AU651021B2 - Fungicidal 2-amidazolin-5-one and 2-amidazoline-5-thione derivatives - Google Patents

Fungicidal 2-amidazolin-5-one and 2-amidazoline-5-thione derivatives Download PDF

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AU651021B2
AU651021B2 AU30310/92A AU3031092A AU651021B2 AU 651021 B2 AU651021 B2 AU 651021B2 AU 30310/92 A AU30310/92 A AU 30310/92A AU 3031092 A AU3031092 A AU 3031092A AU 651021 B2 AU651021 B2 AU 651021B2
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carbon atoms
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alkyl
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Guy Lacroix
Raymond Peignier
Regis Pepin
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Bayer CropScience SA
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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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Description

AUSTRALIA 65102 1 PATENTS ACT 1990 COMPLETE SPECIFICATION NAME OF APPLICANT(S): Rhone-Poulenc Agrochimle ADDRESS FOR SERVICE: DAVIES COLLISON CAVE Patent Attorneys 1 Little Collins Street, Melbourne, 3000.
00 00 eo oorea ao a O 00 ooe OOBe o s0 o INVENTION TITLE: Fungicidal 2-amidazolin-5-one and 2-amidazoline-5-thione derivatives The following statement is a full description of this invention, including the best method of performing it known to me/us:- 0 0 0 o o r «o o oa 0 0 -I 0 00 O0 01 00 0- 0o o a eo a 6 DO 0 i _s 1 a The present invention relates to new imidazolinone or imidazolinthione compounds for use in plant protection. It also relates to the processes for the preparation of the said compounds and to the products which can optionally be used as intermediates in the preparation processes. It then relates to the use of these compounds as fungicides, to the fungicidal compositions based on these compounds and to the processes for combating fungal diseases of crops using these. compounds.
One object of the present invention is to provide compounds which have improved properties in the treatment of fungal di3eases.
.o 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.
It has now been found that these objects can S" 20 be achieved by virtue of the products of the invention, S00* which are 2-imidazolin-5-one or .0 derivatives of general formula (I) 2' R N A-R 2 3 R
N
\B)n-R4 wn D in which: i W is a sulphur or oxygen atom or an S=O group A represents 0 or S n 0 or 1 B represents NR 5 or 0 or S or CR 5 R, or SO2 or C=0.
RI and R 2 which are identical or different, 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, alkylsulphonylalkyl, monoalkylaminoalkyl, alkenyl or alkynyl radical containing 2 to 6 carbon atoms or a dialkylaminoalkyl or cycloalkyl radical containing 3 to 7 carbon atoms or Pre,, r'e\y an aryl radical co-pisingf phenyl, naphthyl, ~thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl, or methylenedioxyphenyl, optionally substituted by 1 to 3 groups chosen from R 7 Or an arylalky aryloxyalkyl, arylthioalkyl or ae o arylsulphonylalkyl radical, the terms a-r nd- ley--- 0 oo ingthe definitions given abov or R and R 2 can form, with the carbon to which they 25 are bonded on the ring, a carbocycle or a heterocycle having from 5 to 7 atoms, it being possible for these rings to be fused to a phenyl, optionally substituted by 1 to 3 groups chosen from R,; S l 3
R
3 represents: an alkyl group containing 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, alkylsulphonylalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, 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 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 R 7 a:aa: R 4 represents: a hydrogen atom when n is equal to 1 or an alkyl group containing 1 to 6 carbon atoms or e" 4 an alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group 0 containing 2 to 6 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 aryl radical, comp isgphenyl, naphthyl, S thienyl, furyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl or methylenedioxyphenyl, optionally substituted by 1 to 3 groups chosen from R7 or -an arylalkyl, aryloxyalkyl, aryllthioalkyl or arylsulphonylalkyl radical, t-he i-Frms aryl And aky -hviffthp- dfinitinn- gi.er above or -an amino group disubstituted by 2 identical or different groups chosen from: -an alkyl radical containing 1 to 6 carhon atoms an alkoxyalkyl, alkenyl or alkynyl radical containing 3 to 6 carbon~ atoms a cycloalkyl madical containing 3 to 7 carbon atoms an arylalkyl, sucah as de-Fin-ebol phenyl or naphthyl radical, optic:±ally substituted by 1 to 3 groups chosen f rom R7 or 444$ -a thienylmethyl or furfuryl rad4.cal -a pyrrolidino, piperidino, morpholino or piperazino group, optionally substituted by alkyl ,.,*containing 1 to 3 carbon atoms; R51 represents: I H, except when R 4 is H, 1 or 25 an alkyl, haloalkyl, alkylsulphonyl or 254 haloalkylsulphonyl radical containing 1 to 6 carbon atoms or -an alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkylsuiphonyl or cyanoalkylsuiphonyl radical containing 2 to 6 carbon atoms or an alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl or cyanoalkoxycarbonyl 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, phenylacetyl and phenylpropionyl; arylcarbonyl, benzoyl, optionally substituted by 1 to 3 groups from
R
7 thienylcarbonyl; furylcarbonyl; pyridylcarbonyl; benzyloxvcarbonyl; furfuryloxycarbonyl; tetrahydrofurfuryloxycarbonyl; t.hienylmethoxycarbonyl; pyridylmethoxycarbonyl; phenoxycarbonyl or (phenylthio)carbonyl, the phenyl being itself optionally substituted by 1 to 3 groups from R 7 (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 disubstituted by
L"
r~
U
DllC1 an alkyl or haloalkyl group containing 1 to 6 carbon atoms or a cycloalkyl, alkenyl or alkynyl group 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; 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 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 15
S
e r Ir rr r r r r r rrrtr~
R
7 groups; an alkylthioalkylsulphonyl group containing 3 to 20 8 carbon atoms or a cycloalkylsulphonyl group containing 3 to 7 carbon atoms;
R
6 represents: a hydrogen atom or a cyano group or 25 an alkyl group containing 1 to 6 carbon atoms or a cycloalkyl grot.p containing 3 to 7 carbon atoms or an acyl or alkoxycarbonyl group containing 2 to 6 carbon atoms or It ft I (t 14 t 0 a benzoyl group, optionally substituted by 1 to 3 R, groups; R, 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 15 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 Ia, are known *1 1
R
2 N
SR
3 SO R 5 Ia R, n -cn-R4 W R 6 in which W, Ri to R 6 and n have the same 8 meaning as in formula I.
Denoted S-alkylated derivatives of 5,5-diphenyl-2-thiohydantoin and of hydantoin, they have been especially studied for their pharmacological properties: a) Zejc, Dissertationes Pharmaceuticae et pharmacologicae, Warsaw, 20 507-524 and 525-537 i (1968) b) Lucka-Sobstel, B. and Zejc, A., Dissertationes Pharmaceuticae et pharmacologicae, 22 13-19 (1970) c) Fetter, Harsanyi, Nyitrai, J. and Lempert, Acta Chemica (Budapest), 78 325-333 (1973).
