46, 47, 50, 52, 54, 5, 57, 59, 61, 63 to 67, 71, 72, 74, 78, 82, 84 and Fi I 16 Example 6: In vivo test on Septoria tritici (leaf spot of wheat): An aqueous suspension, of concentration 1 g/l, 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 0.3 ml then the volume is adjusted to 60 ml with water.

Wheat plants (Darius variety), sown on a 4 15 50:50 peat-pozzuolana substrate and grown under glass at a temperature of 10-12 0 C, 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 spraying with an aqueous solution which does not contain the active substance.

24 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 V, t 25 culture.

After contamination, the plants are placed in a humid atmosphere at 18°C. Marking is carried out days after contamination in comparison with the control 1- L V i 101~1~Lllll~- 17plants.

Under these conditions, good (at least 75%) or total protection is seen, at a dose of 1 g/l, with the compounds: 1, 4 to 6, 9, 19, 20, 23, 32, 33, 35 to 37, 40, 42 to 47, 48, 50, 52, 54, 55, 57, 58, 60, 62 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.

Comparative Example The efficacy of compounds A, to A, of the present invention and compounds P, to P 7 of EP 551048 on Puccinia recondita (responsible for brown rust of wheat) was tested. The conditions of this test are described in Example 3 and the doses at which the compounds were tested were 0.333 g/l or 0.037 g/l. The corresponding fungicidal efficacy was represented respectively by E(0.333) or E(0.037) and is expressed in The results are shown in Tables 1 and 2 below.

A-CH

3 CH N L, C I Ctortc t Ct l t' cI t 951218,p:ope\dab,5 i 8.SPE, 17 17a Table I Compound R 6 X A Position with E(0.037) E(0.333 respect present N% _________application A, 4-F-4-PhO 0 covered and 95 N.A.

exemplified ___(compound n' 85)

A

2 4-PhO 0 covered and 90 N.A.

exemplified ___(compound n' 66)

A

3 4-Me-4-PhO 0 covered, not N.A. __________exemplified

A

4 4-PhO 3-F 0 covered and 95 N.A.

exemplified (compound n' As 3-PhO 0 covered and N.A. exemplified (compound no 82)

A

6 2,4-di(F)- 3-F 0 covered and 90 N.A.

4-PhO exemplified ___(compound r? 83)

A

7 2,4-di(F)- 0 covered and 95 N.A.

4-PhO exemplified ___(compound no 84) UUU U

U

C

S C~ St

U

U U Ut Ct

U

U U

SI

UU(~

C U U St St

U

It St U

U

S Ut V SICCt U L 95121 8,PAOPcI&a,5 I880.SPE, 17 17b Table 2 Compound R 6 X A Position with E(0.037) E(0.333) respect to BP 551048 P, 4-F-4-PhO S covered, not 25 N.A.

exemplified

P

2 4-PhO S covered and 25 N.A.

exemplified (compound no 89)

P

3 4-Me-4-PhO S covered, not N.A. exemplified

P

4 4-PhO 3-F S covered, not 25 N.A.

exemplified

P

5 3-PhO S covered, not N.A. exemplified

P

6 2,4-di(F)- 3-F S covered, not 0 N.A.

4-PhO exemplified

P

7 2,4-di(F)- S covered, not 0 N.A.

4-PhO exemplified Me methyl N.A. Not applicable 15 It can be seen in Table 1 that compounds A, to A 7 of the present invention all possess a much higher efficacy than the respective analogue compounds P, to P 7 in Table 2 of EP 551048.

The difference of efficacy which reaches in nearly all the cases 70% and for two compounds is about 90% demonstrates that the compounds of the present invention are 20 quite active against a disease of the cereals which is very important to fight on a practical level. This activity is not observed for the closest compounds of EP 551048.

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.

951218,p:\oper\dab,51880.SPE,17 ¢t~lt t t t rre C t t tLE rt I rt t t St C C t r trt~ c e r (1 'Let<*' c( -17c 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, Ct"t t &te t C tt Co 1218,pAoper\dab,5 I 880,SPE, 17 is

I

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 arc by weight.

