ITMI20101575A1 - PHENYLAMIDINE WITH HIGH FUNGICIDAL ACTIVITY AND RELATED USE - Google Patents
PHENYLAMIDINE WITH HIGH FUNGICIDAL ACTIVITY AND RELATED USE Download PDFInfo
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- 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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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- 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
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- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/39—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
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- 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
- C07D213/60—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
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- 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
- C07D213/60—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/70—Sulfur atoms
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- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/32—One oxygen, sulfur or nitrogen atom
- C07D239/34—One oxygen atom
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- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
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- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D277/34—Oxygen atoms
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- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D277/36—Sulfur atoms
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- 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
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Description
"Fenilammidine ad elevata attività fungicida e relativo "Phenylammidines with high fungicidal activity and relative
USO " USE "
La presente invenzione riguarda fenilammidine ad elevata attività fungicida e relativo uso, in particolare nuove 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 relative use, in particular new substituted phenylamidines with 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 2007/061966, 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 2007/061966, WO 2008/110279.
In particolare, nella domanda di brevetto WO 2007/061966 sono descritte fenilammidine contenenti, in posizione 4 del fenile, catene alcossiliche variamente sostituite. In particular, in the patent application WO 2007/061966 phenylamidines containing, in the 4 position of the phenyl, variously substituted alkoxy chains are described.
I prodotti descritti in questo e altri documenti risultano però spesso insoddisfacenti sia sotto il profilo del livello di attività nei confronti dei funghi fitopatogeni sia, o in alternativa, sotto il profilo della fitotossicità nei confronti di importanti colture agricole. However, the products described in this and other documents are often unsatisfactory both in terms of the level of activity towards phytopathogenic fungi and, or alternatively, in terms of phytotoxicity towards important agricultural crops.
La Richiedente ha ora sorprendentemente trovato che nuove fenilammidine sostituite in posizione 4 del fenile da specifici raggruppamenti alchilossi, alchiltio, cicloalchilossi o cicloalchiltio, a loro volta eventualmente sostituiti da particolari gruppi aloalchilossi, aloalchiltio, fenossi, feniltio, eterociclilossi od eterocicliltio, esibiscono un'eccellente attività fungicida, oltre a risultare 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 new phenylamidines substituted in the 4 position of the phenyl by specific alkyloxy, alkylthio, cycloalkyloxy or cycloalkylthio groupings, in turn optionally replaced by particular haloalkyloxy, haloalkylthio, phenoxy, phenylthio, heterocyloxy or heterocyclylthio groups, exhibit an excellent fungicidal activity, as well as being 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:
in cui: in which:
- Ri e R2, uguali o diversi tra loro, rappresentano un alchile C1-C6, oppure, congiuntamente all'atomo di N cui sono legati, possono formare un anello eterociclico contenente da 3 a 6 atomi eventualmente sostituito da alogeni ; - Ri and R2, the same or different from each other, represent a C1-C6 alkyl, or, together with the N atom to which they are bonded, they can form a heterocyclic ring containing from 3 to 6 atoms possibly replaced by halogens;
- R3e R4uguali o diversi tra loro, rappresentano un atomo di idrogeno, un atomo di alogeno, un alchile C4-C6, un alcossile C1-C6, un aloalcossile C1-C6, un gruppo CF3, un gruppo CF2H, un gruppo CFH2, un gruppo ciano; - A rappresenta un gruppo Αχ o A2, dove Αχ e A2sono rappresentati dalle seguenti sottostrutture: - R3 and R4 the same or different from each other, they represent a hydrogen atom, a halogen atom, a C4-C6 alkyl, a C1-C6 alkoxyl, a C1-C6 haloalkoxyl, a CF3 group, a CF2H group, a CFH2 group, a cyan group; - A represents a group Αχ or A2, where Αχ and A2 are represented by the following substructures:
Ax= R-Xi-(CH2)nl-Cy-(CH2)n-X-; Ax = R-Xi- (CH2) nl-Cy- (CH2) n-X-;
A2= R'-X2(CR5R6)n2-X-; A2 = R'-X2 (CR5R6) n2-X-;
- X e X2, uguali o diversi tra loro, rappresentano un atomo di ossigeno od un atomo di zolfo; - X and X2, the same or different from each other, represent an oxygen atom or a sulfur atom;
- Xi rappresenta un atomo di ossigeno, un atomo di zolfo oppure un legame diretto; - Xi represents an oxygen atom, a sulfur atom or a direct bond;
- Cy rappresenta il residuo bivalente di un anello cicloalchilico C3-C6, un anello alocicloalchilico C3-C6, un anello eterociclico saturo; - Cy represents the divalent residue of a C3-C6 cycloalkyl ring, a C3-C6 haloalkyl ring, a saturated heterocyclic ring;
- R rappresenta un alchile C1-C6, un aloalchile C1-C6, un anello fenilico o un anello eterociclico saturo od insaturo, oppure rappresenta anche un atomo di idrogeno se Xi è un legame diretto, con esclusione del caso in cui Cy assume il significato di anello cicloesilico; - R'rappresenta un aloalchile Ci-C6, un anello fenilico o un anello eterociclico saturo od insaturo; - R represents a C1-C6 alkyl, a C1-C6 haloalkyl, a phenyl ring or a saturated or unsaturated heterocyclic ring, or also represents a hydrogen atom if Xi is a direct bond, with the exception of the case in which Cy takes on the meaning of cyclohexyl ring; - It represents a C-C6 haloalkyl, a phenyl ring or a saturated or unsaturated heterocyclic ring;
