NZ245489A - 2-imidazolin-5-one and 5-thione derivatives and fungicidal compositions - Google Patents

2-imidazolin-5-one and 5-thione derivatives and fungicidal compositions

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Publication number
NZ245489A
NZ245489A NZ245489A NZ24548992A NZ245489A NZ 245489 A NZ245489 A NZ 245489A NZ 245489 A NZ245489 A NZ 245489A NZ 24548992 A NZ24548992 A NZ 24548992A NZ 245489 A NZ245489 A NZ 245489A
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New Zealand
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compounds
mixture
mes
carbon atoms
phenyl
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NZ245489A
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Guy Lacroix
Raymond Peignier
Regis Pepin
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Rhone Poulenc Agrochimie
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Publication of NZ245489A publication Critical patent/NZ245489A/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
    • C07C331/16—Isothiocyanates
    • C07C331/18—Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms
    • C07C331/20—Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/14—Dithiocarbamic acids; Derivatives thereof
    • C07C333/18—Esters of dithiocarbamic acids
    • C07C333/20—Esters of dithiocarbamic acids having nitrogen atoms of dithiocarbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/84—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/86—Oxygen and sulfur atoms, e.g. thiohydantoin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Description

New Zealand Paient Spedficaiion for Paient Number £45489 % 4 5 4 8 Priority Date{s): i Complete SpcclfxciOr i3L-si_ Class: ©.Cfcn.fl-wal... «W, J.V.. .Cp~tpHO!^loU; S«^.ft»*oVoLl:..A!Ciif^»4aV5^.rj3..
Pubncatfon Date:.. ...?J.MRJ996 P.O. Journal No: .'.M*?.?-. «"\ ^ i** ir N.Z. PATfnj OFFICE 16 DEC 1992 NEW ZEALAND THE PATENTS ACT 1953 PATENTS FORM NO.5 COMPLETE SPECIFICATION "FUNGICIDAL 2-IMIDAZOLIN-5-ONE AND 2—IMIDAZOLINE—5—THIONE DERIVATIVES" Dw U/»— IaW Pierre Baizet,/frSP-9*ft3-Lyon OP, 69363 Lyon CodoK-fr, France, hereby 2^3-1? declare the invention for which we pray that a patent may be e, Rhone-Poulenc Agrochimie, a French body corporate of 14-20 Rue granted to us and the method by which it is to be performed, to be particularly described in and by the following statement (Followed by page la) 245 489 The present invention relates to new imidazolinone or imidazolinethione compounds. It also 5 relates to processes for the preparation of the compounds, to fungicidal compositions containing them and to the use of these compounds as fungicides.
One object of the present invention is to provide compounds which have improved properties in the 10 treatment of fungal diseases.
Another object of the present invention is to provide compounds which have a use spectrum in the field of fungal diseases which is also improved.
The present invention provides 2-imidazolin-15 5-one or 2-imidazoline-5-thione derivatives of general formula (I) R3 - (I) N\ (B)n—R4 W in which: - W is sulphur or oxygen , or an S=0 group > 20 - A represents 0 or S ; - n = o or l ; - B represents -N= or NRS or O or S or CRjR* or S02 or C=0; - R, and Rj, which are identical or different, may each , ^ o A- , v <.r," r-r; n. n f c *•>,- 2 245489 represent: - H, provided that one of the 2 groups is different from H, or - an alkyl or haloalkyl radical containing 1 to 6 carbon atoms or - an alkoxyalkyl, alkylthioalkyl, alkylsulphonyl-alkyl, monoalkylaminoalkyl, alkenyl or alkynyl radical containing 2 to 6 carbon atoms or - a dialkylaainoalkyl or cycloalkyl radical containing 3 to 7 carbon atoms or - an aryl radical selected from phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl, or methylenedioxyphenyl, optionally substituted by 1 to 3 groups chosen from R7 or - an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulphonylalkyl radical, the terms aryl and alkyl having the definitions given above or - R, and Rj can form, with the carbon to which" they are bonded on the ring, a carbocycle or a heterocycle having from 5 to 7 atoms, it being possible for this rings to be fused to a phenyl, the carbocycle or heterocycle- being optionally substituted by 1 to 3 groups chosen from R7; - R3 represents: - an alkyl group containing 1 to 6 carbon atoms or - an alkoxyalkyl, alkylthioalkyl, alkylsulphonyl-alkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl group containing 2 to 6 245 489 carbon atoms or - a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group containing 3 to 6 carbon atoms or * - a N,N-dialkylcarbamoylalkyl group containing 4 to 8 carbon atoms or - an arylalkyl group, the alkyl part being a radical containing 1 to 6 carbon atoms and the aryl part is phenyl, naphthyl, thienyl, furyl or pyridyl, optionally substituted by 1 to 3 groups chosen from Rjj - 1*4 represents: hydrogen when n is equal to 1 or - an alkyl group containing l to 6 carbon atoms or - an alkoxyalkyl, alkylthioalkyl, haloalkyl, 15 cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group containing 2 to 6 carbon atoms or - a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group containing 3 to 6 carbon atoms or - an N,N-dialkylcarbamoylalkyl group containing 4 to 8 carbon atoms or - an aryl radical, comprising phenyl, naphthyl, thienyl, furyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolyl, isoguinolyl or methylenedioxyphenyl, optionally substituted by 1 to 3 groups chosen from R7 or - an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulphonylalkyl radical, wherein alkyl has 1 to 6 carbon atoms and aryl is phenyl, nag^jvyj^ ^ ° f r / thienyl, furyl. or pyridyl, optionally substituted by 1 to 3 groups^chbsen U , from R7 or !i t?r'^ !>■» v A \\ -- ' - X ... . - 4 2: <l,.) * - an amino group disubstituted by 2 identical or different groups chosen from: - an alkyl radical containing 1 to 6 carbon atoms or - an alkoxyalkyl, alkenyl or alkynyl radical containing 3 to 6 carbon atoms or - a cycloalkyl radical containing 3 to 7 carbon atoms or - an arylalkyl radical, wherein alkyl has 1 to 6 carbon atoms and aryl is a phenyl, naphthyl, thienyl, furyl or pyridyl, optionally substituted by 1 to 3 groups chosen from R7, a phenyl or naphthyl radical, optionally substituted by 1 to 3 groups chosen from R7 or - a thienylmethyl or furfuryl radical; or - a pyrrolidino, piperidino, morpholino, thiazolo or piperazino group, optionally substituted by alkyl containing 1 to 3 carbon atoms; or together with Rj, is an alkylene chain of 4 to 6 carbon atoms, optionally substituted by alkyl containing 1 to 3 carbon atoms, and forming with B-a carbocycle or heterocycle; - Rs represents: - H, except when R, is H, or - an alkyl, haloalkyl, alkylsulphonyl or •haloalkylsulphonyl radical containing 1 to 6 carbon atoms or - an alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkylsulphonyl or cyanoalkylsulphonyl radical containing 2 to 6 carbon atoms or - an alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl or cyanoalkoxy car bony 1 radical containing 3 to 6 carbon atoms or - a formyl radical or - a cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl or alkynylcarbonyl radical containing 3 to 6 carbon atoms or - a cycloalkylcarbonyl radical containing 4 to 8 carbon atoms or - a phenyl; arylalkylcarbonyl optionally substituted by 1 to 3 groups R7/ especially phenyl-acetyl and phenylpropionyl; arylcarbonyl, especially benzoyl, optionally substituted by 1 to 3 groups from R7; thienylcarbonyl; furylcarbonyl; pyridylcarbonyl; benzyloxycarbonyl; furfuryloxycarbonyl; tetrahydro- furfuryloxycarbonyl; thienylmethoxycarbonyl; pyridyl-methoxycarbonyl; phenoxycarbony1 or (phenylthio)carbonyl, the phenylthio or phenoxy being itself optionally substituted by 1 to 3 groups from R7; (alkylthio)carbonyl; (haloalkylthio)carbonyl; (alkoxyalkylthio)carbonyl; (cyanoalkylthio)carbonyl; (benzylthio)carbonyl; (furfurylthio)carbonyl; (tetrahydrofurfurylthio)carbonyl; (thienylmethylthio)-carbonyl; (pyridylmethylthio)carbonyl; or arylsulphonyl radical or - a carbamoyl radical, optionally mono- or 245489 6 disubstituted by - an alkyl or haloalkyl group containing 1 to 6 carbon atoms or - a cycloalkyl, alkenyl or alkynyl group 5 containing 3 to 6 carbon atoms or - an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group containing 2 to 6 carbon atoms or - a phenyl, optionally substituted by 1 to 3 R7 groups; - a sulphamoyl group, optionally mono- or disubstituted by - an alkyl or haloalkyl group containing 1 to 6 carbon atoms or - a cycloalkyl, alkenyl or alkynyl group 15 containing 3 to 6 carbon atoms or - an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group containing 2 to 6 carbon atoms or - a phenyl, optionally substituted by 1 to 3 R; groups; or - an alkylthioalkylsulphonyl group containing 3 to 8 carbon atoms or a cycloalkylsulphonyl group containing 3 to 7 carbon atoms; - R$ represents: - hydrogen or 25 ' - a cyano group or - an alkyl group containing 1 to 6 carbon atoms or a cycloalkyl group containing 3 to 7 carbon atoms or i '> - AUG 1995 2 4 ; 7 - an acyl or alkoxycarbonyl group containing 2 to 6 carbon atoms or - a benzoyl group, optionally substituted by 1 to 3 R, groups; - R7 represents: - a halogen atom or - an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulphonyl radical containing 1 to 6 carbon atoms or - a cycloalkyl, halocycloalkyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio radical containing 3 to 6 carbon atoms or - a nitro or cyano group or - an amino radical, optionally mono- or disubstituted by an alkyl or acyl radical containing 1 to 6 carbon atoms or an alkoxycarbonyl radical containing 2 to 6 carbon atoms - a phenyl, phenoxy or pyridyloxy radical, these radicals optionally being substituted; and their salts.