In a general man~ner, the compositions according to the invention customarily contain from approximately 0.05 to 95 t (by weight) of a compound according to the invention (uubsaquently called active substance), one or more solid or liquid oupports and, optionally, on. or more surface-active agents.

The term "support"l in the present account indicates an organic or inorganic, natural or synthetic substance, with which the compound is combined to facilitate its application to thae plant, to seeds or to i 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 sil.-te, silica, resins, waxes, solid fertilizers, or l.-.quid (water; alcohols, C especially butanol, The surface-.active agent can be an emulsifying, clispersing or wetting agent of ionic or non-ionic typo or a mixture of such surface-active agents. For example, salts of polyacrylic acids, salts of lignosulphonic acids, salts of phonylsuiphonic or naphthiaienesulphonic acids, polycondensates of ethylene owide on fatty alcohols or on fatty acicn or on fatty &mines, substituted phenols (especially alkylphencla or 19 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 15 weight). Their content of surface-active agent is 1 advantageously between 5 and 40 by weight.

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

As solid composition forms, powders for 4 ,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 25 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 can moreover be I it i r0 P'4 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 *oee mentioned.

The emulsifiable or soluLle 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 j by dilution.

By way of example, here is the composition of

I

21 some emulsifiable concentrates: Example EC 1: active substance 400 g/l alkali metal dodecylbenzenesulphonate 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 20 The concentrated suspensions, which can I4 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, r 1 22 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 polyoxyethylated tristyrylphenol phosphate 50 g polyoxyethylated alkylphenol 50 g sodium polycarboxylate 20 g ethylene glycol 50 g organopolysiloxane oil (antifoam) 1 g polysaccharide 1.5 g t water 316.5 g The wettable powders (or powders for spraying) are usually prepared such that they contain to 95 of active substance, and they usually contain, in addition to the solid support, from 0 to 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, Scolorants, To obtain the powders for spraying or wettable powders, the active substances are mixed r 23 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: 15 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 i m~i neutral calcium lignosulphonate (dispersing agent) calcium carbonate (inert filler) q.s.

12 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.' dispersing agent 8 calcium carbonate (inert filler) q.s.p. 1( ti S S St

S

50 )0 Example WP 4: active substance ethoxylated fatty alcohol (wetting agent) ethoxylated phenylethylphenol (dispersing agent) Example WP active substance mixture of anionic and nonionic surfactants (wetting agent) 90 4 6 50 2.5 IU Ic i i

IF-

sodium lignosulphonate (dispersing agent) 5 kaolinic clay (inert support) 42.5 The aqueous dispersions and emulsions, for 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 the invention can be formulated in the form of water-dispersible granules 4 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 t S 90 and preferably between 25 and 90 The remainder of the granules is essentially composed of a solid filler and optionally of surfaceactive adjuvants conferring properties of dispersibility in water to the granules. These granules can be essentially of two distinct types depending on 26 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 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 alkiline earth metal lignosulphonate, the remainder bei:ia rormed by non-ionic or anionic wetting agents such as an alkali metal or alkaline I 15 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, 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.

27 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 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: $aa active substance 75 S 15 wetting agent (sodium alkylaa: naphthalenesulphonate) 2 dispersing agent (sodium polynaphthalenesulphonate) 8 Sinert filler insoluble in water I 20 (kaolin) 15 t* 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 28 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 a preferred 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.

Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.