- R5e R6uguali o diversi tra loro rappresentano un atomo di idrogeno o un alchile C1-C6; - R5 and R6 equal or different from each other represent a hydrogen atom or a C1-C6 alkyl;
- n e ni, uguali o diversi tra loro,rappresentano un numero compreso tra 0 e 3; - n and ni, the same or different from each other, represent a number between 0 and 3;
- n2 rappresenta un numero compreso tra 1 e 6; - n2 represents a number between 1 and 6;
- nei significati di Cy, R ed R', gli anelli cicloalchilico C3-C6, alocicloalchilico C3-C6, fenilico, eterociclico saturo, eterociclico insaturo, possono essere opzionalmente sostituiti da uno o più sostituenti scelti tra: un atomo di alogeno, un alchile C1-C6, un aloalchile C1-C6, un alcossile Ci-Cg, un aloalcossile Ci-Cg, un cicloalchile C3-C6, un alocicloalchile C3-C6, un cicloalcossile C3-C6, un alocicloalcossile C3-C6, un cicloalchilalchile C3-C10, un alocicloalchilalchile C4-C10, un cicloalchilalcossile C4-C10, un alchenile C2-C6, un aloalchenile C2-Ce, un alchenilossi C2-C6, un aloalchenilossi C2-C6, un alchinile C2-C6, un aloalchinile C2-C6, un alchinilossi C3-C6, un aloalchinilossi C3-C7, un alchiltio Ci-Ce, un aloalchiltio Ci-Ce, un gruppo ciano, un gruppo nitro, un gruppo alcossicarbonilico C2-Cg, un gruppo aloalcossicarbonilico C2-Cg, un gruppo alchilcarbonilico C2-Cg, un gruppo aloalchilcarbonilico C2-Cg, un gruppo alchilamminocarbonilico C2-Cg, un gruppo dialchilamminocarbonilico C3-C13, un gruppo alchilammino Ci-Ce, un gruppo dialchilammino C2-Ci2, un gruppo fenile, un gruppo fenossi, un gruppo feniltio, un gruppo eterociclile saturo od insaturo, un gruppo eterociclilossi , un gruppo eterocicliltio . - in the meanings of Cy, R and R ', the cycloalkyl rings C3-C6, haloalkyl C3-C6, phenyl, saturated heterocyclic, unsaturated heterocyclic, can optionally be replaced by one or more substituents selected from: a halogen atom, an alkyl C1-C6, a C1-C6 haloalkyl, a C1-Cg alkoxy, a C3-Cg haloalkoxyl, a C3-C6 cycloalkyl, a C3-C6 haloalkyl, a C3-C6 cycloalkoxyl, a C3-C6 haloalkoxyl, a C3-cycloalkyl alkyl C10, a C4-C10 haloalkylalkyl, a C4-C10 cycloalkylalkoxy, a C2-C6 alkenyl, a C2-C6 haloalkenyl, a C2-C6 alkenyloxy, a C2-C6 haloalkenyloxy, a C2-C6 alkynyl, a C2-C6 haloalkynyl, a C3-C6 alkynyloxy, a C3-C7 haloalkyloxy, an alkylthio Ci-Ce, a haloalkylthio Ci-Ce, a cyano group, a nitro group, a C2-Cg alkoxycarbonyl group, a C2-Cg haloalkoxycarbonyl group, a C2 alkylcarbonyl group -Cg, a C2-Cg haloalkylcarbonyl group, a C2-Cg alkylaminocarbonyl group, a dialkylaminocar group C3-C13 bonyl group, a C3-C1 alkylamino group, a C2-Ci2 dialkylamino group, a phenyl group, a phenoxy group, a phenylthio group, a saturated or unsaturated heterocyclyl group, a heterocyclyloxy group, a heterocyclylthio group.
Esempi di alogeno sono: fluoro, cloro, bromo, iodio . Examples of halogen are: fluorine, chlorine, bromine, iodine.
Esempi di alchile Ci-C6, lineari o ramificati, sono metile, etile, n-propile, isopropile, n-butile, isobutile, sec-butile, tert-butile, n-pentile, 3-metilbutile, n-esile, 3 ,3-dimetilbut ile. Examples of C6-C6 alkyl, linear or branched, are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 3-methylbutyl, n-hexyl, 3, 3-dimethylbutyl.
Esempi di aloalchile C1-C6 sono fluorometile, difluorometile, trif luorometile, clorometile, diclorometile, 2,2,2-trif luoroetile, 1, 1,2,2-tetraf luoroetile, pentaf luoroetile, eptafluoropropile, 4 ,4,4-triclorobutile, 4,4-dif luoropentile, 5,5-dif luoroesile . Examples of C1-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 alcossile C1-C6, lineari o ramificati, sono metossi, etossi, n-propossi, isopropossi, nbutossi, isobutossi, sec-butossi, tert-butossi , npentossi, 3-met ilbutossi , esilossi, 3,3-dimetilbutossi . Examples of linear or branched C1-C6 alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, nbutoxy, isobutoxy, sec-butoxy, tert-butoxy, npentoxy, 3-methylbutoxy, hexyloxy, 3,3-dimethylbutoxy.
Esempi di aloalcossile C1-C6 sono fluorometossi , difluorometossi, trifluorometossi, clorometossi , diclorometossi , 2,2,2-trif luoroetossi, 1,1,2,2-tetrafluoroetossi, 1,1,2,3, 3,3-esaf luoropropossi, 4,4,4-triclorobutossi , 4,4-difluoropentossi, 5,5-difluoroesilossi. Examples of C1-C6 haloalkoxy are fluoromethoxy, difluoromethoxy, trifluoromethoxy, chloromethoxy, dichloromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 1,1,2,3, 3,3-hexafluoropropoxy , 4,4,4-trichlorobutoxy, 4,4-difluoropentoxy, 5,5-difluorohexyloxy.
Esempi di cicloalchile C3-C6 sono ciclopropile, ciclobutile, ciclopentile, cicloesile. Examples of C3-C6 cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.
Esempi di alocicloalchile C3-C8 sono 2,2-diclorociclopropile, 2 ,2-difluorociclopropile, 2,2,3,3-tetraf luorociclobutile, 3,3-dif luorociclopentile, 2-fluorocicloesile. Examples of C3-C8 haloalkyl are 2,2-dichlorocyclopropyl, 2, 2-difluorocyclopropyl, 2,2,3,3-tetrafluorocyclobutyl, 3,3-difluorocyclopentyl, 2-fluorocyclohexyl.
Esempi di anello eterociclico sono: furile, tienile, piridile, pirrolile, pirazolile, imidazolile, 1.2.3-triazolile, 1,2,4-triazolile, tetrazolile, piridazinile, pirimidinile, pirazinile, 1,2,4-triazinile, 1,3,5-triazinile, tetrazinile, ossazolile, isossazolile, tiazolile, isotiazolile, 1,2,4-ossadiazolile, 1,3,4-ossadiazolile, 1,2,4-tiadiazolile, 1.3.4-tiadiazolile, tiazinile, ossazinile, benzofurile, benzotienile, indolile, benzimidazolile, benzotriazolile, chinolile, chinazolile, chinossalile, benzossazolile, benzotiazolile, naftiridile. Examples of heterocyclic ring are: furyl, thienyl, pyridyl, pyrrolyl, pyrazolyl, imidazolyl, 1.2.3-triazolyl, 1,2,4-triazolyl, tetrazolyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,2,4-triazinyl, 1, 3,5-triazinyl, tetrazinyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,4-thiadiazolyl, 1.3.4-thiadiazolyl, thiazinyl, oxazinyl, benzofuryl, benzothienyl, indolyl, benzimidazolyl, benzotriazolyl, quinolyl, quinazolyl, quinoxalyl, benzoxazolyl, benzothiazolyl, naphthyridyl.
