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ITMI20120256A1 - PHENYLAMIDINE WITH FUNGICIDAL ACTIVITY AND ITS USE - Google Patents

PHENYLAMIDINE WITH FUNGICIDAL ACTIVITY AND ITS USE Download PDF

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ITMI20120256A1
ITMI20120256A1 IT000256A ITMI20120256A ITMI20120256A1 IT MI20120256 A1 ITMI20120256 A1 IT MI20120256A1 IT 000256 A IT000256 A IT 000256A IT MI20120256 A ITMI20120256 A IT MI20120256A IT MI20120256 A1 ITMI20120256 A1 IT MI20120256A1
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general formula
alkyl
agricultural crops
formula
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Christian Badaracco
Alexia Elmini
Lucio Filippini
Marilena Gusmeroli
Franco Pellacini
Gregorio Valea
Matteo Santino Vazzola
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Chemtura Corp
Isagro Spa
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/52—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing groups, e.g. carboxylic acid amidines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
    • C07C257/12—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to hydrogen atoms

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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)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

"Fenilammidine ad attività fungicida e relativo uso" "Phenylammidines with fungicidal activity and their use"

La presente invenzione riguarda fenilammidine ad elevata attività fungicida e il relativo uso, in particolare fenilammidine sostituite dotate di elevata attività fungicida ed il loro uso per il controllo di funghi fitopatogeni di importanti colture agricole. The present invention relates to phenylamidines with high fungicidal activity and their use, in particular substituted phenylamidines having a high fungicidal activity and their use for the control of phytopathogenic fungi of important agricultural crops.

Fenilammidine ad attività fungicida sono descritte nelle domande di brevetto internazionale WO 2000/46184, WO 2003/093224, WO 2007/031508, WO 2007/031512, WO 2007/031513, WO 2007/031523, WO 2007/031524, WO 2008/110279. Phenylammidines with fungicidal activity are described in international patent applications WO 2000/46184, WO 2003/093224, WO 2007/031508, WO 2007/031512, WO 2007/031513, WO 2007/031523, WO 2007/031524, WO 2008/110279 .

In particolare, nella domanda di brevetto internazionale WO 00/46184 sono descritte N'-(4-fenossi)fenilammidine ad attività fungicida sostituite sull'anello fenossi da vari raggruppamenti. I prodotti specificamente descritti in questo documento risultano però spesso insoddisfacenti sotto il profilo del livello di attività nei confronti dei funghi fitopatogeni e/o sotto il profilo della fitotossicità nei confronti di importanti colture agricole. D'altra parte, nella domanda di brevetto internazionale N. WO 2008/110278 sono riportate numerose fenilammidine di analoga struttura ad attività erbicida. In particular, in the international patent application WO 00/46184 N '- (4-phenoxy) phenylamide with fungicidal activity substituted on the phenoxy ring by various groupings are described. However, the products specifically described in this document are often unsatisfactory in terms of the level of activity towards phytopathogenic fungi and / or in terms of phytotoxicity towards important agricultural crops. On the other hand, in international patent application No. WO 2008/110278 numerous phenylamidines with a similar structure with herbicidal activity are reported.

La Richiedente ha ora sorprendentemente trovato che N,N-dialchil-N '-(4-fenossi)fenilammidine aventi particolari combinazioni di sostituenti sul gruppo fenossi e sull'atomo di azoto dialchilato, oltre ad esibire un'eccellente attività fungicida a basse dosi, risultano molto ben tollerate da molte specie vegetali consentendo quindi l'utilizzo pratico di questi composti per il controllo di microorganismi fitopatogeni di importanti colture agricole. The Applicant has now surprisingly found that N, N-dialkyl-N '- (4-phenoxy) phenylamide having particular combinations of substituents on the phenoxy group and on the dialkylated nitrogen atom, in addition to exhibiting an excellent fungicidal activity at low doses, they are very well tolerated by many plant species, thus allowing the practical use of these compounds for the control of phytopathogenic microorganisms of important agricultural crops.

Costituiscono pertanto oggetto della presente invenzione nuove fenilammidine di formula generale (I): Therefore, new phenylamidines of general formula (I) form the subject of the present invention:

m cui : m which:

- Ar rappresenta un gruppo fenile sostituito da almeno un gruppo scelto tra alchiltio Ci-C6, aloalchiltio Ci-Ce, alcossi C2-C6, aloalcossi C2-C6, cicloalchiltio C3-Ce, alocicloalchilt io C3-C6, cicloalcossi C3-C6, alocicloalcossi C3-C6, cicloachilalchiltio C4-C7, alocicloalchilalchilt io C4-C7, cicloalchilalcossi C4-C7, alocicloalchilalcossi C4-C7; ed opzionalmente da uno o due ulteriori sostituenti, uguali o diversi tra loro, scelti tra un atomo di alogeno, un alchile Ci-C6, un aloalchile Ci-C6; - Ar represents a phenyl group substituted by at least one group selected from alkylthio C1-C6, haloalkylthio C1-Ce, alkoxy C2-C6, haloalkoxy C2-C6, cycloalkylthio C3-Ce, haloalkylthio C3-C6, cycloalkoxy C3-C6, haloalkoxy C3-C6, C4-C7 cycloachylalkylthio, C4-C7 haloalkylalkylthio, C4-C7 cycloalkylalkoxy, C4-C7 haloalkylalkoxy; and optionally by one or two further substituents, the same or different from each other, selected from a halogen atom, a C1-C6 alkyl, a C1-C6 haloalkyl;

- Ri rappresenta un alchile C2-C6; - Ri represents a C2-C6 alkyl;

- R2rappresenta un alchile Ci~Ce,‘ - R2 represents a Ci ~ Ce alkyl, '

oppure Ri ed R2, congiuntamente all'atomo di N cui sono legati, formano un anello eterociclico contenente da 4 a 7 atomi, eventualmente sostituito da atomi di alogeno ; or Ri and R2, together with the N atom to which they are bonded, form a heterocyclic ring containing from 4 to 7 atoms, possibly replaced by halogen atoms;

- R3ed R4, uguali o diversi tra loro, rappresentano un atomo di idrogeno, un atomo di alogeno, un alchile Ci-Ce, un alcossile C1-C6, un aloalcossile C1-C6, un gruppo CF3, un gruppo CF2H, un gruppo CFH2, un gruppo ciano. - R3 and R4, the same or different from each other, represent a hydrogen atom, a halogen atom, a C-Ce alkyl, a C1-C6 alkoxy, a C1-C6 haloalkoxyl, a CF3 group, a CF2H group, a CFH2 group , a cyan group.

Esempi di alogeno sono fluoro, cloro, bromo, iodio. Examples of halogen are fluorine, chlorine, bromine, iodine.

Esempi di alchile Ci-C6sono metile, etile, npropile, isopropile, n-butile, isobutile, sec-butile, tert-butile, n-pentile, 3-metilbutile, n-esile, 3,3-dimetilbutile . Examples of C6-C6 alkyl are methyl, ethyl, npropyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 3-methylbutyl, n-hexyl, 3,3-dimethylbutyl.

Esempi di aloalchile Ci-C6sono fluorometile, difluorometile, trifluorometile, clorometile, diclorometile, 2,2,2-trifluoroetile, 1,1,2,2-tetrafluoroetile, pentafluoroetile, eptafluoropropile, 4,4,4-triclorobutile, 4,4-difluoropentile, 5,5-difluoroesile. Examples of C6-C6 haloalkyl are fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, pentafluoroethyl, heptafluoropropyl, 4,4,4-trichlorobutyl, 4,4- difluoropentyl, 5,5-difluorohexyl.

Esempi di alchiltio C1-C6 sono metiltio, etiltio, propiltio, butiltio, pentiltio, esiltio. Examples of C1-C6 alkylthio are methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio.

