EA040946B1 - HERBICIDALLY ACTIVE 3-PHENYLISOXAZOLINE-5-CARBOXAMIDES OF TETRAHYDRO- AND DIHYDROFURANOUS CARBOXAMIDES AND THEIR APPLICATION - Google Patents

Description

The invention relates to the technical field of herbicides, in particular herbicides for the selective control of weeds and weeds in crops of useful plants.

In particular, the present invention relates to a substituted 3-phenylisoxazoline-5-carboxamide of the general formula (I) according to the invention and its agrochemically acceptable salts, a herbicidal agent and a plant growth regulator containing said compound, a method for controlling unwanted plants using said compound, or said herbicidal agent; and using said compound or said herbicidal agent to control unwanted plants.

WO 1995/014681 A1, WO 1995/014680 A1, WO 2008/035315 A1, WO 2005/051931 A1 and WO 2005/021515 A1 describe, inter alia, respectively, 3-phenylisoxazoline-5-carboxamides, which are substituted on the phenyl ring at 3 - and 4-position alkoxy residues. WO 1998/057937 A1 describes, inter alia, compounds which are substituted in the 4-position on the phenyl ring with alkoxy radicals. WO 2006/016237 A1 describes, inter alia, compounds which are substituted in the 4-position on the phenyl ring with amido residues. The compounds described in the previously mentioned documents have a pharmacological effect.

WO 2005/021516 A1 discloses 3-(([3-(3-tert-butylphenyl)-5-ethyl-4,5-dihydro-1,2-oxazol-5yl]carbonyl)amino)-5-fluoro-4 -oxopentanoic acid and 3-(([3-(3-tert-butylphenyl)-5-isopropyl-4,5dihydro-1,2-oxazol-5-yl]carbonyl)amino)-5-fluoro-4-oxopentanoic acid as pharmacologically active compounds.

3-phenylisoxazoline-5-carboxamides are known from DE 4026018 A1, EP 0 520 371 A2 and DE 4017665, which have a hydrogen atom in the 5-position of the isoxazoline ring. These compounds are described there as agrochemically active protectants, i. e. as compounds that eliminate the undesirable herbicidal effect of herbicides in relation to cultivated plants. The herbicidal activity of these compounds has not been disclosed. Priority, previously unpublished European Patent Application No. 10170238 describes herbicidally and fungicidally active 3-phenylisoxazoline-5-carboxamides and 3-phenylisoxazoline-5-thioamides, which have a hydrogen atom in the 5-position of the isoxazoline ring. From Monatshefte Chemie (2010) 141, 461 and Letters in Organic Chemistry (2010), 7, 502, 3-phenylisoxazoline-5-carboxamides are also known, which have a hydrogen atom in the 5-position of the isoxazoline ring. Some of these compounds are fungicidal but not herbicidal.

WO 2014/048827 describes the herbicidal action of 3-phenylisoxazoline-5-carboxylic acids, 3-phenylisoxazoline-5-carboxylic acid esters, 5-carbaldehydes and 5-nitriles.

WO 2014/048853 describes isoxazoline-5-carboxamides and -5-thioamides with heterocycles in the 3 position (herbicide and fungicide).

WO 2014/048940 has quinoline as a specific heterocycle at the 3-position (fungicide), WO 2014/048882 has alkoxy as a specific residue at the 5-position.

WO 2014/048882 describes isoxazoline-carboxamides with alkoxy as a particular residue in the 5 position.

WO 2012/130798 describes herbicidally and fungicidally active 3-phenylisoxazoline-5-carboxamides and -5-thioamides of substituted heterocycles.

The herbicidal action of these known compounds, in particular at a low application rate or their compatibility with crop plants, must be improved.

As a result of these reasons, there is a need for stronger herbicides and/or plant growth regulators for selective use in plant cultures or for use in non-cultivated plants, and these active substances should preferably have other preferred properties for use, such as improved compatibility with cultivated plants.

Therefore, the subject of the present invention is to provide compounds with herbicidal action (herbicides), which, even at a relatively low application rate, are highly effective against economically important pests and preferably, with good effectiveness against pests, should be selectively used in cultivated plants, and when this preferably they should show good compatibility with cultivated plants. Preferably, these herbicidal compounds should be particularly effective and efficient against a wide range of weeds, and preferably additionally show good efficacy against many weeds.

In addition to the herbicidal action, numerous compounds of the formula (I) also have a fungicidal action, which, however, is only slightly manifested.

Surprisingly, it has been found that the following 3-phenylisoxazoline-5-carboxamides of tetrahydro- and dihydrofurancarboxylic acid amides of formula (I) and their salts exhibit excellent herbicidal activity against a wide range of economically important mono- and dicotyledonous annual pests.

The objects of the present invention are therefore 3-phenylisoxazoline-5-carboxamide of the general formula (I)

- 1 040946

and its agrochemically acceptable salts, in which

R ¹ and R ² are respectively hydrogen,

R ³ means (C ₁ -C ₃ )alkyl, (C ₃ -C ₄ )cycloalkyl, (C ₂ -C ₃ )alkenyl, (C ₂ -C ₃ )alkynyl or (C ₁ -C ₃ )alkoxy which are substituted m residues selected from the group consisting of fluorine, chlorine, bromine, cyano, (C1C ₂ )alkoxy and hydroxy;

Y means oxygen;

W means oxygen;

Z means a group selected from Z-1 to Z-4, where Z-1 to Z-4 have the following meaning:

Z-1 Z-2 z-z Z-4 and the arrow means, respectively, the connection with the C=W group of the formula (I);

R ¹¹ are hydrogen, or (C ₁ -C ₃ )alkyl or (C ₃ -C ₆ )cycloalkyl which are substituted by m residues selected from the group consisting of fluorine and chlorine,

R ¹² is hydrogen or cyano, or

OR ⁷ , S(O)nR ⁵ , NR6R ⁸ , NR6COR ⁸ , (C1-C6) alkyl, (C ₃ -C ₆ ) cycloalkyl, (C ₂ -C ₃ ) alkenyl or (C ₂ C ₃ ) alkynyl, which substituted with m residues selected from the group consisting of fluorine, chlorine, bromine, cyano and hydroxy; or

R ¹¹ and R ¹² together with the nitrogen atom to which they are attached form a saturated, partially or fully unsaturated five- or six-membered ring which, in addition to the said nitrogen atom, contains r carbon atoms, n oxygen atoms and p elements from the group consisting of NR ⁷ and NCOR ⁷ as ring atoms; moreover, the carbon atom carries p oxo groups;

X ² , X ⁴ and X ⁶ mean, independently of each other, respectively, hydrogen or fluorine,

X ³ and X ⁵ mean independently of each other hydrogen, fluorine, chlorine, bromine, hydroxy or cyano, or (C ₁ -C ₃ )alkyl, (C ₁ -C ₃ )alkoxy, (C ₃ -C ₄ )cycloalkyl, (C ₂ -C ₃ )alkenyl or (C ₂ -C ₃ )alkynyl which are substituted by m residues from the group consisting of fluorine, chlorine and bromine;

R ⁵ means (C ₁ -C ₆ )alkyl, (C ₃ -C ₆ )cycloalkyl or phenyl, which are substituted by m residues selected from the group consisting of fluorine, chlorine and hydroxy;

R ⁶ is hydrogen or R ⁵ ;

R ⁷ means hydrogen, or (C ₁ -C ₆ )alkyl or (C ₃ -C ₆ )cycloalkyl, which are substituted by m residues selected from the group consisting of fluorine, chlorine and (C ₁ -C ₂ )alkoxy;

R ⁸ means hydrogen, or (C ₁ -C ₆ )alkyl, (C ₃ -C ₆ )cycloalkyl or phenyl, which are substituted by m residues selected from the group consisting of fluorine, chlorine and (C1-C ₂ )alkoxy;

m is equal to ordinal 0, 1, 2 or 3;

n is equal to ordinal 0, 1 or 2;

p is equal to the ordinal number 0 or 1; and r is equal to ordinal 3, 4, or 5.

Alkyl means a saturated, linear or branched hydrocarbon residue, respectively, with the indicated number of carbon atoms, for example, C ₁ -C ₆ -alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl, 1.1 -dimethylethyl, pentyl, 1-methylbutyl, 2methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2dimethylpropyl,1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4 -methylpentyl, 1,1-dimethylbutyl, 1,2dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2 -trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2methylpropyl.

Halogen-substituted alkyl means linear or branched alkyl groups, where the hydrogen atoms in these groups may be partially or completely replaced by halogen atoms, for example, C ₁ -C ₂ -haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl , chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro,2difluoroethyl, 2 ,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and 1,1,1-trifluoroprop-2-yl.

- 2 040946

Alkenyl means unsaturated, linear or branched hydrocarbon residues, respectively, with the indicated number of carbon atoms and a double bond in any position, for example, C ₂ -C ₆ alkenyl, as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3pentenyl, 4- pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2methyl-2-butenyl, 3-methyl-2-butenyl, 1- methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3- methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3- pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-penteny l, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl- 1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3- butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl2-butenyl, 2- ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2- propenil.

Alkynyl means linear or branched hydrocarbon residues, respectively, with the indicated number of carbon atoms and a triple bond at any position, for example, C ₂ -C ₆ alkynyl, such as ethynyl, 1-propynyl, 2-propynyl (or propargyl), 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 3-methyl-1-butynyl, 1-methyl-2-butynyl, 1methyl-3- butynyl, 2-methyl-3-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 3-methyl- 1-pentynyl, 4-methyl-1-pentynyl, 1-methyl-2pentynyl, 4-methyl-2-pentynyl, 1-methyl-3-pentynyl, 2-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl4-pentynyl, 3-methyl-4-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3- butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl.

Cycloalkyl means a carbocyclic, saturated ring system preferably with 3 to 8 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. If a substituted cycloalkyl is optionally present, then a substituted cyclic system is also present, with double bond substituents on the cycloalkyl moiety also present, for example an alkylidene group such as methylidene.

If optionally substituted cycloalkyl is present, then also polycyclic aliphatic systems are present, such as, for example, bicyclo[1.1.0]butan-1-yl, bicyclo[1.1.0]butan-2-yl, bicyclo[2.1.0] pentan-1-yl, bicyclo[2.1.0]pentan-2-yl, bicyclo[2.1.0]pentan-5-yl, bicyclo[2.2.1]hept-2yl (norbornyl), adamantan-1-yl and adamantane -2-yl.

If a substituted cycloalkyl is also present, then a spirocyclic aliphatic system is also present, such as spiro[2.2]pent-1-yl, spiro[2.3]hex-1-yl, spiro[2.3]hex-4-yl, 3spiro[2.3 ]hex-5-yl.

Cycloalkenyl means a carbocyclic, non-aromatic, partially unsaturated ring system, preferably with 4-8 carbon atoms, e.g. , 1,3-cyclohexadienyl or 1,4-cyclohexadienyl, where there are also double bond substituents on the cycloalkenyl moiety, for example an alkylidene group such as methylidene. If, if necessary, a substituted cycloalkenyl is present, the explanation also applies to a substituted cycloalkyl.

Alkyl means a saturated, linear or branched hydrocarbon residue, respectively, with the indicated number of carbon atoms, for example, C ₁ -C ₆ -alkoxy, such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methyl-propoxy, 2-methylpropoxy, 1 ,1-dimethylethoxy, Pentoxy, 1methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1,1dimethylpropoxy, 1,2-dimethylpropoxy,1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy , 4methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2 -trimethylpropoxy, 1,2,2trimethylpropoxy, 1-ethyl-1-methylpropoxy and 1-ethyl-2-methylpropoxy. Alkyl substituted with halogen means linear or branched alkoxy residues with the corresponding number of carbon atoms, where the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms, for example, C ₁ -C ₂ -haloalkoxy, such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy , fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlordifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2trifluoroethoxy, 2-chloro-2-fluoroethoxy , 2-chloro-1,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2trichloroethoxy, pentafluoroethoxy and 1,1,1-trifluoroprop-2-oxy.

The term aryl means, if necessary, a substituted mono-, bi- or polycyclic aromatic system, preferably with 6-14, particularly preferably 6-10 ring carbon atoms, for example phenyl, naphthyl, anthryl, phenanthrenyl, and the like, preferably phenyl.

The term optionally substituted aryl also includes multicyclic systems such as tetrahydronaphthyl, indenyl, indenyl, fluorenyl, biphenylyl, the connection being on the aromatic system. According to the systematics, aryl, as a rule, also includes the concept, if necessary, substituted phenyl.

The above aryls are preferably substituted with, for example, hydrogen, halogen, alkyl, haloalkyl, hydroxy, alkoxy, cycloalkoxy, aryloxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, halocycloalkyl, aryl, arylalkyl, heteroaryl, heterocyclyl, alkenyl, alkylcarbonyl, cycloalkylcarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl , гидроксикарбонилом, циклоалкоксикарбонилом, циклоалкилалкоксикарбонилом, алкоксикарбонилалкилом, арилалкокси-карбонилом, арилалкоксикарбонилалкилом, алкинилом, алкинилалкилом, алкилалкинилом, трис-алкилсилилалкинилом, нитро, амино, циано, галоалкокси, галоалкилтио, алкилтио, гидротио, гидроксиалкилом, гетероарилалкокси, арилалкокси, гетероциклилалкокси, гетероциклилалкилтио, гетероциклилокси , heterocyclylthio, heteroaryloxy, bis-alkylamino, alkylamino, cycloalkylamino, hydroxycarbonylalkylamino, alkoxycarbonylalkylamino, arylalkoxycarbonylalkylamino, alkoxycarbonylalkyl(alkyl)amino, amino-carbonyl, alkylaminocarbonyl, b s-alkylaminocarbonyl, cycloalkylaminocarbonyl, hydroxycarbonylalkylaminocarbonyl, alkoxycarbonylalkylaminocarbonyl, arylalkoxycarbonylalkylaminocarbonyl.

The heterocyclic residue (heterocyclyl) contains at least one heterocyclic ring (=carbocyclic ring in which at least one C-atom is replaced by a heteroatom, preferably one heteroatom from the group N, O, S, P) which is saturated, unsaturated, partially saturated or heteroaromatic, and may be unsubstituted or substituted, and the junction is on the ring atom. If a heterocyclic residue or a heterocyclic ring is optionally substituted, it may be annelated with other carbocyclic or heterocyclic rings. If, if necessary, a substituted heterocyclyl is present, then multicyclic systems are also present, such as, for example, 8-aza-bicyclo[3.2.1]octanyl, 8-aza-bicyclo[2.2.2]octanyl or 1-aza-bicyclo[2.2 .1]heptyl. If, if necessary, a substituted heterocyclyl is present, then spirocyclic systems are also present, such as, for example, 1-oxa-5-aza-spiro[2.3]hexyl. Unless otherwise stated, the heterocyclic ring preferably contains 3-9 ring atoms, particularly preferably 3-6 ring atoms, and one or more, preferably 1-4, particularly preferably 1, 2 or 3 heteroatoms in the heterocyclic ring, preferably from group N , O, and S, but the two oxygen atoms must not be next to each other, as, for example, with one heteroatom from the group N, O and S 1- or 2- or 3-pyrrolidinyl, 3,4-dihydro-2H-pyrrole -2- or 3-yl, 2,3-dihydro-III-pyrrol-1- or 2- or 3- or 4- or 5-yl; 2,5-dihydro-III-pyrrol-1- or 2- or 3-yl, 1- or 2- or 3- or 4-piperidinyl; 2,3,4,5-tetrahydropyridin-2- or 3- or 4- or 5-yl or 6-yl; 1,2,3,6-tetrahydropyridin-1- or 2- or 3- or 4- or 5- or 6-yl; 1,2,3,4-tetrahydropyridin-1- or 2- or 3- or 4- or 5- or 6-yl; 1,4dihydropyridin-1- or 2- or 3- or 4-yl; 2,3-dihydropyridin-2- or 3- or 4- or 5- or 6-yl; 2,5-dihydropyridine-2- or 3- or 4-, or 5-, or 6-yl, 1- or 2-, or 3-, or 4-azepanil; 2,3,4,5-tetrahydro1H-azepin-1- or 2-, or 3-, or 4-, or 5-, or 6-, or 7-yl; 2,3,4,7-tetrahydro-1H-azepin-1- or 2-, or 3-, or 4-, or 5-, or 6-, or 7-yl; 2,3,6,7-tetrahydro-1H-azepin-1- or 2- or 3- or 4-yl; 3,4,5,6tetrahydro-2H-azepin-2- or 3- or 4- or 5- or 6- or 7-yl; 4,5-dihydro-1H-azepin-1- or 2- or 3- or 4-yl; 2,5-dihydro-1H-azepin-1- or -2-, or 3-, or 4-, or 5-, or 6-, or 7-yl; 2,7-dihydro-1Nazepin-1- or -2- or 3- or 4-yl; 2,3-dihydro-1H-azepine-1- or -2-, or 3-, or 4-, or 5-, or 6-, or 7yl; 3,4-dihydro-2H-azepin-2- or 3- or 4- or 5- or 6- or 7-yl; 3,6-dihydro-2H-azepin-2- or 3- or 4- or 5- or 6- or 7-yl; 5,6-dihydro-2H-azepin-2- or 3- or 4- or 5- or 6- or 7-yl; 4,5-dihydro3H-azepin-2- or 3- or 4- or 5- or 6- or 7-yl; 1H-azepine-1- or -2- or 3- or 4- or 5- or 6- or 7-yl; 2H-azepin-2- or 3- or 4- or 5- or 6- or 7-yl; 3H-azepin-2- or 3- or 4- or 5- or 6- or 7-yl; 4H-azepin-2- or 3- or 4- or 5- or 6- or 7-yl, 2- or 3-oxolanyl (= 2- or 3-tetrahydrofuranyl); 2,3-dihydrofuran-2- or 3- or 4- or 5-yl; 2,5-dihydrofuran-2- or 3-yl, 2- or 3- or 4-oxanyl (= 2- or 3- or 4-tetrahydropyranyl); 3,4-dihydro-2H-pyran-2- or 3- or 4- or 5- or 6-yl; 3,6-dihydro-2H-pyran-2- or 3- or 4- or 5- or 6-yl; 2H-pyran-2- or 3- or 4- or 5- or 6-yl; 4H-pyran-2- or 3- or 4-yl, 2- or 3- or 4-oxepanyl; 2,3,4,5-tetrahydrooxepin-2- or 3- or 4- or 5- or 6- or 7-yl; 2,3,4,7-tetrahydrooxepin-2- or 3- or 4- or 5- or 6- or 7-yl; 2,3,6,7tetrahydrooxepin-2- or 3- or 4-yl; 2,3-dihydrooxepin-2- or 3- or 4- or 5- or 6- or 7-yl; 4,5-dihydrooxepin-2- or 3- or 4-yl; 2,5-dihydrooxepin-2- or 3- or 4- or 5- or 6- or 7-yl; oxepin-2- or 3- or 4- or 5- or 6- or 7-yl; 2- or 3-tetrahydrothiophenyl; 2,3-dihydrothiophen-2 or 3- or 4- or 5-yl; 2,5-dihydrothiophen-2- or 3-yl; tetrahydro-2H-thiopyran-2- or 3- or 4-yl; 3,4dihydro-2H-thiopyran-2- or 3- or 4- or 5- or 6-yl; 3,6-dihydro-2H-thiopyran-2- or 3- or 4- or 5- or 6-yl; 2H-thiopyran-2- or 3- or 4- or 5- or 6-yl; 4H-thiopyran-2- or 3- or 4-yl. Preferred 3-ring and 4-ring heterocycles are, for example, 1- or 2-aziridinyl,

