FR2590573A1 - HETEROCYCLIC COMPOUNDS, PROCESS FOR THE PRODUCTION THEREOF AND FUNGICIDE APPLICATIONS THEREOF - Google Patents

Abstract

The invention relates to the field of pesticides. It relates to new heterocyclic compounds of formula: (CF DRAWING IN BOPI) in which X, Y and Z, which may be identical or different, represent an optionally substituted alkyl, cycloalkyl, aryl, aralkyl (in particular benzyl), alkenyl group. or heterocyclic; or a hydrogen atom, provided that when Y is a hydrogen atom, X is not a methyl group or a hydrogen atom and that when Y is a methyl group, X is not a hydrogen atom . The compounds of the invention are endowed with fungicidal activity.

Description

The present invention relates to heterocyclic compounds useful as

  fungicides, their methods of preparation, fungicidal compositions which

  contain and methods of combating

  especially fungal infections of plants. The invention provides a compound of general formula (I): Y

I (I)

  In which X, Y and Z, which may be the same,

  different, represent a group, possibly

  killed, alkyl, cycloalkyl, aryl, aralkyl (especially benzyl),

  alkenyl or heterocyclic; or a hydrogen atom

  gene; or Z is alkoxycarbonyl, with the proviso that when Y is hydrogen, X is not methyl or hydrogen, and further provided that when Y is methyl, X is not a hydrogen atom. Alkyl groups can be in the form of straight chains or branched chains and preferably contain 1 to

6 carbon atoms.

  Several compounds corresponding to the general formula (I), in which Y is a hydrogen atom and X is a hydrogen atom or a methyl group, which are natural compounds, some endowed with fungicidal activity, have been described in literature and not

  are not claimed as part of this invention.

  tion. Examples of these compounds are thiolutin (I, X = Z = CH3, Y = H) (see The Merck Index, 9th edition, 1976, page 1206, and the references cited therein), holomycin (I, X = Y = H, Z = CH3) (see The Merck Index, 9th Edition, 1976, page 620, and the references cited therein) and xenorhabdin antibiotics (see CSIRO (1984), Australian Patent Application No. 127,365). Compounds (I) derived from natural thiolutin, wherein X is a methyl group and

  Y is a hydrogen atom, are the subject of the British patent

  (1956) published under No. 753,331. Similarly, the compound (I) wherein Y is a methyl group and X

  and Z are both hydrogen atoms, is a

  posed with antibiotic activity (see B. Jensen,

J. Antibiotics, 1969, 22, 231).

  Alkyl groups which are preferred for X, Y and Z are alkyl groups having 1 to 6 atoms

  carbon, especially 1 to 4 carbon atoms. Groups

  Preferred cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The alkyl group in aralkyl groups preferably contains

1 to 4 carbon atoms.

  Preferred alkenyl groups contain 3 to 6 carbon atoms and include an allyl group

  optionally substituted, for example the 3-phenyl-

allyl-1.

  The compounds of the invention may have centers of chirality. Such compounds are obtained

  generally in the form of racemic mixtures. Toute-

  both these and other mixtures can be divided into

  individual isomers by

  in the prior art, and the present invention

covers these isomers.

  Examples of suitable substituent groups

  of the benzene ring for X, Y and Z when

  aralkyl, aralkenyl or aryl, especially benzyl, phenylallyl or phenyl, are phenyl

  optionally substituted and a phenoxy group optionally

  substituted by halo, halogen

  alkyl, alkyl, alkoxy (in particular containing 1 to 4 carbon atoms). The aryl group, in particular the phenyl group,

  advantageously not substituted or advantageously

  1, 2 or 3 substituents on the nucleus, which can

  be identical or different, as defined above.

  Examples of groups X, Y and Z are groups

  phenyl, 2-, 3- or 4-chlorophenyl, 2,4- or 2,6-dichloro-

  phenyl, 2,4- or 2,6-difluorophenyl, 2-, 3- or 4-fluorophenyl

  phenyl, 2-, 3- or 4-bromophenyl, 2-, 3- or 4-methoxy-

  phenyl, 2,4-dimethoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 2-fluoro-4chlorophenyl, 2-chloro-4-fluorophenyl, 2-, 3- or 4-methylphenyl, 2, 3 or 4-ethylphenyl, 2-, 3- or 4-trifluoromethylphenyl, 4-phenylphenyl

  (4-biphenylyl), 2-chloro-4-methoxyphenyl), 2-fluorophenyl

  4-methoxyphenyl, 2-chloro-4-methylphenyl, 2-fluorophenyl

  4-methylphenyl, 4-isopropylphenyl, 2-methyl-4-chloro

  phenyl or 2-methyl-4-fluorophenyl.

  When X, Y and Z represent an alkyl group, it may be a straight-chained or branched-chain alkyl group having 1 to 6, for example 1 to 4 carbon atoms; methyl, ethyl, propyl (n- or isopropyl) and butyl (n-, sec.-, iso- or tert-butyl) are mentioned as examples; when X, Y and Z represent an alkenyl group, it may be

of the allyl group.