Esempi di aloalchiltio 0ι-06sono difluorometiltio, 2,2,2-trifluoroetiltio, 1,1,2,2-tetrafluoroetiltio, 2,2,3,3-tetrafluoropropiltio, 2,2,3,4,4,4-esafluorobutiltio, 4,4-dicloropentiltio, 5,5-dicloroesiltio. Examples of haloalkylthio 0ι-06 are difluoromethylthio, 2,2,2-trifluoroethylthio, 1,1,2,2-tetrafluoroethylthio, 2,2,3,3-tetrafluoropropylthio, 2,2,3,4,4,4-hexafluorobutylthio, 4,4-dichloropentylthio, 5,5-dichloroesylthio.

Esempi di alcossi C2-C6sono etossi, propossi, butossi, pentossi, esilossi. Examples of C2-C6 alkoxy are ethoxy, propoxy, butoxy, pentoxy, hexyloxy.

Esempi di aloalcossi C-C sono 2,2,2-trifluoroetossi, 1,1,2,2-tetrafluoroetossi, 2,2,3,3-tetrafluoropropossi, 2,2,3,4,4,4-esafluorobutossi, 4,4-dicloropentossi, 5,5-dicloroesilossi. Examples of C-C haloalkoxy are 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2,2,3,3-tetrafluoropropoxy, 2,2,3,4,4,4-hexafluorobutoxy, 4,4 -dichloropentoxy, 5,5-dichlorohexyloxy.

Esempi di cicloalchiltio C3-C6 sono ciclopropiltio, ciclobutiltio, ciclopentiltio, cicloesiltio. Examples of C3-C6 cycloalkylthio are cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio.

Esempi di alocicloalchilt io C3-C6 sono 2,2-diclorociclopropiltio, 2,2,3,3-tetrafluorociclobutiltio, 3,3-difluorociclopentiltio, 2-fluorocicloesiltio. Examples of C3-C6 haloalkylthio are 2,2-dichlorocyclopropylthio, 2,2,3,3-tetrafluorocyclobutylthio, 3,3-difluorocyclopentylthio, 2-fluorocyclohexylthio.

Esempi di cicloalcossi C3-C6 sono ciclopropossi, ciclobutossi, ciclopentossi, cicloesilossi. Examples of C3-C6 cycloalkoxy are cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexyloxy.

Esempi di alocicloalcossi C3-C6 sono 2,2diclorociclopropossi, 2,2,3,3-tetrafluorociclobutossi, 3,3-difluorociclopentossi, 2-fluorocicloesilossi. Examples of C3-C6 haloalkoxy are 2,2dichlorocyclopropoxy, 2,2,3,3-tetrafluorocyclobutoxy, 3,3-difluorocyclopentoxy, 2-fluorocyclohexyloxy.

Esempi di cicloalchilalchiltio C4-C7 sono ciclopropilmetiltio, ciclobutilmetiltio, ciclopentilmetiltio, cicloesilmetiltio. Examples of C4-C7 cycloalkylalkylthio are cyclopropylmethylthio, cyclobutylmethylthio, cyclopentylmethylthio, cyclohexylmethylthio.

Esempi di alocicloalchialchiltio C4-C7 sono 2,2-diclorociclopropilmetiltio, 2,2,3,3-tetrafluorociclobutilmetiltio, 3,3-difluorociclopentilmetiltio, 2-fluorocicloesilmetiltio . Examples of C4-C7 haloalkyalkylthio are 2,2-dichlorocyclopropylmethylthio, 2,2,3,3-tetrafluorocyclobutylmethylthio, 3,3-difluorocyclopentylmethylthio, 2-fluorocyclohexylmethylthio.

Esempi di cicloalchilalcossi C4-C7 sono ciclopropilmetossi, ciclobutilmetossi , ciclopentilmetossi, cicloesilmetossi . Examples of C4-C7 cycloalkylalkoxy are cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy.

Esempi di alocicloalchialcossi C4-C7 sono 2,2-diclorociclopropilmetossi, 2,2,3,3-tetrafluorociclobutilmetossi, 3,3-difluorociclopentilmetossi, 2-fluorocicloesilmetossi . Examples of C4-C7 haloalkyalkoxy are 2,2-dichlorocyclopropylmethoxy, 2,2,3,3-tetrafluorocyclobutylmethoxy, 3,3-difluorocyclopentylmethoxy, 2-fluorocyclohexylmethoxy.

Esempi di anelli eterociclici da 4 a 7 atomi eventualmente alogenati sono: azetidina, 3,3-difluoroazetidina, pirrolidina, piperidina, 4-fluoropiperidina, morfolina. Examples of heterocyclic rings from 4 to 7 possibly halogenated atoms are: azetidine, 3,3-difluoroazetidine, pyrrolidine, piperidine, 4-fluoropiperidine, morpholine.

Esempi rappresentativi di composti di formula generale (I) sono quelli in cui R, Ri, R2, R3 e R4assumono i significati riportati in tabella 1. Representative examples of compounds of general formula (I) are those in which R, Ri, R2, R3 and R4 have the meanings shown in table 1.

Composti di formula generale (I) preferiti sono quelli in cui R2, R3, R4 rappresentano un metile ed Ri rappresenta un etile. Preferred compounds of general formula (I) are those in which R2, R3, R4 represent a methyl and R1 represents an ethyl.

Ulteriormente preferiti sono i composti in cui Ar rappresenta un fenile sostituito da un gruppo alo alchiltio C1-C6 od aloalcossi C2-C6. Further preferred are the compounds in which Ar represents a phenyl substituted by a halo alkylthio C1-C6 or haloalkoxy C2-C6 group.

I composti di formula generale (I) vengono preparati dalla corrispondente anilina di formula (II), secondo lo schema di reazione 1. The compounds of general formula (I) are prepared from the corresponding aniline of formula (II), according to the reaction scheme 1.

Schema 1 Scheme 1

Sono noti dalla letteratura vari metodi per effettuare questa trasformazione; i più utilizzati sono i seguenti: Various methods for carrying out this transformation are known from the literature; the most used are the following:

a) trattamento dell'anilina di formula (II) con un acefale di formula RIR2NC(OR5), dove R5 rappresenta un alchile, secondo quanto descritto in "Synthetic Communications", 24 (1994), pagg.1617-1624; a) treatment of aniline of formula (II) with a head of formula RIR2NC (OR5), where R5 represents an alkyl, as described in "Synthetic Communications", 24 (1994), pages 1617-1624;

b) trattamento dell'anilina di formula (II) con un'ammide di formula HCONR1R2 in presenza di POCI3 o SOCI2,secondo quanto descritto in "Tetrahedron", 46 (1990), pagg.6058-6112; b) treatment of the aniline of formula (II) with an amide of formula HCONR1R2 in the presence of POCI3 or SOCI2, as described in "Tetrahedron", 46 (1990), pages 6058-6112;

c) trattamento dell'anilina di formula (II) con un ortoestere di formula HC(OR5), dove R5rappresenta un alchile, per formare il corrispondente imminoetere seguito dal riscaldamento dello stesso in presenza di un'ammina di formula HNRIR2,secondo quanto descritto in US4209319; c) treatment of the aniline of formula (II) with an orthoester of formula HC (OR5), where R5 represents an alkyl, to form the corresponding iminoether followed by heating it in the presence of an amine of formula HNRIR2, as described in US4209319;

d) trattamento dell'anilina di formula (II) con fosgene per formare l'isocianato corrispondente seguito dalla reazione con un'ammide di formula HCONR1R2, secondo quanto descritto in WO 00/46184; d) treating the aniline of formula (II) with phosgene to form the corresponding isocyanate followed by the reaction with an amide of formula HCONR1R2, according to what is described in WO 00/46184;

e) trattamento dell'anilina di formula (II) con C2H5OCH=NCN per formare una N-cianoammidina seguita da reazione con un'ammina di formula HNR1R2,secondo quanto descritto in WO 00/46184; e) treating the aniline of formula (II) with C2H5OCH = NCN to form an N-cyanoamidine followed by reaction with an amine of formula HNR1R2, as described in WO 00/46184;

f) trattamento dell'anilina di formula (II) con N,N-dimetilformammide in presenza di un solfonilcloruro, quale ad esempio 2-piridilsolfonilcloruro o fenilsolfonilcloruro, per formare la corrispondente dimetilammidina (Ri=R2=Me) seguita da reazione con un'ammina di formula HNRIR2,secondo quanto descritto in "Tetrahedron", 56 (2000), pagg.8253-8262 ed in "Journal Combinatorial Chemistry" il (2009), pagg.126-130. f) treatment of the aniline of formula (II) with N, N-dimethylformamide in the presence of a sulfonyl chloride, such as for example 2-pyridylsulfonyl chloride or phenylsulfonyl chloride, to form the corresponding dimethylamide (Ri = R2 = Me) followed by a reaction with a amine of formula HNRIR2, as described in "Tetrahedron", 56 (2000), pages 8253-8262 and in "Journal Combinatorial Chemistry" il (2009), pages 126-130.