Certain specific compounds of the formula I, of formula la, are known 245489 in which W, R, to R$ and n have the same meaning as in formula I.
Denoted S-alkylated derivatives of 5,5-diphenyl-2-thiohydantoin and of 5,5-dimethyldithio-5 hydantoin, they have been especially studied for their pharmacological properties: a) Lucka-Sobstel, B. and Zejc, A., Dissertationes Pharmaceuticae et pharmacologicae, 22 (1), 13-19 (1970) b) Fetter, J., Harsanyi, K., Nyitrai, J. and Leropert, K., Acta Chemica (Budapest), 78 (3), 325-333 15 (1973).
No agricultural fungicidal activity has been described for these compounds.
Other specific compounds of formula I have been described by Bohme, Martin and Strahl in Archiv 20 der Pharmazie, 313. 10-15 (1980) (ref. d). They are the 3 following compounds: N^/SCH3 R—( R=H, CH3, phenyl r T ° CH-j One specific group of compounds within formula (I), which includes the three compounds 25 mentioned above is the group of compounds of formula lb. 7;. $ \[ ^ % r* •• I? £ C 2 4 5 4 C R N; ,SRi lb Rf y1*-N'R" W R5 in which W and R, to Rj have the same meaning as in formula I.
The compounds of formula la can be prepared 5 according to the processes known per se described in the abovementioned references and in the following references: e) Biltz, H., Chemische Berichte 42, 1792-1801 (1909) f) Chattelain, M. and Cabrier, P., Bulletin de la Soci§t6 Chimique de France, 14. (1947), 639-642 g) Carrington, C.H. and Warring, W.S., Journal of the Chemical Society, (1950) 354-3 65 h) Lampert, K., Breuer, J. and Lemper- _ 15 Streter, M., Chemische Berichte, 92, 235-239 (1959) i) Shalaby, A. and Daboun, H.A., Journal fttr Praktische Chemie, 313 (6), 1031-1038 (1971) j) Simig, G., Lemper, K. and Tamas, J., Tetrahedron, 2j) (22), 3571-3578 (1973) 20 k) Schmidt, U., Heimgartner, H. and Schmidt, H., Helvetica Chemica Acta, 62. (1979), 160-170 1) Muraoka, M., Journal of the Chemical Society, Perkin Transactions I, (1990), 3003-3007 24548 or according to one of the processes A, B, C or D described below.
The compounds of formula lb can be obtained according to the process described by Bohme, Martin and 5 Strahl in Archiv der Pharmazie, 313. 10-15 (1980) (reference d) or according to one of the processes described below. In the following description, unless otherwise specified, substituents in formulae are "as hereinbefore defined".
Process A: Process for the preparation of the compounds of formula (I).
The preparation of the compounds of formula (I) by S-alkylation of the 2-thiohydantoins (II) is carried out according to the reaction scheme: H c R2v Bass XI + R,X (I) /\ V + 3' Ri "CB)n-R4 so,vent W (D) in which X represents a chlorine, bromine or 15 iodiivn> .torn or a sulphate group, or an alkylsulphonyloxy or arylsulphonyloxy group, alkyl and aryl being as defined above for R, and R2. It is possible to use, as base, an alkoxide, for example potassium tert-butoxide, an alkali metal or alkaline-20 earth metal hydroxide, an alkali metal carbonate tertiary amine. It is possible to use, as solven ethers, cyclic ethers, alkyl esters, acetonitriie alcohols containing 1 to 3 carbon atoms, or arom^ jbc / : I V c 0 245 ;.i solvents, for example tetrahydrofuran, at a temperature of between -5°C and +80°C.
This process is suitable for the compounds in which W represents a sulphur or oxygen atom.
The 2-thiohydantoins of formula (II) can be obtained according to the processes described in the literature such as, for example, in the following references: e) Biltz, H., Chemische Berichte, 42, 1792-10 1801 (1909) n) Eberly and Dains, Journal of the American Chemical Society, 58, (1936), 2544-2547 0) Carrington, C.H., Journal of the Chemical Society, (1947), 681-686 g) Carrington, C.H. and Warring, W.S., Journal of the Chemical Society, (1950), 354-365 h) Lampert, K., Breuer, J. and Lemper-Streter, M., Chemische Berichte, £2:, 235-239 (1959) 1) Koltai, E., Nyitrai, J., Lempert, K. and 20 Buries, L., Chemische Berichte, 104. 290-300 (1971) or alternatively according to one of processes E or F described below and which form part of the invention.
Process B: Preparation of the compounds Ic. 25 The preparation of the 2-methylthio-2- imidazolin-5-ones of formula (Ic) by cyclisation of the iminodithiocarbonates of formula (V) is carried out according to the overall scheme: 12 24 5 4 R2\ Base ► a) V + cs2 + *ch3i Rf C02H b) .SCH3 r4— (B)n-NH2 .SCH, R2N N=C mn R2n InJ=Cv ^SCH3 illi ► 2\/ vSCH3 R{ C02H R/;c-NH-CB)n-R4 0 an) (V) R2 N=cCSCH3 2\< ^sch3 c) R1/;C-NH-(B)n-R4 O (V) a) The iminodithiocarbonates (III) can be prepared by carrying out the preparation according to the conditions described in the literature for analogous compounds: - C. Alvarez Ibarra et al., Tetrahedron Letters, 26 (2), 243-246 (1985) - E. Melendez et al., Synthesis, 1981. 961 according to: R2\ NH2 gase X + cs2 + 2 ch3i ► (in) R{ co2h b) The compounds of formula (V) are obtained 10 by condensing the compounds of formula (III) with 2 4 13 amines or hydrazines of formula (IV). To carry out the condensation, the acid (III) must be activated in the acid chloride form, in the dicyclohexylisourea form using dicyclohexylcarbodiimide or in the imidazolide form using carbonyldiimidazole. Condensation is carried out under the usual conditions for this type of reaction. carried out by simple heating in an aromatic solvent at reflux. It is possible to use, as solvent, especially xylene, chlorobenzene or dichlorobenzene.
Process C: Derivatisation of the compounds (Ib#) and (Id')- Process CI: Preparation of the compounds lb by N-derivatisation of the compounds lb'.
The compounds of formula (lb') (compounds (lb) in which Rj is a hydrogen atom) can be alkylated, acylated, alkoxycarbonylated, carbamoylated or sulphamoylated according to the following general -scheme: c) Cyclisation of the compounds (V) is lb' lb Rj represents here an alkyl, alkoxycarbonyl, acyl, arylcarbonyl, alkylsulphonyl, arylsulphonyl, 2 4 kf carbamoyl or sulphamoyl group, such as defined above.