  When Z is alkoxycarbonyl, preferred alkoxycarbonyl groups are (C1-C4) alkoxycarbonyl, for example methoxy or ethoxycarbonyl. Examples of the compounds of the invention are illustrated in Table I. They correspond to Formula I and in each case the groups X, Y and Z are as shown in the table. "Ph" represents

  C6H5, i.e., the phenyl group. Approved compounds.

  those in which X is an alkyl group containing 1 to 4 carbon atoms; the benzyl group; phenyl group; an alkoxyphenyl group whose alkoxy group contains 1 to 4 carbon atoms; or

  an allyl group; or those in which Y is hydro-

  gene, the methyl group or phenyl; or those in the-

  Z is an alkyl group containing 1 to 4 carbon atoms and substituted, where appropriate, with fluorine, chlorine or methoxy; or represents a methoxy- or ethoxy-carbonyl group, or represents the 3-phenylallyl-1 group. ZLIT (.Dpp) LOZ amumoo 68-98

SOZ-UO

91Z DD1 bTF7 gilDZOO

SHZ: DZ OD

he úEaD H

113 ZH3 -

  ticf 113l q-d "I0 / D 'x' -ID llv ú vo HeD7-OD il il il il il úE !. [03 ú ll EIID E [In1 uT) s a somO '_ X

uoisni op LUTOc 5 A Sap soa.g nN.

x o <N. s There is

Z-- DN1S - 8

  AI nav a 'q VL o ox Nt Lfl cmJ -ZlD4tld -Zil [tId -ZiD3tid -Z11t3lc1 ZtlOtd -ZlItOHa Il L ICID ú1,3 ú 1s Elto úl,) ti ú ITABLEAUI (Continued) ys OI S. I = r N -X fi Z x X Numbers XYZ Compound Melting Point .. (c) 12 PIICH2-l Cl, Ph 225

-CH2 CH

  PhCH 2 CH 2 CH 2 O 3 96-98 PhCI 2-1 (C 12) 4 CH 3 142-144 PhCH 2 --H C (Cl 3) 3 Oil 16 Ph CH 3 Cl 2 287 17 C 2 H 15 H C 113 223-226 (dec)

18 C215 H CF3 204-205

19 C2II25 3

  CHH2115 219-223 - CH2 CII.C1l2i C3 228-231

CH3 ACH3

  21 - C112 112 H, C15-156 CH1 2 22 p-C1130-C6114-H CH {3a, ru n% FI% FI "" '4 w T A B T. E A U I (Continued) Y

S //S.7___IC _C O Z

  X x Numbers of XYZ Melting Point Compounds - (OC) 23 i-C3H7 t CH3 24 i-C3I7 CH3 Hi n-C41 [9 It CF3 26 n-C3117 HI COOC2H5 27 i-C3H7 fi COOCH3 28 CH3 Ph COOC2H5 29 ClH3 Ph CF3 i-C3t7 H C2OCH3 127-130

31 1_-C3117 H CF3 129-133

32 PlIC [l2 1CH3 C13 / C3

C 186-189

C12

  _ __ _ _ _ __ _ _ _ _ _ _ _ _ _ __ _ _ _ _ _ _ _ _ _ _ __ _ _ _ _ _ _ _ _ _ _ __ _ _ _ _ _ _ _ _ _ _ __ _ _ _ _ _ _ _ _ _ _ __ _ _ _ _ _ _ _ _ _ _ _

  NB. Ph represents phenyl, i.e., C6H5 -Jlji tn o o nC tA The compounds of the invention of general formula (I) can be prepared by the steps illustrated in Schemes 1-4. Throughout Schemes 1-4, the terms Y, Y and Z are as defined above; R1 R2 and R3, which may be the same or different, are alkyl or aralkyl groups; R and R2 may together form part of a ring; and A and B are suitable halogen atoms or leaving groups which may be the same

or different.

  Thus, compounds of the general formula (I) can be prepared by treating compounds of the general formula (II) with an oxidizing agent such as iodine (see, for example, Schmidt and Geiger, Annalen, 1963, 664, 168). or air (see, for example, K. Hagio and N. Yoneda, Chem Pharm Bull, 1974, 47, 1484) in a suitable solvent such as dichloromethane (see

diagram 1).

  Compounds of general formula (II), which may exist as mixtures of geometric isomers, may be prepared from compounds of general formula (III) by treatment with an alkali metal such as lithium (when R = R = benzyl) in a suitable solvent such as liquid ammonia (see, for example, G. Bchi and G. Lukas, J. Amer Chem Soc., 1964, 36,

  5654) or by treatment with salts of transition metals

  such as mercury (II) acetate or acetal

  copper (II) (when R = R = tert-butyl); or 1 2

  R = R = alkylidene, for example methylene or isopropyl

  propylidene) in a suitable solvent such as

  trifluoroacetic acid, followed by treatment with hydrogen sulphide

  gene in a suitable solvent such as dimethyl

  formamide (see, for example, 0. Nishimura, C. Kitada

  and M. Fujino, Chem. Pharm. Bull., 1978, 26, 1576).

  Compounds of general formula (III), which exist as geometric isomeric mixtures which can be separated, can be prepared from compounds of general formula (IV) by treatment with an acylating agent such as acetyl chloride, the presence or absence of an acid acceptor (such as triethylamine) in a suitable solvent such as

  dichloromethane or chloroform or tetrahydro-

  furan and at a suitable temperature (for example

0 to 80 ° C).

  Compounds of general formula (IV) which exist as geometric isomeric mixtures which can be separated can be prepared from compounds of general formula (V) by treatment with a salt of an amine YNH 2, such as acetate ammonium

  or anilinium acetate, with or without a suitable solvent

  nable (such as acetic acid) and at a

  suitable (for example 80 to 160-C).

