WO2007065661A1 - Derives biphenyle portant un groupe acetylene, convenant comme microbiocides - Google Patents

Derives biphenyle portant un groupe acetylene, convenant comme microbiocides Download PDF

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WO2007065661A1
WO2007065661A1 PCT/EP2006/011719 EP2006011719W WO2007065661A1 WO 2007065661 A1 WO2007065661 A1 WO 2007065661A1 EP 2006011719 W EP2006011719 W EP 2006011719W WO 2007065661 A1 WO2007065661 A1 WO 2007065661A1
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alkyl
compound
haloalkyl
halo
formula
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PCT/EP2006/011719
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English (en)
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Josef Ehrenfreund
Harald Walter
Camilla Corsi
Hans Tobler
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Syngenta Participations Ag
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • 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
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
    • A01N35/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond

Definitions

  • the present invention relates to novel carboxamides derived from novel ortho- substituted anilines.
  • the carboxamides have microbiocidal activity and, in particular, fungicidal activity.
  • the invention also relates to the preparation of these compounds, to the novel ⁇ rt/io-substituted aniline intermediates used in their preparation, to
  • compositions which comprise at least one of the novel carboxamides as an active ingredient, to the preparation of the compositions and to the use of the active ingredients or compositions in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, especially fungi.
  • the present invention provides a compound of formula (I):
  • E is aryl or a 5- or 6-membered heterocyclic ring containing one to three heteroatoms, independently selected from oxygen, nitrogen and sulphur, each aryl group or heterocyclic ring being substituted by the groups R 3 , R 4 and R 5 ;
  • each R 1 where there is more than one, is independently halo, Ci -2 alkyl, C ⁇ haloalkyl or
  • n is 0 or an integer of from 1 to 4;
  • R 2 is -B ⁇ CCR ⁇ NCOR 8 ), -B 2 -N(R 9 )-C(X)-(YR 10 ), cyano-C,. 6 alkyl, cyano-C 1-6 haloalkyl or cyano-C 3-7 cycloalkyl optionally substituted, where the size of the cycloalkyl ring allows, with 1 to 6 methyl groups and/or halogen atoms;
  • R 3 , R 4 and R 5 are each, independently, H, halo, cyano, nitro, formyl, C ⁇ alkyl,
  • A is one of the groups A 1 , A 2 or A 3 :
  • R 6 is halo, C ⁇ alkyl, C 1-4 haloalkyl, Ci. 4 alkoxy, C 1-4 haloalkoxy, Ci -4 alkylthio or
  • n is 0 or an integer of from 1 to 4;
  • B 1 is a bond or a Ci -8 alkylene bridge
  • B 2 is a Cj. 8 alkylene bridge
  • R 7 is hydrogen, Q -4 alkyl, C ⁇ aloalkyl or C 3-7 cycloalkyl
  • R 8 is Ci ⁇ alkyl, Ci -6 haloalkyl, C 3-6 alkenyl, C 3-6 haloalkenyl, C 3 . 6 alkinyl, C 3-7 cycloalkyl, C 3-7 halocycloalkyl or C 3-7 cycloalkyl-Ci. 2 alkyl;
  • R 9 is hydrogen, Ci- 6 alkyl, Ci ⁇ haloalkyl, C 3-6 alkenyl, C 3 . 6 haloalkenyl, C 3-6 alkinyl, C 3 . 7 cycloalkyl, C 3 . 7 halocycloalkyl or C 3 . 7 cycloalkyl-C 1-2 alkyl;
  • R 10 is Ci -4 alkyl or Ci -4 haloalkyl
  • Y is -O- or -S-.
  • Halo either as a lone substituent or in combination with another substituent (e.g. haloalkyl) is generally fluoro, chloro, bromo or iodo, usually fluoro, chloro or bromo and typically fluoro or chloro.
  • Alkyl moieties used in all substituent definitions with the exception of R 2 are straight or branched chains and, depending on whether they contain 1 or 2, 1 to 4 or 1 to 6 carbon atoms, are, for example, methyl, ethyl, rt-propyl, n-butyl, /z-pentyl, n-hexyl, wo-propyl, sec-butyl, w ⁇ -butyl, terf-butyl, rce ⁇ -pentyl, rc-hexyl or 1,3-dimethylbutyl.