No agricultural fungicidal activity has been described for these compounds.
n Other specific compounds of formula I have been described by Bbhme, Martin and Strahl in Archiv der Pharmazie, 313, 10-15 (1980) (ref. They are the 3 following compounds: l i SCH3 R H R=H, CH 3 phenyl O CH3 These compounds are thus included in the compounds of formula Ib, which form part of the invention:
.I_
9
R
2
N-.[.SR
3 R NN- 4 Ib W in which W and R, to R 5 have the same meaning as in formula I.
The compounds of formula Ia can be prepared according to the processes known per se described in the abovementioned references and in the following references: e) Biltz, Chemische Berichte 42, 1792- 1801 (1909) f) Chattelain, M. and Cabrier, Bulletin de la Societe Chimique de France, 14 (1947), 639-642 S* g) Carrington, C.H. and Warring, W.S., Journal of the Chemical Society, (1950) 354-365 h) Lampert, Breuer, J. and Lemper- Streter, Chemische Berichte, 92,. 235-239 (1959) Shalaby, A. and Daboun, Journal fir Praktische Chemie, 313 1031-1038 (1971) j) Simig, Lemper, K. and Tamas, J., Tetrahedron, 29 3571-3578 (1973) k) Schmidt, Heimgartner, H. and Schmidt, Helvetica Chemica Acta, 62 (1979), 160-170 4 1) Muraoka, Journal of the Chemical Society, Perkin Transactions I, (1990), 3003-3007 or according to one of the processes A, B, C or D described below.
The compounds of formula Ib can be obtained according to the process described by Bbhme, Martin and Strahl in Archiv der Pharmazie, 313, 10-15 (1980) (reference d) or according to one of the processes described below.
Process A: Process for the preparation of the compounds of formula The preparation of the compounds of formula by S-alkylation of the 2-thiohydantoins (II) is carried out according to the reaction scheme: S1 ioo o a Base A* 1 R3X X R f (B)n-R4 solvent
W
a SalI in which X represents a chlorine, bromine or "15 iodine atom or a sulphate group, or an alkylsulphonyloxy or arylsulphonyloxy group, alkyl and S aryl being as defined above for R I and R 2 It is possible to use, as base, an alkoxide, for example potassium tert-butoxide, an alkali metal or alkalineearth metal hydroxide, an alkali metal carbonate or a tertiary amine. It is possible to use, as solvent, ethers, cyclic ethers, alkyl esters, acetonitrile, j s .potssim tet-btoxdean akal meal o alalie- I I ii alcohols containing 1 to 3 carbon atoms, or aromatic solvents, for example tetrahydrofuran, at a temperature of between -5°C and 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, Chemische Berichte, 42, 1792- 1801 (1909) n) Eberly and Dains, Journal of the American Chemical Society, 58, (1936), 2544-2547 o) Carrington, Journal of the Chemical 15 Society, (1947), 681-686 i g) Carrington, C.H. and Warring, W.S., Journal of the Chemical Society, (1950), 354-365 Lampert, Breuer, J. and Lemper- Streter, Chemische Berichte, 92, 235-239 (1959) i) Koltai, Nyitrai, Lempert, K. and Burics, Chemische Berichte, 104, 290-300 (1971) or alternatively according to one of Sprocesses E or F described below and which form part of the invention.
Process B: Preparation of the compounds Ic.
The preparation of the 2-methylthio-2of formula (Ic) by cyclisation of the iminodithiocarbonates of formula is carried out 12 according to the overall scheme:
R
2 NH2 a)>
I
1 C0 2
H
CS
2 2
CH
3 1 13ase b) R t :S SCH 3 ~SCH 3 R, C0 2
H
(Ea)
R
4 -(B)n-NI1 S aIV) 2 CH 3 R 1 ,2NH-B)ni-R 4 0
MV
A R 2
N-YSCH
3
N
R
1 B~-R 0 CI I I f C Ct I I C I 41 C, U 3 *3 C Cf II I'.I a) The ixninodithiocarbonates (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, 26 243-246 (1985) E. IMelendez et al., Synthesis, 1981, 961 according to:
CR
2
NH
2 R, C0 2
H
CS
2 2
CH
3 1 Base (in) b) The compounds of formula are obtained all 0; ;jf a
IW
54**
V
a, Ia a a 13 by condensing the compounds of formula (III) with amines or hydrazines of formula 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.
c) Cyclisation of the compounds is 10 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 and 15 Process Cl: Preparation of the compounds Ib by N-derivatisation of the compounds Ib'.
The compounds of formula (compounds (Ib) in which R 5 is a hydrogen atom) can be alkylated, acylated, alkoxycarbonylated, carbamoylated or sulphamoylated according to the following general scheme:
R
2 N-Y SR 3 RIX N.N'R4 WV
H
Base So ven t RX
R
5 represents here an alkyl, alkoxycarbonyl, n L- s: 14 acyl, arylcarbonyl, alkylsulphonyl, arylsulphonyl, 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 R0O, when .5 is acyl.
It is possible to use, as base, alkali .aetal hydrides, alkoxides or a tertiary amine. The reaction can be carried out at a temperature of between 10 and +50"C. It is possible to use, as solvent, for example ethers, cyclic ethers, dimethylformamide, dimethyl sulphoxide or aromatic solvents.
SCarbamoylation of the compounds can be carried out by reacting with isocyanates or isothiocyanates according to the scheme:
R
2 N SR 3
R
2 N SR 3 R R 5 N=C=Y Ib' Y NHR The reaction is carried out under the same 2. conditons as those described above, it being possible for the base, however, to be used in catalytic *1 quantity.
-I 20 Process C2: Preparation of the compounds Id.
The compounds Id' (compounds Id in which R, is S; a hydrogen atom, can be alkylated in position 4 according to the scheme:
SR
3 Base
R
2 N_,SR 3 y -2X SR n-R s olvent R (B)n -R 4 o0 Id d X represents a chlorine, bromine or iodine atom. It is possible to use, as base, an alkoxide, a metal hydride or an ar.ide. The reaction can be carried K out at a temperature of between -30"C and +80"C. It is I 5 possible to use, as solvent, ethers, cyclic ethers, dimethylformamide, dimethyl sulphoxide or aromatic solvents.
Process D: Preparation of the S-oxidised derivatives of the 10 The compounds of formula in which W Srepresents a S=O group are obtained by oxidising the 2imidazoline-5-thiones according to the scheme: i.R 2
AR
3 Oidin R2~N R N'(B)n-R R, '(B)n-R S S It is possible to use peroxides, especially 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 I
J
temperature of berween -20°C and Process E: Preparation of the dithiohydantoins 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:
R
2
R
1
-CH-N=C=S
lil~ r rii, rirrci rr I~ riri ri 1i R 4
-N=C=S
Base solvent
H
R
2 R
S
(VI)
C
I
i 4 i l •orl4i .0 e.
S* I At least one of the groups R, or R 2 must be electron-withdrawing (aryl, substituted aryl, alkoxy- 10 carbonyl, and the like). The isothiocyanate R 4 -NCS must not be able to form an anion; aryl isothiocyanates can be used in particular in this reaction.
It is possible to use, as base, potassium tert-butoxide, lithium or sodium bis(trimethylsilyl)- 15 amide or alkali metal hydrides. It is possible to use ethers or cyclic ethers as solvent. The reaction is carried out at a temperature below -60 C. The anion must b(e 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 Process F: Preparation of the 2-thiohydantoins of formula (VII).