  Compounds of the general formula (V) which exist as geometric isomeric mixtures which can be separated can be prepared from compounds of the (VI) -A type (which can exist as mixtures of geometric isomers and which are in equilibrium). with (VI) -B compounds by treatment with oxalyl chloride or bromide in the presence of an acid acceptor (such as triethylamine) in a suitable solvent (such as dichloromethane or chloroform) and at a suitable temperature (such

  that a temperature of -78 to 25 C) (diagram 2).

  Alternatively, compounds of general formula (V) may be prepared from esters of general formula (VII) by treatment with a base

  suitable (such as sodium hydride, diisopropyl-

  lithium amide or lithium-hexamethyldisilazide) in a suitable solvent (such as tetrahydrofuran or diethyl ether) and at a suitable temperature

(-78 ° C to 25 ° C).

  In addition, compounds of the general formula (V) can be prepared from compounds of the general formula (IV) by hydrolysis in a suitable solvent (such as water or ethanol) in the presence of a suitable catalyst (such as hydrochloric acid) (see, for example, K. Hagio and N. Yoneda, Chem Pharm Bull.,

1974, 47, 1484) (Scheme 1).

  Esters of the general formula (VII) which exist as geometric isomeric mixtures which can be separated can be prepared from compounds of the general formula (VI) -A (which can exist as mixtures of geometric isomers and which are in equilibrium with (VI) -B compounds by treatment with a suitable acylating agent such as

  ethyloxalyl chloride or methyl chloride

  oxalyl in the presence or absence of an acid acceptor (such as triethylamine) in a suitable solvent such as dichloromethane or chloroform) and at least one

  suitable temperature (such as 0 C).

  Compounds of General Formula (VI) -A

  (which may exist as mixtures of geometric isomers

  and which are in equilibrium with compounds of the type (VI) -B) can be prepared from ketones of the general formula (VIII) by treatment with an amine X-NH 2 in the presence of a dehydrating agent (such as tetrachloride of titanium) in a suitable solvent

  (such as diethyl ether) and at a suitable temperature.

nable (-78 to 25 C).

  Ketones of general formula (VIII) can

  can be prepared from ketones of general formula

  (IX) by treatment with a thiol of general formula

  R SH or R SH in the presence of a base (such as sodium hydride, sodium methoxide) in a suitable solvent (such as diglyme, ethanol or tetrahydrofuran) and at a suitable temperature

  (such as a temperature of -25 to 50 C).

  Alternatively, ketones of the general formula (VIII) can be prepared from 5-keto esters of the general formula (X) by treatment with a salt (such as lithium chloride) in a solvent

  (such as dimethylsulfoxide) and at a

  suitable temperature (such as 110 to 189 ° C) (see, for example, A. P. Krapcho, J. F. Weimaster,

  J.M. Eldridge, E.G.E. Jahngen, Jr., A. J. Lovey, W.P.

  Stephens, J. Org. Chem., 1978, 43, 138) or by decar-

  Boxylation of 5-keto acids of general formula (XI) using standard methods as indicated in the chemical literature (see, for example, H. O. House,

  Modern Synthetic Methods, second edition, page 511).

  5-keto acids of the general formula (XI)

  can be prepared from R-keto esters of

  general mule (X) using standard methods as indicated in the chemical literature (see, for example, H.O. House, Modern Synthetic Methods, second

edition, page 511).

  5-keto esters of the general formula (X)

  can be prepared from esters of general formula

  (XII) or (XIII) by treatment with a base (such as sodium hydride) in a suitable solvent (such as tetrahydrofuran) and at a suitable temperature

  (such as a temperature of 0 to 100 C) (scheme 3).

  Compounds of the general formula (IV), wherein X is Y, which exist as geometric isomeric mixtures which can be separated, can be prepared from compounds of the general formula (V) wherein X is an aryl substituent (such as phenyl) by treatment with a salt of an amine

  Y-NH 2 such as ammonium acetate, with or without

  suitable (such as acetic acid) and at a suitable temperature (such as 80 to 160 ° C) (Figure 4).

SCHEME 1

y s \ S 0

Y (1)

  HS N kz -C HSX CHN N0 m x y Ris Z IlI

R2R I

/ (III)

there

R1 N

CH frTOR

RAS X X

(IV) \

R1S OH

CH 0

R2S X

(V)

SCHEME 2

R! S -OHs I

CHR2 X

RIS x% I RlS

CH ô

I o R2s X (V) oR3 (V _)

(V'I) -B

  AC 2 -z: / CH 2 B C 11 o (IX) R S CH. C.sub.2 -C.sub.OC-C0R.sub.3 O.sub.O, SR.sub.2.sup.-1c: c ': N, C.N.N.X.

(VI) -A

Sa2 he Sa2 Il1 o

(VIII)

  ## EQU1 ##

EO T

7 = X (AI)

SZE HD H1

I VHRHOS

HD ú vWN1IDS

úZS06SZ

(IIIx) EODx Sg - +

(TIIX)

  The compounds of formula I and compositions containing them are variously active against a wide variety of fungal and bacterial diseases, including, for example, against: Plasmopara viticola (mildew) growing on grapevine and

  Phytophthora infestans (downy mildew) develops

  on potato and tomato, and other species of Phytophthora, Phytophthora parasitica, Phytophthora cinnamomi, Phytophthora palmivora and Phytophthora capsici growing on various commercially important crops Pseudoperonospora cubensis growing on cucurbitaceae Peronospora tabacina developing on the tobacco Peronospora parasitica developing on the cabbage Peronospora destructor developing on the onion Bremia lactuca developing on lettuce Pythium species, developing on several

  cultivated plants important from the commercial point of view.