  • alkyl moities are methyl or ethyl.
  • Alkyl moieties used in the substituent definition of R 2 are straight or branched chains and are, for example, methyl, ethyl, n-propyl, w ⁇ -propyl, sec-butyl, wo-butyl, tert-buty ⁇ or neo-pentyl.
  • Prefered definitions for R 2 are substituents R 2 a to R 2 m.
  • Haloalkyl moieties are alkyl moieties which are substituted by one or more of the same or different halogen atoms and are, for example, monofluoromethyl,
  • difluoromethyl trifluoromethyl, monochloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2,2-difluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl, 1-fluoroethyl, 2- chloroethyl, pentafluoroethyl, l,l-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl, and typically trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.
  • Alkoxy is, for example, methoxy, ethoxy, propoxy, /s ⁇ -propoxy, n-butoxy, iso- butoxy, sec-b ⁇ Xoxy and tert-butoxy , and usually methoxy or ethoxy.
  • Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2- difluoroethoxy and 2,2,2-trichloroethoxy, and usually difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.
  • Alkylthio is, for example, methylthio, ethylthio, propylthio, /so-propylthio, n- butylthio, wo-butylthio, sec-butylthio or t ⁇ rt-butylthio, and usually methylthio or ethylthio.
  • Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, /r-propoxyethyl, /s ⁇ propoxymethyl or /sopropoxyethyl.
  • Alkenyl and alkynyl radicals are derived from the alkyl radicals mentioned.
  • the alkenyl and alkynyl groups can be mono- or di-unsaturated, alkenyl is, for example, allyl; alkinyl is, for example, propargyl.
  • Cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.
  • the aryl group that E may be includes phenyl, naphthyl, anthracyl, fluorenyl and indanyl, but is usually phenyl.
  • the heterocyclic ring that E may be includes any 5- or 6-membered heterocyclic ring containing one to three oxygen, nitrogen or sulphur heteroatoms.
  • heterocyclic rings are pyrrolyl, thienyl, pyrazolyl, thiazolyl, oxazolyl, imidazolyl, triazolyl, thiadiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, oxazinyl, thiazinyl, triazinyl, 3,4-dihydro-2H-pyran, 3,4-dihydro-2H-thiinyl and 2,3-dihydro-[l,4]oxathiinyl and their 4-oxides and 4,4-dioxides.
  • the heterocyclic ring contains at least one substituent, which is one of the groups R 3 , R 4 and R 5 , with a value other than H.
  • Typical values of the groups R 3 , R 4 and R 5 are H, fluoro, chloro, bromo, iodo, cyano, methyl, ethyl, trifluoromethy], difluoromethyl and monofluoromethyl.
  • the compounds of formula (I) may exist as different geometric or optical isomers or in different tautomeric forms. These may be separated and isolated by well-known (usually chromatographic) techniques, and all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms, such as deuterated compounds, are part of the present invention.
  • E, R 1 , A and n are as defined above and R 2 is cyano-Cj-ealkyl, cyano-C 1-6 haloalkyl, or cyano-C 3 . 7 cycloalkyl optionally substituted, where the size of the cycloalkyl ring allows, with 1 to 6 methyl groups and/or halogen atoms.
  • R 7 is preferably hydrogen, methyl, ethyl or trifluoromethyl.
  • R is preferably methyl, ethyl, trifluoroethyl or cyclopropylmethyl.
  • R 7 is preferably hydrogen, methyl, ethyl or trifluoromethyl and R 8 is preferably methyl, ethyl, trifluoroethyl or cyclopropylmethyl.
  • E, R 1 , A and n are as defined above and R 2 is -B 2 -N(R 9 )-C(X)-(YR 10 ).
  • Y is preferably -O-.
  • R 9 is preferably hydrogen, methyl or ethyl, most preferably methyl.
  • R 10 is preferably methyl, ethyl or isopropyl.
  • Y preferably -O-
  • R 9 is preferably hydrogen, methyl or ethyl
  • R 10 is preferably methyl, ethyl or isopropyl.