- 4 040946 oxiranil, thiiranil, 1- or 2- or 3-azetidinyl, 2- or 3-oxetanyl, 2- or 3-thietanyl, 1,3-dioxetan2-yl. Other examples of heterocyclyls are a partially or fully hydrogenated heterocyclic residue with two heteroatoms from the group N, O and S, such as, for example, 1- or 2-, or 3-, or 4-pyrazolidinyl; 4,5-dihydro-3H-pyrazol-3- or 4- or 5-yl; 4,5-dihydro-1H-pyrazol-1- or 3- or 4- or 5-yl; 2,3-dihydro-1H-pyrazol-1- or 2- or 3- or 4- or 5-yl; 1- or 2-, or 3-, or 4-imidazolidinyl; 2,3-dihydro-1H-imidazol-1-or 2- or 3- or 4-yl; 2,5-dihydro-III-imidazol-1- or 2- or 4- or 5-yl; 4,5-dihydro-1H-imidazol-1- or 2- or 4- or 5-yl; hexahydropyridazin-1- or 2- or 3- or 4-yl; 1,2,3,4-tetrahydropyridazin-1- or 2- or 3- or 4- or 5- or 6-yl; 1,2,3,6-tetrahydropyridazin-1- or 2- or 3- or 4- or 5- or 6-yl; 1,4,5,6-tetrahydropyridazin-1- or 3- or 4- or 5- or 6-yl; 3,4,5,6-tetrahydropyridazin-3- or 4- or 5-yl; 4,5-dihydropyridazin-3- or 4yl; 3,4-dihydropyridazin-3- or 4- or 5- or 6-yl; 3,6-dihydropyridazin-3- or 4-yl; 1,6dihydropyridazin-1- or 3- or 4- or 5- or 6-yl; hexahydropyrimidin-1- or 2- or 3- or 4-yl; 1,4,5,6-tetrahydropyrimidin-1- or 2- or 4- or 5- or 6-yl; 1,2,5,6-tetrahydropyrimidin-1- or 2- or 4- or 5- or 6-yl; 1,2,3,4-tetrahydropyrimidin-1- or 2- or 3- or 4- or 5- or 6-yl; 1,6dihydropyrimidin-1- or 2- or 4- or 5- or 6-yl; 1,2-dihydropyrimidin-1- or 2- or 4- or 5- or 6-yl; 2,5-dihydropyrimidin-2- or 4- or 5-yl; 4,5-dihydropyrimidin-4- or 5- or 6-yl; 1,4-dihydropyrimidin-1- or 2- or 4- or 5- or 6-yl; 1- or 2- or 3-piperazinyl; 1,2,3,6-tetrahydropyrazin-1- or 2- or 3- or 5- or 6-yl; 1,2,3,4-tetrahydropyrazin-1- or 2- or 3- or 4- or 5- or 6-yl; 1,2-dihydropyrazin-1- or 2- or 3- or 5- or 6-yl; 1,4-dihydropyrazin-1- or 2- or 3-yl; 2,3-dihydropyrazin-2- or 3- or 5- or 6-yl; 2,5-dihydropyrazin-2- or 3-yl; 1,3-dioxolane 2- or 4- or 5-yl; 1,3-dioxol-2-or 4-yl; 1,3-dioxane-2- or 4- or 5-yl; 4H-1,3-dioxin-2- or 4- or 5- or 6-yl; 1,4-dioxane-2- or 3- or 5- or 6-yl; 2,3-dihydro-1,4-dioxin-2- or 3- or 5- or 6yl; 1,4-dioxin-2- or 3-yl; 1,2-dithiolan-3- or 4-yl; 3H-1,2-dithiol-3-or 4- or 5-yl; 1,3-dithiolan-2 or 4-yl; 1,3-dithiol-2- or 4-yl; 1,2-dithian-3-or 4-yl; 3,4-dihydro-1,2-dithiin-3- or 4- or 5- or 6yl; 3,6-dihydro-1,2-dithiin-3- or 4-yl; 1,2-dithiin-3- or 4-yl; 1,3-dithian-2- or 4- or 5-yl; 4H-1,3dithiin-2- or 4- or 5- or 6-yl; isoxazolidin-2- or 3- or 4- or 5-yl; 2,3-dihydroisoxazol-2 or 3- or 4- or 5-yl; 2,5-dihydroisoxazol-2- or 3- or 4- or 5-yl; 4,5-dihydroisoxazol-3- or 4- or 5-yl; 1,3-oxazolidin-2- or 3- or 4- or 5-yl; 2,3-dihydro-1,3-oxazol-2- or 3- or 4- or 5-yl; 2,5-dihydro-1,3-oxazol-2- or 4- or 5-yl; 4,5-dihydro-1,3-oxazol-2- or 4- or 5-yl; 1,2-oxazinan-2 or 3- or 4- or 5- or 6-yl; 3,4-dihydro-2H-1,2-oxazin-2- or 3- or 4- or 5- or 6-yl; 3,6dihydro-2H-1,2-oxazin-2- or 3- or 4- or 5- or 6-yl; 5,6-dihydro-2H-1,2-oxazin-2- or 3- or 4- or 5- or 6-yl; 5,6-dihydro-4H-1,2-oxazin-3- or 4- or 5- or 6-yl; 2H-1,2-oxazin-2- or 3- or 4- or 5- or 6-yl; 6H-1,2-oxazin-3- or 4- or 5- or 6-yl; 4H-1,2-oxazin-3- or 4- or 5- or 6-yl; 1,3-oxazinan-2- or 3- or 4- or 5- or 6-yl; 3,4-dihydro-2H-1,3-oxazin-2- or 3- or 4- or 5- or 6-yl; 3,6-dihydro-2H-1,3-oxazin-2- or 3- or 4- or 5- or 6-yl; 5,6-dihydro-2H-1,3-oxazin-2- or 4 or 5- or 6-yl; 5,6-dihydro-4H-1,3-oxazin-2- or 4- or 5- or 6-yl; 2H-1,3-oxazin-2- or 4- or 5- or 6-yl; 6H-1,3-oxazin-2- or 4- or 5- or 6-yl; 4H-1,3-oxazin-2- or 4- or 5- or 6-yl; morpholin-2- or 3- or 4-yl; 3,4-dihydro-2H-1,4-oxazin-2- or 3- or 4- or 5- or 6-yl; 3,6-dihydro2H-1,4-oxazin-2- or 3- or 5- or 6-yl; 2H-1,4-oxazin-2- or 3- or 5- or 6-yl; 4H-1,4-oxazin-2 or 3-yl; 1,2-oxazepan-2- or 3- or 4- or 5- or 6- or 7-yl; 2,3,4,5-tetrahydro-1,2-oxazepin-2- or 3- or 4- or 5- or 6- or 7-yl; 2,3,4,7-tetrahydro-1,2-oxazepin-2- or 3- or 4- or 5- or 6- or 7-yl; 2,3,6,7-tetrahydro-1,2-oxazepin-2- or 3- or 4- or 5- or 6- or 7-yl; 2,5,6,7-tetrahydro-1,2oxazepin-2- or 3- or 4- or 5- or 6- or 7-yl; 4,5,6,7-tetrahydro-1,2-oxazepin-3- or 4- or 5- or 6- or 7-yl; 2,3-dihydro-1,2-oxazepin-2- or 3- or 4- or 5- or 6- or 7-yl; 2,5-dihydro-1,2oxazepin-2- or 3- or 4- or 5- or 6- or 7-yl; 2,7-dihydro-1,2-oxazepin-2- or 3- or 4- or 5- or 6- or 7-yl; 4,5-dihydro-1,2-oxazepin-3- or 4- or 5- or 6- or 7-yl; 4,7-dihydro-1,2oxazepin-3- or 4- or 5- or 6- or 7-yl; 6,7-dihydro-1,2-oxazepin-3- or 4- or 5- or 6- or 7yl; 1,2-oxazepin-3- or 4- or 5- or 6- or 7-yl; 1,3-oxazepan-2- or 3-, or 4-, or 5-, or 6-, or 7yl; 2,3,4,5-tetrahydro-1,3-oxazepin-2- or 3- or 4- or 5- or 6- or 7-yl; 2,3,4,7-tetrahydro-1,3oxazepin-2- or 3- or 4- or 5- or 6- or 7-yl; 2,3,6,7-tetrahydro-1,3-oxazepin-2- or 3- or 4- or 5- or 6- or 7-yl; 2,5,6,7-tetrahydro-1,3-oxazepin-2- or 4- or 5- or 6- or 7-yl; 4,5,6,7tetrahydro-1,3-oxazepin-2- or 4-, or 5-, or 6-, or 7-yl; 2,3-dihydro-1,3-oxazepin-2- or 3- or 4- or 5- or 6- or 7-yl; 2,5-dihydro-1,3-oxazepin-2- or 4- or 5- or 6- or 7-yl; 2,7-dihydro-1,3oxazepin-2- or 4- or 5- or 6- or 7-yl; 4,5-dihydro-1,3-oxazepin-2- or 4- or 5- or 6- or 7yl; 4,7-dihydro-1,3-oxazepin-2- or 4- or 5- or 6- or 7-yl; 6,7-dihydro-1,3-oxazepin-2- or 4- or 5- or 6- or 7-yl; 1,3-oxazepin-2- or 4- or 5- or 6- or 7-yl; 1,4-oxazepan-2- or 3- or 5- or 6- or 7-yl; 2,3,4,5-tetrahydro-1,4-oxazepin-2- or 3- or 4- or 5- or 6- or 7-yl; 2,3,4,7tetrahydro-1,4-oxazepin-2- or 3-, or 4-, or 5-, or 6-, or 7-yl; 2,3,6,7-tetrahydro-1,4-oxazepin-2 or 3- or 5- or 6- or 7-yl; 2,5,6,7-tetrahydro-1,4-oxazepin-2- or 3- or 5- or 6- or 7-yl; 4,5,6,7-tetrahydro-1,4-oxazepin-2- or 3- or 4- or 5- or 6- or 7-yl; 2,3-dihydro-1,4-oxazepin-2 or 3- or 5- or 6- or 7-yl; 2,5-dihydro-1,4-oxazepin-2- or 3- or 5- or 6- or 7-yl; 2,7dihydro-1,4-oxazepin-2- or 3- or 5- or 6- or 7-yl; 4,5-dihydro-1,4-oxazepine-2- or 3-, or 4-,

- 5 040946 or 5-, or 6-, or 7-yl; 4,7-dihydro-1,4-oxazepin-2- or 3- or 4- or 5- or 6- or 7-yl; 6,7dihydro-1,4-oxazepin-2- or 3- or 5- or 6- or 7-yl; 1,4-oxazepine-2- or 3-, or 5-, or 6-, or 7yl; isothiazolidin-2- or 3- or 4- or 5-yl; 2,3-dihydroisothiazol-2- or 3- or 4- or 5-yl; 2,5-dihydroisothiazol-2- or 3- or 4- or 5-yl; 4,5-dihydroisothiazol-3- or 4- or 5-yl; 1,3-thiazolidin 2- or 3- or 4- or 5-yl; 2,3-dihydro-1,3-thiazol-2- or 3- or 4- or 5-yl; 2,5-dihydro-1,3-thiazol-2 or 4- or 5-yl; 4,5-dihydro-1,3-thiazol-2- or 4- or 5-yl; 1,3-thiazinan-2- or 3- or 4- or 5- or 6yl; 3,4-dihydro-2H-1,3-thiazin-2- or 3- or 4- or 5- or 6-yl; 3,6-dihydro-2H-1,3-thiazin-2- or 3- or 4- or 5- or 6-yl; 5,6-dihydro-2H-1,3-thiazin-2- or 4- or 5- or 6-yl; 5,6-dihydro-4H-1,3-thiazin-2- or 4- or 5- or 6-yl; 2H-1,3-thiazin-2- or 4- or 5- or 6-yl; 6H-1,3-thiazin-2- or 4- or 5- or 6-yl; 4H-1,3-thiazin-2- or 4- or 5- or 6-yl. Other examples of heterocyclyl are a partially or fully hydrogenated heterocyclic residue with 3 heteroatoms from the group N, O and S, such as, for example, 1,4,2-dioxazolidin-2- or 3- or 5-yl; 1,4,2-dioxazol-3- or 5-yl; 1,4,2dioxazinan-2- or -3- or 5- or 6-yl; 5,6-dihydro-1,4,2-dioxazin-3- or 5- or 6-yl; 1,4,2dioxazin-3- or 5- or 6-yl; 1,4,2-dioxazepan-2- or 3- or 5- or 6- or 7-yl; 6,7-dihydro-5H-1,4,2dioxazepin-3-, or 5-, or 6-, or 7-yl; 2,3-dihydro-7H-1,4,2-dioxazepin-2- or 3- or 5- or 6- or 7-yl; 2,3-dihydro-5H-1,4,2-dioxazepin-2- or 3- or 5- or 6- or 7-yl; 5H-1,4,2-dioxazepin-3-, or 5-, or 6-, or 7-yl; 7H-1,4,2-dioxazepin-3-, or 5-, or 6-, or 7-yl. Structure examples for optionally substituted heterocycles are also listed below.

The above heterocycles are preferably substituted with, for example, hydrogen, halogen, alkyl, haloalkyl, hydroxy, alkoxy, cycloalkoxy, aryloxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, halocycloalkyl, aryl, arylalkyl, heteroaryl, heterocyclyl, alkenyl, alkylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, heteroaryl , алкоксикарбонилом, гидроксикарбонилом, циклоалкоксикарбонилом, циклоалкилалкоксикарбонилом, алкоксикарбонилалкилом, арилалкокси-карбонилом, арилалкоксикарбонилалкилом, алкинилом, алкинилалкилом, алкилалкинилом, трис-алкилсилилалкинилом, нитро, амино, циано, галоалкокси, галоалкилтио, алкилтио, гидротио, гидроксиалкилом, оксо, гетероарилалкокси, арилалкокси, гетероциклилалкокси , heterocyclylalkylthio, heterocyclyloxy, heterocyclylthio, heteroaryloxy, bis-alkylamino, alkylamino, cycloalkylamino, hydroxycarbonylalkylamino, alkoxycarbonylalkylamino, arylalkoxycarbonylalkylamino, alkoxycarbonylalkyl(alkyl)amino, aminocarbonyl, alkylamine ocarbonyl, bisalkylaminocarbonyl, cycloalkylaminocarbonyl, hydroxycarbonylalkylaminocarbonyl, alkoxycarbonylalkylaminocarbonyl, arylalkoxycarbonylalkylaminocarbonyl.

If the basic substance is substituted by one or more residues from the list of residues (=groups) or from the main group of residues, then, accordingly, it can be simultaneously replaced by several identical and/or structurally different residues.

If we are talking about a partially or fully saturated nitrogen heterocycle, then it can be associated with the rest of the molecule both with the help of carbon and with the help of nitrogen.

As substituents for a substituted heterocyclic residue, the following substituents are taken into account, also additionally oxo and thioxo. An oxo group as a substituent on a ring C-atom then means, for example, a carbonyl group in a heterocyclic ring. Which also preferably includes lactones and lactams. An oxo group can also arise on ring heteroatoms, which can be at different stages of oxidation, for example, at N and S, and in this case form, for example, a divalent group N(O), S(O) (also abbreviated SO) and S( O) ₂ (also abbreviated as SO ₂ ) in a heterocyclic ring. In the case of -N(O)- and -S(O)-groups, respectively, both enantiomers are present.