X represents a halogen, a sulphate group or an optionally substituted phenoxy, or an alkylsulphonyl-oxy or arylsulphonyloxy group, or a group R5O, when R5 is acyl.
It is possible to use, as base, alkali metal hydrides, alkoxides or a tertiary amine. The reaction can be carried out at a temperature of between -30°C and +50°C. It is possible to use, as solvent, for example ethers, cyclic ethers, dimethylformamide, dimethyl sulphoxide or aromatic solvents.
Carbamoylation of the compounds (lb') can be carried out by reacting with isocyanates or isothiocyanates according to the scheme: NHR The reaction is carried out under the same conditions as those described above, it being possible for the base, however, to be used in catalytic quantity.
Process C2: Preparation of the compounds Id.
The compounds Id' (compounds Id in which Rj is a hydrogen atom, can be alkylated in position 4 according to the scheme: 2 4 5; l& SR3 sr3 B (b)n—r4 O (B)n—R4 O / a Id X represents a chlorine, bromine or iodine atom. It is possible to use, as base, an alkoxide, a metal hydride or an amide. The reaction can be carried out at a temperature of between -30°C and +80°C. It is possible to use, as solvent, ethers, cyclic ethers, dimethylformamide, dimethyl sulphoxide or aromatic solvents.
Process D: Preparation of the S-oxidised derivatives of the 2-imidazoline-5-thiones.
The compounds of formula (I) in which w represents a ~=0 group are obtained by oxidising the 2-imidazoline-5-thiones according to the scheme: peracids, as oxidising agent. The oxidising agent must be used in a stoichiometric quantity. Oxidation is carried out in chloroform or in methylene chloride at a temperature of between -20°C and +20°C.
O It is possible to use peroxides, especially : Preparation cf the 2k $ v] f.\ ■ t 16 dithiohvdantoins of formula (VI).
The dithiohydantoins of formula (VI) can be obtained by trapping the alpha anions of the isothiocyanates with isothiocyanates which cannot form anions according to the scheme: Base Rj—CH-N=C=S + R4-N=C=S solvent At least one of the groups R, or R2 must be electron-withdrawing (aryl, substituted aryl, alkoxycarbonyl, and the like) . The isothiocyanate R^NCS must not be able to form an anion; aryl isothiocyanates can 10 be used in particular in this reaction.
It is possible to use, as base, potassium tert-butoxide, lithium or sodium bis(trimethylsilyl)-amide or alkali metal hydrides. It is possible to use ethers or cyclic ethers as solvent. The reaction is 15 carried out at a temperature below -60°C. The anion must be trapped as it is formed. To achieve this, the mixture of the 2 isothiocyanates is run onto the base in solution at a temperature below -60°C.
Process F: Preparation of the 20 2-thiohydantoins of formula (VII).
The preparation of the 2-thiohydantoins (VII) from the isothiocyanates derived from the amino acids 24 17 (VIII) (in which R is such that OR is a displaceable leaving group, for example R is alkyl) is carried out according to the reaction: reactants is heated at a temperature of between 110°C and 180°C in an aromatic solvent such as toluene, xylene or the chlorobenzenes; - in basic medium: the cyclisation is carried 10 out in the presence of one equivalent of a base such as an alkali metal alkoxide, an alkali metal hydroxide or a tertiary amine. Under these conditions, cyclisation takes place at a temperature of between -10 and +86°C. It is possible to use ethers, cyclic ethers, alcohols, 15 esters, DMF, DMSO and the like as solvent.
The isothiocyanates can be prepared according to one of the processes mentioned in Sulfur Reports, Volume 8 (5), pages 327-375 (1989).
Process G: Preparation of the compounds of 20 formula I in a single stage.
During cyclisation of the 2-thiohydantoins according to process F, if the cyclisation is carried (vn) Cyclisation can be carried out in two ways: - thermally: in this case, the mixture of the 18 out in basic medium, the thiohydantoin is in the thiolate form at the end of the reaction and can be reacted directly with an alkyl halide R3X or with R3X in which X is alkylsulphonyloxy, aryl-sulphonyloxy [or the 5 group -O-SO3-R3] to form (I). Processes A and F are thus linked together according to the scheme: Process H: Preparation of the compounds of formula Ie, in which (B)n is a sulphur atom.
These compounds can be obtained by reacting a sulphuryl halide R^SX in which X is halogen, especially the chloride R4SCI with an irnidazolinone of formula IX according to the scheme: 0 (D 0 ix 2 A 51 8 9 19 The reaction is generally carried out at a temperature of between -20°C and +30°C, in the presence of one molar equivalent of a base. As base, it is possible to use alkali metal hydrides, alkali metal alkoxides or tertiary amines as base. As solvent, it is possible to use polar solvents, for example ethers, cyclic ethers, dimethylformamide, dimethyl sulphoxide or aromatic solvents. The imidazolinones (IX) can be prepared by processes analogous to process A.
The compounds which are preferred for their better fungicidal activity and/or for their ease of synthesis are: 1) the compounds of formula lb, 2) the compounds of formula I, in particular lb, in which Pj is a hydrogen atom, 3) the compounds in which Rj and R2 are different from H, 4) the compounds in which Rj represents an alkyl group containing 1 to 3 carbon atoms, 5) the compounds in which R, represents a phenyl ring, optionally substituted by R7, 6) the compounds in which R3 represents an alkyl group containing 1 to 3 carbon atoms, phenyl ring, optionally substituted by R7, 8) the compounds in which R3 represents methyl group.
The examples below are given by way of 1 UJ 't O a U- ir> LL CD O CD n i H- CD ! <x a 1 24 5 illustration of the compounds according to the invention, of the processes for their preparation and of their antifungal properties.
The structures of all the products were established by at least 1 of the following spectral techniques: proton NMR spectrometry, carbon-13 NMR spectrometry, infrared spectrometry and mass spectrometry.
In the tables below, the methyl and phenyl radicals are represented respectively by Me and Ph, and Cst means a physical constant, that is to say either a melting point (M.p.) or the refractive index (no0).
Example 1: Preparation of compound No. 34 according to process A. 0.9 g (3 mmol) of 3-benzyl-5-methyl-5-phenyl-2-thiohydantoin is dissolved in 30 ml of anhydrous tetrahydrofuran. The mixture is cooled to 0°C and then 0.34 g (3 mmol) of potassium tert-butoxide is added. The mixture is left to react for 10 min at 0°C and-then 0.46 g (3.3 mmol) of methyl iodide is run in dropwise at this temperature: potassium iodide is observed to precipitate. The temperature of the mixture is allowed to return to room temperature. The mixture is diluted with 100 ml of ethyl acetate. The solution is washed 2 times with 100 ml of water on each occasion. The solution is dried over sodium sulphate and is then treated with active charcoal. The solution is concentrated under reduced pressure: 0.6 g of 2 4 21 l-benzyl-4-methyl-2-methylthio-4-phenyl-2-imidazolin-5 one (compound No. 34) is recovered in the form of a pale-yellow solid melting at 68°C.
The compounds described below were prepared in the same way: 22 2 4 5 A s , '7 <i r- : NO.
R2 R3 R4 R5 W CRt 1 Me Me Ph H S M.p.= 127 °C 3 Me 2-oxopropyl Ph H s M.p.= 130°C 9 Me Me Ph H 0 M.p.= 149 °C Me .