II composto di formula (II) può essere preparato per riduzione del corrispondente nitroderivato di formula (III), come riportato nello schema di reazione 2, secondo metodi ben noti in chimica organica, come descritto ad esempio in "Advanced Organic Chemistry", Jerry March, 4<a>Edizione, 1992, John Wiley & Sons Pub., pagg. 1216-1217 e referenze ivi citate. The compound of formula (II) can be prepared by reduction of the corresponding nitro-derivative of formula (III), as reported in reaction scheme 2, according to well-known methods in organic chemistry, as described for example in "Advanced Organic Chemistry", Jerry March , 4th Edition, 1992, John Wiley & Sons Pub., Pp. 1216-1217 and references cited therein.

Schema 2 Scheme 2

Le condizioni di reazione preferite per questi substrati prevedono l'utilizzo dello stagno cloruro in acido cloridrico concentrato, secondo quanto descritto in dettaglio nella domanda internazionale WO 00/46184. The preferred reaction conditions for these substrates provide for the use of tin chloride in concentrated hydrochloric acid, as described in detail in the international application WO 00/46184.

Il composto di formula (III) può essere preparato per reazione del composto di formula (IV) con un composto di formula ArX, dove Ar ha il significato sopra riportato ed X rappresenta un gruppo uscente quale ad esempio un atomo di alogeno, in presenza di una base, preferibilmente carbonato di potassio o sodio idruro, secondo lo schema di reazione 3. The compound of formula (III) can be prepared by reaction of the compound of formula (IV) with a compound of formula ArX, where Ar has the above meaning and X represents a leaving group such as for example a halogen atom, in the presence of a base, preferably potassium carbonate or sodium hydride, according to reaction scheme 3.

Schema 3 Scheme 3

I composti di formula (IV) vengono ottenuti con metodi ben noti in letteratura secondo quanto descritto in "Canadian Journal Chemistry" 62 (1984) pagg.1446-1451 e in " Australian Journal Chemistry" 44 (1991) pagg .151-156 . The compounds of formula (IV) are obtained with methods well known in the literature as described in "Canadian Journal Chemistry" 62 (1984) pages 1446-1451 and in "Australian Journal Chemistry" 44 (1991) pages 151-156.

Alternativamente il composto di formula (III) può anche essere ottenuto per reazione del composto di formula (V), dove X' rappresenta un atomo di alogeno, con un composto di formula ArOH in presenza di una base, preferibilmente carbonato di potassio o sodio idruro, secondo lo schema di reazione 4. Alternatively, the compound of formula (III) can also be obtained by reaction of the compound of formula (V), where X 'represents a halogen atom, with a compound of formula ArOH in the presence of a base, preferably potassium carbonate or sodium hydride , according to reaction scheme 4.

Schema 4 Scheme 4

I composti di formula (V) vengono ottenuti per nitrazione del corrispondente arilalogenuro con una miscela di acido nitrico e acido solforico concentrato, secondo quanto descritto in " Tetrahedron" 36 (1980) pagg. 3535-3541. The compounds of formula (V) are obtained by nitration of the corresponding arylhalide with a mixture of nitric acid and concentrated sulfuric acid, as described in "Tetrahedron" 36 (1980) pp. 3535-3541.

Come detto, i composti di formula generale (I) sono dotati di un'attività fungicida molto elevata che si esplica nei confronti di numerosi funghi fitopatogeni che attaccano importanti colture agricole. As mentioned, the compounds of general formula (I) are endowed with a very high fungicidal activity which is expressed against numerous phytopathogenic fungi that attack important agricultural crops.

Esempi di funghi fitopatogeni che possono essere efficacemente trattati e combattuti con i composti di formula generale (I) sono quelli appartenenti alle classi dei Basidiomiceti, Ascomiceti, Deuteromiceti o funghi imperfetti, Oomiceti: Puccinia spp., Ustilago spp., Tilletia spp., Uromyces spp., Phakopsora spp., Rhizoctonia spp., Erysiphe spp., Sphaerotheca spp., Podosphaera spp., Uncinula spp., Helminthosporium spp., Rhynchosporium spp., Pyrenophora spp., Monilinia spp., Sclerotinia spp., Septoria spp. (Mycosphaerella spp.), Venturia spp., Botrytis spp., Aiternaria spp., Fusarium spp., Cercospora spp., Cercosporella herpotrichoides, Colletotrichum spp., Pyricularia oryzae, Sclerotium spp., Phytophtora spp., Pythium spp., Plasmopara viticola, Peronospora spp., Pseudoperonospora cubensis, Bremia lactucae. Examples of phytopathogenic fungi that can be effectively treated and combated with the compounds of general formula (I) are those belonging to the classes of Basidiomycetes, Ascomycetes, Deuteromycetes or imperfect fungi, Oomycetes: Puccinia spp., Ustilago spp., Tilletia spp., Uromyces spp., Phakopsora spp., Rhizoctonia spp., Erysiphe spp., Sphaerotheca spp., Podosphaera spp., Uncinula spp., Helminthosporium spp., Rhynchosporium spp., Pyrenophora spp., Monilinia spp., Sclerotoria spp., (Mycosphaerella spp.), Venturia spp., Botrytis spp., Aiternaria spp., Fusarium spp., Cercospora spp., Cercosporella herpotrichoides, Colletotrichum spp., Pyricularia oryzae, Sclerotium spp., Phytophtora spp., Pythoparappicola, Pythoparappicola. , Peronospora spp., Pseudoperonospora cubensis, Bremia lactucae.

Le principali colture che possono essere protette con i composti secondo la presente invenzione comprendono cereali (grano, orzo, segale, avena, riso, mais, sorgo, ecc.), fruttiferi (melo, pero, susino, pesco, mandorlo, ciliegio, banano, vite, fragola, lampone, mora, ecc.), agrumi (arancio, limone, mandarino, pompeimo, ecc.), leguminose (fagiolo, pisello, lenticchia, soia, ecc.), orticole (spinacio, lattuga, asparago, cavolo, carota, cipolla, pomodoro, patata, melanzana, peperone, ecc.), cucurbitacee (zucca, zucchina, cetriolo, melone, anguria, ecc.), piante oleoginose (girasole, colza, arachide, ricino, cocco, ecc.), tabacco, caffè, tè, cacao, barbabietola da zucchero, canna da zucchero, cotone. The main crops that can be protected with the compounds according to the present invention include cereals (wheat, barley, rye, oats, rice, corn, sorghum, etc.), fruit trees (apple, pear, plum, peach, almond, cherry, banana , grapevine, strawberry, raspberry, blackberry, etc.), citrus fruits (orange, lemon, mandarin, pompeii, etc.), legumes (bean, pea, lentil, soy, etc.), vegetables (spinach, lettuce, asparagus, cabbage , carrot, onion, tomato, potato, eggplant, pepper, etc.), cucurbits (pumpkin, courgette, cucumber, melon, watermelon, etc.), oil plants (sunflower, rapeseed, peanut, castor, coconut, etc.), tobacco, coffee, tea, cocoa, sugar beet, sugar cane, cotton.