According to the invention, the term heteroaryl means heteroaromatic compounds, i.e. fully unsaturated aromatic heterocyclic compounds, preferably 5-7-membered rings with 1-4, preferably 1 or 2 identical or different heteroatoms, preferably O, S or N. The heteroaryls according to the invention are, for example, 1H-pyrrol-1-yl; 1H-pyrrol-2-yl; 1Hpyrrol-3-yl; furan-2-yl; furan-3-yl; thien-2-yl; thien-3-yl, 1H-imidazol-1-yl; 1H-imidazol-2-yl; 1Nimidazol-4-yl; 1H-imidazol-5-yl; 1H-pyrazol-1-yl; 1H-pyrazol-3-yl; 1H-pyrazol-4-yl; 1H-pyrazol-5yl, 1H-1,2,3-triazol-1-yl, 1H-1,2,3-triazol-4-yl, 1H-1,2,3-triazol-5-yl, 2H- 1,2,3-triazol-2-yl, 2H-1,2,3triazol-4-yl, 1H-1,2,4-triazol-1-yl, 1H-1,2,4-triazol-3- yl, 4H-1,2,4-triazol-4-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2- yl, 1,2,3-oxadiazol-4-yl, 1,2,3-oxadiazol-5-yl, 1,2,5oxadiazol-3-yl, azepinyl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyrazin-2-yl, pyrazin-3-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyridazin-3-yl, pyridazin-4-yl, 1, 3,5-triazin-2-yl, 1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl, 1,2,4-triazin-6-yl, 1,2, 3-triazin-4-yl, 1,2,3-triazin-5-yl, 1,2,4-, 1,3,2-, 1,3,6- and 1,2,6-oxazinyl, isoxazole -3-yl, isoxazol-4-yl, isoxazol-5-yl, 1,3-oxazol-2-yl, 1,3oxazol-4-yl, 1,3-oxazol-5-yl, isothiazol-3-yl , isothiazol-4-yl, isothiazol-5-yl, 1,3-thiazol-2-yl, 1,3thiazol-4-yl, 1,3-thiazol-5-yl, oxepinyl, thiepinyl, 1,2,4 -triazolonyl and 1,2,4-diazepinyl, 2H-1,2,3,4tetrazol-5-yl, 1H-1,2,3,4-tetrazol-5-yl, 1,2,3,4-oxatriazole -5-yl, 1,2,3,4 -thiatriazol-5-yl, 1,2,3,5oxatriazol-4-yl, 1,2,3,5-thiatriazol-4-yl. Further, the heteroaryl groups according to the invention may be substituted by one or more identical or different residues. If two adjacent

- 6 040946 carbon atoms are a component of another aromatic ring, then we are talking about annelled heteroaromatic systems, like benzofused or several times annelled heteroaromatic compounds. For example, quinolines are preferred (for example, quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, ); isoquinolines (eg, isoquinolin-1-yl, isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl, isoquinolin-8-yl); quinoxaline; quinazoline; cinnoline; 1,5-naphthyridine; 1,6naphthyridine; 1,7-naphthyridine; 1,8-naphthyridine; 2,6-naphthyridine; 2,7-naphthyridine; phthalazine; pyridopyrazine; pyridopyrimidine; pyridopyridazines; pteridines; pyrimidopyrimidine. Examples of heteroaryl are also 5- or 6-membered benzo-fused rings from the group 1H-indol-1-yl, 1H-indol-2-yl, 1H-indol-3-yl, 1H-indol-4-yl, 1H-indol-5- yl, 1H-indol-6-yl, 1H-indol-7-yl, 1benzofuran-2-yl, 1-benzofuran-3-yl, 1-benzofuran-4-yl, 1-benzofuran-5-yl, 1- benzofuran-6-yl, 1-benzofuran-7-yl, 1-benzothiophen-2-yl, 1-benzothiophen-3-yl, 1-benzothiophen-4-yl, 1-benzothiophen-5yl, 1-benzothiophen-6-yl, 1-benzothiophen-7-yl, 1H-indazol-1-yl, 1H-indazol-3-yl, 1H-indazol-4-yl, 1H-indazol-5-yl, 1H-indazol-6-yl, 1H- indazol-7-yl, 2H-indazol-2-yl, 2H-indazol-3-yl, 2Nindazol-4-yl, 2H-indazol-5-yl, 2H-indazol-6-yl, 2H-indazol-7- yl, 2H-isoindol-2-yl, 2Nisoindol-1-yl, 2H-isoindol-3-yl, 2H-isoindol-4-yl, 2H-isoindol-5-yl, 2H-isoindol-6-yl; 2Nisoindol-7-yl, 1H-benzimidazol-1-yl, 1H-benzimidazol-2-yl, 1H-benzimidazol-4-yl, 1Hbenzimidazol-5-yl, 1H-benzimidazol-6-yl, 1H-benzimidazol-7- yl, 1,3-benzoxazol-2-yl, 1,3-benzoxazol-4-yl, 1,3-benzoxazol-5-yl, 1,3-benzoxazol-6-yl, 1,3-benzoxazol-7-yl, 1,3-benzothiazol-2-yl, 1,3-benzothiazol-4-yl, 1,3-benzothiazol-5-yl, 1,3-benzothiazol-6-yl, 1,3-benzothiazol-7-yl,1, 2-benzisoxazol-3-yl, 1,2-benzisoxazol-4-yl, 1,2-benzisoxazol-5-yl, 1,2-benzisoxazol-6-yl, 1,2-benzisoxazol-7-yl, 1,2-benzisothiazol- 3-yl, 1,2-benzisothiazol-4-yl, 1,2-benzisothiazol-5-yl, 1,2-benzisothiazol-6-yl, 1,2-benzisothiazol-7-yl.

The term halogen means fluorine, chlorine, bromine or iodine. If this term is used for a residue, then halogen means a fluorine, chlorine, bromine or iodine atom.

The compounds of formula (I), depending on the species and the compounds of the substituents, may be present as stereoisomers. For example, if one or more asymmetric substituted carbon and/or sulfoxide atoms are present, enantiomers and diastereomers can thus arise. Stereoisomers may arise when mixtures are prepared by conventional separation methods, for example by chromatographic separation methods. It is also possible to selectively obtain stereoisomers using stereoselective reactions using optically active starting materials and/or auxiliary substances.

The present invention may also apply to all stereoisomers and mixtures thereof, which are contained in formula (I), but do not have a specific definition. However, in what follows, for brevity, only the compounds of formula (I) are referred to, although they can be represented both as pure compounds and, if necessary, as mixtures with various components of isomeric compounds.

Depending on the kind of substituents mentioned above, the compounds of formula (I) have acidic properties and, together with inorganic or organic bases or metal ions, can also optionally form internal salts or adducts. If the compounds of formula (I) contain hydroxy, carboxy or other acid-inducing groups, these compounds can be converted into salts with bases. Suitable bases are, for example, hydroxides, carbonates, hydrogen carbonates of alkali and alkaline earth metals, in particular sodium, potassium, magnesium and calcium, further ammonia, primary, secondary and tertiary amines with (C1- _C4 ) alkyl groups, mono-, di - and trialkanolamines (C1-C ₄ )alkanols, choline, as well as chlorocholine, as well as organic amines, such as trialkylamines, morpholine, piperidine or pyridine. These salts are compounds in which the acidic hydrogen has been replaced by an agriculturally suitable cation, for example metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or also ammonium salts, salts with organic amines or quaternary ammonium salts, for example with cations of the formula [NRR'RR'] ⁺ , where RR' respectively independently of each other represent an organic residue, in particular alkyl, aryl, arylalkyl or alkylaryl. The alkylsulfonium and alkylsulfoxonium salts are also taken into account as (C1C ₄ )trialkylsulfonium and (C1-C ₄ )trialkylsulfoxonium salts.

Compounds of formula (I) during addition of suitable inorganic or organic acids, such as mineral acids, such as HCl, HBr, H ₂ SO ₄ , H ₃ PO ₄ or HNO ₃ , or organic acids, such as carboxylic acids , as formic acid, acetic acid, propionic acid, oxalic acid, lactic or salicylic acid or sulfonic acids, such as rtoluenesulfonic acid, to an alkaline group, such as amino, alkylamino, dialkylamino, piperidino, morpholino or pyridino, can form salts . These salts contain the conjugate base of the acid as an anion.

Suitable substituents which are present in deprotonated form, such as sulfonic acids or carboxylic acids, for example, can form internal salts with groups that are protonated on their side, such as amino groups.

- 7 040946

If a group is substituted several times by residues, this means that this group is substituted by one or more of the same or different residues mentioned.

In all of the following formulas, substituents and symbols, unless otherwise indicated, have the same meaning as in formula (I). The arrows in the chemical formula indicate the places of attachment to the residual molecule.

In the following, preferred, particularly preferred and highly preferred meanings are described, respectively, for the individual substituents. The remaining substituents of the general formula (I), which are not named below, have the above meanings.

R ¹² preferably means hydroxy.

Within the framework of the present invention, it is possible to combine individual preferred, particularly preferred and most preferred values for the substituents R1-R ³ , R5-R ⁸ , R ¹⁰ -R ¹² , X ² -X ⁶ , W, Y and Z, as well as the ordinal numbers m , n, p and r in any way with each other.

This means that the present invention provides compounds of general formula (I) in which, for example, the substituent R ¹ has a preferred meaning and the substituents R5 to R ⁷ have a common meaning, or the substituent R ² has a preferred meaning, the substituent R ³ has a particularly a preferred value or a highly preferred value, and the remaining substituents have a general meaning.

The following are examples of compounds of general formula (I) in table form. In the next table. 1, the substituents defined in formula (I) are indicated individually.

Table 1

Compounds of general formula (I), where X^X^X^R^R ² ^ and Y=W=O

Example - No. ^{x3 x5 R3} Z ^{R11 R12} 1-1 F F SNz Z-4 n cyc-propyl 1-2 F F CH=CH ₂ Z-1 n SNz 1-3 F F SNz Z-1 -(CH ₂ )4- 1-4 F F SNz Z-1 n cyc-propyl 1-5 F F SNz Z-1 n SNz 1-6 F F CH=CH ₂ Z-1 -(CH ₂ ) ₄ - 1-7 F F SNz Z-2 n SNz 1-8 F F SNz Z-2 n cyc-propyl 1-9 F F SNz Z-2 -(CH ₂ ) ₄ - 1-10 F H SNz Z-1 n O-CH3 1-11 F F (S) - CH=CH ₂ Z-1 n O-CH3 1-12 F F (S) - sn=sn ₂ Z-1 n O-S ₂ H ₅ 1-13 F F (S) - sn=sn ₂ Z-1 n O-CH(CH3) ₂ 1-14 F F (S) - sn=sn ₂ Z-1 n _{SO2CF3 _} 1-15 F F (S) - sn=sn ₂ Z-1 n N(CH ₃ ) ₂ 1-16 F F (S) - sn=sn ₂ Z-1 n _{SO2CH3 _} 1-17 F F (S) - sn=sn ₂ Z-1 SNz SNz 1-18 F F (S) - sn=sn ₂ Z-1 n cyc-propyl 1-19 F F (S) - sn=sn ₂ Z-1 n NH-(C=O)-OC(CH ₃ )3 1-20 F F (S) - sn=sn ₂ Z-1 n CH ₂ -CH ₂ -CO ₂ Me 1-21 F F (S) - sn=sn ₂ Z-1 n CH ₂ -CO ₂ Me 1-22 F F (S) - sn=sn ₂ Z-1 n (3 S)-CH(CH ₃ )-CH ₂ -CO ₂ Et 1-23 F F (R) - CH Z-1 n SO ₂ Me 1-24 F F (R) - CH Z-1 n ome 1-25 F F (R) - CH Z-1 Me Me 1-26 F F (R) - CH Z-1 n NMe ₂ 1-27 F F (R) - CH Z-1 n [3-chloro-5-(trifluoromethyl)pyride in-2-yl]methyl 1-28 F F (R) - CH Z-1 n SO ₂ CH ₂ -CH ₂ -CH ₃ 1-29 F F (S) - sn=sn ₂ Z-1 n SO ₂ CH ₂ -CH ₂ -CH ₃ 1-30 F F (R) - CH Z-1 n _{SO2CF3 _}

Compounds according to the invention can be obtained in various ways, which are presented below as examples.

- 8 040946

Scheme 1

Ph-NCO or CI-CO-OEt

In scheme 1 and subsequent schemes (X) _p denotes the substituents X ² , X ³ , X ⁴ , X ⁵ and X ⁶ . Such 1,3 dipolar cycloadditions of nitrile oxides with suitable dipolarophiles are described, for example, in the review: 1,3 dipolar Cycloaddition Chemistry, Padwa, ed. Wiley, New York, 1984; Kanemasa and Tsuge, Heterocycles 1990, 30, 719. For the presentation of chlorooximes, see Kim, Jae N., Ryu, Eung KJ Org. Chem. 1992, 57, 6649).

Compounds of the invention which are substituted at the 4- and 5-positions of the isoxazoline ring system can also be prepared by 1,3-dipolar cycloaddition using the appropriate 1,2-disubstituted olefins as dipolarophiles. During this reaction, mixtures of diastereoisomers are most often formed, which can be separated using column chromatography. Optically active isoxazolines can be obtained by chiral HPLC preliminary or last steps, also by enantioselective reactions such as enzymatic ether or amide elimination, or by the use of chiral auxiliary reagents on dipolarophiles, as described by Olssen, (J. Org. Chem. 1988, 53, 2468).

Substituted amides of 2-alkoxyactylic acid can also be used to prepare compounds according to the invention (Scheme 3). Acrylic acid esters described in Scheme 2 are obtained after hydrolysis and formation of amides.

Scheme 2

However, carbodiimides such as EDCI (Chen, F. M. F.; Benoiton, N. L. Synthesis 1979, 709) have been proposed for activating acrylic acids. For the preparation of acrylic acid amides, see US 2,521,902, JP60112746, J. of Polymer Science 1979, 17(6), 1655. Suitable substituted acrylic acid amides can be prepared during 1,3-cycloaddition with nitrile oxides to the compounds of the invention (Scheme 3 ).

Scheme 3

Transformations of functional groups R ³ are possible both at the stage of alkenes and at the stage of isoxazolines.

The collection of compounds of formula (I) and/or their salts, which can be synthesized as a result of the above reactions, can also be obtained by a comparative method, and this can be done manually, partially automatic or fully automated. In this case, for example, it is possible to carry out an automation of the reaction, processing or purification of the product or intermediate products. Such a method is described, for example, in D. Tiebes in Combinatorial Chemistry - Synthesis, Analysis, Screening (Herausgeber Gunther Jung), Verlag Wiley 1999, p. 1-34.

The subject of the present invention is also a plant growth regulating agent containing one or more of the above compounds of general formula (I) or salts thereof.

The compounds according to the invention of formula (I) (and/or their salts), hereinafter referred to as compounds according to the invention, have excellent herbicidal action against a wide range of economically important mono- and dicotyledonous annual harmful plants.

Therefore, the subject of the present invention is a herbicidal agent containing one or more of the above compounds of general formula (I) or salts thereof.

- 9 040946

In a preferred embodiment of the invention, the herbicidal agent further comprises a formulation aid.

In a preferred embodiment of the invention, the herbicidal agent contains at least one additional biologically active substance from the group of insecticides, acaricides, herbicides, fungicides, protective agents and/or plant growth regulators.

Preferably, the above herbicidal agent contains a protective agent.

In a preferred embodiment of the invention, the protective agent is selected from the group consisting of mefenpyr-diethyl, cyprosulfamide, isoxadifenethyl, cloquintoset-mexil, benoxacor and dichloramide.

The subject of the present invention is also a method for controlling unwanted plants, wherein an effective amount of at least one of the above compounds of formula (I) or one of the above herbicidal agents is applied to the unwanted plants or to the locus of the unwanted plants.

In a preferred embodiment of the aforementioned method for controlling unwanted plants, the compounds according to the invention can be applied, for example, in the pre-sowing (if appropriate also when fertilizing the soil), pre-emergence and/or post-emergence period. In particular, mono- and dicotyledonous weeds that can be controlled with the compounds of the invention should be mentioned as examples, but the invention should not be limited by these names.

Monocotyledonous plant species: Aegilops (egilops), Agropyron (couch grass), Agrostis (bent grass), Alopecurus (foxtail), Apera (broomstick), Avena (oats), Brachiaria (brachiaria), Bromus (bonfire), Cenchrus (cenchrus), Commelina (commelina), Cynodon (piggy), Cyperus (satiate), Dactyloctenium (dactyloctenium), Digitaria (rosichka), Echinochloa (barberry), Eleocharis (bog), Eleusine (dagussa), Eragrostis (polevichka), Eriochloa (wool), Festuca (fescue), Fimbristylis (fimbristilis), Heteranthera (heteranthera), Imperata (emperata), Ischaemum (bearded man), Leptochloa (leptochloa), Lolium (chaff), Monochoria (monochoria), Panicum (millet), Paspalum (paspalum), Phalaris (canary), Phleum (arzhanets), Roa (bluegrass), Rottboellia (rotbellia), Sagittaria (arrowhead), Scirpus (bulrush), Setaria (bristle), Sorghum (sorghum).

Dicotyledon weed species: Abutilon (rope rope), Amaranthus (amaranth), Ambrosia (ragweed), Anoda (anode), Anthemis (navel), Aphanes (cuff), Artemisia (wormwood), Atriplex (quinoa), Bellis (daisy), Bidens (succession), Capsella (shepherd's purse), Carduus (thistle), Cassia (cassia), Centaurea (cornflower), Chenopodium (gum), Cirsium (thistle), Convolvulus (bindweed), Datura (datura), Desmodium (telegraph plant ), Emex (emex), Erysimum (jaundice), Euphorbia (euphorbia), Galeopsis (pickulnik), Galinsoga (galinsog), Galium (bedstraw), Hibiscus (okra), Ipomoea (morning glory), Kochia (cochia), Lamium (larvae ), Lepidium (bugbug), Lindernia, Matricaria (chamomile), Mentha (mint), Mercurialis (wildweed), Mullugo (shellfish), Myosotis (forget-me-not), Papaver (poppy), Pharbitis (farbitis), Plantago (plantain), Polygonum (highlander), Portulaca (purslane), Ranunculus (buttercup), Raphanus (radish), Rorippa (buckwheat), Rotala (rotala), Rumex (sorrel), Salsola (saltwort), Senecio (ragwort), Sesbania (sesbania), Sida (sida), Sinapis (sesbania), Solanum (nightshade), Sonchus (thistle thistle), Sphenoclea (sphenoclea), Stellaria (chickweed), Taraxacum (dandelion), Thlaspi (yarutka), Trifolium (clover), Urtica (nettle), Veronica (veronica), Viola (violet), Xanthium (cocklebur).

If the compounds according to the invention are applied to the surface of the earth before the sprouts germinate, then the growth of the sprouts of the weeds is completely stopped, or the weeds grow to the cotyledon stage, but then their growth stops.

When the active ingredients are applied to the green parts of plants in post-emergence application, after treatment, growth stops, and harmful plants at the stage of growth at which they were at the time of application or completely die after a certain period of time, thus eliminating competition very early and for a long period as harmful weeds.

The compounds of the invention may be selective in crops of useful plants and may also be used as non-selective herbicides.