  Other mildew and other fungal diseases

  and bacterial, for example: Venturia inaequalis (scab) developing on apples Pyricularia oryzae developing on rice Cercospora arachidicola developing on

  peanut and other species of the genus Cercospora.

  Erysiphe graminis growing on barley

and other whites.

  Xanthomonas oryzae growing on rice. Some of the compounds also showed a wide range of activities against fungi

  in vitro. They are endowed with activity against various

  sites developing after fruit picking (eg Penicillium digatatum and Italicum grow

  lopper on oranges and Gloeosporium musarum is

  loppant on bananas). In addition, some of the compounds are active as seed disinfectants against:

  Fusarium spp., Septoria spp., Tilletia spp. (it is-

  ie, decay, wheat disease transmitted by seed

  these), Ustilago spp., Helminthosporium spp. developing on cereals, Rhizoctonia solani growing on cotton and developing Corticium sasakii

on rice.

  Compounds can migrate acropetically

in the plant tissue.

  The compounds can be used as

  which for fungicidal purposes, but they are advantageous-

  formulated in compositions for such use. The inventors

  therefore proposes a fungicidal composition comprising

  a compound of general formula (I) as defined above

  above and, optionally, a carrier or diluent.

  The invention also proposes a method

  to fight fungi, which consists of applying

  to a plant, to seeds of a plant or at the place of the plant or seeds, a compound such

as defined above.

  The compounds can be applied from

  for example, they can be applied, formally or non-formulated, directly to the foliage of a plant, or they can also be applied to shrubs and trees, seeds or other which plants, shrubs or trees grow or are to be planted, or they may be applied by spraying, dusting or in cream or paste form or applied as a vapor; or in the form of slow release granules. The application may be of interest to any part of the plant, shrub or tree, for example the foliage, stems, branches or roots, or the soil surrounding the roots, or the seed before it be sown; or the soil in a general way,

  paddy water or hydroponic systems.

  The compounds of the invention may also be injected into plants or trees and may also be applied by spraying onto vegetation

  using electrodynamic techniques of spraying

  tion. The term "plant" as used herein includes seedlings, shrubs

  and trees. In addition, the fungicidal method of the invention

  tion includes preventive, protective, protective

  phylactic and eradication treatment.

  The compounds are advantageously used in agriculture and horticulture in the form of a composition. The type of composition that is used

  in each case depends on the particular purpose

  wise. The compositions can be in the form

  dusting powders or granules comprising the

  active ingredient and a solid diluent or carrier, for example fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, magnesia powder, Fuller's clay, gypsum, Hewitt earth, diatomaceous earth anddelakaolinite These granules may be preformed granules which are suitable for application to the ground without further treatment. These granules can be prepared either by impregnating the active ingredient with pellets of a filler, or by forming pellets of a mixture of the active ingredient and a powder filler. Seed disinfection compositions, for example, may include an agent (such as mineral oil) to facilitate adhesion of the composition to the seeds; alternatively, the active ingredient can be formulated for seed disinfection in

  using an organic solvent (for example N-methyl-

  pyrrolidone or dimethylformamide).

  The compositions may also be in the form of powders, granules or dispersible grains comprising a wetting agent which facilitates the dispersion in liquids of the powder or grains which may also contain fillers and suspending agents. Aqueous dispersions or emulsions can

  be prepared by dissolving one or more ingredients

  active ingredients in an organic solvent, possibly containing

  one or more wetting, dispersing or emulsifying agents and then adding the mixture to water which may also contain one or more wetting, dispersing or emulsifying agents. Suitable organic solvents are dichlorethylene, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylenes, trichlorethylene, furfuryl alcohol, tetrahydrofurfuryl alcohol and ethers. glycol (by

  for example 2-ethoxyethanol and 2-butoxyethanol).

  Compositions for use

  may also be in the form of aerosols.

  in which case the formulation is contained in a pressure vessel in the presence of a propellant

  such as fluorotrichloromethane or dichlorodifluoro-

  methane. The compounds can be mixed in the state

  dry with a pyrotechnic mixture to form a composi-

  able to generate smoke in confined spaces

containing the compounds.

  Alternatively, the compounds can be used in a microencapsulated form. They can also be formulated into biodegradable polymeric formulations to achieve a controlled slow release

of the active substance.

  By incorporating suitable additives, for example additives to improve distribution, adhesion strength and resistance to rain on

  treated surfaces, the differences can be better

  compositions for various purposes.

  The compounds can be used in the form of mixtures with fertilizers (e.g.

  fertilizer containing nitrogen, potassium or phosphorus

* phore). Compositions which comprise only fertilizer granules to which the compound is

  is incorporated, for example in the form of a coating.

  These granules advantageously contain up to

  25% by weight of the compound. The invention thus also proposes

  a fertilizer composition comprising the compound of general formula (I) or a salt or metal complex

of this compound.

  The compositions may also be in the form of liquid preparations for use in baths or by spraying, which are in

  dispersions or aqueous emulsions containing

  the active ingredient in the presence of one or more

  surfactants, for example one or more wetting agents.

  lants, dispersing agents, emulsifiers or suspending agents; or which are formulations

  suitable for use in

  Electrodynamic spraying techniques. The agents mentioned above may be cationic agents,

  anionic or nonionic. Cationic agents

  are quaternary ammonium compounds, for example

  for example, cetyltrimethylammonium bromide.