Esempi di anelli eterociclici da 3 a 6 atomi eventualmente alogenati sono: aziridina, azetidina, 3,3-difluoroazetidina, pirrolidina, piperidina, 4-fluoropiperidina. Examples of heterocyclic rings from 3 to 6 possibly halogenated atoms are: aziridine, azetidine, 3,3-difluoroazetidine, pyrrolidine, piperidine, 4-fluoropiperidine.
Esempi di composti preferiti, di formula generale (I), in cui A assume il significato di Ai, sono riportati in Tabella 1. Examples of preferred compounds, of general formula (I), in which A assumes the meaning of Ai, are reported in Table 1.
Ai = R-Xi-(CH2)ni-Cy-(CH2)n<_>X<_> Ai = R-Xi- (CH2) ni-Cy- (CH2) n <_> X <_>
Tabella 1 Table 1
1.5 i,3-C5H90 0 HCF2CF20/0 Me Me -(CH2)4-1.6 1,3-C5H90 0 HCF2CF20/0 Me Me -(CH2)5-1.7 1,4-C6H1Q0 0 HCF2CF20/0 Me Me -(CH2)4-1.8 1,4-C6H1Q0 0 HCF2CF20/0 Me Me -CH2CF2CH2-1.9 1 4<~>C6H100 0 HCF2CF20/0 Me Me Me Me 1.10 1 4<~>C6H100 0 HCF2CF20/0 Me Me Me Et 1.11 1 4<~>C6H100 s HCF2CF20/0 Me Me Me Et 1.12 1 4<~>C6H10s s HCF2CF20/0 Me Me Me Et 1.13 1 4<~>C6H100 s HCF2CF20/0 Me Me Me Me 1.14 1,4-C6H1Qs s HCF2CF20/0 Me Me Me Me 1.15 1,3-C5HBs s HCF2CF20/0 Me Me Me Me 1.16 1,3-C5HBs s HCF2CF20/0 Me Me Me Et 1.17 1,3-C5HB0 s HCF2CF20/0 Me Me Me Me 1.18 1 3—05Η80 s HCF2CF20/0 Me Me Me Et 1.19 1 4^C6H10s s HCF2CF21/1 Me Me Me Me 1.20 1 3—05Η8s s HCF2CF21/1 Me Me Me Me 1.21 1 3—05Η8s s HCF2CF21/1 Me Me Me Et 1.22 1,3-C5HB0 s HCF2CF21/1 Me Me Me Me 1.23 1,3-C5H90 s HCF2CF21/1 Me Me Me Et 1.24 1,4-C6H1Q0 0 HCF2CF21/1 Me Me Me Et 1.25 1,3-C5HB0 0 HCF2CF21/1 Me Me -CH2CF2CH2-1.26 1,3-C5HB0 0 HCF2CF21/1 Me Me -(CH2)4-1.27 1 3—05Η80 0 HCF2CF21/1 Me Me -(CH2)5-1.28 1 4<^>C6H100 0 HCF2CF21/1 Me Me -(CH2)4-1.29 1 4<^>C6H100 0 HCF2CF21/1 Me Me -CH2CF2CH2-1.30 1 3—05Η8s s HCF2CF21/1 Me Me -CH2CF2CH2-1.31 1,3-C5HBs s HCF2CF21/1 Me Me -(CH2)4-1.32 1,3-C5HBs s HCF2CF21/1 Me Me -(CH2)5-1.33 1,4-C6H1Qs s HCF2CF21/1 Me Me -(CH2)4-1.34 1,4-C6H1Qs s HCF2CF21/1 Me Me -CH2CF2CH2-1.35 1,2-C3H40 0 HCF2CF21/1 Me Me Me Me 1.36 1,2-C3H40 0 HCF2CF21/1 Me Me Me Et 1.37 1,2-C3H40 0 HCF2CF21/1 Me Me Me iPr 1.38 1,2-C3H4s s HCF2CF21/1 Me Me Me Me 1.39 1,2-C3H4s s HCF2CF21/1 Me Me Me Et 1.40 1,2-C3H4s s HCF2CF21/1 Me Me Me iPr 1.5 i, 3-C5H90 0 HCF2CF20 / 0 Me Me - (CH2) 4-1.6 1,3-C5H90 0 HCF2CF20 / 0 Me Me - (CH2) 5-1.7 1,4-C6H1Q0 0 HCF2CF20 / 0 Me Me - ( CH2) 4-1.8 1,4-C6H1Q0 0 HCF2CF20 / 0 Me Me -CH2CF2CH2-1.9 1 4 <~> C6H100 0 HCF2CF20 / 0 Me Me Me Me 1.10 1 4 <~> C6H100 0 HCF2CF20 / 0 Me Me Me Et 1.11 1 4 <~> C6H100 s HCF2CF20 / 0 Me Me Me Et 1.12 1 4 <~> C6H10s s HCF2CF20 / 0 Me Me Me Et 1.13 1 4 <~> C6H100 s HCF2CF20 / 0 Me Me Me Me 1.14 1,4-C6H1Qs s HCF2CF20 / 0 Me Me Me Me 1.15 1,3-C5HBs s HCF2CF20 / 0 Me Me Me Me 1.16 1,3-C5HBs s HCF2CF20 / 0 Me Me Me Et 1.17 1,3-C5HB0 s HCF2CF20 / 0 Me Me Me Me 1.18 1 3—05Η80 s HCF2CF20 / 0 Me Me Me Et 1.19 1 4 ^ C6H10s s HCF2CF21 / 1 Me Me Me Me 1.20 1 3—05Η8s s HCF2CF21 / 1 Me Me Me 1.21 1 3—05Η8s s HCF2CF21 / 1 Me Me Me Et 1.22 1,3-C5HB0 s HCF2CF21 / 1 Me Me Me Me 1.23 1,3-C5H90 s HCF2CF21 / 1 Me Me Me Et 1.24 1,4-C6H1Q0 0 HCF2CF21 / 1 Me Me Me Et 1.25 1,3-C5HB0 0 HCF2CF21 / 1 Me Me -CH2CF2CH2-1.26 1,3-C5HB0 0 HCF2CF21 / 1 Me Me - (CH2) 4-1.27 1 3—05Η80 0 HCF2CF21 / 1 Me Me - (CH2) 5-1.28 1 4 <^> C6H100 0 HCF2CF21 / 1 Me Me - (CH2) 4- 1.29 1 4 <^> C6H100 0 HCF2CF21 / 1 Me Me -CH2CF2CH2-1.30 1 3—05Η8s s HCF2CF21 / 1 Me Me -CH2CF2CH2-1.31 1,3-C5HBs s HCF2CF21 / 1 Me Me - (CH2) 4-1.32 1 , 3-C5HBs s HCF2CF21 / 1 Me Me - (CH2) 5-1.33 1,4-C6H1Qs s HCF2CF21 / 1 Me Me - (CH2) 4-1.34 1,4-C6H1Qs s HCF2CF21 / 1 Me Me -CH2CF2CH2-1.35 1,2-C3H40 0 HCF2CF21 / 1 Me Me Me Me 1.36 1,2-C3H40 0 HCF2CF21 / 1 Me Me Me Et 1.37 1,2-C3H40 0 HCF2CF21 / 1 Me Me Me iPr 1.38 1,2-C3H4s s HCF2CF21 / 1 Me Me Me Me 1.39 1,2-C3H4s s HCF2CF21 / 1 Me Me Me Et 1.40 1,2-C3H4s s HCF2CF21 / 1 Me Me Me iPr
1,3-C5H8= 1,3-ciclopentile; 1,4-C6HI0= 1,4-cicloesile; 1,2-C3H4= 1,2-ciclopropile. 1,3-C5H8 = 1,3-cyclopentyl; 1,4-C6HI0 = 1,4-cyclohexyl; 1,2-C3H4 = 1,2-cyclopropyl.