R,
I.:
The preparation of the 2-thiohydantoins (VII) from the isothiocyanates derived from the amino acids (VIII) is carried out according to the reaction:
R
2 -CN=C=S
R
4 -(B)n-NT-1 2
CO
2
R
C*
I 4 St
I
Cyclisation can be carried out in two ways: thermally: in this case, the mixture of the 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 It is possible to use ethers, cyclic ethers, alcohols, 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 pages 327-375 (1989).
Process G: Preparation of the compounds of formula I in a single stage.
During cyclisation of the 2-thiohydantoins according to process F, if the cyclisation is carried out in basic ruedium, the thiohydantoin is in the thiolate form at the end of the reaction and can be reacted directly with an alkyl halide or alkyl sulphate
R
3 X or with R 3 X in which X is an alkylsulphonyloxy or ryl-sulphonyloxy to form Processes A and F are thus linked together according to the scheme:
R
R2 B" M R,-C-N=C=S
R
4 CO2R r ~e o t ra ~1
I
c~ 4( t Bltt f I
II
O
R S^ (B)n-R4 Rz N
R
3
X
7
R
2 N SR, R 1/ (B)n -R 4 0 1 rr tr r (r) 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 chloride RSC1 with an imidazolinone of formula IX according to the scheme: Pi t I!
IL
i"; 8 t
R
2 N-r"
SR
3 R >1 NH 0 Base R.
R
4 SCI solvent R, S -R 3 19 The reaction is carried out at a temperature of between -20°C and +30 0 C, in the presence of one molar equivalent of a base. As solvent, 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 examp' ethers, cyclic ethers, dimethylformamide, dimethyl sulphoxide or aromatic solvents. The imidazolinones (IX) can be prepared by processes analogous to process A.
.0 The compounds which are preferred for their better fungicidal activity and/or for their ease of synthesis are: 1 C C
CC*C
i i i i i i
I
i n ti, kd rrr~ o iii Ir c
~I
r jl j 1) the compounds of formula Ib, 2) the compounds of fo'lula I, in particular 15 Ib, in which R 5 is a hydrogen atom, 3) the compounds in which R, and R 2 are different from H, 4) the compounds in which R 2 represents an alkyl group containing 1 to 3 carbon atoms, 20 5) the compounds in which R represents a phenyl ring, optionally substituted by Ry, 6) the compounds in which R 3 represents an alkyl group containing 1 to 3 carbon atoms, 7) the compounds in which R 4 represents a 25 phenyl ring, optionally substituted by R,, 8) the compounds in which R 3 represents a methyl group.
The examples below are given by way of
MIN--
:1 i:l i i r i i i I ;i I;i i i i r
I
B
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 10 radicals are represented respectively by Me and Ph, and Cst means a physical constant, that is to say either a melting point or the refractive index 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 O'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 6 t *S4 21 I1-benzyl-4 -methyl-2 -methylthio-4 -phenyl -2 -i-midazolin-5 pne (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: It
I
St .11111 'a U~3 22
R
2
SR
3 NI N-R 4 dw R5 r
I
t d r f r I 1! i :i :i ir r
J
1, ~ic c c,
I
I
c.
r i i r t
I
i 'l No. R2 R3 R4 R5 w Cst 1 Me Me Ph H 127_C 3 Me 2-oxopropyl Ph H S 130 0
C
9 Me Me Ph H 0 149 0
C
10 Me Me neta-tolyl H 0 124 0
C
11 Me Me para-tolyl H 0 150 0
C
12 Me Et 1 Ph H 0 118 C 13 Me Me 4-fluoroPh H 0 144C 14 Me allyl Ph TH 0 92*C Me Me ortho-tolylIH 0 926C 16 Me Me I 3-chioroPh IH 0 120C 17 Me iso-propy. Ph IH 0 18 Me Me 4-chioroPh H 0 149*C 19 Me Me tert-butyl H 0 73C 20 Me Me 2-chloroPh H 0 134C -Me 1.5G- 3 0- 5 22 Me Me Ph Me 0 124*C 23 Me Me Ph acetyl 0 132C 24 Me Me 4-methoxyPh H 0 138C 25 Me n-propyl Ph H 0 90 0
C
40 Me Me 2 -methoxyPh H 0 1100C 41 Me Me acetyl H 0 M.p.
II
.41.11
'I.
No. R 2
R
3 R4 R W Cst 43 Me Me 4-N0 2 -Ph H 0 Mp=13 44 -Me Me 2-pyridyl H S 1140C Me Me 2-pyridyl H 0 147*C 46 Me Me 3-pyridyl H 0 140*C 47 me IMe 3-pyridyl H S 176*C 54 _M Me 2, 6-Me 2 Ph H S 146*C 73 Me JMe 2-thia- Me 0 1160C I zolyl_ Me CHF 2 Ph H 0 800C 8 Me Me 4-Me- H 0
R
2 SR 3 O I No. R 2
R
3
R
4 n R5W Cst 26 Me Me Ph 0 M.P= 123*C 27 Ph IMe lPh 0 -S MP=120'C
I'
It
'A
I
28 29 i. I me 0 1 s 850C 1440C
I
N~
TOL
24
I
No. R 2
R
3
R
4 n R 5 W Cst 3 0 Me Me Ph 0 -0 70 0
C
31 Me Me Me 0 -0 58*C 32 Ph Me Me 0 -0 M.P.=-170 0
C
33 H Me Ph 0 -0 250 0
C
34 Me Me Ph 1 H 0 68 0
C
Me Me 2-thienyl 1 H 101 76*C 36 Me Me Me 1 Me 0 n 20 1.553 37 Me Me 2-furyl 1 H 0 "honey-like consistency" 38 Me Me 3-pyridyl 0 0 J "honey-like I I consistency" Ph IMeS IMe t0 H I fM.p.=1440C 52 Me MeS Ph 1 ICO)i 1_ honey-like 4 consistency" 57 Me MeS 2-MePh 0 10 "honey-like I consistency' 4 10 04 0 0 I0006t c_ i- 4 4e 4 44 The following were also prepared: 4-(3-pyridyl)-4-methyl-l-(N-phenylamino)-2- (compound 51: M.p.
156 C); 4-phenyl-4-methyl-l-(benzyloxy)-2- (compound 56: honey-like consistency).
Example 2: Preparation of compound No. 7 according to process B.
10 a) N-[bis(methylthio)methylene]-2-phenylglycine (compound (III) with R I phenyl and R 2
H):
100 g (0.66 mol) of phenylglycine are dissolved at +5 0 C in 335 g of 22 aqueous potassium hydroxide (1.3 mol). 55.3 g of carbon disulphide are 15 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 20 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 h and then 103 g of methyl iodide are again run in and left to react for 1 h. The mixture is diluted with 25 300 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 4 S 84 *i 4 8 4L
(I(
Ii i r reduced pressure. 49.5 g of N-[bis(methylthio)methylene]-2-phenylglycine (yield 31 are recovered in the for.n of a yellow solid melting at 112"C.
b) 2'-(metachlorophenyl)[N-(bis(methylthio)methylene)-2-phenylglycyl]hydrazide (compound V with R, phenyl, R 2 H, R 4 metachlorophenyl, n 1, B NH): 3.38 g (16.4 mmol) of dicyclohexylcarbodiimide 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 0 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 20 recovered in the form of a pinkish powder melting at 146'C.