Me meta-tolyl H 0 M.p.= 124°C 11 Me Me para-tolyl H 0 ; M.p.= 150°C 12 Me Et Ph H 0 M.p.= 118°C 13 Me Me 4-fluoroPh H r- 0 M.p.= 144 °C 14 Me allyl Ph H 0 M.p.= 92 °C Me Me ortho-tolyl H 0 M.p.= 92 °C 16 Me Me 3-chloroPh H 0 M.p.= 120°C 17 Me iso-propyl Ph H 0 Mtp.= 95 °C 18 Me Me 4-chloroPh H 0 M.p.= 149°C 19 Me Me tert-butyl H 0 M.p.— 73°C Me Me 2-chloroPh i- H 0 M.p.= 134°C 21 Me Me -(CH^- 0 ng° = 1.551 22 Ma Me Ph Me 0 M.p.= 124°C 23 Me Me Ph acetyl 0 M.p.= 132°C 24 Me Me 4-methoxyPh H 0 M.p.= 138°C Me n-propyl Ph H 0 M.p.= 90°C 40 Me Me 2-methoxyPh H 0 M.p.= 110°C 41 Me Me acetyl H 0 M.p.= 55°C 2 4 5 4 8 23 No. rs r3 r* rs W Cst 43 Me Me 4-N02-Ph H O M.p.= 133°C 44 Me Me 2-pyridyl ' H S M.p.= 114 °C 45 Me Me 2-pyridyl H O M.p.= 147°C 46 Me Me 3-pyridyl H O : M.p.= 140°C 47 Me Me 3-pyridyl H S i M.p.= 176°C 54 Me j Me 2,6-MejPh h 3 e s : M.p.= 146°C 73 Me Me 2-thia- 1 Me O ; M.p.= 116°C 75 Me ; chf2 Ph H 0 M.p.= 80°C 80 Me Me 3-pyridyl-CH= - O M.p.= 92°C 81 Me Me 2-pyridyl- CH= - O M.p.= 106°C 82 Me Me 4-Me-S02-Ph h O M.p.= 130°C No.
Rs R3 R4 n R5 w Cst 26 Me Me Ph 0 _ s M.p.= 123 °C 27 Ph Me Ph 0 s M.p.= 120°C 28 Me Me Me 0 s M.p.= 85°C 29 Ph Me Me 0 — s M.p.= 144°C 2 4 S 4 8 0 Mo.
R2 *3 n RJ W Cst Me Me , Ph 0 — O M.p.= 70°C 31 Me Me Me 0 _ 0 M.p.= 58 °C 32 Ph Me Me 0 — 0 M.p.= 170°C 33 H Me Ph 0 o M.p.= 250 °C 34 Me Me Ph 1 H 0 M.p.= 68 °C Me Me 2-thienyl 1 H o M.p.= 76°C 36 Me Me Me 1 Me 0 n^° = 1.553 37 Me Me 2-furyl 1 H o "honey-like consistency" 38 Me Me 3-pyridyl 0 - o "honey-like consistency" 50 Ph Me Me 0 s M.p.=144°C 52 Me Me Ph ;1 H 0 "honey-like consistency" 57 Me Me 2-MePh 0 - o "honey-like consistency" 245 The following were also prepared: - 4—(3—pyridyl)-4-methyl-l-(N-phenylamino)-2-methylthio-2-imidazolin-5-one (compound 51: M.p. 156°C); - 4-phenyl-4-methyl-l-(benzyloxy)-2-methylthio-2-imidazolin-5-one (compound 56: honey-like consistency).
Example 2: Preparation of compound No. 7 according to process B. a) N-[bis(methylthio)methylene]-2-phenyl-glycine (compound (III) with R, = phenyl and Rj = H) : 100 g (0.66 mol) of phenylglycine are dissolved at +5°C in 335 g of 22 % aqueous potassium hydroxide (1.3 mol). 55.3 g of carbon disulphide are added while stirring the mixture vigorously: a precipitate appears and the mixture turns orange in colour. The mixture is left to react for 3 h at room temperature and then 103 g (0.73 mol) of methyl iodide are run in while keeping the temperature of the mixture below 30°C. The mixture is left to react for 0.5 h and then 74 g (0.66 mol) of a 50 % potassium hydroxide solution are added. The mixture is left to react for 0.5 h and then 103 g of methyl iodide are again run in and left to react for 1 h. The mixture is diluted with 300 ml of water. The mixture is acidified to pH = 4 with IN hydrochloric acid. The product is extracted with 500 ml of ethyl acetate. The solution is dried over magnesium sulphate and then concentrated under 26 reduced pressure. 49.5 g of N-[bis(methylthio)-methylene]-2-phenylglycine (yield = 31 %) are recovered in the form of a yellow solid melting at 112°C. b) 2/-(metachlorophenyl)[N-(bis(methylthio)-methylene)-2-phenylglycyl]hydrazide (compound V with R, «= phenyl, Rj *= H, R4 = metachlorophenyl, n = 1, B = NH): 3.38 g (16.4 mmol) of dicyclohexylcarbo-diimide are added to a solution of 2.95 g (16.4 mmol) of N-[bis(methylthio)methylene]-2-phenylglycine in methylene chloride (40 ml), and the mixture is then left to react for 0.5 h at room temperature. 2.34 g (16.4 mmol) of metachlorophenylhydrazine are added. The mixture is heated for 0.5 h at 30°c. The insoluble material is filtered off. The filtrate is washed with 2 times 30 ml of water on each occasion. The solution is concentrated: a honey-like product is obtained which is purified by chromatography on a silica column. After purification, 2.5 g of 2'-(metachlorophenyl)[N-(bis(methylthio)methylene)-2-phenylglycyl]hydrazide are recovered in the form of a pinkish powder melting at 146°c. c) l-Metachlorophenyl-2-methylthio-4-phenyl-2-imidazolin-5-one (compound No. 7): 1.92 g (5 mmol) of 2(metachlorophenyl)[N-(bis(methylthio)methylene)-2-phenylglycyl]hydrazide is dissolved in 30 ml of xylene. The reaction mixture is heated for 4 h at reflux. The mixture is concentrated under reduced pressure. The resulting honey-like 24 5 4 27 product is triturated with 10 ml of ether: the product crystallises. The precipitate is filtered and the product is dried in a desiccator under vacuum. Compound No. 7 is thus obtained, with a yield of 56 %, in the 5 form of a yellow powder melting at 196°c.
By carrying out the preparation in a similar way, the compounds which appear in the following table were prepared: 2 4 *) A c; q mmt 1 4 V./ '5,,A *3 NO.
R3 *4 R5 W cst 4 H Me 2-chloroPh H 0 M.p.= 130°C H Me Ph H 0 M.p.= 190°C 6 H Me 4-chloroPh H o i M.p.= 162 °C 7 • H Me 3-chloroPh H ^ 0 , M.p.= 196°C 8 " H Me meta-tolyl H ' ✓ o ' M.p.= 182 °C 59 H Me 2, 4-(CH3)2Ph H 0 .
M.p.= 64 °C 61 H Me 2 , 5- (CH3) 2Ph H o M.p.= 162 °C 63 H Me 2-EtPh H ' 0 ■ M.p.= 126°C 69 H Me 2 , 5- (Cl) 2Ph H 0 „ M.p.= 144 °C 71 H Me 3 , 5- (Cl) 2Ph H 0 M.p.= 146°C 4-Phenyl-l- (N-phenylamino) -2-methylthio-2.-imidazolin-5-one (compound 120) was also prepared.
Example 3: Preparation of 4-methyl-l-(N-15 methyl-N-phenylamino)-2-methylthio-4-phenyl-2- imidazolin-5-one (compound No. 22) by alkylation (methylation) according to process CI. 0.4 g (3.5 mmol) of potassium tert-butoxide is added to a solution of 4-methyl-l-phenylamino-2-20 methylthio-4-phenyl-2-imidazolin-5-one (compound No. 9) (1 g, 3.2 mmol) in anhydrous tetrahydrofuran (30 ml), cooled beforehand to 0°C. The mixture is left to react for 0.5 h at 0°C. 0.5 g (3.5 mmol) of methyl iodide is 245 then added and then the mixture is left to react for 0.5 h at room temperature. The reaction mixture is poured into 100 ml of water and the product is extracted with 100 ml of diethyl ether. The ethereal solution is dried over magnesium sulphate and then concentrated. The product crystallises when triturated in 10 ml of diisopropyl ether. It is filtered and then dried under vacuum. 0.73 g (yield: 70 %) of compound 22 is thus obtained in the form of a pale-yellow powder melting at 124°C.