Due to their herbicidal and growth regulating properties, the active compounds can also be used to control harmful plants in cultures of known or new plants modified by genetic engineering or conventional mutagenesis. As a rule, transgenic plants are distinguished by particularly advantageous properties, for example, their resistance to certain active substances used in the agricultural processing industry, in particular to certain herbicides, resistance to plant diseases or their pathogens, such as certain insects or microorganisms, such as fungi, bacteria or viruses. Other special properties are generally related to the harvested crop, in terms of quantity, quality, storage stability, composition and special components. Thus, transgenic plants with an increased starch content or a modified starch property, or plants with a different fatty acid composition in the harvested crop, are known. Other special properties are tolerance or resistance to abiotic stressors, such as

- 10 040946 heat, cold, drought, high salt content and ultraviolet radiation.

It is preferable to use the compounds of formula (I) according to the invention or their salts in certain economic transgenic crops of useful and ornamental plants,

Compounds of formula (I) can be used as herbicides in useful commercial crops that are resistant to the phytotoxic effects of herbicides or have been made resistant by genetic engineering.

Conventional methods for obtaining new plants that exhibit new altered qualities compared to previously existing plants are, for example, classical cultivation methods and the creation of mutated plants. Alternatively, new plants with modified properties can be obtained using genetic engineering techniques (see, for example, EP 0221044, EP 0131624). Described, for example, in many cases: genetic changes in cultivated plants caused by changes in the starch synthesized in plants (for example, WO 92/011376 A, WO 92/014827 A, WO 91/019806 A); transgenic crop plants that are resistant to certain herbicides such as glufosinate (see, for example, EP 0242236 A, EP 0242246 A) or glyphosate (WO 92/000377 A) or sulfonylurea (EP 257993 A, US 5,013,659) or combinations or mixtures these herbicides due to gene packaging, as transgenic crop plants, for example, corn or soybeans under the trade name Optimum™ GAT™ (ALS glyphosate tolerance);

transgenic crop plants, for example cotton, which can produce Bacillus thuringiensis toxins (Bt toxins) that make plants resistant to certain pests (EP 0142924 A, EP 0193259 A);

transgenic crop plants with altered fatty acid composition (WO 91/013972 A);

genetically modified crop plants with new compounds or secondary substances, for example, new phytoalexins, which cause increased resistance to diseases (EP 309862 A, EP 464461 A) genetically modified plants with reduced photorespiration, which have high yield and increased tolerance to stress factors (EP 0305398 A);

transgenic crop plants that produce pharmaceutically or diagnostically important proteins (molecular farming);

transgenic crop plants that are of high yield or improved quality;

transgenic crop plants that differ, for example, in combinations of new properties (gene packaging).

The person skilled in the art is aware of many molecular biological technologies that can be used to produce new transgenic plants with altered properties; see, for example, I. Potrykus and G. Spangenberg (ed.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg or Christou, Trends in Plant Science 1 (1996) 423-431).

For genetic engineering manipulations of this kind, nucleic acid molecules can be delivered into plasmids that allow mutagenesis or modification of the nucleotide DNA sequence. With standard techniques, for example, cation exchange can be carried out, partial sequences can be removed, or natural or synthetic sequences added. Adapters or linkers can be attached to the fragments to connect DNA fragments to each other, see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd Ed. Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker Gene und Klone, VCH Weinheim 2nd ed. 1996.

Generating plant cells with reduced activity of a gene product can, for example, be achieved by expressing at least one corresponding antisense RNA, one sense RNA to extract RNA interference, or by expressing at least the corresponding generated ribosome by a specific transcript of said gene product. In addition, DNA molecules can be used that span the overall encoded sequence of the gene product, including possible flanking sequences present, as well as DNA molecules that span only a portion of the encoded sequence, which portion must be long enough to cause an antisense effect in cells. It is also possible to use DNA sequences that indicate a high degree of homology to the encoded sequences, but are not completely identical.

When nucleic acid molecules are expressed in plants, the synthetic protein can be localized in any compartment of the plant cell. But in order to achieve localization in a specific compartment, the encoded region can, for example, be associated with DNA sequences that provide localization in one specific compartment. Such sequences are known to the skilled person (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106). Expression of nucleic acid molecules can also occur in plant cell organelles.

Transgenic plant cells can be regenerated by known methods into whole plants. In the case of transgenic plants, in principle, we can talk about plants of any species, i.e. both monocots and dicots. Thus, commercially available transgenic plants may have altered properties due to increased expression, suppression or inhibition of homologous (=natural) genes or gene sequences, or the expression of heterologous (=foreign) genes or gene sequences.

Advantageously, compounds according to the invention can be used in transgenic crops which are resistant to growth substances, such as 2,4 D, dicamba, or to herbicides that inhibit essential plant enzymes, such as acetolactate synthase (ALS), EPSP synthase, glutamine. synthase (HS) or hydroxyphenylpyruvate dioxygenase (HFPDH), or herbicides from the group of sulfonylurea, glyphosate, glufosinate or benzoyloxazole and similar active ingredients, or any combination of these active ingredients.

Particularly preferably, the compounds according to the invention can be used in transgenic crop plants which are resistant to a combination of glyphosates and glufosinates, sulfonylurea glyphosates or imidazolinones. Very preferably, the compounds according to the invention can be used in transgenic crop plants, such as corn or soybeans with the trade name or designation Optimum™ GAT™ (ALS glyphosate tolerance).

When the active ingredients according to the invention are used in transgenic crops, in addition to the observed results in relation to harmful plants, in other crops results often occur that are specific to these transgenic crops, for example, a modified or specially extended range of weeds that can be controlled, a modified application amount , which can be used for application, preferably good compatibility with herbicides to which transgenic crops are resistant, as well as the effect on the growth and yield of transgenic crops.

Therefore, the subject of the invention is also the use of the compound of formula (I) according to the invention or the aforementioned herbicidal agent for controlling unwanted plants.

Preferably, the compound of formula (I) according to the invention is used to control unwanted plants in crops of useful plants.

Preferably, the beneficial plants are transgenic beneficial plants.

The compounds according to the invention can be used in the form of powder for injection, emulsifiable concentrates, spray solutions, sprays or granulates in the form of conventional preparations. It is therefore also an object of the invention to provide herbicidal and plant growth regulating agents which contain the compounds according to the invention.

Compounds according to the invention can be formulated in various ways, depending on what biological and/or chemical-physical parameters are given. For example, the following formulation options are taken into account: sprayable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, spray solutions, suspension concentrates (SC), dispersion in oil or water phase, oil emulsion solutions, capsule suspensions (CS), spray agent (DP), dressing agents, granulates for spreading and tillage, granules (GR) in the form of microgranules , dispersion granules, coated and absorption granulates, water-dispersible granules (WG), water-soluble granules (SG), ultra-low volume formulations (ULV), microcapsules and waxes. These particular types of formulations are in principle known to those skilled in the art and are described, for example, in: Winnacker-Kuchler, Chemische Technologie, vol. 7, C. Hanser Verlag Munich, 4th ed. 1986, Wade van Valkenburg, Pesticide Formulations, Marcel Dekker, N.Y., 1973, K. Martens, Spray Drying Handbook, 3rd ed. 1979, G. Goodwin Ltd. London.

These particular types of formulation aids, such as inerts, surfactants, solvents, and other additives, are also known and are described, for example, in: Watkins, Handbook of Insecticide Dust Diluents and Carriers, 2nd ed., Darland Books, Caldwell N.J. , H.v. Olphen, Introduction to Clay Colloid Chemistry, 2nd ed., J. Wiley & Sons, N.Y., C. Marsden, Solvents Guide, 2nd ed., Interscience, N.Y. 1963, McCutcheon's Detergents and Emulsifiers Annual, M.C. Publ. Corp., Ridgewood N.J., Sisley and Wood, Encyclopedia of Surface Active Agents, Chem. Publ. Co. Inc., N.Y. 1964, Schonfeldt, Grenzflachenaktive Athylenoxid-addukte, Wiss. Verlagsgesell., Stuttgart 1976, Winnacker-Kuchler, Chemische Technologie, vol. 7, C. Hanser Verlag Munich, 4th ed. 1986.

Based on these formulations, combinations can also be obtained with other active ingredients, such as insecticides, acaricides, herbicides, fungicides, as well as protective agents, fertilizers and/or growth regulators, for example, in the form of finished formulations or in the form mixing in a container.

Suitable combination partners for the compounds according to the invention in mixed formulations or mixing in a container are, for example, known active ingredients, which are based, for example, on the inhibition of, for example, the enzyme acetolactate synthase,

- 12 040946 enzyme acetyl-CoA carboxylase, cellulose synthase, enolpyruvate shikimate-3-phosphate synthase, glutamine synthase, p-hydroxyphenylpyruvate dioxygenase, phytoene desaturase, photosystem I, photosystem II, protoporphyrinogen oxidase, as described, for example, in Weed Research 26 (1986) 441-445 or The Pesticide Manual, 15th ed., The British Crop Protection Council and the Royal Soc. of Chemistry, 2006 and the literature cited there. In the following, known herbicides or plant growth regulators are mentioned as examples, which can be combined with the compounds according to the invention, these active ingredients being either indicated under the general name in the English version according to the International Organization for Standardization (ISO) or under the chemical name, or have a code number. In this case, all forms of application are present, such as, for example, acids, salts, esters, as well as all isomeric forms, such as stereoisomers and optical isomers, even if they are not explicitly indicated.

Examples of such herbicidal mixing partners are:

acetochlor, acifluorophen, acifluorophen-sodium, aclonifen, alachlor, allidochlor, alloxidim, alloxidim-sodium, ametrin, amicarbazone, amidochlor, amidosulfuron, 4-amino-3-chloro-6-(4-chloro-2-fluoro3-methylphenyl)- 5-fluoropyridine-2-carboxylic acid, aminocyclopyrapyrachlor, aminocyclopyrachlor-potassium, aminocyclopyrachlor-methyl, aminopyralide, amitrol, ammonium sulfamate, anilophos, asulam, atrazine, azadenidine, azimsulfuron, beflubutamide, benazoline, benazoline-ethyl, bensulfuralin, benfuresate, bensulfuron-methyl, bensulide, bentazon, benzobicyclop, benzofenap, bicyclopyrone, bifenox, bilanafos, bilanafos sodium, bispyribac, bispyribac sodium, bromacyl, bromobtide, bromophenoxime, bromoxynil, bromoxynyl butyrate, -potassium, -heptanoate and -octanoate, busoxinone , butachlor, butafenacil, butamiphos, butenachlor, butralin, butroxydim, butylate, cafenstrol, carbetamide, carfentrazone, carfentrazone-ethyl, chloramben, chlorbromuron, chlorfenac, chlorfenac-sodium, chlorfenprop, chlorflurenol, chlorflurenol-methyl, chloride zones, chlorimuron, chlorimuron-ethyl, chlorophthalim, chlorotoduron, chlorthal-dimethyl, chlorsulfuron, cinidon, cinidone-ethyl, cinmethylin, cinosulfuron, clacifos, cletodim, clodinafop, clodinafop-propargyl, clomazone, clomeprop, clopyralid, cloransulam, cloransulam-methyl, cumiluron, cyanamide, cyanazine, cycloate, cyclopyrimorate, cyclosulfomurone, cyclooxydim, cyhalofop, cyhalofop-butyl, cyprazine, 2,4-D, 2,4-D-butotyl, -butyl, -dimethylammonium, -diolamine, -ethyl, 2- ethylhexyl, -isobutyl, -isooctyl, -isopropylammonium, -potassium, -triisopropanolammonium and -trolamine, 2,4-DB, 2,4-OB-6util, -dimethylammonium, isooctyl, -potassium and -sodium, daimuron (dimron), dalapon, dazomet, n-decanol, desmedifam, detosyl pyrazolate (DTP), dicamba, diclobenil, 2-(2,4-dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, 2-( 2,5-dichlorobenzyl)-4,4dimethyl-1,2-oxazolidin-3-one, dichlorprop, dichlorprop-R, diclofop, diclofop-methyl, diclofop-Rmethyl, diclosulam, difenzoquat, diflufenican, diflufenzopyr, diflufenzopyr-sodium, dimefuron , dimepipe rat, dimethachlor, dimethamethrin, dimethenamid, dimethenamid-R, dimetrasulfuron, dinitramine, dinoterb, diphenamide, diquat, diquat-dibromide, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, etametsulfuron, etametsulfuron-methyl, etiosin, etofumesat, ethoxyphene, ethoxyphenethyl, ethoxysulfuron, etobenzanide, F-9600, F-5231, i.e. N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5dihydro-5-oxo-1H-tetrazol-1-yl]phenyl]ethanesulfonamide, F-7967, i.e. 3-[7-Chloro-5-fluoro-2(trifluoromethyl)-1 H-benzimidazol-4-yl] -1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1 H,3H)-dione, fenoxaprop , fenoxaprop-R, fenoxaprop-ethyl, fenoxaprop-R-ethyl, fenoxasulfone, fenquinotrion, fentrizamide, flamprop, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-R, fluazifop-butyl, fluazifop -p-butyl, flucarbazone, flucarbazone sodium, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac, flumiclorac-pentyl, flumioxazine, fluometuron, flurenol, flurenol-butyl, -dimethylammonium and -methyl, fluoroglycofen, fluoroglycofen -ethyl, flupropanate, flupyrsulfuron, flupyrsulfuron-methylsodium, fluridone, flurochloridone, fluroxypyr, fluroxypyr-meptyl, flurtamone, flutiacet, flutiacet-methyl, fomesafen, fomesafen-sodium, foramsulfuron, fosamine, glufosinate, glufosinate ammonium, glufosinate-P-sodium -P-ammonium, glufosinate-P-sodium, glyphosate, glyphosatammonium, -isopropylammonium, -diammonium, dimethylammonium, -potassium, -sodium and -trimesium, H-9201, i.e. O-(2,4-dimethyl-6-nitrophenyl)-O-ethyl-isopropylphosphoramidothioate, galauxifen, halauxifen-methyl, halosafen, halosulfuron, halosulfuron-methyl, haloxifop, haloxifop-P, haloxifop-ethoxyethyl, haloxifop-P-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, hexazinon, HW-02, i.e. 1(dimethoxyphosphoryl)-ethyl-(2,4-dichlorophenoxy)acetate, imazametabenz, imazametabenz-methyl, imazamox, imazamox-ammonium, imazapik, imazapir-ammonium, imazapir, imazapyr-isopropylammonium, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr- immonium, imazosulfuron, indanophane, indaziflam, iodosulfuron, iodosulfuron-methyl-sodium, ioxynil, ioxynyl-octanoate, -potassium and sodium, ipfencarbazone, isoproturon, isouron, isoxaben, isoxaflutol, carbutylate, KUH-043, i.e. 3-({[5(difluoromethyl)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfonyl)-5,5-dimethyl-4,5-dihydro1,2-oxazole, ketospiradox , lactofen, lenacil, linuron, MCPA, MCPA-butyl, -dimethylammonium, -2-ethylhexyl, -isopropylammonium, -potassium and -sodium, MSRV, MSRV-methyl, -ethyl and -sodium, mecoprop, mecoprop-sodium, and - butotyl, mecoprop-R, mecoprop-R-butotyl, -dimethylammonium, -2-ethylhexyl and -potassium, mefenacet, mefluidide, mesosulfuron, mesosulfuron-methyl, mesotrione, metabenzthiazuron, metam, metamifop, metamitron, metazachlor, metazosulfuron, metabenzthiazuron, methio

- 13 040946 pyrsulfuron, methiozolin, methyl isothiotsmanate, metobromuron, metolachlor, S-metolachlor, methosulam, methoxuron, metribuzin, metsulfuron, metsulfuron-methyl, molinate, monolinuron, monosulfuron, monosulfuron ether, MT-5950, i.e. N-[3-chloro-4-(1-methylethyl)phenyl]-2-methylpentαnamide, NGGC011, napropamide, NC-310, i.e. 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole, neburon, nicosulfuron, nonylic acid (pelargonic acid), norflurazone, oleic acid (fatty acid), orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazop, oxasulfuron, oxacyclomefone, oxyfluorophen, paraquat, paraquat dichloride, pebulate, pendimethalin, penoxsulam, pentachlorophenol, pentoxazone, petoxamide, mineral oil, phenmedifam, picloram, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron, primisulfuron-methyl, prodiamine, profoxidim, promethone, promethrin, propachlor, propanil, propaquizafop, propazin, profam, propisochlor, propoxycarbazone, propoxycarbazone sodium, propyrisulfuron, propizamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotol, pyrazolinate (pyrazolate), pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz , pyribambenz-isopropyl, pyribambenz-propyl, pyribambenzoxime, pyributicarb, pyridafol, pyridate, pyrifthalide, pyriminobac, pyriminobak- methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamin, quizalofop, quizalofop-ethyl, quizalofop-R, quizalofop-R-ethyl, quizalofop-R-tefuryl, rimsulfuron, saflufenacil, setoxydim, siduron, simazine, symetrin, SL-261, sulcotrione, sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosulfuron, SYN-523, SYP-249, i.e. 1-ethoxy-3methyl-1-oxobut-3-en-2-yl-5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate, SYP-300, i.e. 1-[7-fluoro3-oxo-4-(prop-2-yn-1-yl)-3,4-dihydro-2H-1,4-benzoxazin-6-yl]-3-propyl-2-thioxoimidazolidin- 4,5dione, 2,3,6-TBA, TCA (trifluoroacetic acid), TCA-sodium, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbumetone, terbutylazine, terbutrin, tenylchlor, thiazopyr, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, thiafenacil, tolpyralate, topramesone, tralkoxydim, triafamon, tri-allate, triasulfuron, triaziflam, tribenuron, tribenuron-methyl, triclopyr, trietazine, trifloxysulfuron, trifloxysulfuron sodium, trifludimoxazine, trifluralin, triflusulfuron-sodium, methyl, tritosulfuron, urea sulfate, vernolate, XDE-848, ZJ-0862 i.e. 3,4-dichloro-K-{2-[(4,6-dimethoxypyrimidin-2yl)oxy]benzyl}aniline, as well as the following compounds:

Examples of possible mixing partners for plant growth regulators are:

acibenzolar, αcibenzolar-S-methyl, 5-aminolevulinic acid, ancimidol, 6-benzylaminopurine, brassinolide, catechin, chlormequat chloride, cloprop, cyclanilide, 3-(cycloprop-1-enyl)propionic acid, daminoside, dazomet, n-decanol, dikegulac, dikegulac-sodium, endothal, endothal-dicalium, disodium, and mono(N,N-dimethylalkylammonium), ethephon, flumetraline, flurenol, flurenol-butyl, flurprimidol, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid ( IAA), 4-indol-3-ylbutyric acid, isoprothiolane, probenazole, jasmonic acid, jasmonic acid methyl ester, maleic hydrazide, mepiquat chloride, 1-methylcyclopropene, 2-(1-naphthyl)acetamide, 1-naphthylacetic acid, 2-naphthyloxyacetic acid, nitrophenolate mixture, 4-oxo-4[(2phenylethyl)amino]butyric acid, paclobutrazol, N-phenylphthalic acid polyamide, prohexadione, prohexadione-calcium, prohydrojasmon, salicylic acid, strigolactone, teknazen, thidiazuron, triacontanol, trinexapac, trinexapac-ethyl, tsitodef , unico nazol, uniconazole-R.