  Suitable anionic agents are soaps, salts of aliphatic monoesters of sulfuric acid (for example sodium lauryl sulphate) and salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, sodium lignosulphonate, calcium or ammonium, butylnaphthalenesulphonate).

  and a mixture of diisopropyl- and triisopropyl-naphthalene-

sodium ethenesulfonates).

  Suitable nonionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl or cetyl alcohol,

  or with alkylphenols such as octyl- or nonyl-phenol and octyl-

  cresol. Other nonionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of said partial esters with ethylene oxide, and lecithins. Suitable suspending agents are hydrophilic colloids (for example polyvinylpyrrolidone and the sodium salt of carboxymethylcellulose) and vegetable gums (for example gum arabic and

gum tragacanth).

  Compositions for use as aqueous dispersions or emulsions are generally presented in the form of a concentrate containing a high proportion of the active ingredient (s), and the concentrate must be diluted with water.

  before use. These concentrates must often be

  to withstand storage for extended periods and after such storage, they must be able to

  be diluted with water to form

  aqueous solutions which remain homogeneous for a sufficient period of time to be

  the classical and electrodynamic equipment of sprayers

  authorization. Concentrates can contain without

  deny up to 95%, advantageously 3 to 35 ', for ex-

  25 to 60 ° C of one or more active ingredients. These concentrates advantageously contain organic acids (for example alkaryl or arylsulfonic acids such as xylenesulphonic acid or

  dodecylbenzenesulphonic acid), since the pre-

  The presence of these acids may increase the solubility of the active ingredient or ingredients in polar solvents frequently used in concentrates. These also advantageously contain a high proportion of surfactants so as to obtain sufficiently stable emulsions in water. After dilution to form aqueous preparations, these preparations may contain varying amounts

  of one or more active ingredients according to the purpose

  but an aqueous preparation containing 0.0005% or 0.01% to 10% by weight of one or more ingredients

assets can be used.

  The compounds of general formula (I) may be mixed with earth, peat or other rooting media for the protection of plants against fungal diseases transmitted by seed,

transmitted by soil or foliage.

  The compositions of the present invention may also comprise one or more other compounds having biological activity, for example compounds

  endowed with a similar or complementary fungicidal activity

  or compounds that influence the growth of

  plants or endowed with herbicidal or insecticidal activity. -

  The other fungicidal compound may be, for example, a compound that is able to combat diseases of cereal ears (eg wheat) as

  Septoria, Gibberella and Helminthosporium spp.

  seed and soil, and downy mildew and ofdium from grapevine and white and apple scab, etc. These mixtures of fungicides may have a broader field of activity than the compound of general formula (I) alone; in addition, the other fungicide can exert a synergistic effect on the fungicidal activity of the compound of general formula (I). Examples of the other fungicidal compound are: imazalil, benomyl, carbendazim, thiophanate-methyl, captafol,

  captan, sulfur, triforine, dodemorph, tridemorph, pyrazo

  phos, furalaxyl, ethirimol, tecnazene, dimethirimol, bupirimate, chlorothalonil, vinclozolin, procymidone, iprodione, metalaxyl, forsetylaluminum, carboxin, oxycarboxin, fenarimol, nuarimol, fenfuram, metfuroxan,

  nitrothal-isopropyl, triadimefon, thiabendazole,

  diazole, triadimenol, biloxazole, dithianon, binapacryl, quinomethionate, guazitine, dodine, fentin acetate, fentin hydroxide, dinocap, folpet, dichlofluanid, ditalimphos, kitazine, cycloheximide, dichlobutrazole, a dithiocarbamate, a copper compound, a compound

  of mercury, 1- (2-cyano-2-methoxyiminoacetyl) -3-ethyl-

  urea, fenapanil, ofurace, pro-piconazole, etaconazole

and fenpropemorph.

  Suitable insecticides are the

  Pirimor, Croneton, Dimethoate, Metasystox and

thion.

  The other compound influencing growth

  plants can be a compound that destroys the

  its herbs or inhibits the formation of seed carrier, improves the level or duration of plant growth influence of the compounds of general formula (I), inhibits

  selectively less desirable plant development.

  (for example grasses) or to act more rapidly

  more slowly, the compound of general formula

  (I) as an agent influencing the growth of

  your. Some of these other agents are herbicides.

  Examples of advantageous compounds influencing

  plant growth, which can exert a synergism when mixed or used with the compounds of the invention are gibberellins (eg GA3, GA4 or GA7), auxins (eg indole- acetic acid, indole-butyric acid, acid

  naphthoxyacetic acid or naphthylacetic acid), cyto-

  kinins (eg, kinetin, diphenylurea,

  benzimidazole, benzyladenine or benzylamino-

  purine), phenoxyacetic acids (for example 2,4-

  D or MCPA), substituted benzoic acids (for example triiodobenzoic acid), morphotins (for example chlorofluorecol), maleic hydrazide, glyphosate, glyphosine, alcohols and long-chain fatty acids, dikegulac, fluoridamid, mefluidide, substituted quaternary ammonium and phosphonium compounds (eg chlormequat, chlorphonium

  mepiquat), ethephon, carbetamide, 3,6-dichloro-

  methyl anisate, daminozide *, asulam, acid

  abscisic, isopyrimol, 1- (4-chlorophenyl) -

  4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylic acid, hydroxybenzonitriles (e.g., bromoxynil),

  difenzoquat, benzoylprop-ethyl, 3,6-di-

  chloropicolinic and tecnazene. Synergism will most likely occur with those of the above compounds which are quaternary ammonium compounds,

  especially those with an asterisk.