In particolare, i composti di formula (I) si sono dimostrati notevolmente efficaci nel controllo di Plasmopara viticola su vite, Phytophtora infestans e Botrytis Cinerea su pomodoro, Puccinia recondita, Erisiphae graminis, Helminthosporium teres, Septoria nodorum e Fusarium spp. su cereali, nel controllo di Phakopsora pachyrhizi su soia, nel controllo di Uromyces Appendiculatus su fagiolo, nel controllo di Venturia inaequalis su melo, nel controllo di Sphaerotheca fuliginea su cetriolo. In particular, the compounds of formula (I) have proved remarkably effective in the control of Plasmopara viticola on grapevine, Phytophtora infestans and Botrytis Cinerea on tomato, Puccinia recondita, Erisiphae graminis, Helminthosporium teres, Septoria nodorum and Fusarium spp. on cereals, in the control of Phakopsora pachyrhizi on soybeans, in the control of Uromyces Appendiculatus on beans, in the control of Venturia inaequalis on apple trees, in the control of Sphaerotheca fuliginea on cucumber.

Inoltre, i composti di formula generale (I) sono efficaci anche nel controllo di batteri e virus fitopatogeni, quali ad esempio Xanthomonas spp., Pseudomonas spp., Erwinia amylovora, il virus del mosaico del tabacco. Furthermore, the compounds of general formula (I) are also effective in the control of phytopathogenic bacteria and viruses, such as for example Xanthomonas spp., Pseudomonas spp., Erwinia amylovora, the tobacco mosaic virus.

I composti di formula (I) sono in grado di esplicare un'azione fungicida a carattere sia curativo sia preventivo ed esibiscono una fitotossicità molto bassa o nulla sulle colture trattate. The compounds of formula (I) are capable of carrying out a fungicidal action of both curative and preventive character and exhibit a very low or zero phytotoxicity on the treated crops.

E' quindi ulteriore oggetto della presente invenzione l'uso dei composti di formula (I) per il controllo di funghi fitopatogeni di colture agricole. The use of the compounds of formula (I) for the control of phytopathogenic fungi of agricultural crops is therefore a further object of the present invention.

Per gli impieghi pratici in agricoltura è spesso preferibile utilizzare composizioni fungicide contenenti i composti secondo la presente invenzione opportunamente formulati. For practical uses in agriculture it is often preferable to use fungicidal compositions containing suitably formulated compounds according to the present invention.

Sono un ulteriore oggetto della presente invenzione composizioni fungicide comprendenti almeno un composto di formula (I), un solvente e/o diluente solido o liquido, eventualmente un tensioattivo. A further object of the present invention are fungicidal compositions comprising at least one compound of formula (I), a solid or liquid solvent and / or diluent, optionally a surfactant.

Le suddette composizioni fungicide possono presentarsi sotto forma di polveri secche, polveri bagnabili, concentrati emulsionabili, emulsioni, microemulsioni, paste, granuli, granuli disperdibili in acqua, soluzioni, sospensioni, ecc.: la scelta del tipo di composizione dipenderà dall'impiego specifico. The aforementioned fungicidal compositions can be in the form of dry powders, wettable powders, emulsifiable concentrates, emulsions, microemulsions, pastes, granules, water-dispersible granules, solutions, suspensions, etc .: the choice of the type of composition will depend on the specific use.

Le composizioni fungicide vengono preparate in maniera nota, per esempio diluendo o sciogliendo la sostanza attiva con un mezzo solvente e/o un diluente solido o liquido, eventualmente in presenza di tensioattivi. The fungicidal compositions are prepared in a known manner, for example by diluting or dissolving the active substance with a solvent medium and / or a solid or liquid diluent, optionally in the presence of surfactants.

Come diluenti solidi, o supporti, possono essere ad esempio utilizzati: silice, caolino, bentonite, talco, farina fossile, dolomite, carbonato di calcio, magnesia, gesso, argille, silicati sintetici, attapulgite, seppiolite. As solid diluents or supports, for example, silica, kaolin, bentonite, talc, diatomaceous earth, dolomite, calcium carbonate, magnesia, gypsum, clays, synthetic silicates, attapulgite, seppiolite can be used.

Come solventi o diluenti liquidi possono essere ad esempio utilizzati, oltre all'acqua, solventi organici aromatici (xiloli o miscele di alchilbenzoli, clorobenzene, ecc.), paraffine (frazioni di petrolio), alcooli (metanolo, propanolo, butanolo, ottanolo, glicerina, ecc.), esteri (acetato di etile, di isobutile, alchil carbonati, esteri alchilici dell'acido adipico, esteri alchilici dell'acido glutarico, esteri alchilici dell'acido succinico, esteri alchilici dell'acido lattico, ecc.), olii vegetali (olio di colza, olio di girasole, olio di soia, olio di ricino, olio di mais, olio di arachidi, e loro esteri alchilici), chetoni (cicloesanone, acetone, acetofenone, isoforone, etilamilchetone, ecc.), ammidi (N,N-dimetilformammide, N-metilpirrolidone, ecc.), solfossidi e solfoni (dimetilsolfossido, dimetilsolfone, ecc.), e loro miscele. As liquid solvents or diluents, in addition to water, for example, aromatic organic solvents (xylols or mixtures of alkylbenzols, chlorobenzene, etc.), paraffins (petroleum fractions), alcohols (methanol, propanol, butanol, octanol, glycerin) can be used. , etc.), esters (ethyl acetate, isobutyl acetate, alkyl carbonates, alkyl esters of adipic acid, alkyl esters of glutaric acid, alkyl esters of succinic acid, alkyl esters of lactic acid, etc.), oils vegetables (rapeseed oil, sunflower oil, soybean oil, castor oil, corn oil, peanut oil, and their alkyl esters), ketones (cyclohexanone, acetone, acetophenone, isophorone, ethylamylketone, etc.), amides ( N, N-dimethylformamide, N-methylpyrrolidone, etc.), sulfoxides and sulfones (dimethylsulfoxide, dimethylsulfone, etc.), and their mixtures.

Come tensioattivi possono essere utilizzati sali di sodio, di calcio, di potassio, di trietilammina o trietanolammina di alchilnaf talensolfonati, polinaftalensolfonati, alchilsolfonati, arilsolfonati, alchilarilsolfonati, policarbossilati, solfosuccinati, alchilsolfosuccinati, lignin solfonati, alchilsolfati; ed ancora possono essere utilizzati alcoli grassi polietossilati, alchilfenoli polietossilati, esteri del sorbitolo polietossilati, polipropossi polietossilati (block polymers). As surfactants, sodium, calcium, potassium, triethylamine or triethanolamine salts of alkylnaphthalenesulfonates, polynaphthalenesulphonates, alkylsulfonates, arylsulfonates, alkylaryl sulphonates, polycarboxylates, sulphosuccinates, alkylsulfosuccinates, alkyl sulphonates, alkyl sulphonates, alkyl sulphonates, alkyl sulphonates, alkyl sulphonates, alkyl sulphonates, alkyl sulphonates, alkyl sulphonates, alkyl sulphonates can be used; and polyethoxylated fatty alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitol esters, polypropoxy polyethoxylates (block polymers) can also be used.

Le composizioni fungicide possono anche contenere additivi speciali per particolari scopi, ad esempio anticongelanti quali glicole propilenico, oppure agenti adesivanti quali gomma arabica, alcool polivinilico, polivinilpirrolidone, ecc.. The fungicidal compositions can also contain special additives for particular purposes, for example antifreeze such as propylene glycol, or adhesive agents such as gum arabic, polyvinyl alcohol, polyvinylpyrrolidone, etc.