  • R 1 , R 2 , A and n are as defined above and E is one of E 1 to E 1 :
  • R a is H, Ci -4 alkyl, Ci -2 haloalkyl, Ci -4 hydroxyalkyl, C] -4 alkoxy(Ci -4 )alkyl or Ci -4 alkylthio(C ]-4 )alkyl;
  • R b is H, halo, cyano, formyl, Ci -2 alkyl, Ci -2 haloalkyl or Ci -2 haloalkoxy;
  • R c is H or halo
  • R d is halo, Ci -2 alkyl, Ci -2 haloalkyl, Ci -2 haloalkoxy or Ci -2 haloalkylthio;
  • R e and R f are independently H, halo, Ci -4 alkyl or Ci -4 haloalkyl;
  • R 8 is halo, cyano, Ci -2 alkyl, Ci -2 haloalkyl, Ci -2 haloalkoxy or Q -2 haloalkylthio;
  • R h is halo, cyano, Ci -2 alkyl, Ci -2 haloalkyl or Ci -2 haloalkoxy;
  • R k is Ci -4 alkyl or Cj -4 haloalkyl
  • R m is H, Ci -4 alkyl, C 1-2 haloalkyl, Ci -4 alkoxy(C M )alkyl or C] 4 alkylthioCQ ⁇ alkyl;
  • R n is halo, Ci -2 alkyl or C ]-2 haloalkyl
  • R° is halo, Ci -2 alkyl, Cj -2 haloalkyl or Ci -2 haloalkoxy;
  • R p is halo, cyano, Ci_ 2 alkyl or Ci -2 haloalkyl
  • R q is halo, Ci -2 alkyl or Ci -2 haloalkyl
  • R r is halo or Ci -2 haloalkyl
  • R a is methyl
  • R b is methyl if R c is halo (especially fluoro or chloro) or otherwise
  • R b is halo, cyano or C 1-2 haloalkyl (especially trihalomethyl, dihalomethyl or monohalomethyl, where halo is fluoro, chloro or bromo, and more especially trifluoromethyl, difluoromethyl or monfluoromethyl)
  • R c is H or fluoro
  • R d is chloro, trifluoromethyl or difluoromethyl;
  • R e and R are independently H or methyl;
  • R s is halo, trifluoromethyl or difluoromethyl;
  • R h is halo, trifluoromethyl or difluoromethyl;
  • R k is chloro, trifluoromethyl or difluoromethyl;
  • R m is methyl;
  • R n is trifluoromethyl or difluoromethyl or difluoromethyl
  • R 2 , A, E and n are as defined above and R 1 is halo, C 1-2 haloalkyl or C 1-2 haloalkoxy.
  • R 1 is halo, C 1-2 haloalkyl or C 1-2 haloalkoxy.
  • n is 0, 1 or 2, and more preferably 0 or 1 . If n is 1 or 2 R 1 is preferably halo, especially F
  • R 1 , R 2 , A, E and n are as defined above and
  • R 6 is halo, C 1-2 haloalkyl or C 1-2 haloalkoxy.
  • m is 0, 1 or 2, and more preferably 0 or 1 . If m is 1 or 2 R 6 is preferably halo, especially F and/or Cl.
  • R 1 , A, E, and n are as defined above and R 2 ' is one of R 2 a to R 2 m:
  • R 2 a to R 2 m hydrogen atoms attached to a carbon atom are depicted as H, H 2 or H 3 depending on the number of hydrogen atoms attached to said carbon atom. Said hydrogen atoms may be located in the schematic drawing above, below, right or left from said carbon atom.