  The use of compounds of general formula

  (I) together with gibberellins may be useful when it is desired to reduce the influence on plant growth by

  example when they are to be used as a fungicide

  des). When the compounds are applied to the soil around

  plants or plant roots, the influence they exert on plant growth can be reduced by also using certain types of

  phenoxybenzoic and their derivatives.

  The following examples illustrate the invention; the temperatures are expressed in degrees centigrade

(C).

EXAMPLE 1

  This example illustrates the preparation of - (methoxyacetylamino) -4-benzyl-1,2-dithiolo [4,3-b] -

  pyrrole-5 (4H) -one (compound N 13 of Table I).

  A solution of tert-

  Butyl mercaptan (41.5 g) in anhydrous methanol (50 ml) was added to a solution of sodium methoxide in anhydrous methanol (formed by the addition of sodium (10.58 g) to anhydrous methanol (200 ml)). The resulting solution

  was cooled to 0 C and a solution of 1,3-dichloro

  acetone (29.21 g) in anhydrous methanol (50 ml) a

  been added in a period of 1 hour. The resulting mixture

  was stirred for another 16 hours at room temperature.

  room temperature, then partitioned between dichloromethane and a dilute solution of sodium hydroxide. The organic phase was dried over magnesium sulphate,

  filtered and evaporated to give a liquid. By distillery

  at 96 ° C / 1 mbar, 1,3-di- (tert-butyl) was obtained.

  1 2 thio) acetone (VII, R = R = t-Bu, see Scheme 2) (26.42 g, 49%). In an alternative method, tert-butyl mercaptan (500 g) was added dropwise over 6.5 hours to a suspension of sodium hydride (% oil dispersion, 163 g) in anhydrous diglyme ( 2.22 liters) under a nitrogen atmosphere. The reaction was exothermic and the rate of addition was adjusted to keep the temperature below

   C. A white suspension formed which thickened

  if the reaction progressed. After stirring overnight, the suspension was diluted with

  400 ml of diglyme and it was cooled to 0-5 C.

  A solution of 1,3-dichloroacetone in diglyme (710 ml) was then added dropwise over a period of 6 hours. The reaction mixture was allowed to warm to room temperature over 1 hour, then methanol (50 ml) was added to destroy the excess sodium hydroxide. The resulting mixture was

  shared between water (4 liters) and toluene (3 liters).

  The aqueous phase was re-extracted with toluene (2 liters), and the combined organic phases

  washed with water (2 x 3 liters), dehydrated and

  centered under vacuum giving 1,3-di- (tert-butyl)

  1 2 thio) acetone (VII, R = R = t = Bu, see scheme 2) (570 g, 88%) which could possibly be used in

  the next synthesis step without further purification.

  A solution of benzylamine (29.8 g) in diethyl ether dehydrated with sodium was added

  (50 ml) to a solution of 1,3-di- (tert-butylthio)

  acetone (25 g) in diethyl ether dehydrated with sodium (150 ml) at room temperature. After 1 hour, tetrachloride was slowly added

  titanium (10.1 g) and stirring was continued at room temperature.

  room temperature for another 3 hours. The resulting mixture

  so much was filtered on celite and the solvent was chased

  under vacuum, giving benzylimine of 1,3-di- (tertiary

  1 2 butylthio) acetone (VI-B, X = Bz, R = R = t-Bu, see Scheme 2) in the form of a brown oil (23.07 g) which was

  used immediately in the next step of the syn-

thesis, without further purification.

  A solution containing benzyl-

  imine of 1,3-di- (t-butylthio) acetone (22.7 g) and triethylamine (7.1 g) in anhydrous dichloromethane (600 ml) to a solution of oxalyl chloride (8.91 g) g) in anhydrous dichloromethane (300 ml) at C. The mixture was stirred for 2 hours, allowed to warm to room temperature, then washed with water, with bicarbonate solution of sodium and with a saturated solution of salt. The organic phase was dried over sodium sulfate, filtered and evaporated to give a brown oil. By trituration with petroleum ether, followed by chromatography of the residue on silica (eluent: mixtures of dichloromethane and diethyl ether), the compound (V, X = Bz, R = R) was obtained. = t-Bu, see Scheme 1) as a brown solid (14.8 g, 56%,

Mp 158 C).

  The compound (V, X = Bz, R = R = t-Bu, see Scheme 1) (1.4 g) and ammonium acetate (2.86 g) were milled together in one unit. fine powder which was then melted at about 140 ° C for 2 hours. We left

  cool the mixture and then it is taken up in dichloromethane

  methane. The organic phase was basified with sodium bicarbonate solution, washed with water and brine, and dried over anhydrous magnesium sulfate. The resulting solution was filtered through a silica buffer (eluent: diethyl ether) to obtain, after evaporation, the compound 1 2 (IV, X = Bz, Y = H, R = R = t-Bu, scheme 1) in the form of a brown solid (1.27 g, 91%)

at 119-120C.