Example 4: Preparation of 4-methyl-l-(N-acetyl-N-phenylamino)-2-methylthio-4-phenyl-2-imidazolin-5-one (compound No. 23) by acylation (acetylation) according to process Cl. 0.4 g (3.5 mmol) of potassium tert-butoxide is added to a solution of 4-methyl-l-phenylamino-2-methylthio-4-phenyl-2-imidazolin-5-one (compound No. 9) (1 g, 3.2 mmol) in anhydrous tetrahydrofuran (30 ml), cooled beforehand to 0°C. The mixture is left to react for 0.5 h at 0°C. 0.25 g (3.5 mmol) of acetyl chloride is then added and the mixture is left to react for 0.5 h at room temperature. The reaction mixture is poured into 100 ml of water and the product is extracted with 100 ml of diethyl ether. The ethereal solution is washed with water to neutrality. The solution is dried over magnesium sulphate and then concentrated. A honey-like product is obtained which is purified by chromatography on a silica column. The 2 4 5 4 8 9 JO purified product crystallises from diisopropyl ether. 0.25 g of compound Mo. 23 is obtained in the form of a white powder melting at 132°C.
By carrying out the preparation in the same 5 way, compounds No. 39 and 42 were obtained.
No.
R2 R3 R* Rs W Cst 23 Me Me Ph acetyl 0 M.p.= 132 °C 39 Me Me Ph formyl 0 "honey-like consistency" 42 Me Me Ph tBuOCO 0 "honey-like consistency" Example 5: Preparation of 4-ethyl-2-methylthio-4-phenyl-l-phenylamino-2-imidazolin-5-one (compound 48) according to process C2. 15 0.55 g of potassium tert-butoxide is added to a solution of 1.5 g (5.05 mmol) of 2-methylthio-4-phenyl-l-phenylamino-2-imidazolin-5-one (compound No. 5) in 50 ml of anhydrous tetrahydrofuran. The mixture is left to react for 30 min at room temperature 20 and then 0.8 g (5.05 mmol) of ethyl iodide is added. The mixture is left to react for 1 h at room temperature. The mixture is diluted with 150 ml of ethyl acetate. The solution is washed with water and 2AI 31 then concentrated under reduced pressure. The product is purified by chromatography on a silica column (Merck 60H silica; eluent: 25 % ethyl acetate/75 % heptane). 0.65 g of compound Mo. 48 is obtained in the form of a beige powder melting at 147°C.
By carrying out the preparation in the same way, compound No. 49 was obtained. 24 5 4 32 No. R; Rj R4 R5 , W Cst 48 Et Me Ph H O M.p.= 147 °C 49 iso-Pr Me Ph H 0 M.p.= 135°C 60 Me Me 2/4-(Me)jPh H 0 ; "honey-like consistency" 62 Me Me 2/5-(Me)2Ph H 0 M.p.= 160°C 64 Me Me 2-EtPh H 0 "honey-like consistency" 65 Me Me 2 ,4 - (Cl) 2Ph H 0 66 Me Me 1-naphthyl H 0 M.p.= 174 °C 70 Me Me 2,5-(Cl)2Ph H 0 - M. PL. = 180°C 72 Me Me 3 , 5- (Cl) 2Ph H 0 M.p.= 200°C 74 chf2 Me Ph H 0 M.p.= 124 °C 79 Me Me 2—cfj-Ph H O M.p.= 91°C 4-Methyl-2-methylthio-4-(4-fluoropheny1)-1- phenylamino-2-imidazolin-5-one (compound 68) was also prepared. 33 Example 6: Preparation of compound 2 according to process D. 1.7 g (5.2 mmol) of 4-methyl-2-methylthio-4- 2 ' • 4 • phenyl-l-phenylamino-2-im.idazoline-5-thione (compound No. 1) is dissolved in 20 ml of chloroform. The solution is cooled to -10°C and then a solution of 1.35 g (5.5 mmol) of metachloroperbenzoic acid and ml of chloroform is added over 10 min. On completion of addition, the temperature is allowed to return to room temperature. The mixture is washed with a saturated aqueous sodium bicarbonate solution and then with distilled water. The organic phase is treated with active charcoal and then concentrated. The resulting honey-like product is taken up in 20 ml of ether: the product dissolves and then a beige solid precipitates.
The precipitate is filtered. The product is dried under reduced pressure. 0.4 g (yield: 2 5 %) of compound No. 2 is thus obtained in the form of a beige powder melting at 150°C The product is of the formula shown above the preceding Table in which the various symbols have the following values.
No.
R2 R3 •w Cst 2 Me Me Ph H s=o M.p.= 150°C Example 7: Preparation of 3,5-diphenyl-5-methyldithiohydantoin according to process E. .1 g (122 mmol) of potassium tert-butoxide 25 are dissolved in 200 ml of tetrahydrofuran in a 500 ml, three-necked, round-bottomed flask under a dry argon - AUG 1995 34 atmosphere. The solution is cooled to -70°C. A solution containing 20 g (122 mmol) of alpha-methylbenzyl isothiocyanate, 16.55 g (122 mmol) of phenyl isothiocyanate and 50 ml of tetrahydrofuran is run in dropwise while keeping the temperature of the mixture below -60°c. On completion of addition, the mixture is held for 0.5 h at -70°C and then is left to return to room temperature. The mixture is poured into 500 ml of water. The mixture is acidified to pH = 1 by addition of N hydrochloric acid. The product is extracted with ethyl acetate (2 extractions, each with 150 ml of solvent). The solution is dried over magnesium sulphate. The solution is concentrated under reduced pressure. The product is crystallised from 50 ml of ether. The precipitate is filtered. 21 g (yield: 58 %) of 3,5-diphenyl-5-methyldithiohydantoin are thus obtained, a yellow powder melting at 157®C.
Example 8: Preparation of 3,5-diphenyl-5-methyl-2-thiohydantoin according to process F. 4.7 g (20 mmol) of ethyl 2-isothiocyanato-2-phenylpropionate are dissolved in 40 ml of xylene. 2.16 g (20 mmol) of phenylhydrazine are added and the mixture is heated for 4 h at reflux. The mixture is cooled to room temperature and a beige solid precipitates. The precipitate is filtered, washed with 5 ml of diisopropyl ether and then dried under vacuum. 4.6 g (yield = 77 %) of 3,5-diphenyl-5-methyl-2-thio-hydantoin are thus obtained in the form of a beige 24 n vJ> powder melting at 164°C.
Example 9: Preparation of 5-methyl-5-phenyl-3-(2-pyridylamino)-2-thiohydantoin according to process F. 2 g (9 mmol) of methyl 2-isothiocyanato-2- phenylpropionate are dissolved in 30 ml of tetrahydrofuran. A solution containing 0.99 g of 2-hydrazino-pyridine and 10 ml of tetrahydrofuran is added: the temperature of the mixture rises from 20 to 30°C and a 10 solid precipitates. The mixture is allowed to react for 0.5 h at 30°C and then is cooled to 5°C. A solution containing 1 g of potassium tert-butoxide and 10 ml of tetrahydrofuran is then added: the mixture becomes violet in colour. The mixture is left to return to room 15 temperature and is left to react for 2 h. The mixture is poured into 150 ml of water. The mixture is neutralised with acetic acid. The product is extracted with 150 ml of ethyl acetate. The solution is washed with water, dried over magnesium sulphate and then-20 treated with active charcoal. The solution is concentrated and the product is crystallised from 20 ml of diethyl ether. The abovementioned product is filtered and is dried under vacuum. 1.6 g (yield: 60 %) of 5-methyl-5-phenyl-3-(2-pyridylamino)-2-thiohydantoin 25 is obtained, a pale-yellow solid melting at 80°C.
The compounds of formula (VII) collated in the following table, which are intermediates of the compounds of formula I and are numbered from number 1001, were prepared according to this process: 245 4 36 (VTD R, = methyl and Rj = phenyl.