Esempi di composti preferiti, di formula generale (I), in cui A assume il significato di A2,sono riportati in Tabella 2. Examples of preferred compounds, of general formula (I), in which A assumes the meaning of A2, are reported in Table 2.
A2= R'-X2-(CR5R6)n2-X-Tabella 2 A2 = R'-X2- (CR5R6) n2-X-Table 2
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(OR7), dove R7 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 (OR7), where R7 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(OR7), 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 (OR7), 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 1'isocianato corrispondente seguito dalla reazione con un'ammide di formula HCONRIR2, secondo quanto descritto, ad esempio, 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 HCONRIR2, according to what is described, for example, 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 di dimetilammidina (Ri=R2=Me) seguita da reazione con un'ammina di formula HNR1R2,secondo quanto descritto in "Tetrahedron", 56 (2000), pagg.8253-8262 e in "Journal Combinatoria! Chemistry" 11 (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 reaction with a amine of formula HNR1R2, as described in "Tetrahedron", 56 (2000), pages 8253-8262 and in "Journal Combinatoria! Chemistry" 11 (2009), pages 126-130.
Le aniline di formula (II) possono essere preparate per riduzione dei corrispondenti nitroder ivati di formula (III) , secondo lo schema di reazione 2: The anilines of formula (II) can be prepared by reduction of the corresponding nitroder ivates of formula (III), according to the reaction scheme 2:
Schema 2 Scheme 2
(III) d i) (III) d i)
Le condizioni di reazione preferite prevedono l'utilizzo dello stagno cloruro in acido cloridrico concentrato secondo quanto descritto in WO 00/46184. The preferred reaction conditions provide for the use of tin chloride in concentrated hydrochloric acid according to what described in WO 00/46184.
Il composto di formula (III), per A che assume il significato di Αχ, (III-l), può essere preparato per reazione del composto di formula (IV) con un composto di formula (V), dove Z è un gruppo uscente e R', XlfCy, n e ni, assumono i significati già visti, in presenza di una base , preferibilmente carbonato di potassio o sodio idruro, secondo lo schema di reazione 3. The compound of formula (III), for A which assumes the meaning of Αχ, (III-1), can be prepared by reaction of the compound of formula (IV) with a compound of formula (V), where Z is a leaving group and R ', XlfCy, n and ni, take on the meanings already seen, in the presence of a base, preferably potassium carbonate or sodium hydride, according to reaction scheme 3.
Schema 3 Scheme 3
Il composto di formula (III), per A che assume il significato di A2, (III-2), può essere ottenuto per reazione del composto di formula (VI), dove W rappresenta un atomo di bromo o cloro, con un composto di formula (VII), in cui R', X2R5, R6, n2 e X assumono i significati già visti, in presenza di una base, preferibilmente carbonato di potassio o sodio idruro, secondo lo schema di reazione 4. The compound of formula (III), for A which assumes the meaning of A2, (III-2), can be obtained by reaction of the compound of formula (VI), where W represents a bromine or chlorine atom, with a compound of formula (VII), in which R ', X2R5, R6, n2 and X take on the meanings already seen, 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 (IV), per X che rappresenta un atomo di zolfo, vengono preparati facendo reagire, in presenza di un catalizzatore di palladio, un composto di formula (VI) con tioacetato di potassio e successivamente saponificando il tioestere così ottenuto, secondo quanto descritto in "Tetrahedron Letters", 48 (2007), pagg.3033-3037. The compounds of formula (IV), for X representing a sulfur atom, are prepared by reacting, in the presence of a palladium catalyst, a compound of formula (VI) with potassium thioacetate and subsequently saponifying the thioester thus obtained, according to as described in "Tetrahedron Letters", 48 (2007), pages 3033-3037.
I composti di formula (IV), per X che rappresenta un atomo di ossigeno, vengono preparati per nitrazione del fenolo corrispondente con acido nitrico o per nitrosazione dello stesso fenolo e successiva ossidazione con acido nitrico o con peracidi secondo quanto descritto in WO 1992/07829, in US 5177106 e in WO 92/88765. The compounds of formula (IV), for X which represents an oxygen atom, are prepared by nitration of the corresponding phenol with nitric acid or by nitrosation of the same phenol and subsequent oxidation with nitric acid or with peracids as described in WO 1992/07829 , in US 5177106 and in WO 92/88765.
I composti di formula (V) e formula (VI), se non sono prodotti commerciali, possono essere facilmente ottenuti mediante metodi facilmente reperibili in letteratura. The compounds of formula (V) and formula (VI), if they are not commercial products, can be easily obtained by methods readily available in the literature.