  Methoxyacetyl chloride (0.57 g) was added to a solution of compound (IV, X = Bz, Y = H, 1 2

  R = R 2 = t-Bu, see Scheme 1) (1.0 g) in tetrahydro-

  furan (50 ml) dehydrated on sodium. The resulting solution

  aunt was stirred at room temperature for

  16 hours. Tetrahydrofuran was removed by evaporation

  and replaced by dichloromethane. The resulting solution was washed with sodium bicarbonate solution and dried over anhydrous magnesium sulfate. Filtration over a silica buffer (eluent: diethyl ether) gave the compound (III, X = Bz, Y = H, Z = CH 2 OCH 3, R = R = t-Bu, see Scheme 1) in the form of an oil (0.87 g, 73%), (CDCl3) 1.37 (18H); 3.48

  (3H, S); 4.04 (2H); 5.22 (2H, s); 6.80 (1H, S);

7.25 (5H, n); 8.18 (1H, broad s).

  Mercury (II) acetate (0.60 g) was added to a solution of the compound (II, X = Bz, Y = H, 1 2

  Z = CH 2 OCH 3, R = R = t-Bu) (0.85 g) in trifluoric acid

  acetic acid (20 ml). The resulting solution was stirred at room temperature for 1 hour and the trifluoroacetic acid was then removed by evaporation in vacuo. The solid residue was redissolved in

  N, N-dimethylformamide (20 ml) and the solution was treated

  hydrogen sulfide at room temperature for 2 hours. Then, nitrogen was bubbled through the reaction mixture to remove traces of hydrogen sulfide and the black slurry was filtered through celite. A solution of iodine (0.48 g) in chloroform (20 ml) was added at room temperature and the solution was stirred at room temperature for 30 minutes. The solvents were removed by evaporation under vacuum and the residue was separated on

  silica (eluent: diethyl ether) giving 6-

  (Methoxyacetylamino) -4-benzyl-1,2-dithiolo [4,3-b] pyrrole

  (4H) -one (compound N 13 of Table I) as a yellow solid. (408 mg, 64%), mp 96-98 ° C (CDCl3) 3.49 (3H, s); 4.02 (2H,

  S); 4.99 (2H, s); 6.48 (1H, s); 7.26 (5H, M); 8.50

  (1H, broad s); m / e 334 (M +)., 289, 275, 261, 241, 91, 45.

EXAMPLE 2

  An emulsifiable concentrate was prepared by mixing the ingredients and stirring the mixture

  until all the constituents are dissolved.

  Compound of Example 1 10% Dichlorethylene 40% Calcium Dodecylbenzenesulfonate 5% "Lubrol" L 10% "Aromasol" H 35%

EXAMPLE 3

  A composition in the form of grains that easily dispersed in a liquid, for example water, was prepared by grinding together the first three

  ingredients in the presence of added water and then

  poring with stirring sodium acetate. The mixture

  resulting product was dried and sieved to 0.152

  0.353 mm to obtain the desired diameter of the grains.

  Compound of Example 2 50% "Dispersol" T 25% "Lubrol" APN5 1.5% Sodium acetate 23.5%

EXAMPLE 4

  The ingredients were all ground together

  to produce an easy-to-dispense powder formulation

stick in liquids.

  Compound of Example 3 45% "Dispersol" T 5% "Lissapol" NX 0.5% "Cellofas" B600 2% Sodium acetate 47.5%

EXAMPLE 5

  The active ingredient has been dissolved in a

  solvent and the resulting liquid was sprayed

  on the kaolinite granules. The solvent was then evaporated off to obtain a granular composition. Compound of Example 4 5% kaolinite granules 95%

EXAMPLE 6

  A composition suitable for use in seed disinfection has been prepared by mixing

the three ingredients.

  Compound of Example 5 50% Mineral Oil 2% Kaolinite 48%

EXAMPLE 7

  A powder for dusting was prepared in

  mixing the active ingredient with talc.

  Compound of Example 6 5% Talc 95%

EXAMPLE 8

  A colloidal formulation was prepared by grinding the constituents indicated below with a ball mill and then forming an aqueous suspension of

ground mixture with water.

  Compound of Example 7 40% "Dispersol" T 10% "Lubrol" APN5 1% Water

EXAMPLE 9

  A powdered formulation was prepared

  persible by mixing together the ingredients listed below and then grinding the mixture until

  all components are thoroughly mixed.

  Compound of Example 8 25% "Aerosol" OT / B 2% "Dispersol" A.C. 5% Kaolinite 28% Silica 40%

EXAMPLE 10

  This example illustrates the preparation of a dispersible powder formulation. The ingredients were mixed and the mixture was then ground in

a pulverizer.

  Compound of Example 9 "Perminal" BX "Dispersol" T Polyvinylpyrrolidone Silica Kaolinite% 1%%%% 34%

EXAMPLE 11

  The ingredients listed below have been formulated as a dispersible powder by mixing, then

grinding of these ingredients.

  Compound of Example 10 25% "Aerosol" OT / B 2% "Dispersol" A 5% Kaolinite 68% In Examples 2 to 11, the proportions

  indicated ingredients are by weight. The other components

  Table I have all been formulated in the same way

than in Examples 2 to 11.

  An explanation of the composi-

  tions or substances represented by the various

  trademarks and trade names mentioned above

above.

LUBROL L:

AROMASOL H:

DISPERSOL T and AC:

LUBROL APN5:

  condensation product of nonylphenol (1 mole) with ethylene oxide (13 moles) solvent consisting of a mixture of alkylbenzenes mixture of sodium sulfate and a condensation product

formaldehyde with naphtha

  sodium ethenesulphonate condensation product of nonylphenol (1 mole) with naphthalene oxide (5.5 moles) CELLOFAS B600: sodium carboxymethylcellulose used as thickener LISSAPOL NX: condensation product of nonylphenol (1 mole) with the oxide of ethylene (8 moles) AEROSOL OT / B: sodium dioctylsulfosuccinate PERMINAL BX: sodium alkylnaphthalenesulphonate.