  • R 1 , A, E, and n are as defined above and R 2 is one of R 2 a' to R 2 u':
  • radicals R 2 a' to R 2 u' hydrogen atoms attached to a carbon atom may be depicted as H, H 2 or H 3 depending on the number of hydrogen atoms attached to said carbon atom. Said hydrogen atoms may be located in the schematic drawing above, below, right or left from said carbon atom. Also, radicals R 2 a ⁇ R 2 b ⁇ R 2 c ⁇ R 2 d', R 2 e', R 2 f , R 2 g' and R 2 h' cover syn- and anti-isomeric forms of the oxime
  • R a' covers the isomeric forms R a' -(syn) and R a'-(anti) ChL O -CH,
  • A is A 1 , A 2 or A 3 (especially A 1 );
  • E is E 1 , E 4 , E 5 , E 6 , E 7 , E 8 , E 9 , E 10 , E 11 or E 12 (especially E 1 , E 5 , E 8 or E 10 , and particularly E 1 );
  • R a and R m are both methyl;
  • R b is methyl, cyano, iodo, trifluoromethyl or difluoromethyl (especially trifluoromethyl or difluoromethyl);
  • R c is H or fluoro;
  • R g , R k , R°, R p , R q and R r are all trifluoromethyl;
  • R h is chloro;
  • R n is
  • R 2 is R 2 a, R 2 b, R 2 C, R 2 d, R 2 e, R 2 f, R 2 g, R 2 h, R 2 k ,R 2 m, R 2 a', R 2 b', R 2 c', R 2 d ⁇ R 2 e', R 2 f, R 2 g', R 2 h', R 2 k' ,R 2 m', R 2 n', R 2 p', R 2 q ⁇ R 2 r', R 2 s', R 2 t'or R 2 u'; and m and n are both 0.
  • R c is H or fluoro
  • R 2 is R 2 a, R 2 b, R 2 C, R 2 d, R 2 e, R 2 f, R 2 g, R 2 h, R 2 k, R 2 m, R 2 a', R 2 b', R 2 c', R 2 d', R 2 e', R 2 T, R 2 g ⁇ R 2 h', R 2 k' ,R 2 m ⁇ R 2 n', R 2 p', R 2 q', R 2 r', R 2 s ⁇ R 2 t'or R 2 u'; and m and n are both 0.
  • A has one of the values A 1 to A 3 defined above in which m is 0, E has one of the values E 1 to E 12 defined above for which the values R a to R r are given in the tables, R 2 has one of the values R 2 a to R 2 m and R 2 a' to R 2 u' defined above and n is 0.
  • Table 5 shows the melting point (m.p.) or molecular peak in the mass spectra (MS) of compounds in Tables 1 to 4.
  • compounds of the formula (I), where E, A, R 1 , R 2 and n have the meanings given above, may be prepared by reacting a compound of the formula (IH), where E has the same meaning as in formula (I) and X 1 is halogen, hydroxy or C 1-6 alkoxy, but preferably chloro or fluoro, with a compound of the formula (II), where R 1 , R 2 and n have the same meaning as in formula (I).
  • the reaction is carried out in the presence of a base, such as triethylamine, H ⁇ nigs base, sodium bicarbonate, sodium carbonate, potassium carbonate, pyridine or quinoline, but preferably triethylamine, and in a solvent, such as diethylether, tert-butyl methyl ether,
  • tetrahydrofuran methylene chloride, chloroform, N, ⁇ f-dimethylformamide or N- methylpyrrolidinone, for between 10 minutes and 48 hours, preferably 12 to 24 hours, and between O 0 C and reflux, preferably 20 to 25 0 C.
  • the reaction may be carried out in the presence of a strong base, for example sodium hydride or sodium hexamethyldisilazane, in a dry polar solvent, preferably tetrahydrofuran, at a temperature between -1O 0 C and the boiling point of the solvent, preferably at ambient temperature.
  • a strong base for example sodium hydride or sodium hexamethyldisilazane
  • a dry polar solvent preferably tetrahydrofuran
  • a coupling agent such as benzotriazol-l-yloxytris(dimethyl- amino) phosphoniumhexafluorophosphate, bis-(2-oxo-3-oxazolidinyl)-phosphinic acid chloride (BOP-Cl), ⁇ f.W-dicyclohexylcarbodiimide or lj'-carbonyl-diimidazole, or an activating agent, such as oxalylic acid chloride, may be used.
  • reaction shown in Scheme 1 may also be carried out where there is a functional group in place of R , which is converted to R later in one or more synthetic steps.
  • Such functional group interconversions are standard procedures for a person skilled in the art.
  • the compounds of the formula (III) are known compounds and may be prepared as described in the chemical literature.
  • the osubstituted anilines of formula (E) are, however, novel compounds, forming another aspect of the present invention, and may be prepared as described below with reference to Scheme 2.
  • the anilines of the formula (II) may be prepared from compounds of the formula (IV), where A has the meaning given above, X is nitro, amino or a protected amino group and X ⁇ 4 i•s R , which has the meaning defined above, or a functional group that can be converted into R 2 by chemical manipulations well known to a person skilled in the art.