Qualora lo si desideri, è possibile aggiungere alle composizioni fungicide contenenti i composti di formula generale (I), altri principi attivi con essi compatibili, quali ad esempio fungicidi diversi da quelli di formula generale (I), fitoregolatori, antibiotici, erbicidi, insetticidi, fertilizzanti e/o loro miscele. If desired, it is possible to add to the fungicidal compositions containing the compounds of general formula (I), other active principles compatible with them, such as for example fungicides other than those of general formula (I), plant growth regulators, antibiotics, herbicides, insecticides, fertilizers and / or their mixtures.

Esempi di fungicidi diversi da quelli di formula generale (I) che possono essere inclusi nelle composizioni fungicide oggetto della presente invenzione sono qui riportati con il loro nome internazionale ISO: acibenzolar, ametoctradin, amisulbrom, ampropylfos, anilazine, azaconazole, azoxystrobin, benalaxyl, benalaxyl-M, benomyl, benthiavalicarb, bitertanol, bixafen, blasticidin-S, boscalid, bromuconazole, bupirimate, buthiobate, captafol, captan, carbendazim, carboxin, carpropamid, chinomethionat, chloroneb, chlorothalonil, chlozolinate, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, debacarb, dichlofluanid, dichlone, diclobutrazol, diclomezine, dicloran, diclocymet, diethofencarb, difenoconazole, diflumetorim, dimethir imol, dimethomorph, dimoxystrobin, diniconazole, dinocap, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, edifenphos, epoxiconazole, etaconazole, ethaboxam, ethirimol, ethoxyquin, etridiazole, famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, fluopicolide, fluopyram, fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, furconazole, furconazole-cis, guazatine, hexaconazole, hymexazol, hydroxyquinoline sulfate, imazalil, imibenconazole, iminoctadine, ipconazole, iprobenfos, iprodione, isoprothiolane, iprovalicarb, isopyrazam, isotianil, kasugamycin, kresoxim-methyl, mancopper, mancozeb, mandipropamid, maneb, mebenil, mepanipyrim, mepronil, meptyldinocap, metalaxyl, metalaxyl-M, metconazole, methfuroxam, metiram, metominostrobin, metrafenone, metsulfovax, myclobutanil, natamycin, nicobifen, nitrothal-isopropyl, nuarimol, ofurace, orysastrobin, oxadixyl, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorofenol e suoi sali, penthiopyrad, phthalide, picoxystrobin, piperalin, Bordeaux mixture, polyoxins, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, proquinazid, prothiocarb, prothioconazole, pyracarbolid, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, pyroxyfur, quinacetol, quinazamid, quinconazole, quinoxyfen, quintozene, rabenzazole, copper hydroxide, copper oxychloride, copper (I) oxide, copper sulfate, sedaxane, silthiofam, simeconazole, spiroxamine, streptomycin, tebuconazole, tebufloquin, tetraconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide, thiophanate, thiophanate-methyl, thiram, tiadinil, tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triarimol, triazbutil, triazoxide, tricyclazole, tridemorf, trifloxystrobin, triflumizole, triforine, triticonazole, uniconazole, uniconazole-P, validamycin, valifenalate, vinclozolin, zineb, ziram, sulfur, zoxamide. Examples of fungicides other than those of general formula (I) which can be included in the fungicidal compositions object of the present invention are reported here under their international name ISO: acibenzolar, ametoctradin, amisulbrom, ampropylfos, anilazine, azaconazole, azoxystrobin, benalaxyl, benalaxyl - M, benomyl, benthiavalicarb, bitertanol, bixafen, blasticidin-S, boscalid, bromuconazole, bupirimate, buthiobate, captafol, captan, carbendazim, carboxin, carpropamid, quinomethionat, cyprocypamidilamid, cyprodilamid, cyprodilamide, cyprocalid, cyprocalid, cyprocalid, cyprodilamide , debacarb, dichlofluanid, dichlone, diclobutrazol, diclomezine, dicloran, diclocymet, diethofencarb, difenoconazole, diflumetorim, dimethir imol, dimethomorph, dimoxystrobin, diniconazole, dinocap, dipyrithione, ditalianimonole, dodifamol, etphemorphine, dodithianimonfos ethirimol, ethoxyquin, etridiazole, famoxadone, phenamidone, phenaminosulf, fenapanil, fen arimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, fluopicolide, fluopyram, fluoroxilamide, fluoroximide, flutolanil, flutriafol, fluxapyroxad, folpet, fosetyl-aluminum, fuberidazole, furalaxyl, furametpyr, furconazole, furconazole-cis, guazatine, hexaconazole, hymexazol, hydroxyquinoline sulfate, imazalrod, imibencoconazole, isproconazole, imibencoconazole, isproconazole, ibencoconazole, isproconazole, ibencoctadine, ip , isothianil, kasugamycin, kresoxim-methyl, mancopper, mancozeb, mandipropamid, maneb, mebenil, mepanipyrim, mepronil, meptyldinocap, metalaxyl, metalaxyl-M, metconazole, methfuroxfo, metiramhal, metycutanrafine - isopropyl, nuarimol, ofurace, orysastrobin, oxadixyl, oxpoconazole, oxycarboxin, pefurazoate, penconaz ole, pencycuron, penflufen, pentachlorofenol and its salts, penthiopyrad, phthalide, picoxystrobin, piperalin, Bordeaux mixture, polyoxins, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, proquinazid, prothiocarb, pyracamostrinostro, pyracarboli pyrazophos, pyribencarb, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, pyroxyfur, quinacetol, quinazamid, quinconazole, quinoxyfen, quintozene, rabenzazole, copper hydroxide, copper oxychloride, copper (I) oxide, sedamaxane, spirthon silly , tebuconazole, tebufloquin, tetraconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide, thiophanate, thiophanate-methyl, thiram, tiadinil, tioxymid, tolclofos-methyl, tolylfluanid, triadifluor, triadolimefon, triadimcl , triforins, triticonazole, uniconazole, uniconazole-P, validamycin, valifenalate , vinclozolin, zineb, ziram, sulfur, zoxamide.

La concentrazione dei composti fenilammidinici di formula generale (I) nelle suddette composizioni può variare entro un ampio intervallo; in generale essa è compresa tra 1% e 90% in peso rispetto al peso totale della composizione, preferibilmente tra 5 e 50% in peso rispetto al peso totale della composizione. The concentration of the phenylamide compounds of general formula (I) in the above compositions can vary within a wide range; in general it is between 1% and 90% by weight with respect to the total weight of the composition, preferably between 5 and 50% by weight with respect to the total weight of the composition.

L'applicazione di queste composizioni può avvenire su ogni parte della pianta, per esempio su foglie, steli, rami e radici, oppure sui semi stessi prima della semina, oppure sul terreno in cui cresce la pianta. The application of these compositions can take place on any part of the plant, for example on leaves, stems, branches and roots, or on the seeds themselves before sowing, or on the ground where the plant grows.

Ulteriore oggetto della presente invenzione è quindi un metodo per il controllo di funghi fitopatogeni in colture agricole, che comprende applicare una dose efficace di almeno una fenilammidina di formula generale (I), utilizzata come tale o formulata in composizioni fungicide come sopra descritte. A further object of the present invention is therefore a method for controlling phytopathogenic fungi in agricultural crops, which comprises applying an effective dose of at least one phenylamide of general formula (I), used as such or formulated in fungicidal compositions as described above.

Ulteriore oggetto della presente invenzione è inoltre un metodo per il controllo di batteri e virus fitopatogeni in colture agricole, che comprende applicare una dose efficace di almeno una fenilammidina di formula generale (I), utilizzata come tale o formulata in composizioni fungicide come sopra descritte. A further object of the present invention is also a method for controlling phytopathogenic bacteria and viruses in agricultural crops, which comprises applying an effective dose of at least one phenylamide of general formula (I), used as such or formulated in fungicidal compositions as described above.

La quantità di composto da applicare per ottenere l'effetto desiderato può variare in funzione di diversi fattori quali, ad esempio, il composto utilizzato, la coltura da preservare, il tipo di patogeno, il grado di infezione, le condizioni climatiche, il metodo di applicazione, la formulazione adottata. The amount of compound to be applied to obtain the desired effect can vary depending on various factors such as, for example, the compound used, the crop to be preserved, the type of pathogen, the degree of infection, the climatic conditions, the method of application, the formulation adopted.