EXAMPLE 12

  The compounds have been tested against various fungal diseases of plants, mainly of the foliar type. The techniques used were as follows: For all trials, plants were grown in John Innes pot culture compost.

  (N 1 and 2) in miniature pots 4 cm in diameter.

  The test compounds were formulated either by ball mill milling with aqueous Dispersol T or as a solution in acetone or

  an acetone / ethanol mixture which has been diluted

  desired treatment immediately before use. The solutions

  tions or suspensions (100 ppm ai) were spray applied to the foliage and applied to the plant roots by the soil. Sprays were applied to maximum retention and root watering to a concentration

  final equivalent to about 40 ppm i.a./sol dry.

  "Tween 20" was added, to a final concentration of 0.05%, when the sprayable compositions

  have been applied to cereals (i.a. means

active ").

  Most of the trials were protective trials in which the compound was applied to soil and roots and foliage 1 or 2 days before

  inoculation of the plant with the pathogen.

  Foliar pathogens were applied by spraying in the form of suspensions

  spores on the leaves of the test plants.

  After inoculation, the plants were installed in a suitable environment to allow

  infection to develop, then they were made

  until the illness is ready for evaluation.

  ation. The time elapsed between inoculation and

  Assessment can vary from 4 to 14 days depending on the disease

and the environment.

  Inhibition of the disease was noted according to the following rating scale: 4 = no disease 3 = traces up to 5% disease on untreated plants 2 = 6-25% disease untreated plants 1 = 26-59% disease on untreated plants 0 = 60-100% disease on plants

untreated.

  The results are shown in Table II.

TABLE II

  N PLUC'INIA VENTURIA PIRICULARIA CERC'WPORA PLASMOPAIA COMPOUND RIlXJNI) l 'A INAEQUA [IIS ORYZAE AII-IWIDIOIA VIl'ICO [A (wheat) (apples) (rice) (peanuts) (vine)

I O 4 A3 0 3

2 O PR 0 PR 3

3 O PR 3 () 4

4 3 o 2 1 3 1 O t 3 3

6 O 4 0 3 4

7 4 O O 0 4

n O O 0 4 4

9 4 4 3 0 4

2 4 3 1 4

11 0 0 O I 0

12 3 3 2 O 2

13 3 3 0 3 3

14 * 2 3) I 4

16k O O) PR 2

17 O 4) 4 4

lla 4 4 2 2 4

19 * 0 0 1

22 0 O O) 1

27 3 4 0 O 4

28 3 C) O 0 4

  PR - no results * foliar spray at 25 ppm only o cw C> -4

Claims (12)

  1. Compound, characterized in that it corresponds to the general formula (I): Y S NsC / Z O s - I   X x wherein X, Y and Z, which may be the same or different, represent an optionally substituted group, alkyl, cycloalkyl, aryl, aralkyl, alkenyl or a heterocyclic group; or a hydrogen atom; or Z is an alkoxycarbonyl group provided that when Y is a hydrogen atom,   X is not a methyl group or a hydrogen atom   gene; and further provided that when Y is a   methyl group, X is not a hydrogen atom.   The compound according to claim 1, wherein one or more of X, Y and Z represent an alkyl group containing 1 to 6 carbon atoms, which   is not substituted or substituted by one or more   halogen atoms, or one or more of X, Y and Z are cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.   3. A compound according to claim 2, wherein   in that the alkyl group contains 1 to 4 atoms of carbon.   4. A compound according to claim 1,   in that one or more of X, Y and Z represent   an alkenyl group containing 3 to 6 carbon atoms.   5. A compound according to claim 1,   wherein one or more of the groups X, Y and Z represent an aralkyl, aralkyl or aryl group optionally substituted by one or more halo, haloalkyl, alkyl, alkoxy, phenyl substituents.   Substituted and phenoxy optionally substituted.   6. A compound according to claim 5, which is   wherein one or more of X, Y, and Z are phenyl or a benzyl group or an allylphenyl group optionally substituted in the benzene ring with one or more halo, C 1 -C 4 alkyl, C 1 -C 6 haloalkyl substituents. CL,: phenyl or phenoxy.   7. The compound of claim 1, wherein   characterized in that X is a C to B alkyl group 1 4   zyl, phenyl, (C1-C4) alkoxy phenyl or methyl.   8. Compound according to claim 1 or   claim 7, characterized in that y tst the hydro-   gene, the methyl group or the phenyl group.   9. Composed according to one of the following:   Claims 1, 7 and 8, characterized in that Z is   a C1-C5 alkyl group optionally substituted with fluorine or chlorine or a lethoxy radical, or represents a methoxy- or ethoxyc group; rbonyle or a 3-phenylallyl-1 group.   10. Intermediates useful for the repair of the compounds according to claim 1, in that they correspond to the formula (VIII) or (IV) of which 1 2   R and R, which may be the same or different, G are alkyl or aralkyl groups and X and - are as defined in any one of reverberations 1 to 9. Intermediates cleaving reen cation 10, characterized in that R and R represent a group _5 tertio-bu.tyle.   12. Fungicidal Composition, Characterized   that it comprises a compound according to any   Claims 1 to 9 and a carrier or diluent.   13. Protection against fungi, which consists in applying to a plant of the plant or to the site of the plant the seed - compound according to any one of claims I to 9 or a composition following ndication 12.   in that of character or at or of r the rev