  • X 2 is nitro
  • the nitro group can be converted to an amino group by reduction or catalytic hydrogenation, using standard techniques well known in the art. If X 2 is is a protected amino group and X 4 is R 2 , it can be deprotected to form the aniline (II).
  • X 4 is a residue that can be converted into R 2 by chemical manipulation, the conversion may be performed either on the compound of the formula (IV) or on the acetylene of the formula (V).
  • Preferred residues are Ci -6 alkyl (branched or linear), C 1-6 haloalkyl containing from 1 to 6 halogen atoms or C 3-7 cycloalkyl, optionally substituted with 1 to 6 methyl groups or halogen atoms, which contains a functional group that can be converted to a cyano entity by known methods in one or several chemical steps.
  • Examples of such groups are common leaving groups for nucleophilic substitutions like halogens, sulfonates, tosylates, hydroxyl groups etc., which can be displaced by cyano via nucleophilic substitution, or groups which can be converted in one or more steps via at least one elimination step to nitriles.
  • Examples of such groups are carboxylic acid, ester, amide, keto and aldehyde groups.
  • Another method for the conversion of X 4 to R 2 is via the formation of free or protected cyanohydrins. .
  • the (protected) OH of the cyanohydrin can then be further transformed, e.g to halogen by halogenation, especially by fluorination, or to hydrogen by reductive methods.
  • T represents a functional group which can be converted to oximes e.g. by reaction with hydroxyl amines (or their salts) which are substituted or not substituted at the oxygen.
  • functional groups T are the aldehyde and keto group. If said oximation is performed with hydroxylamine (or its salt), the resulting oxime can be further modified to form the desired R 2 for example by O-functionalisation with R 8 L (L is a common leaving group for nucleophilic substitution as mentioned above).
  • Compounds of the formula (IV) may be prepared from a compound of the formula (VI), where X has the meaning given above and X is a functional group which allows the insertion of Pd(O) into its connecting bond, such as halo (preferably chloro, bromo or iodo), OSO 2 L 1 (where L 1 is alkyl or haloalkyl) or OP(O)(O-alkyl) 2 , with an alkynyl compound of the formula (V), where X 4 has the meaning given above, using the well known Sonogashira coupling methodology.
  • halo preferably chloro, bromo or iodo
  • OSO 2 L 1 where L 1 is alkyl or haloalkyl
  • OP(O)(O-alkyl) 2 OP(O)(O-alkyl) 2
  • acetylenes of the formula (V) are known compounds. Others can be prepared from suitable precursors by methods described in the literature. Aldehydes of the formula X 4 -CHO are especially versatile precursors for such acetylenes because they can be easily converted into them in one or two steps using known techniques (see, for example,_G.I.Roth et.al., Synthesis, 2004, 59 and references therein).
  • Aldehydes of the formula X 4 -CHO are known or can be conveniently prepared by well known literature methods, for example, by the oxidation of the corresponding alcohols X 4 -CH 2 OH or by the reduction of the corresponding carboxylic acids or derivatives (acid chlorides, esters, amides, etc.).
  • ort/r ⁇ -substituted anilines of the general formula (II) are novel compounds and form a further aspect of the present invention.
  • the invention includes a compound of the formula (II):
  • n is 0, 1 or 2, and more preferably 0.
  • R 1 , R 2 and n are as defined above and A is A 1 or A 3 , preferably A 1 .
  • R 6 in A 1 is preferably halo when m is other than 0.
  • m is preferably 1 or 2.
  • R 1 , A and n are as defined above and R 2 is cyano-C 1-6 alkyl, cyano-C 1-6 haloalkyl, cyano-C 3 . 7 cycloalkyl optionally substituted, where the size of the cycloalkyl ring allows, with 1 to 6 methyl groups and/or halogen atoms.
  • R 1 , A and n are as defined above and R 2 is -B 2 -N(R 9 )-C(X)-(YR 10 ).
  • R is one of R a to R k.
  • anilines are illustrated by the individual compounds of formula (II) listed below in Table 6, in which characterising data is also included.
  • A has one of the values A 1 to A 3 defined above in which m is 0, R 2 has one of the values R a to R m and R a' to R u' defined above and n is 0.