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 combattuti con i composti di formula generale (I) sono quelli appartenenti alle classi dei Basidiomiceti, Ascomiceti, Deuteromicet i 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 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., 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.
Le principali colture che possono essere protette con i composti dell'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 of the invention include cereals (wheat, barley, rye, oats, rice, corn, sorghum, etc.), fruit trees (apple, pear, plum, peach, almond, cherry, banana, vine, 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 Aequalis 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 Aequalis 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 e non esibiscono alcuna fitotossicità sulle colture trattate. The compounds of formula (I) are capable of carrying out a fungicidal action of both curative and preventive character and do not exhibit any 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 dell'invenzione opportunamente formulati . For practical uses in agriculture it is often preferable to use fungicidal compositions containing the compounds of the invention suitably formulated.
Sono un ulteriore oggetto della presente invenzione composizioni fungicide comprendenti uno o più composti 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 one or more compounds 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 alkylnaphthalenesulphonates, polynaphthalenesulphonates, alkylsulfonates, arylsulfonates, alkylaryl sulphonates, polycarboxylates, sulphosuccinates, alkylsulfosuccinates, alkylsulfonates, 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: 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, idrossichinolina solfato, 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, poltiglia bordolese, 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, rame idrossido, rame ossicloruro, rame (I) ossido, rame solfato, 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, zolfo, 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: acibenzolar, ametoctradin, amisulbrom, ampropylfos, anilazine, azaconazole, azoxystrobin, benalaxyl, benalaxyl-M, benomyl, bertanololicarb, bit , bixafen, blasticidin-S, boscalid, bromuconazole, bupirimate, buthiobate, captafol, captan, carbendazim, carboxin, carpropamid, quinomethionat, chloroneb, chlorothalonil, chlozolinate, cyazofamid, cyflrodufenamid, cyprocarbonazim, dichproconazol , diclomezine, dicloran, diclocymet, diethofencarb, difenoconazole, diflumetorim, dimethir imol, dimethomorph, dimoxystrobin, diniconazole, dinocap, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, edifenphole, etoxquinacazole, etoxquinac phenamidone, phenaminosulf, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenox anil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, fluopicolide, fluopyram, fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilfutanamide, flusilfanamide, flutil fosetyl-aluminum, fuberidazole, furalaxyl, furametpyr, furconazole, furconazole-cis, guazatine, hexaconazole, hymexazol, hydroxyquinoline sulfate, imazalil, imibenconazole, iminocothtadine, ipconazole, iprobenfos, isprobenfos, hyprodicarbyl , mancopper, mancozeb, mandipropamid, maneb, mebenil, mepanipyrim, mepronil, meptyldinocap, metalaxyl, metalaxyl-M, metconazole, methfuroxam, metiram, metominostrobin, metrafenone, metsulfovax, mycyclobutin, nitraceous-nitrace, natamolastroxyl, nitrace , oxadixyl, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorofenol and its salts, penthiopyrad, phthalide, picoxystrobin, piperalin, bordolese mush, polyoxins, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, proquinazid, prothiocarb, prothioconazole, pyracarbolid, pyraclostrobin, pyramilostrobin, pyramilostril pyriofenone, pyroquilon, pyroxyfur, quinacetol, quinazamid, quinconazole, quinoxyfen, quintozene, rabenzazole, copper hydroxide, copper oxychloride, copper (I) oxide, copper sulfate, sedaxane, silthiofam, simeconazebole, spiroxamine, tiabucendomazol , thiadifluor, thicyofen, thifluzamide, thiophanate, thiophanate-methyl, thiram, tiadinil, tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triarimol, triazbutil, triazo, triumidiconazole, tricylidiconazole, triforphiconazole, tricylidiconazole, trificonolexy -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 consiste nell'applicazione di dosi efficaci dei composti di formula (I), utilizzati come tali o formulati in composizioni fungicide come sopra descritte. A further object of the present invention is therefore a method for the control of phytopathogenic fungi in agricultural crops, which consists in the application of effective doses of the compounds of 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 illustrare l'invenzione vengono ora forniti i seguenti esempi che sono da ritenersi a scopo illustrativo e non limitativo della stessa . In order to better illustrate the invention, the following examples are now provided which are to be considered for illustrative and not limitative purposes.
ESEMPIO 1 EXAMPLE 1
Preparazione di 2-nitro-5-[3-(idrossi)ciclopentilossi]-p—xilene [intermedio di formula (IV)] Preparation of 2-nitro-5- [3- (hydroxy) cyclopentyloxy] -p-xylene [intermediate of formula (IV)]
10 g di 2,5-dimetil-4-nitrofenolo sono stati sciolti in 160 mi di N,N-dimetilformammide, sono stati quindi aggiunti 13 g di carbonato di potassio, lasciando in agitazione a temperatura ambiente per 30 minuti. 10 g of 2,5-dimethyl-4-nitrophenol were dissolved in 160 ml of N, N-dimethylformamide, then 13 g of potassium carbonate were added, stirring at room temperature for 30 minutes.
Sono stati successivamente aggiunti 11 g di 3-idrossi-l-ciclopentilmetansolfonato e si è portato il tutto ad una temperatura di 100°C per 5 ore. 11 g of 3-hydroxy-1-cyclopentylmethanesulfonate were subsequently added and the whole was brought to a temperature of 100 ° C for 5 hours.
Terminata la reazione, la miscela è stata versata in acqua e acetato di etile ed estratta tre volte. When the reaction was over, the mixture was poured into water and ethyl acetate and extracted three times.
La fase organica è stata anidrificata su solfato di sodio ed evaporata fornendo 28 g del prodotto desiderato. GC-MS: 251 (M<+>). The organic phase was dried over sodium sulphate and evaporated to give 28 g of the desired product. GC-MS: 251 (M <+>).
ESEMPIO 2 EXAMPLE 2
Preparazione del 2-nitro-5- [3-(1,1,2,2-tetrafluoroetossi)ciclopentilossi]—p—xilene [intermedio di formula (III-l)] Preparation of 2-nitro-5- [3- (1,1,2,2-tetrafluoroethoxy) cyclopentyloxy] —p — xylene [intermediate of formula (III-1)]
4 g di 2-nitro-5-[3-(idrossi)ciclopentilossi]-pixilene (preparato come sopra descritto) sono stati sciolti in 42 mi di una miscela di dimetilsolfossido :toluene 1:6, sono stati poi aggiunti 0.9 g di idrossido di potassio macinato e il tutto è stato raffreddato a 0°C. 4 g of 2-nitro-5- [3- (hydroxy) cyclopentyloxy] -pixylene (prepared as described above) was dissolved in 42 ml of a 1: 6 dimethyl sulfoxide: toluene mixture, 0.9 g of hydroxide was then added of ground potassium and the whole was cooled to 0 ° C.