Protective agents which can be used in combination with the compounds of formula (I) according to the invention and, if necessary, in combination with other active ingredients, such as insecticides, acaricides, herbicides, fungicides as described above, preferably selected from the group consisting of :

S1) Compounds of formula (S1)

moreover, the symbols and indices have the following meanings: n _A means a natural number 0-5, preferably 0-3;

- 14 040946

Ra ¹ means halogen, (C1-C ₄ )alkyl, (C1-C ₄ )alkoxy, nitro or (C ₁ -C ₄ )haloalkyl;

W _A means an unsubstituted or substituted divalent heterocyclic residue from the group of partially unsaturated or aromatic heterocycles with five rings with 1-3 ring heteroatoms from the group N and O, with at least one N-atom and not more than one O-atom present in ring, preferably a residue from the group (W _A ¹ )-(W _A 4)

m _A means 0 or 1;

R _a ² means ORA ³ , SRa ³ or NRA ³ RA ⁴ or saturated or unsaturated 3-6-membered heterocycle with at least one N atom and containing up to 3 heteroatoms, preferably from the group O and S, which is linked via N- atom with a carbonyl group in (S1) and is unsubstituted or substituted by residues from the group (C1-C4)alkyl, (C1-C4)alkoxy or, if necessary, substituted by phenyl, preferably means a residue of the formula ORa ³ , NRa ⁴ or N(CH ₃ ) ₂ , especially preferably the formula OR _a ³ ;

R _a ³ means hydrogen or unsubstituted or substituted aliphatic hydrocarbon residue, preferably with 1-18 carbon atoms;

R _a ⁴ means hydrogen, (C ₁ -C ₆ )alkyl, (C ₁ -C ₆ )alkoxy or substituted or unsubstituted phenyl;

R _a ⁵ is H, (C1-C8) alkyl, (C1-C8) haloalkyl, (C1-C4) alkoxy(C1-C8) alkyl, cyano or COORA ⁹ where Ra ⁹ is hydrogen, (C ₁ -C ₈ )alkyl, (C ₁ -C ₈ ) haloalkyl, (C ₁ -C ₄ ) alkoxy-(C ₁ -C ₄ ) alkyl, (C ₁ C ₆ ) hydroxyalkyl, (C ₃ -C ₁₂ ) cycloalkyl or tri-( C ₁ -C ₄ )alkyl-silyl;

R _a ⁶ , Ra ⁷ , Ra ⁸ is or other than hydrogen, (C ₁ -C ₈ )alkyl, (C ₁ -C ₈ ) haloalkyl, (C ₃ C ₁₂ ) cycloalkyl or substituted or unsubstituted phenyl;

preferably:

a) compounds of the dichlorophenylpyrazoline-3-carboxylic acid type (S1 ^a ), preferably compounds such as 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylic acid, ethyl 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylic acid ester (S1-1) (mefenpyr-diethyl), and related compounds as described in WO-A -91/07874;

b) dichlorophenylpyrazolecarboxylic acid derivatives (S1 ^b ), preferably compounds such as 1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylic acid ethyl ester (S1-2), 1(2,4-dichlorophenyl) ethyl ester )-5-isopropylpyrazole-3-carboxylic acid (S1-3), 1-(2,4dichlorophenyl)-5-(1,1-dimethyl-ethyl)pyrazole-3-carboxylic acid ethyl ester (S1-4) and related compounds which are described in EP-A-333131 and EP-A-269806;

c) 1,5-diphenylpyrazole-3-carboxylic acid derivatives (S1 ^c ), preferably compounds such as 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylic acid ethyl ester (S1-5), methyl 1-(2-chlorophenyl)-5-phenylpyrazole-3-carboxylic acid ester (S1-6) and related compounds which are described, for example, in EP-A-268554;

d) compounds of the triazolecarboxylic acid type (S1 ^d ), preferably compounds such as phenchlorazole(-ethyl ester), i.e. 1-(2,4-dichlorophenyl)-5-trichloromethyl-(1H)-1,2,4-triazole3-carboxylic acid ethyl ester (S1-7) and related compounds as described in EP-A-174562 and EP -A346620;

e) compounds of the type 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid or 5,5-diphenyl-2-isoxazoline-3-carboxylic acid (S1 ^e ), preferably compounds such as ethyl ester 5(2 ,4-dichlorobenzyl)-2-isoxazoline-3-carboxylic acid (S1-8) or 5-phenyl-2isoxazoline-3-carboxylic acid ethyl ester (S1-9) and related compounds as described in WO-A91/08202, or 5,5-diphenyl-2-isoxazoline-carboxylic acid (S1-10) or 5,5-diphenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S1-11) (isoxafifen-ethyl) or -n-propyl ester ( S1-12) or 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S1-13) as described in patent application WO-A-95/07897.

S2) quinoline derivatives of formula (S2)

where the symbols and indices have the following meanings:

RB ¹ means halogen, (C ₁ -C ₄ )alkyl, (C ₁ -C ₄ )alkoxy, nitro or (C ₁ -C ₄ )haloalkyl;

n _B is a natural number 0-5, preferably 0-3;

R _b ² means ORB ³ , SRB ³ or NR _b ³ RB ⁴ or saturated or unsaturated 3-6-membered heterocycle with at least one N atom and containing up to

- 15,040,946 heteroatoms, preferably from the group O and S, which is bonded via an N-atom to the carbonyl group in (S2) and is unsubstituted or substituted by residues from _the group (C1- _C4 )alkyl, ( _C1C4 )alkoxy or optionally substituted with phenyl, preferably a residue of the formula

ORB ³ , NHRB ⁴ or N(CH ₃ ) ₂ , particularly preferably of the formula ORB ³

RB ³ means hydrogen or an unsubstituted or substituted aliphatic hydrocarbon residue, preferably with 1-18 carbon atoms;

RB ⁴ means hydrogen, (C ₁ -C ₆ )alkyl, (C ₁ -C ₆ )alkoxy or substituted or unsubstituted phenyl;

TB means (C1 or C ₂ )alkanediyl chain which is unsubstituted or may be substituted by one or two (C1-C ₄ )alkyl radicals or [(C ₁ -C ₃ )alkoxy]carbonyl;

preferably:

a) compounds of the 8-quinolinoxyacetic acid type (S2 ^a ), preferably (1-methylhexyl)ester of (5-chloro-8-quinolineoxy)acetic acid (cloquintoset-mexyl) (S21), (1,3-dimethyl-but-1 -yl)ester of (5-chloro-8-quinolinoxy)acetic acid (S2-2),

(5-Chloro-8-quinolinoxy)acetic acid 4-allyloxy-butyl ester (S2-3), (5-Chloro-8-quinolinoxy)acetic acid 1-allyloxy-prop-2-yl ester (S2-4), (5-chloro-8-quinolinoxy)acetic acid ethyl ester (S2-5), (5-chloro-8-quinolinoxy)acetic acid methyl ester (S2-6), (5-chloro-8-quinolinoxy)acetic acid allyl ester acids (S2-7), 2-(2-propylidene-iminoxy)-1-ethyl ester of (5-chloro-8-quinolinoxy)acetic acid (S2-8), 2-oxo-prop-1-yl ester (5 -chloro-8-quinolinoxy)acetic acid (S2-9) and related compounds as described in EP-A-86 750, EP-A-94 349 and EP-A-191 736 or EP-A-0 492 366, as well as (5-chloro-8-quinolinoxy)acetic acid (S2-10), its hydrates and salts, for example their lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium salts, or phosphonium salts as described in WO-A-2002/34048;

b) compounds of the (5-chloro-8-quinolinoxy)malonic acid type (S2 ^b ), preferably compounds such as (5-chloro-8-quinolinoxy)malonic acid diethyl ester, (5-chloro8-quinolinoxy)malonic acid diallyl ester , (5-chloro-8-quinolinoxy)malonic acid methyl ethyl ester and related compounds as described in EP-A-0582198.

S3) Compounds of formula (S3)

where the symbols and indices have the following meanings:

R _C 1 means (C1-C ₄ )alkyl, (C1-C ₄ )haloalkyl, (C ₂ -C ₄ )alkenyl, (C ₂ -C ₄ )haloalkenyl, (C ₃ C ₇ )cycloalkyl, preferably dichloromethyl;

_RC ² , RC ³ are equal to or different from hydrogen, (C1-C ₄ )alkyl, (C ₂ -C ₄ )alkenyl, (C ₂ -C ₄ ) alkynyl, (C ₁ C ₄ ) haloalkyl, (C ₂ - C ₄ ) haloalkenyl, (C ₁ -C ₄ ) alkylcarbamoyl-(C ₁ -C ₄ ) alkyl, (C ₂ -C ₄ ) alkenylcarbamoyl (C 1 -C ₄ ) alkyl, (C ₁ -C ₄ ) αlkoxy-(C ₁ -C ₄ )alkyl, dioxolanyl-(C1-C ₄ )alkyl, thiazolyl, furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted phenyl, or _RC ² and _RC ³ together form a substituted or unsubstituted heterocyclic ring, preferably an oxazolidine , thiazolidine, piperidine, morpholine, hexahydropyrimidine or benzoxazine ring;

preferably active ingredients of the dichloroacetamide type, which are often used as pre-emergence preservatives (preservatives, for soil application), such as dichloramide (N,N-diallyl-2,2-dichloroacetamide) (S3-1),

R-29148 (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) from Stauffer (S3-2),

R-28725 (3-dichloroacetyl-2,2,-dimethyl-1,3-oxazolidine) from Stauffer (S3-3), benoxacor (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4 -benzoxazine) (S3-4),

PPG-1292 (N-allyl-N-[(1,3-dioxolan-2-yl)methyl]dichloroacetamide) from PPG Industries (S3-5), DKA-24 (N-allyl-N-[(allylaminocarbonyl)methyl ]dichloroacetamide) from Sagro-Chem (S3-6), AD-67 or MON 4660 (3-dichloroacetyl-1-oxa-3-aza-spiro[4,5]decane) from Nitrokemia or Monsanto (S3-7),

TI-35 (1-dichloroacetyl-azepane) from TRI-Chemical RT (S3-8), diclonon (dicyclonone) or BAS145138 or LAB145138 (S3-9), ((RS)-1-dichloroacetyl-3,3,8a- trimethylperhydropyrrolo[1,2-a]pyrimidin-6-one) from BASF, furilazole or MON 13900 ((RS)-3-dichloroacetyl-5-(2-furyl)-2,2-dimethyloxazolidine) (S3-10), as well as their (R)-isomer (S3-11).

S4) N-acylsulfonamides of formula (S4) and their salts

- 16 040946

where symbols and indices have the following meanings:

AD means SO ₂ -NRD ₃ -CO or CO-NRD ₃ -SO ₂ ;

XD means CH or N;

RD ¹ means CO-NRD5RD ⁶ or NHCO-RD ⁷ ;

RD ² means halogen, (C1-C ₄ ) haloalkyl, (C 1 -C ₄ ) haloalkoxy, nitro, (C ₁ -C ₄ ) alkyl, (C 1 -C ₄ ) alkoxy, (C 1 -C ₄ ) alkylsulfonyl, (C 1 -C ₄ )alkoxycarbonyl or (C1-C ₄ )alkylcarbonyl;

RD ³ means hydrogen, (C1-C ₄ )alkyl, (C ₂ -C ₄ )alkenyl or (C ₂ -C ₄ )alkynyl;

RD ⁴ means halogen, nitro, (C1-C ₄ )alkyl, (C1-C ₄ )haloalkyl, (C1-C ₄ )haloalkoxy, C ₆ )cycloalkyl, phenyl, (C1-C ₄ )alkoxy, cyano, (C ₁ -C ₄ )αkylthio, (C1-C ₄ )alkylsulfinyl, C ₄ )alkylsulfonyl, (C ₁ -C ₄ )alkoxycarbonyl or (C1-C ₄ )alkylcarbonyl;

(C3(C1RD ⁵ ) hydrogen, (C ₁ -C ₆ )alkyl, (C ₃ -C ₆ )cycloalkyl, (C2-C ₆ )alkenyl, (C2-C ₆ )alkynyl, (C ₅ C ₆ )cycloalkenyl, phenyl or a 3-6-membered heterocyclyl containing v _D heteroatom from the nitrogen, oxygen and sulfur groups, the last seven residues being substituted by vD substituents from the halogen group, (C ₁ -C ₆ )alkoxy, (C ₁ -C ₆ )haloalkoxy , (C ₁ -C 2 ) alkylsulfinyl, (C ₁ -C ₂ ) alkylsulfonyl, (C ₃ C ₆ ) cycloalkyl, (C 1 -C ₄ ) alkoxycarbonyl, (C ₁ -C ₄ ) alkylcarbonyl and phenyl and, in the case of cyclic residues, also (C1-C ₄ )alkyl and (C1-C ₄ )haloalkyl are substituted;

RD ⁶ is hydrogen, (C ₁ -C ₆ )alkyl, (C ₂ -C ₆ )alkenyl or (C ₂ -C ₆ )alkynyl, the last three residues being replaced by vD residues from the halogen group, hydroxy, (C1 -C ₄ )alkyl, (C1- _C4 )alkoxy and (C1- _C4 )alkylthio, or

RD ⁵ and RD ⁶ together with the nitrogen atom present form a pyrrolidinyl or piperidinyl residue;

RD ⁷ is hydrogen, (C1-C ₄ )alkylamino, di(C1-C ₄ )alkylamino, (C ₁ -C ₆ )alkyl, (C ₃ C ₆ )cycloalkyl, the last 2 residues being substituted with vD substituents from the halogen group , (C1C ₄ )alkoxy, (C ₁ -C ₆ )haloalkoxy and (C1-C ₄ )alkylthio and, in the case of cyclic residues, are also substituted with (C1C ₄ )alkyl and (C1-C ₄ )haloalkyl;

nD means 0, 1 or 2;

mD means 1 or 2;

v _D means 0, 1, 2 or 3;

of these, preferred are compounds of the N-acylsulfonamide type, for example of the following formula (S4 ^a ), which are known, for example, from WO-A-97/45016

where RD ⁷ means (C ₁ -C ₆ )alkyl, (C ₃ -C ₆ )cycloalkyl, the last 2 residues being replaced by vD substituents from the halogen group, (C ₁ -C ₄ )alkoxy, (C ₁ -C ₆ ) haloalkoxy and (C1-C ₄ )alkylthio and, in the case of cyclic residues, are also substituted with (C1-C ₄ )alkyl and (C1-C ₄ )haloalkyl;

RD ⁴ means halogen, (C1-C ₄ )alkyl, (C1-C ₄ )alkoxy, CF ₃ ;

mD means 1 or 2;

v _D means 0, 1, 2 or 3;

as well as acylsulfamoylbenzoic acid amides, for example of the following formula (S4 ^b ), which are, for example, known from WO-A-99/16744,

for example, where

RD ⁵ = cyclopropyl and (RD ⁴ ) = 2-OMe (cyprosulfamides, S4-1),

RD ⁵ = cyclopropyl and (RD ⁴ ) = 5-Cl-2-OMe (S4-2),

RD ⁵ = ethyl and (RD ⁴ ) = 2-OMe (S4-3),

RD ⁵ = cyclopropyl and (RD ⁴ ) = 5-Cl-2-OMe (S4-4), and

RD ⁵ = ethyl and (RD ⁴ ) = 2-OMe (S4-5), as well as compounds of the N-acylsulfamoylphenylurea type of formula (S4 ^c ), which are known, for example, from EP-A-365484

- 17 040946

where R _d ⁸ and Rd ⁹ independently of each other are hydrogen, (C1-Cg) alkyl, (C3-C ₈ ) cycloalkyl, (C ₃ -C ₆ ) alkenyl, (C ₃ -C ₆ ) alkynyl,

R _d ⁴ means halogen, (C ₁ -C ₄ )alkyl, (C1-C ₄ )alkoxy, CF ₃ ;

m _D means 1 or 2;

For example,

1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea,

1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea,

1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea, as well as

N-phenylsulfonyl terephthalamides of the formula (S4 ^d ), which are, for example, known from CN 101838227

for example, where

R _d ⁴ means halogen, (C1-C ₄ )alkyl, (C1-C ₄ )alkoxy, CF ₃ ;

m _D means 1 or 2;

R _d ⁵ means hydrogen, (C ₁ -C ₆ )alkyl, (C ₃ -C ₆ )cycloalkyl, (C ₂ -C ₆ )alkenyl, (C ₂ -C ₆ )alkynyl, (C5C ₆ )cycloalkenyl.

S5) active substances from the class of hydroxy-aromatic compounds and aromatic aliphatic derivatives of carboxylic acid (S5), for example, 3,4,5-triacetoxybenzoic acid ethyl ester, 3,5-dimethoxy-4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4- hydroxysalicylic acid, 4-fluorosalicylic acid, 2-hydroxycinnamic acid, 2,4dichlorocinnamic acid, as described in WO-A-2004/084631, WO-A-2005/015994, WO-A2005/016001.