  • microorganis C ]-6 ms such as fungi, bacteria or viruses.
  • the invention relates to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a compound of formula (I) is applied as acitve ingredient to the plants, to parts thereof or the locus thereof.
  • the compounds of formula (I) according to the invention are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and are used for protecting numerous useful plants.
  • the compounds of formula (I) can be used to inhibit or destroy the diseases that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later e.g. from phytopathogenic microorganisms.
  • compounds of formula (I) as dressing agents for the treatment of plant propagation material, in particular of seeds (fruit, tubers, grains) and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
  • the compounds of formula (I) according to the invention may be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage or in hygiene management.
  • the compounds of formula (I) are, for example, effective against the
  • phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis,
  • novel compounds of formula (I) are effective against phytopathogenic bacteria and viruses (e.g. against Xanthomonas spp, Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus).
  • useful plants to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado,
  • cinnamomum camphor
  • plants such as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.
  • useful plants is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate- synthase) inhibitors, GS (glutamine synthetase) inhibitors) as a result of conventional methods of breeding or genetic engineering.
  • herbicides like bromoxynil or classes of herbicides
  • ALS inhibitors for example primisulfuron, prosulfuron and trifloxysulfuron
  • EPSPS 5-enol-pyrovyl-shikimate-3-phosphate- synthase
  • GS glutamine synthetase
  • crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® , Herculex I® and LibertyLink®.
  • useful plants is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • useful plants is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-O 392 225).
  • PRPs pathogenesis-related proteins
  • Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-O 392 225, WO 95/33818, and EP-A-O 353 191.
  • the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • locus of a useful plant as used herein is intended to embrace the place on which the useful plants are growing, where the plant propagation materials of the useful plants are sown or where the plant propagation materials of the useful plants will be placed into the soil.
  • An example for such a locus is a field, on which crop plants are growing.
  • plant propagation material is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. Preferably "plant propagation material” is understood to denote seeds.
  • the compounds of formula (I) can be used in unmodified form or, preferably, together with carriers and adjuvants conventionally employed in the art of formulation. Therefore the invention also relates to compositions for controlling and protecting against phytopathogenic microorganisms, comprising a compound of formula (I) and an inert carrier, and to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a composition, comprising a compound of formula (I) as acitve ingredient and an inert carrier, is applied to the plants, to parts thereof or the locus thereof.
  • compositions are conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayabble or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances.
  • the methods of application such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • the compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
  • Suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890.
  • the compounds of formula (I) or compositions, comprising a compound of formula (I) as acitve ingredient and an inert carrier can be applied to the locus of the plant or plant to be treated, simultaneously or in succession with further compounds.
  • further compounds can be e.g. fertilizers or micronutrient donors or other preparations which influence the growth of plants. They can also be selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
  • a preferred method of applying a compound of formula (I), or a composition, comprising a compound of formula (I) as acitve ingredient and an inert carrier is foliar application.
  • the frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen.
  • the compounds of formula (I) can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field.
  • the compounds of formula (I) may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
  • a formulation i.e. a composition comprising the compound of formula (I) and, if desired, a solid or liquid adjuvant, is prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface-active compounds (surfactants).
  • extenders for example solvents, solid carriers and, optionally, surface-active compounds (surfactants).
  • the agrochemical formulations will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the compound of formula (I), 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant.
  • Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 1Og to lkg a.i./ha, most preferably from 2Og to 60Og a.i. /ha.
  • convenient rates of application are from lOmg to Ig of active substance per kg of seeds.
  • the rate of application for the desired action can be determined by experiments. It depends for example on the type of action, the developmental stage of the useful plant, and on the application (location, timing, application method) and can, owing to these parameters, vary within wide limits.
  • the compounds of formula (I), or a pharmaceutical salt thereof, described above may also an advantageous spectrum of activity for the treatment and/or prevention of microbial infection in an animal.
  • Animal can be any animal, for example, insect, mammal, reptile, fish, amphibian, preferably mammal, most preferably human.
  • 'Treatment means the use on an animal which has microbial infection in order to reduce or slow or stop the increase or spread of the infection, or to reduce the infection or to cure the infection.