Dopo aver effettuato tre lavaggi vuoto/azoto, la miscela di reazione è stata messa in atmosfera di tetrafluoroetilene a temperatura ambiente e mantenuta in queste condizioni per una notte. After carrying out three vacuum / nitrogen washes, the reaction mixture was placed in a tetrafluoroethylene atmosphere at room temperature and kept under these conditions overnight.
La miscela è stata quindi versata in acqua ed etere etilico, quindi sono state separate le fasi, è stata anidrificato su solfato di sodio e il solvente è stato evaporato. The mixture was then poured into water and diethyl ether, then the phases were separated, dried over sodium sulfate and the solvent was evaporated.
Sono stati ottenuti 4.9 g di prodotto. GC-MS: 351 (M<+>). 4.9 g of product were obtained. GC-MS: 351 (M <+>).
ESEMPIO 3 EXAMPLE 3
Preparazione di 4- [3- (1,1,2,2-tetrafluoroetossi)ciclopentilossi] -2 ,5-xilidina [anilina di formula (II)] Preparation of 4- [3- (1,1,2,2-tetrafluoroethoxy) cyclopentyloxy] -2, 5-xylidine [aniline of formula (II)]
2.4 g di 2-nitro-5- [3-(1,1,2,2-tetraf luoroetossi )-ciclopent ilossi ]-p-xilene in 40 mi di metanolo, sono stati addizionati di 2 g di formiato di ammonio e 0.26 g di Palladio su carbone. 2.4 g of 2-nitro-5- [3- (1,1,2,2-tetraf luoroethoxy) -cyclopentyloxy] -p-xylene in 40 ml of methanol, were added with 2 g of ammonium formate and 0.26 g of Palladium on carbon.
Dopo una notte a temperatura ambiente, si filtra il catalizzatore è stato filtrato e il solvente evaporato . After one night at room temperature, the catalyst was filtered out and the solvent evaporated.
Il grezzo così ottenuto è stato lavato con acqua ed estratto con acetato di etile (3 x 25 mi), quindi essiccato su solfato di sodio ed evaporato. The crude product thus obtained was washed with water and extracted with ethyl acetate (3 x 25 ml), then dried over sodium sulphate and evaporated.
Sono stati ottenuti 1.8 g di prodotto desiderato che è stato utilizzato tal quale. GC-MS: 321 (M<+>). 1.8 g of desired product were obtained which was used as it is. GC-MS: 321 (M <+>).
ESEMPIO 4 EXAMPLE 4
Preparazione di N-etil-N-metil-N' -{4- [3- (1,1,2,2-tetrafluoroetossi) ciclopentilossi] -2,5-xilil}formammidina (Composto N° 1.1) e dei composti N° 1.2-1.76. Preparation of N-ethyl-N-methyl-N '- {4- [3- (1,1,2,2-tetrafluoroethoxy) cyclopentyloxy] -2,5-xylyl} formamide (Compound No. 1.1) and compounds N ° 1.2-1.76.
1,6 g di 4- [3-(1,1,2,2-tetrafluoroetossi) ciclopent ilossi]-2 ,5-xilidina, 8.3 mi di trietilortoformiato e 0.1 g di acido p-toluensolfonico sono stati scaldati a 130°C per 5 ore. 1.6 g of 4- [3- (1,1,2,2-tetrafluoroethoxy) cyclopentyloxy] -2, 5-xylidine, 8.3 ml of triethylorthoformate and 0.1 g of p-toluenesulfonic acid were heated to 130 ° C for 5 hours.
Dopo controllo di reazione in TLC (eluente esano: acetato di etile 7:3), la miscela è stata evaporata, diluita con 15 mi di cloruro di metilene quindi addizionata di 0.58 g di N-etil-N-metilammina . After reaction control in TLC (eluent hexane: ethyl acetate 7: 3), the mixture was evaporated, diluted with 15 ml of methylene chloride then added with 0.58 g of N-ethyl-N-methylamine.
La miscela è stata scaldata a 40°C per 1.5 h, il solvente evaporato e il prodotto così ottenuto è stato purificato su allumina neutra eluendo con esano:acetato di etile 9:1. The mixture was heated at 40 ° C for 1.5 h, the solvent evaporated and the product thus obtained was purified on neutral alumina eluting with hexane: ethyl acetate 9: 1.
Sono stati ottenuti 2.2 g di prodotto desiderato. 2.2 g of desired product were obtained.
<1>H-NMR (δ-ppm, CDC13) = 1.2 (t, 3H); 1.9-2.2 (m, 6H); 2.2 (s, 3H); 3.0 (s, 3H); 3.2 (m, 2H); 4.6 (m, IH); 4.8 (m, IH); 5.4-5.8 (11, IH); 6.5 (s, IH); 6.6 (s, IH); 7.2 (s, IH). <1> H-NMR (δ-ppm, CDC13) = 1.2 (t, 3H); 1.9-2.2 (m, 6H); 2.2 (s, 3H); 3.0 (s, 3H); 3.2 (m, 2H); 4.6 (m, 1H); 4.8 (m, 1H); 5.4-5.8 (11, 1H); 6.5 (s, 1H); 6.6 (s, 1H); 7.2 (s, 1H).
Operando analogamente sono stati ottenuti i composti N° 1.2-1.76, di formula generale (I) in cui A assume il significato di Ai, riportati in Tabella 1 By operating in the same way, compounds N ° 1.2-1.76 have been obtained, of general formula (I) in which A assumes the meaning of Ai, reported in Table 1
Αχ = R-X1-(CH2)nl-Cy-(CH2)n-X-Tabella 1 Αχ = R-X1- (CH2) nl-Cy- (CH2) n-X-Table 1
1,3 C5H8 —1,3-ciclopentile; 1,4-C6H101,4-cicloesile; 1,2-C3H41,2-ciclopropile. 1,3 C5H8 -1,3-cyclopentyl; 1,4-C6H101,4-cyclohexyl; 1,2-C3H41,2-cyclopropyl.