S6) active ingredients from the class of 1,2-dihydroquinoxalin-2-ones (S6), e.g. 1-methyl-3-(2thienyl)-1,2-dihydroquinoxalin-2-one, thienyl)-1,2-dihydroquinoxalin-2-thione, 1-(2-aminoethyl)-3-(2-thienyl)-1,2-dihydro-quinoxalin-2-one-hydrochloride, 1-(2-methylsulfonylaminoethyl)-3 (2-thienyl)-1,2-dihydro-quinoxalin-2-one as described in WO-A-2005/112630.

S7) Compounds of formula (S7) as described in WO-A-1998/38856

where symbols and indices have the following meanings:

RE ¹ , RE ² mean independently of each other halogen, (C1-C ₄ )alkyl, (C ₁ -C ₄ )alkoxy, (C1-C ₄ )haloalkyl, (C1-C ₄ )alkylamino, di(C1-C ₄ ) alkylamino, nitro;

AE stands for COORE ³ or COSRE ⁴

RE ³ , RE ⁴ are independently hydrogen, (C1-C ₄ )alkyl, (C ₂ -C ₆ )alkenyl, (C ₂ -C ₄ ) alkynyl, cyanoalkyl, (C ₁ -C ₄ ) haloalkyl, phenyl , nitrophenyl, benzyl, halobenzyl, pyridinylalkyl and alkylammonium, n _E ¹ is 0 or 1 nE ² , nE ³ is independently 0, 1 or 2, preferably diphenylmethoxyacetic acid, diphenylmethoxyacetic acid ethyl ester, diphenylmethoxyacetic acid methyl ester (Reg. CAS No. 41858-19-9) (S7-1).

S8) Compounds of formula (S8) as described in WO-A-98/27049

where XF means CH or N, nF if XF=N means an integer from 0 to 4, and if XF=CH means an integer from 0 to 5,

RF ¹ means halogen, (C _g C ₄ )alkyl, (C _g C ₄ ) haloalkyl, (C 1 -C ₄ ) alkoxy, (C ₁ -C ₄ ) haloalkoxy, nitro, (C ₁ -C ₄ ) alkylthio, ( C1-C ₄ )alkylsulfonyl, (C ₁ -C ₄ )alkoxycarbonyl, optionally substituted phenyl, optionally substituted phenoxy,

RF ² means hydrogen or (C1-C ₄ )alkyl,

- 18 040946

RF ³ means hydrogen, (C1-C ₈ )alkyl, (C2-C ₄ )alkenyl, (C2-C ₄ )alkynyl or aryl, each of the previously named C-containing residues being unsubstituted or substituted by one or more, preferably up to three identical or different residues from the group consisting of halogen and alkoxy; or their salts, preferably compounds, where

XF means CH, nF means integer 0-2,

RF1 means halogen, (C1-C ₄ )alkyl, (C1-C ₄ )haloalkyl, (C ₁ -C ₄ )alkoxy, (C ₁ -C ₄ )haloalkoxy,

RF ² means hydrogen or (C1-C4)alkyl,

RF ³ means hydrogen, (C1-C ₈ )alkyl, (C ₂ -C ₄ )alkenyl, (C ₂ -C ₄ )alkynyl or aryl, each of the previously named C-containing residues being unsubstituted or substituted by one or more, preferably up to three identical or different residues from the group consisting of halogen and alkoxy;

or their salts.

S9) active substances from the class of 3-(5-tetrazolylcarbonyl)-2-quinolones (S9), e.g.

1,2-dihydro-4-hydroxy-1-ethyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. No. 219479-18-2), 1,2dihydro-4-hydroxy-1-methyl-3 -(5-tetrazolyl-carbonyl)-2-quinolone (CAS Registry No. 95855-00-8), which are described in WO-A-1999/000020.

S10) compounds of formula (S10 ^a ) or (S10 ^b ) as described in WO-A-2007/023719 and WO-A-2007/023764

(S10 ^a ) (S10 ^b ) where RG ¹ is halogen, (C1-C ₄ )alkyl, methoxy, nitro, cyano, CF ₃ , OCF ₃

YG, ZG independently of each other means O or S, nG means an integer 0-4,

RG ² means (C1-C ₁₆ )alkyl, (C ₂ -C ₆ )alkenyl, (C ₃ -C ₆ )cycloalkyl, aryl, benzyl, halobenzyl,

RG ³ means hydrogen or (C ₁ -C ₆ )alkyl.

S11) active ingredients of the oxyimino type (S11) which are used as seed dressings, such as oxabethrinyl ((Z)-1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile) (S11-1) , which is used as a seed dressing for millet against damage caused by metolachlor, fluxofenim (1-(4-chlorophenyl)-2,2,2-trifluoro-1-ethanone-O-(1,3-dioxolane-2 -ylmethyl)-oxime) (S11-2), which is used as a seed dressing for millet against damage caused by metolachlor, and cyometrinil or CGA-43089 ((Z)-cyanomethoxyimino(phenyl)acetonitrile) (S11-3 ), which is used as a seed dressing for millet against damage caused by metolachlor.

S12) active ingredients from the class of isothiochromanones (S12), such as methyl[(3-oxo-1H-2benzothiopyran-4(3H)-ylidene)methoxy]acetate (CAS Reg. No. 205121-04-6) (S12- 1) and related compounds from WO-A-1998/13361.

S13) one or more compounds from the group (S13):

naphthalic anhydride (1,8-naphthalenedicarboxylic acid anhydride) (S13-1), which is used as a protectant for corn seed dressing against damage caused by thiocarbamate herbicides, fenclorim (4,6-dichloro-2-phenylpyrimidine) (S13-2 ) which is used as a protectant against pretilachlor in seeded rice, flurazol (benzyl-2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate) (S13-3) which is used as a protectant for dressing millet seeds against damage caused by alachlor and metolachlor,

CL 304415 (CAS Reg. No. 31541-57-8), (4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid) (S13-4) from American Cyanamid, which is used as a protective products for corn from damage caused by imidazolinones,

MG 191 (CAS Registry No. 96420-72-3) (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5) from Nitrokemia, which is used as a corn preservative,

MG 838 (Reg. No. CAS 133993-74-5),

- 19 040946 (2-propenyl 1-oxa-4-azaspiro[4.5]decane-4-carbodithioate) (S13-6) from Nitrokemia, disulfotone (O,O-diethyl S-2-ethylthioethylphosphordithioate) (S13-7), dietholate (O,O-diethyl-Ophenylphosphorothioate) (S13-8), mephenate (4-chlorophenyl-methylcarbamate) (S13-9).

S14) active ingredients which, in addition to their herbicidal action against harmful plants, also have a protective effect on crop plants such as rice, such as dimepiperate or MY-93 (S-1-methyl-1-phenylethyl-piperidine-1-carbothioate ), which is a protectant for rice against damage caused by the herbicide molinate, daimuron or SK 23 (1-(1-methyl-1-phenylethyl)-3-p-tolyl-urea), which is a protectant for rice against damage, caused by the herbicide imazosulfuron, kumiduron = JC-940 (3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenyl-ethyl)urea, see JP-A60087254), which is a rice protectant against damage caused by certain herbicides, methoxyphenone or NK 049 (3,3-dimethyl-4-methoxy-benzophenone), which is a protective agent for rice against damage caused by certain herbicides,

CSB (1-bromo-4-(chloromethylsulfonyl)benzene) from Kumiai, (CAS Reg. No. 54091-06-4), which is a rice protectant against damage caused by certain herbicides.

S15) Compounds of formula (S15) or their tautomers as described in WO-A-2008/131861 and WO-A2008/131860

ABOUT

where RH ¹ means (C ₁ -C ₆ )haloalkyl residue, and

RH ² means hydrogen or halogen, and

RH ³ , RH ⁴ are independently hydrogen, (C1-C ₁₆ )alkyl, (C ₂ -C ₁₆ )alkenyl or (C ₂ C ₁₆ ) alkynyl, each of the last three residues named being unsubstituted or may be substituted one or more residues from the group of halogen, hydroxy, cyano, (C1-C ₄ )alkoxy, (C1C ₄ ) haloalkoxy, (C1-C ₄ )alkylthio, (C1-C ₄ )alkylamino, di[(C1-C ₄ ) alkyl]amino, [(C1- _C4 )alkoxy]carbonyl, [(C1- _C4 )haloalkoxy]carbonyl, ( _C3 - _C6 )cycloαalkyl which is unsubstituted or substituted, phenyl which is unsubstituted or substituted, and heterocyclyl which is unsubstituted or substituted, or (C ₃ -C ₆ )cycloαalkyl, (C ₄ -C ₆ )cycloalkenyl, (C ₃ -C ₆ )cycloαalkyl which is condensed on the ring side with one 4-6 membered saturated or unsaturated carbocyclic ring, or (C ₄ C ₆ ) cycloalkenyl, which is condensed on the side of the ring by one 4-6-membered saturated or unsaturated carbocyclic ring, each of the 4 last-named wasps tatkov is unsubstituted or may be substituted by one or more residues from the group of halogen, hydroxy, cyano, (C1-C ₄ )alkyl, (C1C ₄ ) haloalkyl, (C1-C ₄ )alkoxy, (C1-C ₄ )haloalkoxy, ( C1-C ₄ )alkylthio, (C1-C ₄ )alkylamino, di[(C1C ₄ )alkyl]amino, [(C1-C ₄ )alkoxy]carbonyl, [(C1-C ₄ )haloalkoxy]carbonyl, (C ₃ -C ₆ )cycloalkyl which is unsubstituted or substituted, phenyl which is unsubstituted or substituted, and heterocyclyl which is unsubstituted or substituted means or

RH ³ means (C 1 -C ₄ )alkoxy, (C ₂ -C ₄ )alkenyloxy, (C ₂ -C ₆ )alkynyloxy or (C ₂ -C ₄ )haloalkoxy, and

RH ⁴ means hydrogen or (C1-C ₄ )alkyl, or

RH ³ and RH ⁴ together with the directly connected N-atom means a 4 to 8-membered heterocyclic ring, which, in addition to the N-atom, can also contain other ring heteroatoms, preferably up to 2 other ring heteroatoms from the group N, O and S, and which is unsubstituted or substituted by one or more of halo, cyano, nitro, (C1-C ₄ )alkyl, (C1-C ₄ ) haloalkyl, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) haloalkoxy, and (C1- _C4 )alkylthio.

S16) active ingredients which are predominantly used as herbicides, but which also have a protective effect on cultivated plants, e.g. (2,4-dichlorophenoxy)acetic acid (2,4-D), (4-chlorophenoxy)acetic acid, ( R,S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop),

4-(2,4-dichlorophenoxy)butyric acid (2,4-DB), (4-chloro-o-tolyloxy)acetic acid (MCPA),

4-(4-chloro-o-tolyloxy)butyric acid,

4-(4-chlorophenoxy)butyric acid,

3,6-dichloro-2-methoxybenzoic acid (dicamba),

1-(ethoxycarbonyl)ethyl-3,6-dichloro-2-methoxybenzoate (lactidichloro-ethyl).

- 20 040946

Particularly preferred protective agents are: mefenpyr-diethyl, cyprosulfamide, isoxadifen-ethyl, cloquintoset-mexil, benoxacor and dichloramide.

Powders for spraying are preparations uniformly dispersed in water, which, along with the active substance, in addition to the diluent or inert substance, also contain non-ionic and / or ionic surfactants (wetting agents, dispersants), for example, polyoxyethylated alkylphenols, polyoxyethylated aliphatic alcohols, polyoxyethylated aliphatic amines, fatty alcohol polyglycol ether sulfates, alkane sulfonates, alkylbenzenesulfonates, sodium lignosulfonic acid, sodium 2,2'-dinaphthylmethane-6,6-disulfonic acid, sodium dibutylnaphthalene sulfate or also sodium oleolmethyltaurine acid. For the preparation of powders for spraying, the herbicidal active ingredients are finely ground, for example, in conventional equipment such as a hammer mill, an air blower and an air jet mill, and are immediately or subsequently mixed with formulation auxiliaries.

Emulsifiable concentrates are obtained by dissolving the biologically active substance in an organic solvent, for example, butanol, cyclohexanone, dimethylformamide, xylene, or also in high-boiling aromatic compounds or hydrocarbons, or organic solvent mixtures, using one or more ionic and/or non-ionic surfactants (emulsifiers). As emulsifiers, for example, the following can be used: calcium salts of alkylarylsulfonic acid, such as Sadodecylbenzenesulfonate or non-ionic emulsifiers, such as polyglycol fatty acid ester, alkylaryl polyglycol ether, fatty alcohol polyglycol ether, propylene oxide-ethylene oxide condensates, alkylpolyether, sorbitan ester, such as sorbitan a fatty acid ester; or a polyoxyethylene sorbitan ester such as, for example, a polyoxyethylene sorbitan fatty acid ester.

Pollinators are obtained by grinding the biologically active substance with finely divided solids such as, for example, talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.

Suspension concentrates may be water or oil based. They can be obtained, for example, by wet grinding with standard bead mills, optionally with the addition of surfactants, as, for example, already mentioned in other types of formulations.

Emulsions, e.g. oil-in-water (EW) emulsions, can be prepared with stirrers, colloid mills and/or static mixers using aqueous organic solvents and optionally surfactants, as for example already mentioned in other types of preparative forms.

Granules can be produced by spraying the active ingredient onto granular inert adsorbents or by applying the concentrate of active ingredients with binders, for example polyvinyl alcohol, sodium polyacrylic acid or also mineral oils, onto the surface of a filler such as sand, kaolinite or granular inert material. Also for the manufacture of fertilizer granules, the appropriate active ingredients are crushed in the usual way, optionally mixed with fertilizers.

Water-dispersible granules are usually produced by conventional methods such as spray drying, fluidized bed granulation, disc granulator granulation, mixing in a high speed mixer granulator and extrusion without solid inert substance.

For the production of granulates using a disk granulator, fluidized bed granulates, extruder and spray drying, see for example the method in the Spray-Drying Handbook 3rd Ed. 1979, G. Goodwin Ltd., London, J.E. Browning, Agglomeration, Chemical and Engineering 1967, p. 147 et al., Perry's Chemical Engineer's Handbook, 5th ed., McGraw-Hill, New York 1973, p. 8-57.

For further details on formulations of plant protection products, see, for example, G.C. Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, p. 81-96 and J.D. Freyer, S.A. Evans, Weed Control Handbook, 5th ed., Blackwell Scientific Publications, Oxford, 1968, p. 101-103.

Agrochemical formulations contain, as a rule, 0.1-99 wt.%, especially 0.1-95 wt.%, compounds according to the invention. In dusting powders, the active ingredient concentration is, for example, 10-90% by weight of the residue to 100% by weight of the usual formulation components. In emulsifiable concentrates, the concentration of active substance can be approximately 1-90%, preferably 5-80% by weight. Dust formulations contain 1-30% by weight of the active ingredient, preferably at least 5-20% by weight of the active ingredient, the dispersion solutions contain about 0.05-80, preferably 2-50% by weight of the active ingredient. In water-dispersible granules, the content of the active ingredient depends in part on whether the active compound is present in liquid or solid form and which granulating aids, excipients, etc. are present. use. In water-dispersible granules, the active ingredient content is, for example, 1-95% by weight, preferably 10-80% by weight.

In addition, the said compounds of active ingredients optionally contain the usual setting, wetting, dispersing, emulsifying, penetrating, preservative, antifreeze and solvent agents, fillers, carriers, dyes, defoamers, brake evaporators and antitranspirants; and agents that affect pH and viscosity.

Based on these formulations, combinations can also be obtained with other pesticidally active ingredients, such as, for example, insecticides, acaricides, herbicides, fungicides, as well as protective agents, fertilizers and/or growth regulators, for example, in the form of ready-made formulations or in mixing in a container.

For use, the formulations normally present are diluted in the usual way with water, for example in the form of spray powders, emulsifiable concentrates, dispersions and water-dispersible granules. Dust formulations, soil granules or granulates, and spray solutions are usually not diluted with other inert substances before use.

When exposed to external conditions such as temperature, humidity, type of herbicide applied, etc. the required rates of the compounds of formula (I) vary. They may vary within certain limits, for example 0.001-1.0 kg/ha or more active substance, but 0.005-750 g/ha is preferred.

Excipient means a natural or synthetic, organic or inorganic substance with which the active ingredients are mixed or combined for improved applicability, for application to plants or parts of plants, or seeds. The filler, which may be solid or liquid, is generally inert and should be used in agriculture.

As solid or liquid fillers, the following are taken into account: for example, ammonium salts and natural stone flour, such as kaolin, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic stone flour, such as highly dispersed silicic acid, aluminum oxide and natural or synthetic silicates, resins, waxes, solid fertilizers, water, alcohol, especially butanol, organic solvents, mineral and vegetable oils, and their derivatives. Mixtures of such fillers may also be used. As solid fillers for granules, take into account: for example, broken and fractionated natural rock, such as calcite, marble, pumice, sepiolite, dolomite, as well as synthetic granulates from inorganic and organic flour, as well as granulates from organic materials, such as sawdust, coconut shell, corncobs and tobacco plant stalks.

As liquefied gaseous diluents or excipients, those liquids are taken into account which are gaseous at normal temperature and normal pressure, for example aerosol propellants such as halocarbons, butane, propane, nitrogen and carbon dioxide.

Adhesion agents such as carboxymethyl cellulose, natural and synthetic powdered, granular or latex polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipid such as cephalin and lecithin, and synthetic phospholipid can be used in formulations. Other additives can be mineral and vegetable oils.

In the case of using water as a diluent, it is also possible, for example, to use organic solvents as co-solvents. The following are generally considered as liquid solvents: Aromatic hydrocarbons such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic hydrocarbons or chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylenes or dichloromethane, aliphatic hydrocarbons such as cyclohexane or paraffin, for example petroleum fractions, minerals and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanop, very polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water.