M- ack 0 loroph rl kr<-o c) l-Matahlo pheny -2-methylthio-4-phenyl- (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 e' under reduced pressure. The resulting honey-like 0 0.00i 00 it t 0 00 0 .0000 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 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: t U* t 44 So t U -IM-11-
R
2 N Y SR 3 0 N, No. R~ Cst 4 ~H Me 2-chioroPh H 0 130 0
C
IH IMe Ph H 0 190 0
C
6 H Me 4-chloroPh H 0 162 0
C
7 H Me j3-chioroPh H 0 196 OC 8 H Me meta-tolyl H 0 182*C 59 H MeS 2, 4 -(CH 3 2 Ph H 0 64*C 61 H MeS 2,5-(CH 3 2 Ph H 0 162 0
C
63 H MeS j2-EtPh H 0 126 0
C
69H{ MeS T2,5-(Cl) 2 Ph H 0 144 0
C
711H MeS 3,5-(Cl) 2 Ph H 0 146 0
CI
it I I #4 6t C. Slot
C
11(4 C 4-Phenyl-1- (N-phenylaanino -methylthio-2 (compound 120) was also prepared.
ExamTple 3: Preparation of 4-methyl-1-(Nmethy1-N-phenyan.-.no) -2-methylthio-4-phenyl-2imidazolin-5-one (compound No. 22) by alkylation (methylation) according to process C1.
0.4 g (3.5 mmol) of potassium tert-butoxide is added to a solution of 4-methyl-1-phenylamino-2i 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 then added and then the mixture is left to react for 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 -t 124°C.
Example 4: Preparation of 4-methyl-l-(Nacetyl-N-phenylamino)-2-methylthio-4-phenyl-2- (compound No. 23) by acylation (acetylation) according to process Cl.
C: '0.4 g (3.5 mmol) of potassium tert-butoxide is added to a solution of 4-methyl-l-phenylamino-2methylthio-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 O'C. 0.25 g (3.5 mmol) of acetyl chloride is then added and the mixture is left to react for 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
"~I
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 purified product crystallises from diisopropyl ether.
0.25 g of compound No. 23 is obtained in the form of a white powder meltin:; at 132"C.
By carrying out the preparation in the same way, compounds No. 39 and 42 were obtained.
R
2 N
SR
3 NR4 No. R, R 3 R4 Rs W Cst ta
**I
lJ 15 sr *r t a a 20 a 23 Me Me Ph acetyl O 132'C 39 Me Me Ph formyl O "honey-like consistency" 42 Me Me Ph tBuOCO O "honey-like consistency" Example 5: Preparation of 4-ethyl-2methylthio-4-phenyl-l-phenylamino-2-imidazolin-5-one (compound 48) according to process C2.
0.55 g of potassium tert-butoxide is added to a solution of 1.5 g (5.05 mmol) of 2-methylthio-4- (compound No. 5) in 50 ml of anhydrous tetrahydrofuran. The "u~ mixture is left to react for 30 min at room temperature and then G.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 then concentrated under reduced pressure. The product is purified by chromatography on a silica column (Merck silica; eluent: 25 ethyl acetate/75 heptane).
0.65 g of compound No. 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.
S t t i i f' ~i r PIP-I 1. N2
SR
3 Ow
R
Wr
RS~
No. R. W Cst [48 Et Me Ph H 1 147 0
C
49 iso-Pr Me Ph H 0 IJ 135"C CO Me MeS 2,4-(Me).Ph H 0 I"honey-like _consistency" 162 Me MeS 2,5-(Me) 2 Ph H O1 M.p. 160C 64 Me MeS 2-EtPh H 0 "honey-like consistency" Me MeS 2,4-(Cl) 2 Ph H 0 U' Me MeS naphthyl H 0 174'C 7 Me MeS 2,5-(Cl) Ph H 0 M.p. 1809C 72 Me MeS 3, 5-(C1) 2 Ph H 0 M.p. 74 CHF 2 MeS Ph H 0 124 0
C
79 Me MeS (2-CF 3 -Ph H 0I)I.p.= 91 0
C
I
9 9i *4~O 4-Methyl-2-methylthio- -(4-fluorophenyl)-1- (compound 68) was also prepared.
1 Example 6: Preparation of compound 2 according to process D.
1.7 g (5.2 mmol) of 4-methyl-2-methylthio-4- (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: 25 of compound No. 2 is thus obtained in the form of a beige powder melting
I.
Iat 150°C.
No.% R 2 R3 R 4
R
5 W Cst 2 Me Me Ph H S=O 150°C l Example 7: Preparation of 3,5-diphenyl-5methyldithiohydantoin according to process E.
15.1 g (122 mmol) of potassium tert-butoxide 23 are dissolved in 200 ml of tetrahydrofuran in a 500 ml, three-necked, round-bottomed flask under a dry argon
I
i-i--ii- 34 atmosphere. The solution is cooled to -70 0 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 i of 3,5-diphenyl-5-methyldithiohydantoin are thus obtained, a yellow powder melting at 157°C.
.Example 8: Preparatio:n of 3,5-diphenyl-5- 2 methyl-2-thiohydantoin according to process F.
4.7 g (20 mmol) of ethyl 2-isothiocyanato-2pherylpropionate 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 ml of diisopropyl ether and then dried under Iuum.
4.6 g (yield 77 of 3,5-diphenyl-5-methyl-2-thiohydantoin are thus obtained in the form of a beige 1,r1 powder melting at 164"C.
Example 9: Preparation of 3-(2-pyridylamino)-2-thiohydantoin according to process F.
2 g (9 mmol) of methyl 2-isothiocyanato-2phenylpropionate are dissolved in 30 ml of tetrahydrofuran. A solution containing 0.99 g of 2-hydrazinopyridine and 10 ml of tetrahydrofuran is added: the temperature of the mixture rises from 20 to 30 0 C and a solid precipitates. The mixture is allowed to react for 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 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 S 20 treated with active charcoal. The solution is concentrated and the product is crystallised from 20 ml of diethyl ether. The abovementioned product is *4 filtered and is dried under vacuum. 1.6 g (yield: 60 of 5-methyl-5-phenyl-3- 2-pyridylamino) -2-thiohydantoin 8 25 is obtained, a pale-yellow solid melting at 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: i-"
H
N
R, N(B)n-R 4 (vII) R, methyl and R 2 phenyl.
U
p044
U
*0 No. n JB R 4 Yield M.p.
1001 1 jNH Ph 66 164 0
C
1002 1 NH meta-tolyl 62 174 0
C
1003 1 CH 2 Ph 46 125 0
C
1004 1 NH para-tolyl 13 162 0
C
1005 1 CH 2 2-thienyl 49.5 134"C 1006 1 NH 4-fluoroPh 30 162 0
C
1007 1 1 JNH ortho-tolyl 38 162 0
C
1008 10 iso-propyl 60.5 146 0
C
1009 1 NH 3-chioroPh 32 78 0
C
1010 1 NH tert-butyl 18 120 0
C
1011 1 NH 4-chioroPh 24 196 0
C
2 1 NH 2-chioroPh 69 172 0
C
1013 0 piperidino 32 206 0
C
1014 1 NH 4-methoxyPh 27 1460C 1015 1 NH 2-ethoxyPh 29 214 0
C
1016 1 CH 2 2-furyl 39 105 0
C
1017 1 NH acetyl 42 2000C 1018 1 NH 4-N0 2 -Ph 41 234 C 1019 1 NH 2-pyridyl 60 800C 1020 1 NH 3-pyridyl 17
C
S U &r I I 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 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
I
150 ml of water on each occasion. The solution is dried 2 20 over magnesium sulphate and then treated with active charcoal. The solution is concentrated: a purplishbrown 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 S° 5 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-
I
1 38 (compound 9) are thus obtained in the form of a beige powder melting at 1490C.