(Jo. n B *4 Yield M.p. 1001 1 nh Ph 66 % 164 °c 1002 1 nh meta-tolyl 62 % 174 °c 1003 ch2 Ph 46 % 12 5° c- 1004 1 nh para-tolyl ' 13 % 1 62 °C 1005 1 ch2 2-thienyl 49.5 % 134 °c^ 1006 1 nh 4-fluoroPh % 162 °c' 1007 nh ortho-tolyl 38 % 162 °c 1008 iso-propyl 60.5 % 146°c 1009 1 nh 3-chloroPh 32 % 78 °c 1010 1 nh tert-butyl 18 % 120 °c- 1011 1 nh 4-chloroPh 24 % 196°C 1012 1 nh 2-chloroPh 69 % 172 °C' 1013 — piperidino 32 % 206°C 1014 1 nh 4-methoxyPh 27 % 146 °c 1015 1 nh 2-methoxyPh 29 % 214 °C 1016 1 ch2 2-furyl 39 % 105 °c 1017 1 nh acetyl 42 % 200°c 1018 1 nh 4-N02-Ph 41 % 234 °c 1019 1 nh 2-pyridyl 60 % 80°c 1020 1 nh 3-pyridyl 17 % 24 5 37 Example 10: Preparation of compound 9 according to process G. 11.1 g (50 mmol) of methyl 2-isothiocyanato-2-phenylpropionate are dissolved in 150 ml of anhydrous tetrahydrofuran. A solution containing 5.4 g (50 mmol) of phenylhydrazine and 50 ml of anhydrous tetrahydrofuran is added progressively over 10 min: the temperature of the mixture rises to 35°c. On completion of addition, the mixture is left to react for 0.5 h at 30°C and the mixture is then cooled to -5°C. A solution containing 5.6 g (50 mmol) of potassium tert-butoxide and 50 ml of anhydrous tetrahydrofuran is added at this temperature: the mixture turns violet in colour and then a precipitate forms. The mixture is left to react for 0.5 h at 0°C and then 8.5 g (60 mmol) of methyl iodide are added. The mixture is left to react for 1 h at room temperature. The mixture is diluted with 200 ml of ethyl acetate. The mixture is washed 2 times with 150 ml of water on each occasion. The solution is dried over magnesium sulphate and then treated with active charcoal. The solution is concentrated: a purplish-brown honey-like product is obtained which is crystallised from 50 ml of ether. The precipitate is washed and then dried under vacuum. A second crop of product is recovered after concentrating the mother liquors and taking up the residual honey-like product in 50 ml of diisopropyl ether. 12 g (yield = 77 %) of 4-methyl-2-methylthio-4-phenyl-l-phenylamino-2- 24 5 38 imidazolin-5-one (compound 9) are thus obtained in the form of a beige powder melting at 149°C.
By carrying out the preparations as above, the following compounds were obtained: Note: In compounds 97, 98, 104, 112 and 113 in the table overleaf, the group R2 is bonded to the ortho-position of the phenyl group R,, to form a 5-membered (compound 98) or 6-membered (compounds 97, 104, 112 and 113) ring. 39 No.
R'« rj R3S b R* m.p. 58 _ Me MeS NH 2, 3-(Me)2Ph 116 °C 67 — Me MeS CH2 PhCH2 honeylike •jonsis-tency 76 Me MeS ch2 3-pyridyl 67 °C 77 ; - Me MeS ch2 2-pyridyl honey- ' like consistency 78 Me MeS N PhCH= 95°C 83 4-Me Me MeS NH Ph 179 °C 84 Me MeS NH 3-Me-2-Pyr 148 °C • 85 4-Cl Me MeS NH Ph 173 °C 86 3 / 4— (MeO) 2 Me MeS NH Ph 165°C 87 3,4- (MeO) 2 Me MeS NH 2-Me-Ph 151°C 88 4-Me Me MeS NH 2-Me-Ph 52 °C 89 4-PhO Me MeS NH Ph 146°C 90 4-Cl Me MeS NH 3-Me-2-Pyr 133 °C 91 4-Cl Me MeS NH 2-pyridyl ' 172 °C 92 R, = PhCH2 Me MeS NH Ph 166°C 93 4-PhO Me MeS NH 2-Me-Ph 130 °C 94 4-F Me MeS NH 2-Me-Ph 120°C 96 4-Cl Me MeS NH 2-Cl-Ph 145°C 97 (CH2)3 MeS NH Ph 158°C 98 _ (CH2)2 MeS NH Ph 85°C 99 4-Cl H MeS NH 4-Cl-Ph 163 °C 100 4-Cl Me MeS NH 4-Cl-Ph 172 °C 24 5 4 40 Mo.
R'» R2 RjS B R4 M.P. 101 4-Cl Me MeS NH 4-F-Ph 170°C 1? 2 4-Cl Me MeS NH 3-Cl-Ph 146°C 103 4-Cl Me MeS NH 4-Me-Ph 178°C 104 — (CH2)3 MeS NH 2-Cl-Ph 168 °C 105 4-Cl Me MeS NH 2-Me-Ph 124°C 106 4-Cl Me MeS NH 3-Me-Ph 136°C 107 ; 4-F Me MeS NH 3-Me-Ph 121°C 108 — Me MeS NH 3-F-Ph 163 °C 109 — Me MeS NH 2, 5-F2-Ph 141°C 110 4-Me Me MeS NH 4-Cl-Ph 168°C HI 4-Me Me MeS NH 2-Cl-Ph 168°C 112 — (CH2)3 MeS NH 4-Cl-Ph 1 • 191°C 113 — (CH2)3 MeS NH 2-Me-Ph j 174<>C 114 4-Me Me MeS NH 3-Cl-Ph 184 °C 115 4-F Me MeS NH 3-Cl-Ph 124 °C 116 4-Me Me MeS NH 4-F-Ph 186 °C 117 4-Me Me MeS NH 4-Me-Ph 157 °C 118 4-F Me MeS NH 4-Me-Ph 158 °C 119 4-Me Me MeS NH 3-Me-Ph 178 °C 121 4-F Me MeS NH 4-Cl-Ph 159°C 122 — Me MeS NH 2,4- (Me) 2-Ph 63 °C 123 — Me MeS NH 3-Cl-2-Pyr 127 °C 124 4-Cl Me MeS NH 2-F-Ph 120 °C 125 4-F Me MeS NH 2-F-Ph 112 °C 126 4-Me Me MeS NH 2-F-Ph 156 °C 24 5 41 Example 11: Preparation of 4-phenyl-4-methyl-1-(phenylthio)-2-methylthio-2-imidazolin-5-one (compound 95: M.p. 112°C). 0.6 g (2.7 mmol) of 2-methylthio-4-methyT-4-5 phenyl-2-imidazolin-5~one in solution in 50 ml of anhydrous tetrahydrofuran (THF) is charged to a 100 ml, three-necked, round-bottomed flask under an inert atmosphere. The solution is stirred with a magnetic stirrer and is cooled to 0°C (ice bath + acetone). ^ «»» 0 ^ 0.30 g (l molar equivalent) of potassium tert-butoxide is added and the mixture is stirred for 10 min at 0°C. A solution containing 0.40 g of phenylsulphenyl chloride and 10 ml of anhydrous THF is then run in. The mixture is then left to return to room temperature for 15 one hour. The reaction mixture is run into 100 ml of water. Extraction is carried out with 100 ml of ethyl acetate. The organic phase is washed 4 times with water and dried over sodium sulphate.
The organic phase is concentrated under 20 vacuum. A yellow honey-like product is obtained which crystallises from isopropyl ether after purification on silica with a yield of 68% (melting point: 112°C).
Example 12: in vitro test: The action of the compounds according to the 25 invention is studied on the following fungi responsible for diseases of cereals and other plants: Fusarium oxvsporum f.sp.melonis Rhizoctonia solani AG4 2 4 5 4 3 42 Helminthosporium qramineum Pseudocercosporella herpotrichoides Alternaria alternata Septoria nodorum 5 Fusariuro roseum Pvthium rostratum Pvthium vexans Each test is carried out in the following way: a nutrient medium consisting of potato, glucose 10 and gelose (PDA medium) is introduced in the supercooled state into a series of Petri dishes (100 ml per dish) after sterilisation in an autoclave at 120°C.
While filling the dishes, an acetone solution of the active material is injected into the supercooled 15 medium to obtain the desired final concentration.
The controls consist of Petri dishes analogous to the above which have been charged with similar quantities of a nutrient medium which does not contain active material.
After 24 hours, each dish is cultured by depositing a fragment of ground mycelium arising from a previous culture of the same fungus.
The dishes are stored for 5 days at 20°C and the growth of the fungus in the dishes containing the 25 active material to be tested is then compared with that of the same fungus in the dish used as the control.
For each compound tested, the degree of inhibition of the fungus studied is thus determined for 24: 43 a dose of 20 ppm.