The agents according to the invention may additionally contain other components such as clomazone, surfactants. As surfactants, emulsifiers and/or foaming agents, dispersants or wetting agents with ionic or non-ionic properties or mixtures of these surfactants are taken into account. Examples thereof are salts of polyacrylic acid, salts of lignosulfonic acid, salts of phenolsulfonic acid or naphthalenesulfonic acid, polycondensates of ethylene oxide with aliphatic alcohols or with aliphatic amines, substituted phenols (preferably alkylphenols or arylphenols), salts of sulfosuccinic acid esters, taurine derivatives (preferably alkyltaurate), phosphate esters polyethoxylated alcohols or phenols, fatty acid esters of polyhydric alcohols, and derivatives of compounds containing sulfates, sulfonates and phosphates, such as alkyl aryl polyglycol ether, alkyl sulfonate, alkyl sulfate, arylsulfonate, protein hydrolysates, lignin sulphite liquor and methylcellulose. The presence of surfactants is necessary if one of the active ingredients and/or one of the excipients is insoluble in water and if the application takes place in water. The amount of surfactants is 5-40 wt.% according to the invention. It is possible to use inorganic pigments such as oxide

- 22 040946 iron, titanium, ferrocyanoblue and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

If necessary, other additional components may also be present, for example protective colloids, binders, adhesives, thickeners, thixotropic agents, penetration enhancers, stabilizers, complexing agent, complexing agents. In general, the active ingredients can be combined with solid or liquid additives that are commonly used for formulation. In general, the compositions and formulations according to the invention contain 0.05-99% by weight, 0.01-98% by weight, preferably 0.1-95% by weight, particularly preferably 0.5-90% by weight of the active ingredient, very preferably 10-70 wt.%. The active ingredients or agents according to the invention can be used in their pure form or, depending on their respective physical and/or chemical properties, in their formulations or in the form of applications derived from them, as aerosols, capsule suspensions, cold mist concentrates, hot mist concentrates. , granulates in capsules, fine granules, liquid concentrate for seed treatment, ready-to-use solution, dusting powder, emulsifiable concentrate, oil-in-water emulsions, water-in-oil emulsions, macro-granulate, micro-granulate, oil-dispersible powder , liquid concentrates for mixing in oil, oil-miscible liquids, foams, pastes, pesticide-coated seeds, suspension concentrates, suspension-emulsion concentrate, soluble concentrate, suspension, spray powders, soluble powder, pollinators and granulates, water-soluble granules or tablets, water-soluble powder Seed processing, wetting powder, natural and synthetic materials impregnated with the active substance, as well as fine-grained substances in capsules made of polymeric substances and in seed coats, as well as preparative forms for ULV cold and hot fog generators.

The formulations mentioned can be prepared in a known manner, for example by mixing the active ingredients with at least one conventional diluent, solvent, emulsifier, dispersant and/or binder or fixative, wetting agent, water repellant, optionally a desiccant and UV stabilizers, and , if necessary, dye and pigment, defoamer, preservative, secondary thickener, adhesive, gibberellins, as well as other processing aids.

The compositions according to the invention contain not only formulations that are ready for use and can be applied to plants or seeds with special equipment, but also commercially available concentrates that must be diluted with water before use.

The active ingredients according to the invention can be present in pure form or in the form of their (conventional) mixtures, as well as the application forms obtained from these formulations in mixtures with other (known) active ingredients, such as insecticides, attractants, sterilants, bactericides, acaricides, nematocides, fungicides, growth regulators, herbicides, fertilizers, preservatives or semiochemicals.

The treatment according to the invention of plants and plant parts with active substances or means is carried out by direct application or exposure to the environment, habitat or storage place by conventional treatment methods, for example, dipping, (spraying) spraying, spraying, spraying, spraying liquid, spraying, dusting, ( scattering) shedding, foaming, coating, pre-coating, watering (flooding), drip irrigation also on plant propagation material, especially seeds, then by dry dressing, wet dressing, pickling in solutions, applying a layer, applying one or more shells and etc. It is then possible to apply the active ingredients using an ultra-low volume method or to inject the active ingredient solution or the active ingredient itself into the soil.

One of the advantages of the present invention is that, due to the special systemic properties of the active ingredients or agents according to the invention, the treatment of seed material with these active compounds or agents protects not only the seed material, but also the plants derived from it after germination from phytopathogenic fungi. In this way, it is possible not to carry out direct processing of crops at the time of sowing or immediately after it.

It is also preferred that the active ingredients or compositions according to the invention can also be particularly applied to transgenic seed material, wherein the plants growing from this seed material are able to express a protein which has an effect on pests. By treating such seed material with the active ingredients or compositions according to the invention by means of expression, for example of an insecticidal protein, certain pests can be controlled. However, another synergistic effect was unexpectedly observed, which further increases the effectiveness of the protection against pest infestation.

The compositions according to the invention are suitable for the protection of the seed material of any plant which is grown in agriculture, in a greenhouse, in forest land or in horticulture and viticulture. This applies in particular to seeds of cereals (such as wheat, barley, rye, triticale, millet and oats), corn, cotton, soybeans, rice, potatoes, sunflowers, beans, coffee, beets (e.g. sugar beet and fodder beets), peanuts, rapeseed, poppy, olives, coconut, cocoa, sugarcane, tobacco, vegetables (like tomatoes, cucumbers, onions and lettuce), turf and ornamental plants (see also below). Of particular importance is the processing of seeds of cereals (like wheat, barley, rye, triticale and oats), corn and rice.

As also described below, the treatment of transgenic seed with the active ingredients or agents according to the invention is of particular importance. This applies to plant seeds that contain at least one heterologous gene that promotes the expression of a polypeptide or protein with insecticidal properties. The heterologous gene in the transgenic seed may, for example, be derived from microbes of the species Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium. Preferably, this heterologous gene is derived from Bacillus sp., the gene product being effective against European corn borer and/or Western corn root beetle. Particularly preferably, the heterologous gene is derived from Bacillus thuringiensis.

Within the scope of the present invention, the agent according to the invention is applied alone or in the form of a suitable formulation to the seed. Preferably, the seed is treated in a state in which it is stable so that damage does not occur during processing. In general, seed treatment can be carried out at any time between harvest and sowing. Usually, seed material is used that does not have additional plant parts, cobs, peel, stems, shells, hairs or fruit pulp. For example, seed may be used which has been harvested, cleaned and dried to a moisture content of less than 15% by weight. Also alternatively, seed material can be used which, for example, after drying, has been treated with water and then dried again.

In general, during the treatment of the seed material, care must be taken to choose the amount of the agent according to the invention and/or other additives applied to the seed material that does not harm the germination of the seeds or harm the plants grown from them. This is especially taken into account when using those active ingredients that, at a certain application rate, can have a phytotoxic effect.

The compositions according to the invention can be applied in pure form, i.e. free of other components and without dilution with water. It is generally preferred to apply the agents to the seed in the form of suitable formulations. Suitable formulations and methods for seed treatment are known to those skilled in the art and are described, for example, in the following documents: .

The active ingredients used according to the invention can be converted into conventional dressing formulations, such as solutions, emulsions, suspensions, powders, foams, seed suspensions or other seed coats, as well as ultra-low volume formulations.

These formulations are prepared in a known manner, for example by mixing the active ingredients with conventional additives, such as conventional diluents as well as solvents or fillers, colorants, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins, and also water.

Colorants which can be present in the dressing formulations used according to the invention include all colorants customary for this purpose. In this case, both pigments that are poorly soluble in water and dyes that are soluble in water can be used. Examples to be mentioned are known dyes Rhodamine B, C.I. pigment red 112 and C.I. solvent red 1.

Suitable wetting agents that can be present in the dressing formulations used according to the invention are all substances customary for wetting agrochemical formulations. Preferably, alkylnaphthalenesulfonates are used, such as diisopropyl or diisobutylnaphthalenesulfonates.

As dispersants and/or emulsifiers that can be present in the dressing formulations used according to the invention, all non-ionic, anionic and cationic dispersants customary for such a formulation are taken into account. Preferably, nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants are used. As suitable non-ionic dispersants, mention should be made in particular of block copolymers of ethylene oxide propylene oxide, alkylphenol polyglycol ethers, and tristyrylphenol polyglycol ether and their phosphated or sulfated derivatives. Suitable anionic dispersants are in particular lignin sulfonates, polyacrylic acid salts and formaldehyde aryl sulfonate condensates.

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As defoamers that can be present in the dressing formulations used according to the invention, all conventional anti-foaming agents for the formulation of agrochemicals are taken into account. Preferably, silicone defoamers and magnesium stearate are used.

As preservatives, all substances suitable for this purpose used in agrochemical compositions can be present in the formulations of the dressing agents used according to the invention. For example, dichlorophen and benzyl alcohol hemiformal should be named.

As secondary thickeners that can be present in the dressing formulations used according to the invention, all substances used for this purpose in the agrochemical preparations are taken into account. Preferably, cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and highly dispersed silicic acid are taken into account.

Adhesives which may be present in the dressing formulations used according to the invention include all binders used for this purpose in dressing agents. Preferably, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose should be named.

The dressing formulations used according to the invention can be used either in pure form or after preliminary dilution with water for the treatment of seed material of various types, also seed material of transgenic plants. At the same time, additional synergistic effects may also occur when interacting with substances formed as a result of expression.

For the treatment of seed with the dressing formulations used according to the invention or compositions obtained from them by adding water, all mixers used for dressing are usually taken into account. In particular, when dressing, the seed material is placed in a mixer, the appropriate required amount of dressing formulations is added, either in pure form or after preliminary dilution with water, and mixed until the formulation is evenly distributed on the seed material. If necessary, also attach the drying process.

The active ingredients according to the invention, with good compatibility with plants, no toxicity to warm-blooded animals and good ecological compatibility, are suitable for protecting plants and plant organs, for increasing the yield, improving the quality of the harvested crop. Preferably they can be used as plant protection products. They have an effect on species with normal susceptibility and resistant species, and also act at all or certain stages of development.

As plants that can be treated according to the invention, the following main cultivated plants can be mentioned: corn, soybeans, cotton, Brassica oilseeds such as Brassica napus (e.g. canola), Brassica rapa, B. juncea (e.g. field mustard) and Brassica carinata, rice, wheat, sugar beet, sugar cane, oats, rye, barley, millet, triticale, flax, grapes and various fruits and vegetables of different botanical classes, such as Rosaceae sp. (e.g. pome fruits such as apples and pears, as well as stone fruits such as apricots, cherries, almonds and peaches, and horticultural crops such as strawberries), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp. ., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (e.g. banana trees and plantations), Rubiaceae sp. (e.g. coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (eg lemons, oranges and grapefruits); Solanaceae sp. (e.g. tomatoes, potatoes, peppers, aubergines), Liliaceae sp., Compositae sp. (e.g. lettuce, artichoke and lettuce chicory - including root chicory, endive chicory or common chicory), Umbelliferae sp. (e.g. carrots, parsley, stalk celery and root celery), Cucurbitaceae sp. (e.g. cucumbers - including pickled cucumbers, pumpkin, watermelon, bottle gourd and melon), Alliaceae sp. (e.g. chives and onions), Cruciferae sp. (e.g. white cabbage, red cabbage, broccoli, cauliflower, cauliflower, Brussels sprouts, pak choi, kohlrabi, radish, horseradish, watercress and bok choy), Leguminosae sp. (eg peanuts, peas and legumes - such as curly beans and beans), Chenopodiaceae sp. (eg chard, fodder beet, spinach, red beet), Malvaceae (eg okra), Asparagaceae (eg asparagus); useful and ornamental plants in the garden and forest; as well as, respectively, genetically modified species of these plants.

As mentioned above, all plants and their parts can be treated according to the invention. In a preferred form of execution, wild-growing or obtained by traditional breeding methods, such as crossing or protoplast synthesis, plants and plants, as well as parts thereof, are treated. In another preferred embodiment, transgenic plants and plants obtained by genetic engineering methods, if necessary in combination with traditional methods (genetically modified organisms), and their parts are treated. The concept of a part or part of a plant has been mentioned above. Particularly preferably, the plants are treated according to the invention, respectively, of conventional or used plant varieties. Plant varieties are understood as plants with new traits (Traits), which were obtained both using traditional breeding methods, using mutagenesis, and using recombinant DNA technologies. These can be varieties, breeds, bio- and genotypes.

The methods of the invention can be used to treat genetically modified organisms (GMOs), such as plants or seeds. Genetically modified plants (or transgenic plants) are plants in which one heterologous gene is stably integrated into the genome. The term "heterologous gene" means in general a gene which is obtained or assembled outside of a plant and which, when introduced into the plant cell nucleus genome, chloroplast genome or mitochondrial genome of a transforming plant, imparts to it new or improved agrochemical or similar properties, due to the expression of a new essential protein or polypeptide, or reprogramming or knocking out another gene that is present in the plant, or other genes that are present in the plant (eg, using antisense technologies, co-suppression technologies, or RNA interference [RNA interference] technologies). A heterologous gene that is present in the genome is also called a transgene. A transgene that is determined by its specific location in the plant genome is called a transformational or transgenic event.

Depending on the plant species or varieties, where they grow and their growth conditions (soil, climate, growing season, nutrition), the treatment according to the invention can also lead to super-additive (synergistic) effects. Thus, for example, the following effects, which exceed the expected ones, are possible: a reduction in application rates and/or an extension of the spectrum of action and/or an increase in the effectiveness of the active substances used according to the invention and the formulations that can be used according to the invention, better plant growth, increased tolerance to high and low temperatures, increased tolerance to dryness or water and salt content in the soil, increased flowering productivity, easier harvesting, faster maturation, larger crops, larger fruits, larger plant sizes, leaf color deeper green, earlier flowering, improved quality and/or increased nutritional value of the crop product, higher fruit sugar content, increased storage stability and/or workability of the crop product.

At certain application rates, the active compound combinations according to the invention can also have a strong effect on plants. They are therefore suitable for mobilizing the plant defense system against attack by unwanted phytopathogenic fungi and/or microorganisms and/or viruses. If necessary, this may be one of the reasons for the increased effectiveness of the combination according to the invention, for example against fungi. Plant strengthening (protection-inducing) substances in this context should also mean those substances or combinations of substances that are capable of stimulating the plant defense system in such a way that the treated plants, if they are in addition grafted with undesirable phytopathogenic fungi, show significant resistance to these undesirable phytopathogenic fungi. Therefore, the substances according to the invention can be used to protect the plant from being attacked by said pathogens for a certain period of time after treatment. The time period during which the protective effect is exerted is generally 1-10 days, preferably 1-7 days after the treatment of the plants with the active ingredients.

Plants and plant varieties that can preferably be treated according to the invention include all plants that have certain hereditary material that gives these plants particularly preferred, useful traits (whether this is due to conventional breeding and/or biotechnology).

Plants and plant varieties, which can also be treated according to the invention, are resistant to one or more biotic stress factors, i. these plants exhibit improved protection against animal and microbiological pests such as nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and/or viroids.

Examples of nematode-resistant plants are, for example, the following plants described in US Patent Applications: 12/192904 11/396808 12/166253 12/166239 12/166124 12/166209 11/762886 12/364335 11/763947 12/252453 12/209354 12/4913 497221.

Plants and plant varieties that can also be treated according to the invention are those that are resistant to one or more abiotic stressors. Abiotic stress conditions can include, for example, drought, cold and hot conditions, osmotic stress, stagnant water, increased soil salt content, increased mineral deposition, ozone conditions, high light conditions, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients or shadow avoidance.

Plants and plant varieties which can also be treated according to the invention are those which are characterized by improved yield qualities. Increased yields in these plants may, for example, be associated with improved plant physiology,

- 26 040946 improved plant growth and improved plant development such as efficient water use, efficient water retention, improved nitrogen utilization, increased carbon assimilation, improved photosynthesis, increased germ vigor and accelerated maturation. Along with this, yields can be increased by improving plant architecture (under stressed and non-stressed conditions), including early flowering, flowering control for hybrid seed production, plant bud development, plant size, internodial number and spacing, root growth, seed sizes, fruit sizes, pod sizes, number of pods or ears, number of grains per pod or ear, seed mass, enhanced seed filling, reduced seed drop, reduced pod bursting, and storage stability. Other features of crop products include seed composition such as carbohydrate content, protein content, oil content and oil composition, nutritional value, reduction of undesirable compounds for nutrition, improved processability and improved shelf life of crop products.

The plants that can be treated according to the invention are hybrid plants that just express the properties of heterosis, respectively, the hybrid effect, which generally leads to higher yields, higher growth, better health and better resistance to biotic and abiotic stress factors. Such plants are typically created by crossing a bred parental line with sterile pollen (the female partner in crossing) with another bred parental line with fertile (reproductive) pollen (the male partner in crossing). Hybrid seed material is typically obtained from plants with sterile pollen and sold to those who are engaged in their further propagation. Plants with sterile pollen can sometimes be obtained (for example, in the case of corn) by removing the panicles (i.e., mechanically removing the male reproductive organs, respectively, inflorescences); however, it is more common when pollen sterility is related to genetic determinants in the plant's genome. In this case, particularly when seeds are the desired product to be harvested from hybrid plants, it is usually useful to ensure that pollen fertility is fully restored in hybrid plants that contain the genetic determinants responsible for pollen sterility. This can be achieved by using when crossing such male partners that contain the appropriate genes that restore fertility (reproductivity), which have the ability to restore pollen fertility in hybrid plants containing genetic determinants responsible for pollen sterility. Genetic determinants responsible for the sterility of pollen can be localized in the cytoplasm. As examples of cytoplasmic pollen sterility (CMS), for example, species of the genus Brassica are described. Genetic determinants of pollen sterility can also be localized in the genome of the cell nucleus. Plants with sterile pollen can also be obtained by plant biotechnology methods such as gene technology. A particularly advantageous means for creating plants with sterile pollen is described in WO 89/10396, where, for example, a single ribonuclease such as Barnase selektiv is expressed in Tapetum cells in pollinated leaves. Fertility can also be restored by expression of a ribonuclease inhibitor such as Barstar in Tapetum cells.

Plants or plant varieties (which can be obtained by plant biotechnology methods such as gene technology) that can be treated according to this invention are herbicide-tolerant plants, that is, plants that are grown tolerant to one or more given herbicides. Such plants may be obtained either by genetic transformation or by plant breeding that includes a single mutation conferring such herbicide tolerance.