Dosi di composto comprese tra 10 g e 5 kg per ettaro di coltura agricola forniscono, in genere, un controllo sufficiente. Compost doses ranging from 10g to 5kg per hectare of agricultural crop generally provide sufficient control.

Allo scopo di meglio descrivere l'invenzione vengono ora forniti i seguenti esempi che sono da ritenersi illustrativi e non limitativi della stessa. In order to better describe the invention, the following examples are now provided which are to be considered illustrative and not limitative thereof.

ESEMPIO 1 EXAMPLE 1

Preparazione di N-etil-N-metil-N' -[4-[3-(1,1,2,2-tetrafluoroetiltio)fenossi]-2 ,5-xilil]formammidina (Composto N°l). Preparation of N-ethyl-N-methyl-N '- [4- [3- (1,1,2,2-tetrafluoroethylthio) phenoxy] -2, 5-xylyl] formamide (Compound No. 1).

a) Preparazione del 3- (1,1,2,2-tetrafluoroetiltio)-fenolo a) Preparation of 3- (1,1,2,2-tetrafluoroethylthio) -phenol

2 g di 3-mercaptofenolo vengono sospesi in una miscela costituita da 36 mi di toluene e 5,2 mi di dimetilsolfossido; si aggiungono 0,17 g di idrossido di potassio in polvere e si raffredda a -25°C. 2 g of 3-mercaptophenol are suspended in a mixture consisting of 36 ml of toluene and 5.2 ml of dimethyl sulfoxide; 0.17 g of powdered potassium hydroxide are added and it is cooled to -25 ° C.

Dopo aver effettuato il vuoto, si immette tetrafluoroetilene nell'apparecchiatura e si mantiene a -25° C per 20 minuti. After carrying out the vacuum, tetrafluoroethylene is introduced into the apparatus and it is kept at -25 ° C for 20 minutes.

Dopo avere controllato la completezza della reazione mediante GC-MS, la miscela viene versata in acqua, portata a PH 3 per aggiunta di acido cloridrico diluito ed estratta con acetato di etile. After having checked the completeness of the reaction by GC-MS, the mixture is poured into water, brought to PH 3 by adding dilute hydrochloric acid and extracted with ethyl acetate.

La fase organica viene lavata con acqua, anidrificata su solfato di sodio, filtrata ed evaporata. The organic phase is washed with water, dried over sodium sulphate, filtered and evaporated.

Il prodotto grezzo ottenuto (1,5 g) viene utilizzato per la reazione successiva. GC-MS: 226 (M<+>). b) Preparazione del 2-nitro-5-[3-(1,1,2,2-tetrafluoroetiltio)fenossi]-p-xilene [composto di formula (III)] Ad una soluzione di 1,3 g di 3-(l,1,2,2-tetrafluoroetiltio)fenolo sciolti in 10 mi di N,N-dimetilformammide, vengono aggiunti 0,8 g di carbonato di potassio. The crude product obtained (1.5 g) is used for the subsequent reaction. GC-MS: 226 (M <+>). b) Preparation of 2-nitro-5- [3- (1,1,2,2-tetrafluoroethylthio) phenoxy] -p-xylene [compound of formula (III)] To a solution of 1.3 g of 3- ( 1,2,2-tetrafluoroethylthio) phenol dissolved in 10 ml of N, N-dimethylformamide, 0.8 g of potassium carbonate are added.

Si porta la miscela di reazione ad 80°C e si gocciola una soluzione di 1,3 g di 5-bromo-2-nitro-pxilene sciolti in 5 mi di N,N-dimetilformammide. The reaction mixture is brought to 80 ° C and a solution of 1.3 g of 5-bromo-2-nitro-pxylene dissolved in 5 ml of N, N-dimethylformamide is dropped.

Terminata l'aggiunta, si scalda a 120°C per 8 ore, si controlla in TLC (eluente esano:acetato di etile 8:2), poi si diluisce con acqua e si estrae con acetato di etile. At the end of the addition, the mixture is heated to 120 ° C for 8 hours, checked in TLC (eluent hexane: ethyl acetate 8: 2), then diluted with water and extracted with ethyl acetate.

La fase organica viene lavata con acqua, anidrificata su solfato di sodio, filtrata e concentrata. The organic phase is washed with water, dried over sodium sulphate, filtered and concentrated.

Il prodotto grezzo ottenuto (1,8 g) viene usato per la reazione successiva. GC-MS: 375 (M<+>). The obtained crude product (1.8 g) is used for the next reaction. GC-MS: 375 (M <+>).

c) Preparazione di 4-[3-(1,1,2,2-tetrafluoroetiltio)fenossi]-2,5-xilidina [composto di formula (II)] 1,7 g di 2-nitro-5- [3-(1,1,2,2-tetrafluoroetlitio)fenossi]-p-xilene vengono diluiti con 32 mi di una miscela etanolo:acqua 1:1; si addizionanono 0,32 mi di acido acetico glaciale e si scalda a 90°C. c) Preparation of 4- [3- (1,1,2,2-tetrafluoroethylthio) phenoxy] -2,5-xylidine [compound of formula (II)] 1.7 g of 2-nitro-5- [3- (1,1,2,2-tetrafluoroethlitio) phenoxy] -p-xylene are diluted with 32 ml of a 1: 1 ethanol: water mixture; 0.32 ml of glacial acetic acid are added and the mixture is heated to 90 ° C.

Si aggiungono 1,4 g di ferro in polvere e si mantiene in agitazione la miscela a 90°C per 1,5 ore. 1.4 g of powdered iron are added and the mixture is kept stirred at 90 ° C for 1.5 hours.

Dopo controllo di reazione in TLC (eluente esano: acetato di etile 8:2), la miscela viene raffreddata, filtrata su celite ed evaporata per togliere la maggior parte del solvente. After reaction control in TLC (eluent hexane: ethyl acetate 8: 2), the mixture is cooled, filtered on celite and evaporated to remove most of the solvent.

Il residuo così ottenuto viene trattato con una soluzione satura di bicarbonato di sodio, quindi viene estratta con acetato di etile. The residue thus obtained is treated with a saturated solution of sodium bicarbonate, then it is extracted with ethyl acetate.

La fase organica, dopo lavaggio con acqua, viene anidrificata su solfato di sodio, poi filtrata ed evaporata. The organic phase, after washing with water, is dried over sodium sulphate, then filtered and evaporated.

Il prodotto grezzo viene purificato per cromatografia su gel di silice eluendo con eptano :acetato di etile 85:15. Si ottengono 0,9 g del prodotto desiderato. GC-MS : 345 (M<+>). The crude product is purified by chromatography on silica gel eluting with heptane: ethyl acetate 85:15. 0.9 g of the desired product are obtained. GC-MS: 345 (M <+>).

d) Preparazione di N-et il-N-met il-N '- [4- [3-(1,1,2,2-tetraf luoroet iltio)fenossi] -2,5-xilil] formammidina 0,5 g di 4- [3-(1,1,2,2-tetrafluoroetiltio) -fenossi ]-2,5-xilidina, 2,5 mi di trietilortof ormiato e 0,05 g di acido p-toluensolf onico vengono scaldati a 130°C per 2 ore. d) Preparation of N-etil-N-methyl-N '- [4- [3- (1,1,2,2-tetrafluoroethylthio) phenoxy] -2,5-xylyl] formamide 0.5 g of 4- [3- (1,1,2,2-tetrafluoroethylthio) -phenoxy] -2,5-xylidine, 2.5 ml of triethylorthoformate and 0.05 g of p-toluenesulfonic acid are heated to 130 ° C for 2 hours.