The following results are then obtained: A good activity, that is to say a degree of inhibition of the fungus of between 80 % and 100 was 5 found for: - Compounds 9, 13, 16, 22, 26 and 34 for Pvthium rostratum and Pvthium vexans.
- Compound 26 for Fusarium oxvsporum and . Fusarium roseum.
- Compounds 11, 16, 22 and 26 for Alternaria alternata.
- Compounds 11, 16 and 26 for Rhizoctonia solani.
- Compounds 16 and 26 for Pseudocercosporella 15 herpotrichoides.
- Compounds 11, 16 and 26 for Septoria nodorum.
- Compounds 9, 11, 16 and 26 for Helminthosporium qramineum.
Example 13: In vivo test on Plasmopara viticola (grape downy mildew): An aqueous suspension of the active material to be tested is prepared, by fine milling, having the following composition: ~ active material: 60 mg - Tween 80 surface-active agent (oleate of polyoxyethylenated derivative of sorbitan) diluted to 10 % in water: 0.3 ml 2 4 f:" t ' \ L\ 44 - volume made up to 60 ml with water.
This aqueous suspension is then diluted with water to produce the desired concentration of active material.
Vine cuttings (Vitis vinifera), Chardonnay variety, are grown in pots. When these plants are 2 months old (8-10-leaf stage, height of 10 to 15 cm), they are treated by spraying with the above aqueous suspension.
Plants used as controls are treated with an aqueous solution which does not contain the active material.
After drying for 24 hours, each plant is infected, by spraying, with an aqueous suspension of 15 spores of Plasmopara viticola obtained from a 4-5 day culture, and then suspended at a concentration of 100,000 units per cm3.
The infected plants are then incubated for two days at approximately 18°C in an atmosphere 20 saturated with moisture and then for 5 days at approximately 20-22°C under 90-100 % relative humidity.
Reading is carried out 7 days after infecting, by comparison with the control plants.
Under these conditions, a good (at least 25 75 %) or complete protection is observed, at a dose of 1 g/1, with the following compounds: 1, 2, 9, 10, 12, 13, 15, 16, 18, 20, 22, 23, 24, 25, 30, 31, 34, 35, 37, 39 to 43, 45, 48, 55 to 58, 60, 62, 64, 68, 73, 75, 76, 2 4 5 4 8 45 83 to 85, 8G to 91, 93 to 98, 101 to 108.
Example 14; In vivo test on Puccinia recondite (brown rust of wheat): An aqueous suspension of the active material 5 to be tested is prepared, by fine milling, having the following composition: - active material: 60 mg - Tween 80 surface-active agent (oleate of polyoxyethylenated derivative of sorbitan) diluted to 0 " 10 % in water: 0.3 ml - volume made up to 60 ml with water.
This aqueous suspension is then diluted with water to produce the desired concentration of active material.
Wheat, in pots, sown on a 50/50 peat/pozzolana earth substrate, is treated at the 10 cm high stage by spraying the above aqueous suspension.
After 24 hours, an aqueous suspension of spores (100,000 sp/cm3) is sprayed on the wheat; this 20 suspension was obtained from infected plants. The wheat is then placed for 24 hours in an incubation cell at approximately 20°C and at 100 % relative humidity, and then for 7 to 14 days at 60 % relative humidity.
Monitoring of the condition of the plants is 25 carried out between the 8th and 15th day after infection, by comparison with an untreated control.
Under these conditions, a good (at least 75 %) or complete protection is observed, at a dose of 24 p k n o 46 1 g/1, with the following compounds: 2, 9, 10, 15, 18, 20 to 22 and 39, 55, 57, 64, 68, 75, 83 to 85, 88 to 90, 93, 94 and 98.
Example 15: In vivo test on Phytophthora 5 infaatanM (tomato late blight): An aqueous suspension of the active material to be tested is prepared, by fine milling, having the following composition: - active material: 60 mg - Tween 80 surface-active agent (oleate of polyoxyethylenated derivative of sorbitan) diluted to 10 % in water: 0.3 ml - volume made up to 60 ml with water.
This aqueous suspension is then diluted with 15 water to produce the desired concentration of active material.
Tomato plants (Marmande variety) are grown in pots. When these plants are one month old (5 to 6-leaf stage, 12 to 15 cm high), they are treated by spraying 20 the above aqueous suspension at various concentrations of the compound to be tested.
After 24 hours, each plant is infected by spraying with an aqueous suspension of spores (30,000 sp/cm3) of Phytophthora infestans. 25 After this infecting, the tomato plants are incubated for 7 days at approximately 20°C in an atmosphere saturated with moisture.
Seven days after infecting, the results 2 4 47 obtained in the case of the plants treated with the active material to be tested are compared with those obtained in the case of the plants used as controls. Under these conditions, a good (at least 75 %) or " complete protection is observed, at a dose of 1 g/1, with the following compounds: 2, 9, 15, 30, 39, 45, 55, 68, 75, 84, 85, 90, 94, 98, 107 and 108.
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 the Phycomycetes, Basidiomycetes, Ascomycetes, Adelomycetes or Fungi Imperfecti, in particular grape downy mildew, tomato late blight and brown rust of wheat.
Generally, the compounds of formula (I) and salts thereof, will be used in the form of a fungicidal composition.
Accordingly, as a further feature, the present invention provides a fungicidal composition which comprises a compound of formula (I) or an ' agriculturally acceptable salt thereof, in association with an agriculturally acceptable diluent, carrier and/or surface-active agent.
These compositions, which can be used as fungicidal agents, contain, as active material, a compound according to the invention as described above as a mixture with solid or liquid vehicles which are 2/ c H 'J 48 acceptable in agriculture, and surface-active agents which are also acceptable in agriculture. In particular, the customary inert vehicles and the customary surface-active agents can be used.
These compositions can also contain all kinds of other ingredients such as, for example, protective colloids, adhesives, thickening agents, thixotropic agents, penetration agents, stabilising agents, sequestering agents and the like. More generally, the compounds used in the invention can be used in combination with any of the solid or liquid additives which correspond to the usual formulating techniques.
Generally, the compositions according to the invention usually contain from 0.05 to approximately 95 % (by weight) of a compound according to the invention (subsequently called active material), one or more solid or liquid vehicles and, optionally, one or more surface-active agents.
The term "vehicle", in the present account, means a natural or synthetic, organic or inorganic material with which the compound is combined in order to facilitate its application to the plant, to seeds or to the soil. This vehicle is therefore generally inert and it has to be acceptable in agriculture, especially to the treated plant. The vehicle can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilisers, and the like) or liquid (water, alcohols, especially butanol, and the like). 49 The surfaco-active agent can be an emulsifying, dispersing or wetting agent of ionic or nonionic type or a fixture of such surface-active agents. There may be cited, for example, salts of " poly(acrylic acids), salts of lignosulphonic acids, salts of phenolsulphonic or naphthalenesulphonic acids, polycondensates of ethylene oxide with fatty alcohols or fatty acids or fatty amines, substituted phenols (especially alkylphenols or arylphenols), salts of esters of sulphosuccinic acids, derivatives of taurine (especially alkyltaurates), phosphoric esters of polyoxyethylenated alcohols or phenols, esters of fatty acids and of polyols, and the derivatives of the above compounds having a sulphate, sulphonate or phosphate functional group. The presence of at least one surface-active agent is generally indispensable where the compound and/or the inert vehicje ;ire not soluble in water and where the vector agent of the application is water.
Thus, the compositions for agricultural use according to the invention can contain the active materials according to the invention within very wide limits, ranging from 0.05 * to 95 % (by weight). Their surface-active agent content is advantageously between 5 % and 40 % by weight.
These compositions according to the invention are themselves in fairly diverse, solid or liquid forms. 24 n <r 50 There may be mentioned, as solid composition forms, powders for dusting (containing the compound at a content of up to 100 %) and granules, especially those obtained by extrusion, by compacting, by 5 impregnation of a granulated vehicle, or by granulation from a powder (the content of the compound in these granules being between 0.5 and 80 % for the latter cases), tablets or effervescent tablets.