By carrying out the preparations as above, the following compounds were obtained:
R
2 S- CH 3 444 tt.
9 t t
.I
t
I
S
p
I
*I S
S
*54 No. R'I R 2 R3 B M.p.
58 Me MeS NH 2,3-(Me) Ph 116 C 67 Me MeS (CH 2 2 Ph honeylike consistency 76 Me MeS CH 2 3-pyridyl 670C 77 Me MeS CH 2 2-pyridyl honeylike consistency 781- Me MeS N PhCH= 95 C 83 1 4-Me Me MeS NH Ph 179 C 84 1- Me MeS NH 3-Me-2-pyridyl 148*C 85 1 4-Cl Me- MeS NH Ph 1730C 86 1 3,4-(Meo) 2 Me MeS NH Ph 1650C 87 13,4-(MeO), Me MeS NH I 2-Me-Ph 3.51 *C 88 1 4-Me Me MIeS NH f 2-Me-Ph 520C 89 4-PhO Me MeS NH Ph 1460C 90 4-Cl Me MeS NH 3-Me-2-pyridyl 1330C 91 1 4-Cl Me MeS NH 2-pyridyl 1720C 92*1 R, PhCH 2 Me MeS NH Ph 166"C 93 1 4-PhO Me MeS NH 2-Me-Ph J 1300C 94 4-F Me MeS NH 2-Me-Ph 1200C 96 4-Cl Me MeS NH 2-Cl-Ph 145 'C 97- (CH 2 3 MeS NH Ph 158-C 98 (CH 2 2 MeS NH jPh 856C 99 4 -Cl H MeS NH f 4-Cl-Ph 163 C 100 14-Cl Me MeS I NH 4-Cl-Ph 1720C (A P' 's'n- No. R 3 B R, P.
101 4-Cl Me -MeS NH 4-F-Ph 170*C 102 4-Cl Me MeS NH 3-Cl-Ph 1460C 103 1 4-Cl Me MeS NH 4-Me-Ph 1780C 1 0 4
CH
2 3 MeS NH f.2-Cl-Ph J168*C 105 14-Cl Me MeS NH I2-Me-Ph 1240C 106 4-Cl Me MeS NH 3-M1e-Ph 1360C 1074-F JMe MeS NH 3-Me-Ph 121"C 108 MeS NH 3-F-Ph 1630C 109 J-me MeS NH 2,5-F 2 -Ph 141*C 110 14-Me Me MeS NH j 4 -Cl-Ph16C 111 14-Me Me MeS NH j2-Cl-Ph 168*C 112 -(CHA) 3 NH I4-Cl-Ph 1910C 113 -(CH 2 3 MeS NH2-Me-Ph 174 C 114 4-Me me MeS NH I3-Cl-Ph 184-C 115 4-F Me MeS NH J3-Cl-Ph 124*C 116 4-Me Me MeS NH 4-F-Ph 1860C 117 4-Me Me MeS NH 4-Me-Ph 157*C 118 4-F Me MeS NH 4-Me-Ph 1580C 119 J4-Me Me MeS NH 3-Me-Ph 178"C 121 4-F Me MeS NH 4-Cl-Ph 1590C 122 Me MeS NH 2, 4- (Me) 2 -Ph 630C 123 Me _meS N-Cl-2-Pyr 1270C 124 4-Cl Me IMeS NH 2-F-Ph 120*C 125 14-F Me MeS NH 2-F-Ph 1120C 126 14-Me Me IMeS NH 2-F-Ph 16
C,
*These compounds have the following formulae: Compound 97: N. S-CH 3 j Compound 98: N S H Compound 104: Compound 112:
.S-CH
3 Compound 113: NHQ0
CH
3 94O427,p:\oper~e,30310rhospe,40 40b Compound 92: This compound does not follow the general formula on page 38.
L
U'
U,
4 [7 94 0 4 2 7.p:%oper~ee,30310rho.sp,40 7 CC-C T~ 41 Example 11: Preparation of 4-phenyl-4-methyll-(phenylthio)-2-methylthio-2-imidazolin-5-one (compound 95: M.p. 112"C).
0.6 g (2.7 mmol) of 2-methylthio-4-methyl-4phenyl-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).
0.30 g (1 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 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 i t for diseases of cereals and other plants: Fusarium oxysporum f.sp.melonis Rhizoctonia r'olani AG4 i~l~r)rC1C Helminthosporium gramineum Pseudocercosporella herpotrichoides Alternaria alternata Septoria nodorum Fusarium roseum Pvthium rostratum Pythium vexans Each test is carried out in the following way: a nutrient medium consisting of potato, glucose 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 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 acti--n material.
20 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 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 43 a dose of 20 ppm.
The following results are then obtained: A -ood activity, that is to say a degree of inhibition of the fungus of between 80 and 100 was found for: Compounds 9, 13, 16, 22, 26 and 34 for Pythium rostratum and Pythium vexans.
Compound 26 for Fusarium oxysporum 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 herpotrichoides.
Compounds 11, 16 and 26 for Septoria nodorum.
Compounds 9, 11, 16 and 26 for SHelminthosporium 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 polyoxyethvyenated derivative of sorbitan) diluted to 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.
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 spores of Plasmopara viticola obtained from a 4-5 day culture, and then suspended at a concentration of 100,000 units per cm 3 The infected plants are then incubated for two days at approximately 18°C in an atmosphere saturated with moisture and then for. 5 days at approximately 20-22 0 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 75 or complete protection is observed, at a dose of 1 g/l, 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, il-- i 83 to 85, 88 to 91, 93 to 98, 101 to 108.
Example 14: In vivo test on Puccinia recondita (brown rust of wheat): 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 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/cm 3 is sprayed on the wheat; this 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 or complete protection is observed, at a dose of C V l 1 g/l, with the following compounds: 2, 9, 10, 15, 18, to 22 and 39, 55, 57, 64, 68, 75, 83 to 85, 88 to 93, 94 and 98.
Example 15: In vivo test on Phycophchora infestans (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 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.
Tomato plants (Marmande variety) are grown in pots. When these plants are one month old (5 to 6-leaf t stage, 12 to 15 cm high), they are treated by spraying the above aqueous suspension at various concentrations i of the compound to be tested.
After 24 hours, each plant is infected by spraying with an aqueous suspension of spores (30,000 sp/cm 3 of Phytophthora infestans.
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 _1 iil 1 1.
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/l, with the following compounds: 2, 9, 15, 30, 39, 45, 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.
For their practical use, the compounds according to the invention are rarely used cl their own. Most often they form part of compositions. These compositions, which can be used as fungicidal agents,
C
20 contain, as active material, a compound according to the7-invention as described above as a mixture with solid or liquid vehicles which are 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 t can be used. These compositions also form part of the invention.