t It t It. j' I I i t t Stt I v 951218,p:\ope\dabs18O.SPE,2 8

Claims

1. 2-Alkoxy-2-imidazolin-5-one compounds of general formula (I) O-R 3 N ON-R 4 in which: R' represents phenyl, thienyl or benzothienyl, each of these radicals being optionally substituted by 1 to 3 groups chosen from amongst the meaning of R 6 R 2 represents an alkyl or haloalkyl radical with from 1 to 3 carbon atoms, R' and R 2 can additionally form, with the carbon to which they are bonded to the ring, a carbocycle having from 5 to 7 atoms, it being possible for these rings to be fused with a phenyl, each of these radicals being optionall, substituted by 1 to 3 groups chosen from amongst the meanings of R 6 R 3 represents an alkyl or haloalkyl group with from 1 to 3 carbon atoms; S; R 4 represents phenyl or pyridinyl, each of these radicals being optionally substituted by 1 to 3 groups chosen from amongst the meanings of R 6 R 5 represents a hydrogen atom or an formyl or alkanoyl radical with from 2 to 6 carbon atoms, aroyl, alkoxycarbonyl with from 2 to 6 carbon atoms, aryloxycarbonyl, 25 alkylsulphonyl or arylsulphonyl; and T R 6 represents: C t halogen atom or S an alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, cyanoalkoxy, alkylthio, haloalkylthio, cyanoalkylthio or alkylsulphonyl radical with from 1 to 6 carbon atoms or 951218,p:\oper\dab,5 1880SPE,29 ~I *=ZZA 30 a cycloalkyl, hialocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio radical with from 3 to 6 carbon atoms or the nitro or cyano or thiocyanato group or an amino radical optionally monosubstituted by an alkyl or alkanoyl radical with from I to 6 carbon atoms or alkoxycarbonyl with from 2 to 6 carbon atoms 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 tUtU Ut t~ e C U~ Ct Ut ICC Ut U C U C C C tUt C USC, C C C C Ut Ut C~ (C U U Ut U U U tC U 1 CCCI C C 95121 8,p:\oper\dab,51I880.SPE,30 31 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 the nitro or cyano or thiocyanato group or an amino radical optionally Mron D4ted by an alkyl or acyl radical with from 1 to 6 carbon atoms or *rr ii alkoxycarbonyl with from 2 to 6 carbon atoms a phenyl, phenoxy, phenylthio, phenylsulphonyl or pyridyloxy radical, and their salt forms.

2. Compounds according to Claim 1, characterized in that they correspond to the general Sformula. II: tttc R 2 N O-R 3 X- 'N-R4 R6- N II in which R' to R 6 have the same meanings as in the formula I. 32

3. Process for the preparation of compounds according to Claim 1, characterized in that I 2-alkylthio-2-imidazo.in-5-ones of' formula (III) are reacted with an alkyl R30H in the presence of strong base, according to the scheme: SR-R' O-R 3 R2 R2 for the formula I and R' 1 representing an alkyl group Wiith I. to 3 carbon atomA.

4. Fungicidal compositions comprising one or more imidazolin-5-ons of general formula I or a malt thereof as defined in claimn 1, in association with I.S one or more solid or liquid supports acceptable in agriculture and/or surtace-active agents acceptable in agriculur-e.

S. Fungicidal compositions comprising one salt thereof an defined in claim 2, in association with one or more solid or liquid supports acceptable in arclueand/or surface-active agents t accepablein arclue

6. rngicdalcompositions acrigt Claim 4 or 5, characterized in that they contain from *to 95 1 by weight of compounds according to F claims I. or 2.

7. Method for the treatment Of crops Ettacked or su.sceptible to being attack~ed by fungal disase, carater~edin that an effective quanti.ty of an imidazolin-5-ons according to Claim 1 or 2 or a oatteeo racmpstolccrigt any oeo Claims 4 to 6 is applied. a.

Method according to Claim 7, characterized in that the effective does is betwoen 0. 005 and 5 lcg/ha.

9. Method According to Claim 8, characterized in that the effective dose ±5 between 0.01 and 1 ]cgfha. mr _J 34 A compound according to claim 1, a process for the preparation thereof, a fungicidal composition comprising a said compound, or a method of use thereof, substantially as hereinbefore described with reference to the Examples. i1. The steps, features, compositions and compound- disclosed herein or referred to or indi a in the specification and/or clai hsis application, individuall collectively, and any and all combinations Sany two or more of- said oteps or feat-ures. f t t f t t f DATED this TWENTY FOURTH day of NOVEMBER 1993 t t Rhone-Poulenc Agrochimie by DAVIES COLLISON CAVE Patent Attorneys for the applicant(s) TIi