The compounds of formula (I) can also be used 10 in the form of powders for dusting; it is also possible to use a composition comprising 50 g of active material and 950 g of talc; it is also possible to use a composition comprising 20 g of active material, 10 g of finely divided silica and 970 g of talc; these 15 constituents are mixed and milled and the mixture is applied by dusting.
As composition forms which are liquid or intended to constitute liquid compositions during application, there may be mentioned solutions, in 20 particular water-soluble concentrates, einulsif iable concentrates, emulsions, suspension concentrates, aerosols, wettable powders (or sprayable powder), pastes or gels.
The emulsifiable or soluble concentrates most 25 often comprise 10 to 8C % of active material, while the ready-to-apply solutions or emulsions contain 0.001 to 20 % of active material.
In addition to the solvent, the emulsifiable 2 4 i 51 concentrates can contain, when this is necessary, 2 to 20 % of suitable additives such as the stabilising agents, surface-active agents, penetration agents, corrosion inhibitors, dyes or adhesives mentioned ~ 5 above.
It is possible, by diluting these concentrates with water, to obtain emulsions of any desired concentration which are particularly suitable for application to crops.
By way of example, the composition of several emulsfiable concentrates will now be given: EC Example 1 - active material 400 g/1 - alkaline dodecylbenzenesulphonate 24 g/1 15 - oxyethylenated nonylphenol containing molecules of ethylene oxide 16 g/1 - cyclohexanone 200 g/1 - aromatic solvent qs 1 litre According to another emulsifiable concentrate 20 formula, there are used: EC Example 2 - active material 250 g - epoxidised vegetable oil 25 g - mixture of alkylarylsulphonate and of ether of polyglycol and fatty alcohols 100 g - dimethylformamide 50 g - xylene 575 g The suspension concentrates, which can also 2 4 5 6 8 9 52 be applied by spraying, are prepared so as to produce a stable fluid product which does not settle out and they generally contain from 10 to 75 % of active material, from 0.5 to 15 % of surface-active agents, from 0.1 to 5 10 % of thixotropic agents, from 0 to 10 % of suitable additives, such as antifoaming agents, corrosion inhibitors, stabilising agents, penetration agents and adhesives and, as vehicle, water or an organic liquid in which the active material has little or no • - solubility: certain solid organic materials or inorganic salts can be dissolved in the vehicle to help in preventing sedimentation or as antifreeze for the water.
By way of example, the composition of a 15 suspension concentrate will now be given: SC Example 1 - active material 500 g - polyethoxylatea tristyrylphenyl phosphate 50 g - polyethoxylated alkylphenol 50 g 20 - sodium polycarboxylate 20 g - ethylene glycol 50 g - organopolysiloxane oil (antifoam) 1 g - polysaccharide 1.5 g - water 316.5 g 25 The wettable powders (or sprayable powders) are generally prepared so that they contain 20 to 95 % of active material, and they generally contain, in addition to the solid vehicle, from 0 to 30 % of a 24 53 wetting agent, from 3 to 20 % of a dispersing agent and, when necessary, from 0.1 to 10 % of one or more stabilising agents and/or other additives, such as penetration agents, adhesives, or anticaking agent's, 5 dyes, and the like.
In order to obtain the sprayable powders or wettable powders, the active materials are intimately mixed in suitable mixers with the additional substances and the mixture is milled in mills or other suitable 10 grinders. Sprayable powders are thereby obtained whose wettability and suspensibility are advantageous; they can be suspended in water at any desired concentration and these suspensions can be used very advantageously in particular for application to plant leaves. 15 Instead of wettable powders, it is possible to produce pastes. The conditions and methods for producing and using these pastes are similar to those for the wettable powders or sprayable powders.
By way of example, various wettable powder 20 (or sprayable powder) compositions will now be given: WP Example 1 - active material 50 % - ethoxylated fatty alcohol (wetting agent) 2.5 % - ethoxylated phenylethylphenol (dispersing agent) 5 % - chalk (inert vehicle) 42.5 % 54 WP Example 2 - active material 10 % - C13 branched-type synthetic oxo alcohol ethoxylated with 8 to 10 mol of ethylene oxide (wetting agent) 0.75 % - neutral calcium lignosulphonate (dispersing agent) 12 % - calcium carbonate (inert filler) qs 100 % WP Example 3: This wettable powder contains the same ingredients as in the above example, in the proportions below: - active material 75 % - wetting agent 1.50 % - dispersing agent 8 % - calcium carbonate (inert filler) qs 100 % WP Example 4: - active material 90 % - ethoxylated fatty alcohol (wetting agent) 4 % - ethoxylated phenylethylphenol (dispersing agent) 6 % 2 4 8 < 55 WP Example 5: - active material 50 % - mixture of anionic and nonionic surface-active agents (wetting agent) 2.5 % - sodium lignosulphonate (dispersing agent) 5 % - kaolin clay (inert vehicle) 42.5 % The aqueous dispersions and emulsions, for example the compositions obtained by diluting a 10 wettable powder or an emulsifiable concentrate according to the invention using water, are included within the general scope of the present invention. The emulsions can be of water-in-oil or oil-in-water type and they can have a thick consistency like that of a 15 "mayonnaise".
The compounds according to the invention can be formulated in the form of water-dispersible granules also included in the scope of the invention.
These dispersible granules, with an apparent 20 density generally of between approximately 0.3 and 0.6, have a particle size generally between approximately 150 and 2,000 and preferably between 300 and 1,500 microns.
The active material content of these granules 25 is generally between approximately 1 % and 90 %, and preferably between 25 % and 90 %.
The remainder of the granule is essentially composed of a solid filler and optionally of 24: 56 surface-active adjuvants which confer water-dispersibility properties on the granule. These granules can be essentially of two distinct types depending upon whether the filler used is soluble or 5 insoluble 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 10 advantageously accompanied by surface-active agents (at an amount of 2 to 20 % by weight of the granule) of which more than half consists, for example, of at least one essentially anionic dispersing agent such as an alkali metal or alkaline-earth metal polynaphthalene 15 sulphonate or an alkali metal or alkaline-earth metal lignosulphonate, the remainder consisting of nonionic or anionic wetting agents such as an alkali metal or alkaline-earth metal alkylnaphthalene sulphonate.
Moreover, although this is not indispensable, 20 it is possible to add other adjuvants such as anti-foaming agents.
The granule according to the invention can be prepared by mixing the required ingredients and then granulating according to several techniques known 25 per se (pelletiser, fluid bed, atomiser, extrusion, and the like). Generally, the preparation is completed by crushing followed by sieving to the particle size chosen within the abovementioned limits. 2 4 57 Preferably, it is obtained by extrusion, the preparation being carried out as shown in the examples below.
DG Example 1: Disoersible granules 5 90 % by weight of active material and 10 % of urea in the pearl form are mixed in a mixer. The mixture is then milled in a pin mill. A powder is obtained which is moistened with approximately 8 % by weight of water. The damp powder is extruded in a 10 perforated-cylinder extruder. A granule is obtained which is dried and then crushed and sieved so as to retain only the granules with a size of between 150 and 2,000 microns respectively.
DG Example 2: Dispersible granules 15 The following constituents are mixed in a mixer: - active material 75 % - wetting agent (sodium alkylnaphthalene sulphonate) 2 % - dispersing agent (sodium polynaphthalene sulphonate) 8 % - water-insoluble inert filler (kaolin) 15 % This mixture is granulated in a fluid bed, in the presence of water, and is then dried, crushed and 25 sieved so as to produce granules of between 0.15 and 0.80 mm in size.
These granules can be used alone or in solution or dispersion in water so as to produce the 2 4 58 required dose. They can also be used to prepare combinations with other active materials, especially fungicides, the latter being in the form of wettable powders or of granules or aqueous suspensions.
As regards the compositions which are suitable for storing and transporting, they more advantageously contain from 0.5 to 95 % (by weight) of active substance.
The present invention further provides a method of controlling fungal disease at a locus which comprises applying to the locus an effective amount of a compound of formula (I) or an agriculturally acceptable salt thereof.
They are advantageously applied at doses of 0.005 to 5 kg/ha, and more specifically of 0.01 to 1 kg/ha.
NZ245489A 1991-12-20 1992-12-16 2-imidazolin-5-one and 5-thione derivatives and fungicidal compositions NZ245489A (en)

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