Dopo controllo di reazione in TLC (eluente esano: acetato di etile 7:3), la miscela viene concentrata a pressione ridotta, diluita con 5 mi di cloruro di metilene quindi addizionata di 0,18 g di N-etil-N-metilammina . After reaction control in TLC (eluent hexane: ethyl acetate 7: 3), the mixture is concentrated under reduced pressure, diluted with 5 ml of methylene chloride then added with 0.18 g of N-ethyl-N-methylamine.

Si lascia a temperatura ambiente per 48 h, si controlla in TLC (eluente esano:etile acetato 7:3), poi si evapora il solvente. It is left at room temperature for 48 h, controlled in TLC (eluent hexane: ethyl acetate 7: 3), then the solvent is evaporated.

Si ottengono 0,7 g di prodotto desiderato. 0.7 g of desired product are obtained.

<1>H-NMR (δ-ppm, CDC13) = 1.2 (t, 3H); 2.1 (s, 3H); 2.3 (s,3H); 3.0 (s, 3H); 3.4 (br, 2H); 5.6-6.0 (tt, IH); 6.6 (m, IH); 6.8 (m, IH); 7.0-7.3 (m, 4H); 7.5 (s, IH). <1> H-NMR (δ-ppm, CDC13) = 1.2 (t, 3H); 2.1 (s, 3H); 2.3 (s, 3H); 3.0 (s, 3H); 3.4 (br, 2H); 5.6-6.0 (tt, 1H); 6.6 (m, 1H); 6.8 (m, 1H); 7.0-7.3 (m, 4H); 7.5 (s, 1H).

ESEMPIO 2. EXAMPLE 2.

Preparazione dei composti N. 2-11. Preparation of compounds No. 2-11.

Operando in maniera analoga a quanto descritto nell'esempio 1 sono stati ottenuti i composti di formula (I) riportati in Tabella 2. By operating in the same way as described in example 1, the compounds of formula (I) reported in Table 2 were obtained.

Tabella 2 Table 2

ESEMPIO 3 EXAMPLE 3

Determinazione dell' attività fungicida in applicazione preventiva (5 giorni) contro Erysiphe gramini s su grano. Determination of the fungicidal activity in preventive application (5 days) against Erysiphe gramini s on wheat.

Foglie di piante di grano di varietà Salgemma, allevate in vaso in ambiente condizionato a 20° C e al 70% di U.R. (Umidità Relativa), sono state trattate per irrorazione di ambedue le pagine con il composto sotto esame (vedi la seguente tabella 3), disperso in soluzione idroacetonica al 20% in volume di acetone. Leaves of rock salt variety wheat plants, grown in pots in a conditioned environment at 20 ° C and 70% R.H. (Relative Humidity), were treated by spraying both pages with the compound under examination (see the following table 3), dispersed in a hydroacetonic solution at 20% by volume of acetone.

Dopo 5 giorni di permanenza in ambiente condizionato, le piante sono state infettate a secco scuotendovi sopra, per spargere l inoculo, delle piante precedentemente infettate da Erysiphe graminis. After 5 days of stay in a conditioned environment, the plants were dry infected by shaking over them, to spread the inoculum, of the plants previously infected with Erysiphe graminis.

Le piante sono state poi mantenute nella stessa cella, in ambiente saturo di umidità e temperatura compresa tra i 18 e 24°C, per 12 giorni. The plants were then kept in the same cell, in an environment saturated with humidity and a temperature between 18 and 24 ° C, for 12 days.

Trascorso questo periodo di tempo, sono comparsi i sintomi esteriori del patogeno ed è stato quindi possibile procedere alla valutazione dell'intensità dell'infezione, sia sulle parti trattate direttamente con i prodotti (T), sia sulle parti sviluppatesi durante l'esecuzione del test (NT), mediante scala di valutazione visiva della percentuale di area fogliare colpita; la scala prevede come estremi il valore 100 (pianta sana) ed il valore 0 (pianta completamente infetta). After this period of time, the external symptoms of the pathogen appeared and it was therefore possible to proceed with the assessment of the intensity of the infection, both on the parts treated directly with the products (T), and on the parts developed during the execution of the test (NT), using a visual assessment scale of the percentage of affected leaf area; the scale foresees as extremes the value 100 (healthy plant) and the value 0 (completely infected plant).

Nel contempo si è proceduto alla valutazione della fitotossicità (percentuale di necrosi fogliare) indotta sulle piantine di grano dall'applicazione dei prodotti: in questo caso la scala di valutazione varia da 0 (pianta completamente sana) a 100 (pianta completamente necrotizzata). At the same time, the phytotoxicity (percentage of leaf necrosis) induced on the wheat seedlings by the application of the products was assessed: in this case the evaluation scale varies from 0 (completely healthy plant) to 100 (completely necrotized plant).

In Tabella 3 sono riportati i risultati ottenuti effettuando il test descritto con i composti N° 1 e 8. Table 3 shows the results obtained by carrying out the test described with compounds N ° 1 and 8.

Tabella 3 Table 3

Claims (13)