These compositions can also contain all kinds of other ingredients such as, for example, protective i 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, reans a natural or synthetic, organic or inr-ganic material with which the compound is combineu in order to facilitate its application to the plant, to seeds or to the soil. This vehicle is therefore generally inert 2 0 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 fertilLsers, and the li.ke) or liquid (water, alcohols, especially butanol, and the like).
The surface-active agent can be an emulsifying, dispersing or wetting agent of ionic or nonionic type or a mixture of such surface-active agents. There may be cited, for example, sa ,s 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 surfaceactive agent is generally indispensable where the compound and/or the inert vehicle are 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 wi.hin 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 Sforms.
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 impregnation of a granulated vehicle, or by granulation f from a powder (the content of the compound .n these granules being between 0.5 and 80 for the latter cases), tablets or effervescent tablets.
The compounds of formula can also be used 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 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 particular water-soluble concentrates, emulsifiable concentrates, emulsions, suspension concentrates, aerosols, wettable powders (or sprayable powder), pastes or gels.
The emulsifiable or soluble concentrates most often comprise 10 to 80 of active material, while the ready-to-apply solutions or emulsions contain 0.001 to of active material.
In addition to the solvent, the emulsifiable
'CCI
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 above.
i 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/l alkaline dodecylbenzenesulphonate 24 g/l oxyethylenated nonylphenol containing molecules of ethylene oxide 16 g/l cyclohexanone 200 g/l aromatic solvent qs 1 litre According to another emulsifiable concentrate 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 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 of thixotropic agents, from 0 to 10 of suitable _~13_C~ 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 suspension concentrate will now be given: SC Example 1 active material 500 g polyethoxylated tristyrylphenyl phosphate 50 g polyethoxylated alkylphenol 50 g sodium polycarboxylate 20 g ethylene glycol 50 g organopolysiloxane oil (antifoam) 1 g polysaccharide 1.5 g water 316.5 g 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 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 agents, dyes, and the like.
,i it~ i I r
~I
~P1I 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 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.
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 cr sprayable powders.
By way of example, various wettable powder (or sprayable powder) compositions will now be given: WP Example 1 active material 50 ethoxylated fatty alcohol (wetting agent) 2.5 ethoxylated phenylethylphenol 0' 20 (dispersing agent) 5 c chalk (inert vehicle) 42.5 *t t L~ l WP Example 2 active material 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 20 agent) 4 ethoxylated phenylethylphenol (dispersing agent) 6 1 1- 1.
WP Example -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 wettable powder or an emulsifiable concentrate f 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 "mayonnaise".
li 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 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 is generally between approximately 1 and 90 and preferably between 25 and 90 The remainder of the granule is essentially 'I .composed of a solid filler and optionally of 56 surface-active adjuvants which confer waterdispersibility properties on the granule. These granules can be essentially of two distinct types depending upon whether the filler used is soluble or 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 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 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 aikylnaphthalene sulphonate.
eC(I S' Moreover, although this is not indispensable, 20 it is possible to add other adjuvants such as anti- 4i foaming agents.
The granule according to the invention can be prepared by mixing the required ingredients and then granulating according to several techniques known S 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.
r
I-I
Preferably, it is obtained by extrusion, the preparation being carried out as shown in the examples below.
DG Example 1: Dispersible granules 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 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 The following constituents are mixed in a mixer: active material 75 wetting agent (sodium alkylnaphthalene sulphonate) 2 20 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 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 eQ.
0 4 e0
C
C
co 0 *0 C 0o.
*0r cc 0 0000w Cr 0
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cc 0r C c I r 58 required dose. They can also be used to prepare combinations with oth-- active materials, cspecially 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.
A subject of the invention is also the use of the compounds according to the invention for combating fungal diseases of plants by preventative or curative treatment of the latter or of their growth site.
They are advantageously applied at doses of 0.005 to 5 kg/ha, and more specifically of 0.01 to 1 kg/ha.
t t C I I t t t i
.I
R
2 N NI( A w
R
2 SR 3 W
H
~SR Ri. N~ S R Is- R 4 I w
R
R
6 w N.Y
SCH
3 R N S R 3 0 (1c)
H
R- N..~s
."SCH
3 R2><t\,CS
CH
3 R I C0 2
H
w
(H)
R
4 -NI-b
(PV)
(MD
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C
X'C.SCH
3 0 m
(VII)
RI-
N=C=S
UO 2
R
(VIII).
"LI"-~-rr 59a 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.
V1 Vt it tt t 940427,p:oper ee,30310rho.spe,59

Claims (21)

1. Compounds containing an imidazolinone or imidazolinethione group, characterised in that they correspond to the general formula R 2 N--j A-R 3 Ri 4 W. 15 in which: W is a sulphur or oxygen atom or an S=0 group A represents 0 or S n =0 or 1 B represents NR, or 0 or S or CR 5 Rr, or SO, or C=0. R, and R 2 wh- 5 ch are identical or different, 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, mono alkylaininoal kyl, alkenyl or alkynyl radical containing 2 to 6 carbon atoms or a dialkylaminoalkyl or cycloalkyl radical containing 3 to 7 carbon atoms or P r- e'c- .6 an aryl radical comprlsn~hnl naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, L _C 61 quinolyl, isoquinolyl, or methylenedioxyphenyl, pptionally substituted by 1 to 3 groups chosen from R 7 or an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulphonylalkyl radical, the terms ary' and .a.lk r 4av-ng -i f ih i f inm n g0vin abohrv or RI and RZ 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 these rings to be fused to a phenyl, optionally substituted by 1 to 3 groups chosen from R 7 R 3 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 carbon atoms or a dialkylaminoalkyl, alkoxycarbonylalkyl or 7 N-alkylcarbamoylalkyl group containing 3 to 6 carbon 20 atoms or 41 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 S 25 part is phenyl, naphthyl, thienyl, furyl or pyridyl, optionally substituted by 1 to 3 groups chosen from R,; R represents: a hydrogen atom when n is equal to 1 or 62 an alkyl group containing 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkyny. group containing 2 to 6 carbon atoms or a dialkylaininoalkyl, alkoxycarbonylalky. or N-alkylcarbainoylalkyl group containing 3 to 6 carbon atoms or a N,N-dialkylh'arbamoylalkyl group containing 4 to 8 carbon atoms or an aryl radical, cmz1 .peynaphthyl, thienyl, furyl, pyridyl, pyrirnidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl or methylenedioxyphenyl, optionally substituted by 1 to 3 groups chosen from R 7 Or an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulphonylalkyl radical, the trms a-ryl anrd tlkyl hav~ing the diefinitions give:n abev~ or -an amino group disubstituted by 2 identical or 0 different groups chosen from: an alkyl radical. containing 1 to 6 carbon atolfs an alkoxyalkyl, alkenyl or alkynyl radical containing 3 to 6 carbon atoms a cycloalkyl radical containing 3 to carbon or naphthyl radical, optionally substituted by 1 to 3 groups chosen from R7 orw 63 -a thienylmethyl or furfuryl radical -a pyrrolidino, piperidino, morpholino or piperazino group, optionally substituted by alkyl containing 1 to 3 carbon atoms; represents: H, except when R, is H, or an alkyl, haloalkyl, alkylsuiphonyl or haloalkylsuiphonyl radical containing 1 to 6 carbon atoms or .144.1 44 #2 $2 *4 4 C 0. C I It an alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkylsuiphonyl or cyanoalkyl sulphonyl radical containing 2 to 6 carbon atoms or an alkoxyalkoxycarbonyl, Ithioalkoxycarbonyl or cyanoalkoxycarbonyl 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, 0 se~l1,henyl- acetyl and phenyipropionyl; arylcarbonyl, eesreeal benzcql, optionally substituted by 1 to 3 groups from R 7 thienylcarbonyl; furylcarbonyl; pyridylcarbonyl; benzyloxycarbonyl; furfuryloxycarbonyl; tetrahydro- furfuryloxycarbonyl; thienylmethoxycarbonyl; -1 h~y\ i 64 pyridylmethoxycarbonyl; phenoxycarbonyl or (phenylthio)carbonyl, the phenyl being itself optionally substituted by 1 to 3 groups from R,; (alkylthio)carbonyl; (haloalkylth,.o)carbonyl; (alkoxyalkylthio)carbonyl; (cyanoalkylthio)carboj (benzylthio)carbonyl; (furfurylthio)carbonyl; (tetrahydrofurfurylthio)carbonyl; (thienylmethylthio)- carbonyl; (pyridylmethylthio)carbonyl; or arylsulphonyl radical or a carbamoyl radical, optionally mono- or disubstituted by an alkyl or haloalkyl group containing 1 to 6 carbon atoms or a cycloalkyl, alkenyl or alkynyl group 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 7 groups; a sulphamoyl group, optionally mono- or disubstituted by 4 4 an alkyl or haloalkyl group containing 1 to 6 carbon atoms or a cycloalkyl, alkenyl or alkynyl group 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 I_ R 7 groups; an alkylthioalkylsulphonyl group containing 3 to 8 carbon atoms or a cycloalkylsulphonyl group containing 3 to 7 carbon atoms; R, represents: a hydrogen atom or a cyano group or an alkyl group containing 1 to 6 carbon atoms or a cycloalkyl group containing 3 to 7 carbon atoms or an acyl or alkoxycarbonyl group containing 2 to 6 carbon atoms or a benzoyl group, optionally substituted by 1 to 3 R 7 groups; R 7 represents: a halogen atom or i an alkyl, haloalkyl, alkoxy, haloalkoxy, S' 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 I/ a nitro or cyano group or S- 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; I 66 and their salts, with the exception of the compounds for which, when R, and R 2 are simultaneously phenyl or simultaneously methyl, B is CR,R,, A is sulphur and W is O or S; with the exception of the 3 compounds with R, hydrogen, n 1, B NR 5 with Rs and R 4 methyl, AR 3 SCH 3 W O and R 2 being either a hydrogen, a methyl or a phenyl; also with the exception of the compound in which RI is a phenyl, R 2 R 3 and R 4 are methyl, n is equal to zero, and A and W are both sulphur atoms.
2. Compounds according to Claim 1, characterised in that A is a sulphur atom.
3. Compounds according to Claim 1, characterised in that W is an oxygen atom.
4. Compounds according to Claim 2, characterised in that they correspond to the general formula: R N- .SR 3 N Ia i 20 R (C)nR 4 j W R6 in which W, n and R, to R 6 have the same meaning as in Claim 1. Compounds according to Claim 2, characterised in that they correspond to the general i i 67 formula: R N. SR 3 R 4> Ib W R in which W and R, to R 5 have the same meaning as in Claim 1.
6. Compounds according to Claim 2, characterised in that they correspond to the general formula: R 2 NY 3 R, N(B)n--R Ic in which B, n and R, to R 4 have the same meaning as in Claim 1.
7. Compounds according to Claim 2, characterised in that they correspond to the general formula: R2 SR 3 Id R N (B)n R4 in which B, n and R, to R, have the same meaning as in Claim 1. 1
8. Compounds according to one of Claims 1 to 7, characterised in that R, is a hydrogen atom.
9. Compounds according to Claim characterised in that R, is a hydrogen atom (compound Ib'). Compounds according to one of Claims 1 to 9, characterised in that R, and R 2 are not hydrogen atoms.
11. Compounds according to one of Claims 1 to 10, characterised in that R 2 is an alkyl group containing 1 to 3 carbon atoms.
12. Compounds according to one of Claims 1 to 11, characterised in that R, is a phenyl, optionally substituted by a group R 7
13. Compounds according to one of Claims 1 to 12, characterised in that R 3 is an alkyl group containing 1 to 3 carbon atoms.
14. Compounds according to one of Claims 1 to 13, characterised in that R 4 is a phenyl, optionally substituted by a group R 7
15. Compounds according to one of Claims 1 to 14, characterised in that R 3 is a methyl radical. 4" 16. Process (process A) for the preparation of the compounds of formula according to Claim 2, characterised in that an S-alkylation of the 2-thio- hydantoins of formula (III with a compound of formula R 3 X is carried out, in the presence of base and solvent, according to the scheme: 69 Base R 3 X solvent -R 4 in which R 2 R 3 R 4 B and W have the meaning of Claim 1 and X is a chlorine, bromine or iodine atom, or a sulphate group, or an alkyl- sulphonyloxy or arylsulphonyloxy group.
17. Process for the preparation of the 2-methylthio-2-imid.azolin-5-one compounds of formula (Ic) (process B) according to Claim 6, characterised in that a compound of formula is cyclised, by simple a o a heating in an aromatic solvent at reflux, according to the scheme: the scheme: SCH 3 A R2 N SCH3 RI N(B)n-R 4 0 I t (Ic) in which R 1 R 2 B and n have the same meaning as in Claim 1. compounds of formula (V ess B) according to Claim 'R ra c7, c tM r C: ei in that an iminodit- 's -"pra~l P-C- z~L~' p~
18. Process for the preparation of the compounds of formula (Ib) (process Cl) according to the scheme: R\N Base R 2>NBSR3 3 Solvent R N RsX I R 4 R NWR4 RR W H W R Ib' Ib characterised in that, in a solvent in the presence of base, a compound of formula R 5 X is reacted with a compound of formula (Ib) according to Claim 5, in which the group R 5 is a hydrogen atom according to Claim 9 (compound the Si# groups R, to R 4 have the meaning given in Claim 1, the group Rs is an alkyl, alkoxycarbonyl, acyl, aroyl, alkylsulphonyl, arylsulphonyl, carbamoyl or sulphamoyl group and X represents a leaving group preferably a halogen, a sulphate group, an optionally substituted phenoxy, RO 5 when R s is acyl, or an alkylsulphonyloxy or arylsulphonyloxy group or a nonleaving group preferably isocyanate or isothiocyanate.
19. Process for the preparation of the compounds of formula (Id) (process C2) according to the scheme: H N SR 3 Base R2N SR3 I R 2 X A R N -(B)n-R4 sol v e n t RI N:(B)n-R4 O O Id I characterised in that a compound of formula (Id), according to Claim 7, in which R 2 is a hydrogen atom (compound is reacted with a compound of formula R 2 X in a solvent and in the presence of base, at a temperature of between and +80*C, X being a chlorine, bromine or iodine atom and Ri to R 4 B and n having the same meaning as in Claim 1. 94427,p:\oper\ee,30310rbo.spe,70 1 writ it, I.r Si. t -i -71- Process according to Claim 19, characterised in that the base is chosen from the group comprising an alkoxide, a metal hydride or an amide and the solvent is chosen from the group comprising ethers, cyclic ethers, dimethylformamide, dimethyl sulphoxide and aromatic solvents.