  • Prevention means the use on an animal which has no apparent signs of microbial infection in order to prevent any future infection, or to reduce or slow the increase or spread of any future infection.
  • a compound of formula (I) in the manufacture of a medicament for use in the treatment and/or prevention of microbial infection in an animal.
  • a compound of formula (I) as a pharmaceutical agent.
  • a compound of formula (I) as an antimicrobial agent in the treatment of an animal.
  • a pharmaceutical composition comprising as an active ingredient a compound of formula (I), or a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable diluent or carrier.
  • This composition can be used for the treatment and/or prevention of antimicrobial infection in an animal.
  • This pharmaceutical composition can be in a form suitable for oral administration, such as tablet, lozenges, hard capsules, aqueous suspensions, oily suspensions, emulsions dispersible powders, dispersible granules, syrups and elixirs.
  • this pharmaceutical composition can be in a form suitable for topical application, such as a spray, a cream or lotion.
  • this pharmaceutical composition can be in a form suitable for parenteral administration, for example injection.
  • this pharmaceutical composition can be in inhalable form, such as an aerosol spray.
  • the compounds of formula (I) may be effective against various microbial species able to cause a microbial infection in an animal.
  • microbial species are those causing Aspergillosis such as Aspergillus fumigatus, A.flavus, A. terms, A.
  • nidulans and A. niger those causing Blastomycosis such as Blastomyces dermatitidis; those causing Candidiasis such as Candida albicans, C. glabrata, C. tropicalis, C. parapsilosis, C. krusei and C. lusitaniae; those causing Coccidioidomycosis such as Coccidioides immitis; those causing Cryptococcosis such as Cryptococcus neoformans; those causing Histoplasmosis such as Histoplasma capsulatum and those causing
  • Zygomycosis such as Absidia corymbifera, Rhizomucor pusillus and Rhizopus arrhizus.
  • Fusarium Spp such as Fusarium oxysporum and Fusarium solani
  • Scedosporium Spp such as Scedosporium apiospermum and Scedosporium prolificans.
  • intermediate (A) 4 g intermediate (A) are dissolved in 300 ml methanol and 25 ml NaOH (2 molar) are added. The solution is stirred at ambient temperature overnight. Most of the solvent is evaporated and the residue is disolved in water and extracted twice with t-butyl -methyl ether. The aquous phase is acidified with 1 molar HCl and the resulting solid is filtered and washed with water. 3.7 g of intermediate (B) were obtained (97.4 % of theory, m.p.
  • Intermediate (C) 3.3 g intermediate (B) are dissolved in 60 ml dioxane, 0.2 ml Dimethylformamid are added. 0.97 ml oxalic acid dichloride are added dropwise. The solution is stirred for 4 hours at ambient temperature, cooled with ice and 5 ml ammonia (25% in water) are added . The resulting suspension is stirred for 2 hours, diluted with water and extracted with t-butyl-methyl ether. The organic phase is washed with water, 5% HCl and brine and the solvent is removed after drying with sodium sulphate. The resulting solid is recrystallised from toluene. 2.9g of intermediate (C) were obtained (78.1 % of theory, m.p.l84-186°C).
  • Compound 6.10 can be prepared according to the following reaction scheme:
  • Step 2 Preparation of intermediate (F) 7.3 g oxalic acid dichloride in 75 ml dichloromethane are cooled to -60 °C. 12.5 ml dry dimethylsulfoxide is added dropwise while maintaining the temperature below -50 °C. Stirring is continued for 5 minutes and 20.7 g of intermediate (E) dissolved in 50 ml dichloromethane is added dropwise. After the addition is complete the suspension is stirred for another 15 minutes and 54 ml triethylamin are added dropwise while maintaining the temperature at -60 0 C. The suspension is stirred at -60 °C for 30 minutes and then warmed to ambient temperature and stirred overnight.
  • intermediate (F) 7.3 g oxalic acid dichloride in 75 ml dichloromethane are cooled to -60 °C. 12.5 ml dry dimethylsulfoxide is added dropwise while maintaining the temperature below -50 °C. Stirring is continued for 5 minutes and 20.7 g of intermediate (E)
  • intermediate (G) 3 g of intermediate (G) are dissolved in 20 ml dichloromethane and cooled to -40 °C. 1.1 ml diethylaminosulfurtrifluoride are added. The mixture is kept for 2 hours at -20 0 C and after this warmed to 0 °C. Water is added to the reaction mixture, the phases are separated and treated as described for intermediate (F). The solvent is evaporated and the residue is purified by chromatography on silica gel (eluent: hexane:ethyl acetate 9: 1). 1.93 g of intermediate (H) were obtained in the form of a yellow oil.