ESEMPIO 5 EXAMPLE 5
Preparazione di 2-nitro-5- (3-mercapto-2-butiltio)-p— xilene [intermedio di formula (IV)] Preparation of 2-nitro-5- (3-mercapto-2-butylthio) -p— xylene [intermediate of formula (IV)]
1.92 g di idruro di sodio sono stati sospesi in 10 mi di N,N-dimetilf ormammide, il tutto è stato raffreddato a 0°C ed è stata gocciolata una soluzione di 9.80 g di 2,3-butanditiolo sciolti in 80 mi di N,N-dimetilformammide . 1.92 g of sodium hydride were suspended in 10 ml of N, N-dimethylf ormamide, the whole was cooled to 0 ° C and a solution of 9.80 g of 2,3-butanedithiol dissolved in 80 ml of N was dropped. , N-dimethylformamide.
La miscela di reazione è stata riportata a temperatura ambiente e lasciata in agitazione per 15 minuti, poi è stata gocciolata un'altra soluzione di 14.87 g di 2,5-dimetil-4-cloro-nitrobenzene sciolti in altri 50 mi di N,N-dimetilformammide. The reaction mixture was brought back to room temperature and left to stir for 15 minutes, then another solution of 14.87 g of 2,5-dimethyl-4-chloro-nitrobenzene dissolved in another 50 ml of N, N was dropped. -dimethylformamide.
La miscela è stata mantenuta in agitazione a temperatura ambiente per una notte, quindi è stata versata in acqua ed estratta con acetato di etile (80 mi X 3). The mixture was stirred at room temperature overnight, then poured into water and extracted with ethyl acetate (80 ml X 3).
La fase organica, ripetutamente lavata con acqua e anidrificata su solfato di sodio, è stata evaporata a dare un grezzo semisolido che è stato purificato per lavaggio con etere etilico (30 mi). The organic phase, repeatedly washed with water and dried over sodium sulfate, was evaporated to give a semi-solid crude which was purified by washing with ethyl ether (30 ml).
Il solido così ottenuto è stato filtrato ottenendo 15 g di prodotto desiderato. GC-MS: 271 (M<+>). The solid thus obtained was filtered to obtain 15 g of the desired product. GC-MS: 271 (M <+>).
ESEMPIO 6 EXAMPLE 6
Preparazione di 2-nitro-5- [3-(1,1,2,2-tetrafluoroetiltio)-2-butiltio]—p—xilene [intermedio di formula (IH -2)] Preparation of 2-nitro-5- [3- (1,1,2,2-tetrafluoroethylthio) -2-butylthio] —p-xylene [intermediate of formula (IH -2)]
2.85 g di 2-nitro-5- (3-mercapto-2-butiltio)-pxilene sono stati sciolti in 30 mi di una miscela di dimetilsolfossido :toluene 1:5, sono stati poi aggiunti 0.2 g di idrossido di potassio macinato e il tutto è stato raffreddato a 0°C. 2.85 g of 2-nitro-5- (3-mercapto-2-butylthio) -pxylene was dissolved in 30 ml of a 1: 5 dimethyl sulfoxide: toluene mixture, 0.2 g of ground potassium hydroxide was then added and the everything was cooled to 0 ° C.
Dopo aver effettuato tre lavaggi vuoto/azoto, la miscela di reazione è stata messa in atmosfera di tetrafluoroetilene a temperatura ambiente e mantenuta in queste condizioni per una notte. After carrying out three vacuum / nitrogen washes, the reaction mixture was placed in a tetrafluoroethylene atmosphere at room temperature and kept under these conditions overnight.
La miscela è stata versata poi in acqua ed etere etilico, quindi le fasi sono state separate, la fase organica anidrificata su solfato di sodio e il solvente evaporato. The mixture was then poured into water and ethyl ether, then the phases were separated, the organic phase dried over sodium sulphate and the solvent evaporated.
Sono stati ottenuti 3.3 g di prodotto. GC-MS: 371 (M<+>). 3.3 g of product were obtained. GC-MS: 371 (M <+>).
ESEMPIO 7 EXAMPLE 7
Preparazione di 4- [3-(1,1,2,2-tetrafluoroetiltio)-2-butiltio]-2,5-xilidina [anilina di formula (II)] Preparation of 4- [3- (1,1,2,2-tetrafluoroethylthio) -2-butylthio] -2,5-xylidine [aniline of formula (II)]
1.0 g di 2-nitro-5- [3-(1,1,2,2-tetrafluoroetiltio)-2-butiltio]—p-xilene e 1.82 g di stagno cloruro sono stati diluiti con 10 mi di metanolo. 1.0 g of 2-nitro-5- [3- (1,1,2,2-tetrafluoroethylthio) -2-butylthio] -p-xylene and 1.82 g of tin chloride were diluted with 10 ml of methanol.
La miscela è stata raffreddata a 0°C con un bagno di ghiaccio e a questa temperatura sono stati aggiunti, gocciolandoli, 10 mi di HC1 al 37%. The mixture was cooled to 0 ° C with an ice bath and 10 ml of 37% HCl were added dropwise at this temperature.
Finito il gocciolamento la temperatura è stata portata a 70°C per 1.5 h, la reazione controllata in TLC (eluente esano:acetato di etile 7:3), poi la soluzione è stata basificata con carbonato di potassio fino a pH 9, quindi è stata estratta con acetato di etile. After the dripping, the temperature was brought to 70 ° C for 1.5 h, the reaction controlled in TLC (eluent hexane: ethyl acetate 7: 3), then the solution was basified with potassium carbonate up to pH 9, then it was was extracted with ethyl acetate.
La fase organica è stata anidrificata su solfato di sodio, poi filtrata ed evaporata. The organic phase was dried over sodium sulphate, then filtered and evaporated.
Sono stati ottenuti 0.8 g di prodotto. GC-MS: 341 (M<+>). 0.8 g of product were obtained. GC-MS: 341 (M <+>).
ESEMPIO 8 EXAMPLE 8
Preparazione di N-etil-N-metil-N'-{4-[3-(1,1,2,2-tetrafluoroetiltio)-2-butiltio]-2 ,5-xilil}formammidina (Composto N° 2.1) e dei composti N° 2.2-2.53 Preparation of N-ethyl-N-methyl-N '- {4- [3- (1,1,2,2-tetrafluoroethylthio) -2-butylthio] -2, 5-xylyl} formamide (Compound No. 2.1) and of compounds N ° 2.2-2.53
1,5 g di 4- [3-(1,1,2,2-tetrafluoroetiltio)-2-butiltio]-2,5-xilidina, 7.2 mi di trietilortoformiato e 0,1 g di acido p-toluensolfonico sono stati scaldati a 130°C per 5 ore. 1.5 g of 4- [3- (1,1,2,2-tetrafluoroethylthio) -2-butylthio] -2,5-xylidine, 7.2 ml of triethylorthoformate and 0.1 g of p-toluenesulfonic acid were heated at 130 ° C for 5 hours.