21. Process for the preparation of the compounds of formula (process D) according to Claim 1 in which W represents an S=O group, characterised in that an S-oxidation of a compound of formula in which W is a sulphur atom is carried out, this oxidation of 2-imidazoline-5-thiones being carried out with a stoichiometric quantity of peroxides in a solvent at a temperature of between -20°C and +20 0 C. 15 22. Process according to Claim 21, characterised in that the peroxide is a peracid and the solvent is chosen from the group comprising chloroform and methylene chloride.
23. Fungicidal compositions comprising, in combination with one or more solid or liquid vehicles which are agriculturally acceptable and/or surface-active agents which are also agriculturally acceptable, one (or more) active materials which is/are a compound of formula I: r t i i! 940427,p:\oper\ee30310rh0.spe,71 in which: W is a sulphur or oxygen atom or a S=O group A represents 0 or S -n =O0or 1 B represents NR 5 or 0 or S or CR 5 R6 or SO or C=O. and R 2 which are identical or different, represent: H, provided that one of the 2 groups is 10 different from H, or -an alkyl or haloalkyl radical containing 1 to 6 carbon atoms or *9 I -an alkoxyalkyl, alkylthioalkyl, alkylsuiphonyl- alkyl, monoalkylaminoalkyl, alkenyl or alkynyl radicalp containing 2 to 6 *carbon atoms or 9 -a dialkylaminoalkyl or cycloalkyl radical containing 3 to 7 carbon atoms or an aryl radical 9oprs Lgphenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl, or methylenedioxyphenyl, optionally substituted by 1 to 3 groups chosen from R 7 orU -an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulphonylalkyl radical, the t-rmrn agyl and iakyt -av.-nrig th i fipjT~ nng ir a.hne or RI and R 2 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 these rings to be fused to a phenyl, optionally substituted by 1 to 3 groups chosen from R,; R 3 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 carbon atoms or a dialkylaminoalkyl, alkoiycarbonylalkyl or 15 N-alkylcarbamoylalkyl group containing 3 to 6 carbon o V 0 :toms or o" a N,N-dialkylcarbamoylalkyl group containing 4 044 Sto 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 R,; R 4 represents: a hydrogen atom when n is equal to 1 or an alkyl group containing 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group containing 2 to 6 carbon atoms or i __CII~-CI- lm *PIPxi~ 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 Pr eec-dN 'j an aryl radical, Qm0a Usg~phenyl, naphthyl, thienyl, furyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl or methylenedioxyphenyl, optionally substituted by 1 to 3 groups chosen from R, or an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulphonylalkyl radical, -th term aryl and alkyl! -hp~rxin hb e f i ci-ii- ns gir-vPn ahnwm or an amino group disubstituted by 2 identical or different -roups chosen from: 0 0- an alkyl radical containing 1 to 6 carbon O" 0 atoms v* an alkoxyalkyl, alkenyl or alkynyl radical containing 3 to 6 carbon atoms a cycloalkyl radical containing 3 to 7 carbon atoms an arylalkyl, .sach as -dofi-ned above. phenyl or naphthyl radical, optionally substituted by 1 to 3 groups chosen from R, or S 25 a thienylmethyl or furfuryl radical a pyrrolidino, piperidino, morpholino or piperazino group, optionally substituted by alkyl containing 1 to 3 carbon atoms; i R 5 represents: except when R 4 is H, or an alkyl, haloalkyl, alkylsuiphonyl or haloalkylsuiphonyl radical containing 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkylsuiphonyl or cyanoalkylsuiphonyl radical containing 2 to 6 carbon atoms or an alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl or cyanoalkoxycarbonyl 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, esPeciaa1Wphenyl- acetyl and phenyipropionyl; arylcarbonyl, e benzoyl, optionally substituted by 1 to 3 groups from R 7 thienylcarbonyl; furylcarbonyl; pyridylcarbonyl; benzyloxycarbonyl; furfuryloxycarbonyl; tetrahydro- furfuryloxycarbonyl; thienylmethoxycarbonyl; pyridyl- methoxycarbonyl; phenoxycarbonyl or (phenylthio)carbonyl, the phenyl being itself optionally substituted by 1 to 3 groups from R,; (alkylthio)carbonyl; (haloalkylthio)carbonyl; (alkoxyalkyithio)carbonyl; (cyanoalkylthio)carbonyl; 4benzylthio)carbonyl; (furfurylthio)carbonyl; (tetrahydrofurfurylthio)carbonyl; (thienylmethylthio)- carbonyl; (pyridylmethylthio)carbonyl; or arylsulphonyl radical or a carbamoyl radical, optionally mono- or disubstituted by an alkyl or haloalkyl group containing 1 to 6 carbon atoms or a cycloalkyl, alkenyl or alkynyl group 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; 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 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; an alkylthioalkylsulphonyl group containing 3 to carbon atoms or a cycloalklsulphonyl group containing 3 to 7 carbon atoms; i R 6 represents: a hydrogen atom or a cyano group or an alkyl group containing 1 to 6 carbon atoms or a cycloalkyl group containing 3 to 7 carbon atoms or an acyl or alkoxycarbonyl group containing 2 to 6 carbon atoms or a benzoyl group, optionally substituted by 1 to 3 R 7 groups; R 7 represents: a halogen atom or an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulphonyl radical containing to 6 carbon atoms or 15 a cycloalkyl, halocycloalkyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio radical containing 3 to 6 carbon aLoms or i e e 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 i a phenyl, phenoxy or pyridyloxy radical, these radicals optionally being substituted; and their salts. .35 Fungicidal compositions according to Claim 3, characterised in that they contain from 0.5 to 95 by weight of compounds according to one of a -I l -U -2X- Claims 1 to Process for the treatment of crops affected or capable of being affected by fungal diseases, characterised in that there is preventively or curatively applied an effective quantity of a compound according to one of Claims 1 to 15 or of a composition according to Claims 23 or 24.
26. Treatment process according to Claim 25, characterised in that the effective dose is between 0.005 and 5 kg/ha.
27. Treatment process according to Claim 26, characterised in that the effective dose is between 0.01 and 1 kc'ha.
28. A compound of Claim 1, a process for the preparation thereof, a fungicidal composition of Claim 23, or a treatment process of Claim 25 substant±illy as hereinbefore described with reference to the Examples. DATED this 27th day of April, 1994. RHONE-POULENC AGROCHIMIE By Its Patent Attorneys DAVIES COLLISON CAVE 940427p:oper\ee30310rhospe78 9404j,p:\oper\ e331rho .spe78 ABSTRACT The invention relates to or 2-imidazoline-5-thione derivatives of general formula (I) in which group W is a sulphur or oxygen atom or an S=O A represents 0 or S n 0 or 1 B represents NR, or 0 or S or CRsR or SO 2 or Sr C I :"i 1 1 i t i C=O RI to R 4 represent a hydrogen atom or a hydrocarbon radical which is optionally substituted, especially by halogen atoms. The invention also relates to the preparation of these compounds and to their use as broad spectrum fungicides.
AU30310/92A 1991-12-20 1992-12-18 Fungicidal 2-amidazolin-5-one and 2-amidazoline-5-thione derivatives Ceased AU651021B2 (en)

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