  • Example F-1.1 to F-1.3 Emulsifiable concentrates Components F-1.1 F-1.2 F-1.3 compound of Tables 1-4 25% 40% 50%
  • Emulsions of any desired concentration can be prepared by diluting such concentrates with water.
  • Example F-2 Emulsifiable concentrate
  • Emulsions of any desired concentration can be prepared by diluting such concentrates with water.
  • Example F7 Flowable concentrate for seed treatment
  • Silicone oil (in the form of a 75 % emulsion in water) 0. .2 %
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • Example B-I Action against Puccinia recondita / wheat (Brownrust on wheat)
  • Example B-2 Action against Podosphaera leucotricha / apple (Powdery mildew on apple)
  • Example B-3 Action against Venturia inaequalis / apple (Scab on apple)
  • Example B-4 Action against Ervsiphe graminis / barley (Powdery mildew on barley)
  • Example B-5 Action against Botrytis cinerea / grape (Botrvtis on grapes) 5 week old grape seedlings cv. Gutedel are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the grape plants are inoculated by spraying a spore suspension (lxl0 6 conidia/ml) on the test plants. After an incubation period of 4 days at 21 0 C and 95% r.h. in a greenhouse the disease incidence is assessed.
  • Example B-6 Action against Botrvtis cinerea / tomato (Botrvtis on tomatoes)
  • Example B-7 Action against Septoria nodorum / wheat (Septoria leaf spot on wheat)
  • Example B-8 Action against Helminthosporium teres / barley (Net blotch on barley)
  • Example B-9 Action against Alternaria solani / tomato (Early blight on tomatoes)
  • Example B-IO Action against Uncinula necator / grape (Powdery mildew on grapes)
  • Example B-I l Action against Septoria tritici / wheat (Septoria leaf spot on wheat)
  • wheat plants are inoculated by spraying a spore suspension (10xl0 5 conidia/ml) on the test plants. After an incubation period of 1 day at 23 0 C and 95% r.h., the plants are kept for 16 days at 23 0 C and 60% r.h. in a greenhouse. The disease incidence is assessed 18 days after inoculation.

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  • Chemical & Material Sciences (AREA)
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  • Plant Pathology (AREA)
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Abstract

La présente invention a pour objet un composé à activité fongicide de formule (I): où E, R1, n, A et R2 sont tels que définis dans la revendication 1.
PCT/EP2006/011719 2005-12-08 2006-12-06 Derives biphenyle portant un groupe acetylene, convenant comme microbiocides WO2007065661A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP05026774.9 2005-12-08
EP05026774 2005-12-08
EP06008753.3 2006-04-27
EP06008753 2006-04-27

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WO2007065661A1 true WO2007065661A1 (fr) 2007-06-14

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017042142A1 (fr) 2015-09-07 2017-03-16 Bayer Cropscience Aktiengesellschaft Dérivés de 2-difluorométhyl-nicotin(thio)carboxanilide substitués et leur utilisation en tant que fongicides

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004058723A1 (fr) * 2002-12-24 2004-07-15 Syngenta Participations Ag Derives de biphenyle et leur utilisation en tant que fongicides
WO2005028485A1 (fr) * 2003-09-19 2005-03-31 Syngenta Participations Ag Composes de silicium a activite microbiocide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004058723A1 (fr) * 2002-12-24 2004-07-15 Syngenta Participations Ag Derives de biphenyle et leur utilisation en tant que fongicides
WO2005028485A1 (fr) * 2003-09-19 2005-03-31 Syngenta Participations Ag Composes de silicium a activite microbiocide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017042142A1 (fr) 2015-09-07 2017-03-16 Bayer Cropscience Aktiengesellschaft Dérivés de 2-difluorométhyl-nicotin(thio)carboxanilide substitués et leur utilisation en tant que fongicides

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