Dopo controllo di reazione in TLC (eluente esano: acetato di etile 7:3), la miscela è stata evaporata, diluita con 15 mi di cloruro di metilene, quindi addizionata con 0.51 g di N-etil-N-metilammina. After reaction control in TLC (eluent hexane: ethyl acetate 7: 3), the mixture was evaporated, diluted with 15 ml of methylene chloride, then added with 0.51 g of N-ethyl-N-methylamine.
La temperatura è stata portata a 40°C per 1.5 h, il solvente evaporato e il prodotto così ottenuto è stato purificato su allumina neutra eluendo con esano:acetato di etile 9:1. The temperature was brought to 40 ° C for 1.5 h, the solvent evaporated and the product thus obtained was purified on neutral alumina eluting with hexane: ethyl acetate 9: 1.
Sono stati così ottenuti 1.9 g di prodotto desiderato. 1.9 g of desired product were thus obtained.
<1>H-NMR (δ-ppm, CDC13 )= 1.1 (m, 3H); 1.3 (m, 3H); 2.2 (s, 3H); 2.4 (s, 3H); 3.0 (s, 3H); 3.2-3.4 (m, 3H); 3.6 (m, IH); 5.6-6.0 (tt, IH); 6.6 (s, 2H); 7.4 (s, IH). <1> H-NMR (δ-ppm, CDC13) = 1.1 (m, 3H); 1.3 (m, 3H); 2.2 (s, 3H); 2.4 (s, 3H); 3.0 (s, 3H); 3.2-3.4 (m, 3H); 3.6 (m, 1H); 5.6-6.0 (tt, 1H); 6.6 (s, 2H); 7.4 (s, 1H).
Operando analogamente sono stati ottenuti i composti N° 2.2-2.53, di formula generale (I) in cui A assume il significato di A2, riportati in Tabella 2 . By operating in the same way, compounds N ° 2.2-2.53 have been obtained, of general formula (I) in which A assumes the meaning of A2, reported in Table 2.
A2= R<,>-X2-(CR5R6)n2-X-Tabella 2 A2 = R <,> - X2- (CR5R6) n2-X-Table 2
ESEMPIO 9 EXAMPLE 9
Determinazione dell'attività preventiva (5 giorni) dei composti di formula generale (I) contro Erysiphe graminis su grano. Determination of the preventive activity (5 days) of the compounds of general formula (I) against Erysiphe graminis 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 prodotto in 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 product 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, piante precedentemente infettate da Erisiphae graminis. After 5 days of stay in a conditioned environment, the plants were dry infected by shaking on them, to spread the inoculum, plants previously infected with Erisiphae 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 della infezione, sia sulle parti trattate direttamente con i prodotti (T), sia sulle parti sviluppatesi durante l'esecuzione della prova (NT), mediante scala di valutazione visiva della percentuale di area fogliare colpita; la scala prevede come estremi il valore 100 (pianta completamente 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 (completely 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 per i prodotti esaminati: Table 3 shows the results obtained for the products examined:
Tabella 3 Table 3
ESEMPIO 10 EXAMPLE 10
Determinazione dell' attività preventiva (5 giorni) dei composti di formula generale (I) contro Puccinia recondita su grano. Determination of the preventive activity (5 days) of the compounds of general formula (I) against Puccinia recondita 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 prodotto in esame (vedi la seguente tabella 4), 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 product under examination (see the following table 4), dispersed in a hydroacetonic solution at 20% by volume of acetone.
Dopo 5 giorni di permanenza in ambiente condizionato, le piante sono state irrorate su entrambe le pagine fogliari con una sospensione acquosa di conidi di Puccinia recondita (2 mg di inoculo per 1 mi di soluzione per infezione). After 5 days of stay in a conditioned environment, the plants were sprayed on both leaves with an aqueous suspension of conidia of Puccinia recondita (2 mg of inoculum per 1 ml of solution for infection).
Dopo l'irrorazione, le piante sono state mantenute in ambiente saturo di umidità e temperatura compresa tra i 18 e 24°C per il periodo di incubazione del fungo (1 giorno). After spraying, the plants were kept in an environment saturated with humidity and a temperature between 18 and 24 ° C for the incubation period of the fungus (1 day).
Al termine di detto periodo, le piante sono state poste in serra con U.R. 70% e temperatura di 18-24 °C per 14 giorni. At the end of this period, the plants were placed in the greenhouse with U.R. 70% and temperature of 18-24 ° C for 14 days.
Trascorso questo periodo di tempo, sono comparsi i sintomi esteriori del patogeno ed è stato quindi possibile procedere alla valutazione dell'intensità della infezione, sia sulle parti trattate direttamente con i prodotti (T), sia sulle parti sviluppatesi durante l'esecuzione della prova (NT), mediante scala di valutazione visiva della percentuale di area fogliare colpita; la scala prevede come estremi il valore 100 (pianta completamente 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 (completely 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 4 sono riportati i risultati ottenuti per i prodotti esaminati: Tabella 4 Table 4 shows the results obtained for the products examined: Table 4
Claims (14)
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000046184A1 (en) * | 1999-02-06 | 2000-08-10 | Aventis Cropscience Gmbh | N2-phenylamidine derivatives |
| WO2003093224A1 (en) * | 2002-05-03 | 2003-11-13 | E.I. Du Pont De Nemours And Company | Amidinylphenyl compounds and their use as fungicides |
| WO2007061966A2 (en) * | 2005-11-23 | 2007-05-31 | E. I. Du Pont De Nemours And Company | Amidinylphenyl compounds and their use as fungicides |
-
2010
- 2010-08-26 IT IT001575A patent/ITMI20101575A1/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000046184A1 (en) * | 1999-02-06 | 2000-08-10 | Aventis Cropscience Gmbh | N2-phenylamidine derivatives |
| WO2003093224A1 (en) * | 2002-05-03 | 2003-11-13 | E.I. Du Pont De Nemours And Company | Amidinylphenyl compounds and their use as fungicides |
| WO2007061966A2 (en) * | 2005-11-23 | 2007-05-31 | E. I. Du Pont De Nemours And Company | Amidinylphenyl compounds and their use as fungicides |
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