RIVENDICAZIONI 1. Fenilammidine di formula generale (I): CLAIMS 1. Phenylammidines of general formula (I): m cui : - Ar rappresenta un gruppo fenile sostituito da almeno un gruppo scelto tra alchiltio Ci-C6, aloalchiltio Ci-Ce, alcossi C2-C6, aloalcossi C2-C6, cicloalchiltio C3-Ce, alocicloalchilt io C3-C6, cicloalcossi C3-C6, alocicloalcossi C3-C6, cicloachilalchilt io C4-C7, alocicloalchilalchilt io C4-C7, cicloalchilalcossi C4-C7, alocicloalchilalcossi C4-C7; ed opzionalmente da uno o due ulteriori sostituenti, uguali o diversi tra loro, scelti tra un atomo di alogeno, un alchile Ci-C6, un aloalchile Ci-C6; - Ri rappresenta un alchile C2-C6; - R2rappresenta un alchile Ci~Ce,‘ oppure Ri ed R2, congiuntamente all'atomo di N cui sono legati, formano un anello eterociclico contenente da 4 a 7 atomi, eventualmente sostituito da atomi di alogeno ; - R3ed R4, uguali o diversi tra loro, rappresentano un atomo di idrogeno, un atomo di alogeno, un alchile Ci-Ce, un alcossile C1-C6, un aloalcossile C1-C6, un gruppo CF3, un gruppo CF2H, un gruppo CFH2, un gruppo ciano. 2. Fenilammidine secondo la rivendicazione 1, scelte tra i composti di formula generale (I) in cui i sostituenti Ar, Ri, R2, R3e R4assumono i significati sotto riportati: m which: - Ar represents a phenyl group substituted by at least one group selected from alkylthio C1-C6, haloalkylthio C1-Ce, alkoxy C2-C6, haloalkoxy C2-C6, cycloalkylthio C3-Ce, haloalkylthio C3-C6, cycloalkoxy C3-C6, haloalkoxy C3-C6, cycloachylalkyl or C4-C7, haloalkylalkyl or C4-C7, cycloalkylalkoxy C4-C7, haloalkylalkoxy C4-C7; and optionally by one or two further substituents, the same or different from each other, selected from a halogen atom, a C1-C6 alkyl, a C1-C6 haloalkyl; - Ri represents a C2-C6 alkyl; - R2 represents a Ci ~ Ce alkyl, ' or Ri and R2, together with the N atom to which they are bonded, form a heterocyclic ring containing from 4 to 7 atoms, possibly replaced by halogen atoms; - R3 and R4, the same or different from each other, represent a hydrogen atom, a halogen atom, a C-Ce alkyl, a C1-C6 alkoxyl, a C1-C6 haloalkoxyl, a CF3 group, a CF2H group, a CFH2 group , a cyan group. 2. Phenylamide according to claim 1, selected from the compounds of general formula (I) in which the substituents Ar, Ri, R2, R3 and R4 have the meanings reported below: 3. Composizioni fungicide comprendenti almeno un composto di formula (I) secondo la rivendicazione 1 o 2, un solvente e/o diluente solido o liquido, eventualmente un tensioattivo. 3. Fungicidal compositions comprising at least one compound of formula (I) according to claim 1 or 2, a solid or liquid solvent and / or diluent, optionally a surfactant. 4. Composizioni secondo la rivendicazione 3, comprendenti inoltre almeno un principo attivo compatibile con i composti di formula generale (I), scelto tra: fungicidi diversi da quelli di formula generale (I), fitoregolatori, antibiotici, erbicidi, insetticidi, fertilizzanti e/o loro miscele. 4. Compositions according to claim 3, further comprising at least one active ingredient compatible with the compounds of general formula (I), selected from: fungicides other than those of general formula (I), plant growth regulators, antibiotics, herbicides, insecticides, fertilizers and / or their mixtures. 5. Composizioni secondo la rivendicazione 3 o 4, in cui detto almeno un composto di formula generale (I) ha una concentrazione compresa tra 1% e 90% in peso, preferibilmente tra 5 e 50% in peso, rispetto al peso totale della composizione. 5. Compositions according to claim 3 or 4, wherein said at least one compound of general formula (I) has a concentration comprised between 1% and 90% by weight, preferably between 5 and 50% by weight, with respect to the total weight of the composition . 6. Uso di fenilammidine di formula generale (I) secondo la rivendicazione 1 o 2, per il controllo di funghi fitopatogeni di colture agricole. 6. Use of phenylamide of general formula (I) according to claim 1 or 2, for the control of phytopathogenic fungi of agricultural crops. 7. Uso di composizioni secondo una qualsiasi delle rivendicazioni da 3 a 5, per il controllo di funghi fitopatogeni di colture agricole. 7. Use of compositions according to any one of claims 3 to 5, for the control of phytopathogenic fungi of agricultural crops. 8. Uso secondo la rivendicazione 6 o 7, per il controllo di funghi fitopatogeni scelti tra le seguenti classi : Basidi orniceti Ascomicet i Deuter orniceti o funghi imperfetti, Oomiceti: Puccinia spp ., Ustilago spp ., Tilletia spp., Uromyces spp., Phakopsora spp., Rhizoctonia spp., Erysiphe spp., Sphaerotheca spp., Podosphaera spp., Uncinula spp., Helminthosporium spp., Rhynchosporium spp., Pyrenophora spp., Monilinia spp., Sclerotinia spp., Septoria spp. (Mycosphaerella spp.), Venturia spp., Botrytis spp., Aiternaria spp., Fusarium spp., Cercospora spp., Cercosporella herpotrichoides, Colletotrichum spp., Pyricularia oryzae, Sclerotium spp., Phytophtora spp., Pythium spp., Plasmopara viticola, Peronospora spp., Pseudoperonospora cubensis , Bremia lactucae. 8. Use according to claim 6 or 7, for the control of phytopathogenic fungi selected from the following classes: Basidia orniceti Ascomicet i Deuter orniceti or imperfect fungi, Oomycetes: Puccinia spp., Ustilago spp., Tilletia spp., Uromyces spp., Phakopsora spp., Rhizoctonia spp., Erysiphe spp., Sphaerotheca spp., Podosphaera spp., Uncinula spp., Helminthosporium spp., Rhynchosporium spp., Pyrenophora spp., Monilinia spp., Sclerotinia spp., Septoria spp. (Mycosphaerella spp.), Venturia spp., Botrytis spp., Aiternaria spp., Fusarium spp., Cercospora spp., Cercosporella herpotrichoides, Colletotrichum spp., Pyricularia oryzae, Sclerotium spp., Phytophtora spp., Pythoparappicola, Pythoparappicola. , Peronospora spp., Pseudoperonospora cubensis, Bremia lactucae. 9. Uso secondo la rivendicazione 6 o 7, in cui le colture agricole sono scelte tra: cereali, fruttiferi, agrumi, leguminose, orticole, cucurbitacee, piante oleoginose, tabacco, caffè, tè, cacao, barbabietola da zucchero, canna da zucchero, cotone. 9. Use according to claim 6 or 7, in which the agricultural crops are chosen from: cereals, fruit trees, citrus fruits, legumes, vegetables, cucurbits, oil plants, tobacco, coffee, tea, cocoa, sugar beet, sugar cane, cotton. 10. Uso secondo la rivendicazione 6 o 7, per il controllo di: Plasmopara viticola su vite; Phytophtora infestans e Botrytis Cinerea su pomodoro; Puccinia recondita, Erisiphae graminis , Helminthosporium teres, Septoria nodorum e Fusarium spp. su cereali; Phakopsora pachyrhizi su soia; Uromyces Appendiculatus su fagiolo; Venturia inaequalis su melo; Sphaerotheca fuliginea su cetriolo . 10. Use according to claim 6 or 7, for the control of: Plasmopara viticola on grapevine; Phytophtora infestans and Botrytis Cinerea on tomato; Puccinia recondita, Erisiphae graminis, Helminthosporium teres, Septoria nodorum and Fusarium spp. on cereals; Phakopsora pachyrhizi on soy; Uromyces Appendiculatus on bean; Venturia inaequalis on apple trees; Sphaerotheca fuliginea on cucumber. 11. Uso di fenilammidine di formula generale (I) secondo la rivendicazione 1 o 2 o di composizioni secondo una qualsiasi delle rivendicazioni da 3 a 5, per il controllo di batteri e virus fitopatogeni in colture agricole. 11. Use of phenylamidines of general formula (I) according to claim 1 or 2 or of compositions according to any one of claims 3 to 5, for the control of phytopathogenic bacteria and viruses in agricultural crops. 12. Metodo per il controllo di funghi fitopatogeni in colture agricole, che comprende applicare una dose efficace di almeno una fenilammidina di formula generale (I) secondo la rivendicazione 1 o 2 o di una composizione secondo una qualsiasi delle rivendicazioni da 3 a 5. Method for controlling phytopathogenic fungi in agricultural crops, which comprises applying an effective dose of at least one phenylamide of general formula (I) according to claim 1 or 2 or a composition according to any of claims 3 to 5. 13. Metodo per il controllo di batteri e virus fitopatogeni in colture agricole, che comprende applicare una dose efficace di almeno una fenilammidina di formula generale (I) secondo la rivendicazione 1 o 2 o di una composizione secondo una qualsiasi delle rivendicazioni da 3 a 5.13. Method for the control of phytopathogenic bacteria and viruses in agricultural crops, which comprises applying an effective dose of at least one phenylamide of general formula (I) according to claim 1 or 2 or a composition according to any of claims 3 to 5 .
IT000256A 2012-02-21 2012-02-21 PHENYLAMIDINE WITH FUNGICIDAL ACTIVITY AND ITS USE ITMI20120256A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000046184A1 (en) * 1999-02-06 2000-08-10 Aventis Cropscience Gmbh N2-phenylamidine derivatives
WO2007031524A1 (en) * 2005-09-13 2007-03-22 Bayer Cropscience Ag Pesticide pyrimidinyloxy substituted phenylamidine derivatives
WO2007031508A1 (en) * 2005-09-13 2007-03-22 Bayer Cropscience Ag Pesticide phenyloxy substituted phenylamidine derivatives
WO2008110278A2 (en) * 2007-03-12 2008-09-18 Bayer Cropscience Ag Use of n2-phenylamidines as herbicides and herbicidal agents comprising the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000046184A1 (en) * 1999-02-06 2000-08-10 Aventis Cropscience Gmbh N2-phenylamidine derivatives
WO2007031524A1 (en) * 2005-09-13 2007-03-22 Bayer Cropscience Ag Pesticide pyrimidinyloxy substituted phenylamidine derivatives
WO2007031508A1 (en) * 2005-09-13 2007-03-22 Bayer Cropscience Ag Pesticide phenyloxy substituted phenylamidine derivatives
WO2008110278A2 (en) * 2007-03-12 2008-09-18 Bayer Cropscience Ag Use of n2-phenylamidines as herbicides and herbicidal agents comprising the same

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