Herbicide-tolerant plants include, for example, glyphosate-tolerant plants, that is, plants grown tolerant of the herbicide glyphosate or its salts. Plants can become tolerant to glyphosate through a variety of methods. Thus, for example, glyphosate-tolerant plants can be obtained by transforming the plant with a gene that encodes the enzyme 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS). Examples of such EPSPS genes include the AroA gene (CT7 mutant) from the bacterium Salmonella typhimurium (Comai et al., 1983, Science 221, 370-371), the CP4 gene from the bacterium Agrobacterium sp. (Barry et al., 1992, Curr. Topics Plant Physiol. 7, 139145), genes that code for one EPSPS from petunia, one EPSPS from tomato (Shah et al., 1986, Science 233, 478-481), and one EPSPS from tomato (Gasser et al., 1988, J. Biol. Chem. 263, 4280-4289) or one EPSPS from eleusine (WO 01/66704). It may also mean mutated EPSPS. Glyphosate-tolerant plants can also be obtained by expressing a gene that codes for the enzyme glyphosate oxidoreductase. Glyphosate-tolerant plants can also be obtained by expressing a gene that codes for the enzyme glyphosate acetyltransferase. Glyphosate-tolerant plants can also be obtained by selecting plants that contain naturally occurring mutations of the genes mentioned above. Plants that express the EPSPS gene that confers glyphosate tolerance have been described. Plants that express another gene that confers glyphosate tolerance, such as the decarboxylase gene, have been described.

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Other herbicide-resistant plants include, for example, plants that are grown tolerant of herbicides that inhibit the glutamine synthase enzyme, such as bialaphos, phosphinothricin, or glufosinate. Such plants can be obtained by expressing an enzyme that neutralizes the herbicide or a single mutant of the glutamine synthase enzyme resistant to inhibition. Such an effective detoxifying enzyme is, for example, an enzyme that encodes a phosphinothricin acetyltransferase (such as, for example, a bar or pat protein found in Streptomyces species). Plants that express exogenous phosphinothricin acetyltransferase have been described.

Other herbicide-tolerant plants also include plants that are grown tolerant of herbicides that inhibit the hydroxyphenylpyruvate dioxygenase (HPPD) enzyme. In the case of hydroxyphenylpyruvate dioxygenases, these are enzymes that catalyze the reaction in which para-hydroxyphenylpyruvate (HPP) is converted to homogentisate. Plants that are tolerant of HPPD inhibitors can be transformed with a gene that encodes a naturally occurring resistant HPPD enzyme or a gene that encodes a mutated or chimeric HPPD enzyme, as described in WO 96/38567, WO 99 /24585, WO 99/24586, WO 2009/144079, WO 2002/046387 or US 6,768,044. Tolerance to HPPD inhibitors can also be achieved by transforming plants with genes that encode certain enzymes that promote homogentisate production despite inhibition of the native HPPD enzyme by the HPPD inhibitor. Such plants are described in WO 99/34008 and WO 02/36787. Plant tolerance to HPPD inhibitors can also be improved by further transforming in plants a gene that encodes an HPPD tolerant enzyme with a gene that encodes a prephenate dehydrogenase enzyme as described in WO 2004/024928. In addition, plants can be made intolerant to HPPD inhibitors by introducing into the genome a gene that encodes an enzyme that metabolizes or degrades an HPPD inhibitor, such as the CYP450 enzyme (see WO 2007/103567 and WO 2008/150473).

Other herbicide-resistant plants include those grown tolerant of acetolactate synthase inhibitors (ALS inhibitors). Known ALS inhibitors include, for example, sulfonylurea, imidazolinone, triazolopyrimidine, pyrimidinyloxy(thio)benzoate and/or sulfonylaminocarbonyltriazolinon herbicides. Various mutations in the enzyme ALS (also known as acetohydroxy acid synthase, AHAS) are known to confer tolerance to different herbicides or groups of herbicides, such as those described in Tranel und Wright (Weed Science 2002, 50, 700-712) . The production of sulfonylurea-tolerant plants and imidazolinone-tolerant plants has been described. Other plants tolerant to sulfonylurea and imidazolinone are also described.

Other plants tolerant to imidazolinone and/or sulfonylurea can be obtained by induced mutagenesis, selection of cell cultures in the presence of a herbicide, or by mutation selection (see, for example, for soybeans US 5,084,082, for rice WO 97/41218, for sugar beets US 5,773,702 and WO 99/057965, lettuce US 5,198,599 or sunflower WO 01/065922).

Plants or plant varieties (obtained by plant biotechnology methods such as gene technology) that can also be treated according to this invention are transgenic insect-resistant plants, that is, plants that are grown to be resistant to attack by certain target insects. Such plants may be obtained by genetic transformation, or by plant breeding that includes a single mutation conferring such insect resistance.

The term insect-resistant transgenic plant encompasses in this context any plant that contains at least one transgene that includes a coding sequence encoding the following:

1) an insecticidal crystal protein (protein) from Bacillus thuringiensis, or an insecticidal portion thereof, such as the insecticidal crystal proteins listed in Crickmore et al. (Microbiology and Molecular Biology Reviews 1998, 62, 807-813), updated description in Crickmore et al. (2005) in Bacillus thuringiensis Toxin Nomenclatur, described online at: http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/), or an insecticidal portion thereof, e.g., the Cry protein class Cry1Ab, CryAc, CryB, CryC, CryD, CryF, Cry2Ab, Cry3Aa, or Cry3Bb or an insecticidal portion thereof (eg EP-A 1999141 and WO 2007/107302), or such a protein encoded by a synthetic gene as described in US Patent Application 12/249016; or

2) a crystalline protein from Bacillus thuringiensis or part thereof, which in the presence of a second, different crystalline protein from Bacillus thuringiensis or part thereof acts insecticidally as a binary toxin, which consists of crystalline proteins Cy34 and Cy35; or (Nat. Biotechnol. 2001, 19, 668-72; Applied Environm. Microbiol. 2006, 71, 1765-1774) or a dual toxin that consists of the Cry1A or Cry1F proteins and the Cry2Aa or Cry2Ab or Cry2Ae protein (US Patent Application 12 /214022 and EP 08010791.5); or

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3) an insecticidal fusion protein that includes parts of two different insecticidal crystal proteins from Bacillus thuringiensis, such as, for example, a fusion of proteins 1) above or a fusion of proteins 2) above, for example, the Cry1A.1O5 protein, which produced from corn variant MON98034 (WO 2007/027777); or

4) a protein according to one of claims 1)-3) above, in which some, in particular 1-10 amino acids are replaced by another amino acid in order to achieve a higher insecticidal efficacy against the target insects and/or in order to to broaden the spectrum of appropriate target insects, and/or in connection with changes that have been induced in the coding DNA during cloning or transformation, such as the Cry3Bb1 protein in the MON863 or MON88017 maize variant or the Cry3A protein in the MIR 604 maize variant;

5) an insecticidal isolated protein from Bacillus thuringiensis or Bacillus cereus or an insecticidal part thereof, such as vegetative insect toxic proteins (vegetative insecticidal proteins, VIP) as listed at http://www.lifesci.sussex.ac.uk /Home/Neil_Crickmore/Bt/vip.html, for example, proteins of the VIP3Aa protein class; or

6) an isolated protein from Bacillus thuringiensis or Bacillus cereus which, in the presence of another isolated protein from Bacillus thuringiensis or B. cereus, is insecticidal, as well as a binary toxin that consists of the proteins VIP1A and VIP2A (WO 94/21795); or

7) an insecticidal fusion protein that includes portions of various isolated proteins from Bacillus thuringiensis or Bacillus cereus, such as a fusion of proteins 1) or a fusion of proteins 2) above; or

8) a protein according to one of claims 5)-7) above, in which some, especially 1-10 amino acids are replaced by another amino acid in order to achieve a higher insecticidal efficacy against the target insect species and/or in order to to broaden the range of appropriate target insect species, and/or due to changes that have been induced in the coding DNA during cloning or transformation (whereby coding is retained for one insecticidal protein), such as the VIP3Aa protein in the cotton variant COT 102; or

9) an isolated protein from Bacillus thuringiensis or Bacillus cereus which, in the presence of another isolated protein from Bacillus thuringiensis, acts insecticidally, as well as a binary toxin that consists of proteins VIP3 and Cry1A or Cry1F (US patent applications 61/126083 and 61/195019) , or a binary toxin that consists of VIP3 and Cry2Aa or Cry2Ab proteins or Cry2Ae proteins (US Patent Application 12/214,022 and EP 08010791.5); or

10) a protein according to claim 9) above, in which some, in particular, 1-10 amino acids are replaced by another amino acid in order to achieve a higher insecticidal efficacy against the target insect species and/or in order to expand the spectrum of the corresponding target insect species, and/or due to changes that were induced in the coding DNA during cloning or transformation (moreover, coding is retained for one insecticidal protein).

Naturally, the insecticide-resistant transgenic plants in the present invention also include any plant that includes a combination of genes that encode proteins from one of the above classes 1-10. In one form of the invention, an insecticide-resistant plant contains more than one transgene encoding a protein of one of the above classes 110 in order to expand the spectrum of the respective target insect species or in order to slow the development of insect resistance to the plant, as a result of that embed different proteins that are insecticidal to the target insect species but have a different mode of action, such as attaching to different receptor attachment sites in the insect.

Insecticide-resistant transgenic plant as used herein means a plant that contains at least one transgene that contains an RNA double helix sequence that, upon ingestion by an insect pest, inhibits the growth of that pest.

Plants or plant varieties (which have been obtained by plant biotechnology methods such as gene technology) that can also be treated according to this invention are tolerant of abiotic stress factors. Such plants may be obtained by genetic transformation, or by plant breeding that includes a single mutation conferring such stress resistance. Particularly beneficial stress-tolerant plants include the following:

a) plants which contain a transgene capable of reducing the expression and/or activity of a gene responsible for poly(ADP-ribose)polymerase (PARP) in plant cells or in plants.

b) plants that contain a stress tolerance transgene that is capable of downregulating the expression and/or activity of a gene encoding PARG in plants or plant cells;

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c) plants that contain a stress tolerance transgene that encodes a plant functional enzyme of the nicotinamide adenine dinucleotide-salvage biosynthetic pathway, among them nicotinamide adenine dinucleotide synthetase, nicotinate phosphorribosyl transferase, nicotinic acid mononucleotide adenyl transferase, nicotinamide adenine dinucleotide synthetase or nicotinamide phosphoribosyl transferase.

Plants or plant varieties (that have been obtained by plant biotechnology methods such as gene technology) that can also be treated according to this invention are characterized by an altered quantity, quality and/or better shelf life of the crop product and/or altered properties of certain components of the crop product , For example:

1) transgenic plants that synthesize modified starch characterized by altered physicochemical properties, in particular amylose content or amylose/amylopectin ratio, degree of branching, average chain length, side chain separation, viscosity behavior, gel strength, starch grain sizes and/ or the morphology of starch grains compared to starch that is synthesized by wild-type plant or plant cells such that this modified starch is better suited for some applications.

2) transgenic plants that synthesize non-starch carbohydrate polymers, or non-starch carbohydrate polymers, the properties of which are changed in comparison with wild types of plants without genetic modifications. For example, plants that produce polyfructose, preferably of the inulin and levan type, plants that produce alpha-1,4-glucan, plants that produce alpha-1,6-branched alpha-1,4-glucans, and plants that produce alternan.

3) transgenic plants that produce hyaluronan.

4) transgenic plants or hybrid plants like onions with specific properties such as high soluble solids content ('high soluble solids content'), low pungency ('low pungency', LP) and/or long-term storage stability ('long storage', LS).

Plants or plant varieties (which have been obtained by plant biotechnology methods such as gene technology) that can also be treated according to this invention are cotton plants with altered fiber properties. Such plants can be obtained by genetic transformation, or by breeding plants that contain a single mutation that causes such changes in the properties of the fibers; These include:

a) plants, such as cotton plants, which contain an altered form of cellulose synthase genes,

b) plants, such as cotton plants, which contain an altered form of rsw2 or gate/3 nucleic acid homologues; cotton plants, with increased expression of sucrose phosphate synthase;

c) plants, such as cotton plants, with increased expression of sucrose synthase;

d) plants, such as cotton plants, in which the timing of plasmodesmata transmission at the base of the fiber cell is altered, for example, as a result of down regulation of fiber selective β-1,3-glucanase;

e) plants, such as cotton plants, with altered reactivity fibers, for example, as a result of the expression of the N-acetylglucosamine transferase gene, among them also nodC, and the chitin synthase gene.

Plants or plant varieties (which have been obtained by plant biotechnology methods such as gene technology) that can also be treated according to this invention are rapeseed or related Brassica plants with altered oil composition properties. Such plants can be obtained by genetic transformation, or by breeding plants that contain a single mutation that causes such changes in the properties of the oil; These include:

a) plants, such as rapeseed plants, which produce an oil with a high content of oleic acid;

b) plants, such as rapeseed plants, which produce an oil with a low content of linolenic acid;

c) plants, such as rape plants, which produce an oil with a low content of saturated fatty acids.

Plants or plant varieties (which can be obtained using plant biotechnology methods such as gene technology) that can also be treated according to this invention are plants such as potatoes, which are resistant to viruses, for example, potato virus Y (event SY230 and SY233 Tecnoplant, Argentina), or which are resistant to diseases such as haulm rot or tuber rot (potato late blight) (for example, the RB gene), or which show a decrease in sweetness caused by cold (which is carried by the Nt-Inh genes). , II-INV) or that show a dwarfism phenotype (A-20 oxidase gene).

Plants or plant varieties (that have been produced by plant biotechnology methods such as gene technology) that can also be treated according to this invention are rapeseed or related Brassica plants with altered seed shattering properties. Such plants can be obtained by genetic transformation, or by breeding plants that contain a single mutation that causes such altered properties, and includes plants such as rapeseed with delayed or reduced seed cracking.

Particularly useful transgenic plants that can be treated according to this invention are plants with a single transforming event or a combination of transforming events, which in the United States in the Animal and Plant Health Inspection Service (APHIS) US Department of Agriculture (United States Department of Agriculture (USDA)) are the subject of unregulated status petitions granted or pending. Information about this can be obtained at any time from APHIS (4700 River Road Riverdale, MD 20737, USA), for example, at http://www.aphis.usda.gov/brs/not_reg.html. On the date of filing this application with APHIS, these applications are either granted or pending:

Petition: The personal identification number of the petition. A technical description of the transformation events received from APHIS can be found on the website under the application number. However, these descriptions are disclosed based on reviews.

Petition Amendment: Feedback on an earlier petition that requires an addition or additional information.

Institution: The name of the person making the petition.

Subject of regulation: related plant species.

Transgenic phenotype: traits that plants have received as a result of transformation events.

Transform Event or Lines: The name of the event or events (sometimes also called line(s)) that require unregulated status.

APHIS Documents: Various documents that have been published by APHIS regarding the petition or are available from APHIS upon request.

Particularly useful transgenic plants that can be treated according to this invention are plants with one or more genes encoding one or more toxins, are transgenic plants that are sold under the trade names: YIELD GARD® (for example, corn, cotton, soybeans ), KnockOut® (e.g. corn), BiteGard® (e.g. corn), BT-Xtra® (e.g. corn), StarLink® (e.g. corn), Bollgard® (cotton), Nucotn® (cotton), Nucotn 33B ® (cotton), NatureGard® (eg corn), Protecta® and NewLeaf® (potato). Herbicide-tolerant plants that should be mentioned are, for example, corn varieties, cotton varieties and soybean varieties, which are sold under the following trade names: Roundup Ready® (glyphosate tolerance, e.g. corn, cotton, soybeans), Liberty Link®) (phosphinothricin tolerance, eg rapeseed), IMI® (imidazolinone tolerance) and SCS® (sulfonylurea tolerance, eg corn). Herbicide-resistant plants (plants traditionally grown with herbicide tolerance) to be mentioned include varieties sold under the trade name Clearfield® (eg corn).

Particularly useful transgenic plants that can be treated according to the invention are plants that have undergone transformation events or a combination of transformation events and are for example listed in the database of various national or regional authorities (see, for example, http://gmoinfo .jrc.it/gmp_browse.aspx and http://ceragmc.org/index.php?evidcode=&hstIDXCode=&gType=&AbbrCode=&atCo de=&stCode=&coIDCode=&action=gm_crop_database&mode=Submit).

The active substances or agents according to this can also be used in material protection to protect technical materials against damage and destruction by undesirable microorganisms, such as fungi and insects.

Furthermore, the compounds according to the invention, alone or in combination with other biologically active substances, can be used as antifouling agents.

Technical materials are to be understood in this connection as non-living materials prepared for use in technology. For example, technical materials that must be protected from microbial alteration or degradation may include adhesives, clays, paper, wallboard and paperboard, textiles, carpets, leather, wood, paints and plastics, coolants, and others. materials that can be attacked or destroyed by microorganisms. Materials to be protected also include parts of production plants and buildings, such as cooling water circuits, cooling and heating

- 31 040946 ventilation systems, and ventilation and air-conditioning installations, which may be damaged by the growth of microorganisms. In the context of the present invention, preferably adhesives, clays, paper and cardboard, leather, wood, paints, coolants and heat-transfer fluids, particularly preferably wood, are to be mentioned as technical materials within the scope of the present invention. The active ingredients or agents according to the invention can prevent undesirable effects such as rotting, decay, staining, discoloration or mould. In addition, the compounds according to the invention can be used to protect against fouling objects, in particular ship hulls, screens, nets, structures, mooring installations and signal installations, which may be in contact with sea water or sewage.

The method of controlling unwanted fungi of the present invention can also be used to protect storage goods. Goods subject to long-term storage are natural substances of plant or animal origin, or products of their processing, which are obtained from nature and for which long-term protection is required. Goods subject to long-term storage of plant origin, such as, for example, plants or parts of plants, such as stems, leaves, tubers, seeds, fruits, grains, may be protected as freshly harvested or after processing with (pre) drying, moistening, crushing, grinding, pressing or roasting. Goods subject to long-term storage also cover useful wood, whether it is unprocessed, such as construction timber, power masts and fences, or in the form of finished products, such as furniture. Goods subject to long-term storage of animal origin include, for example, animal skins, leather, fur coats and hair. The active ingredients or agents according to the invention can prevent negative effects such as rotting, decay, staining, discoloration or mould.

By way of example, and by no means limiting, are some of the fungal pathogens that can be treated according to the invention: diseases caused by pathogens of powdery mildew, such as, for example, species of the genus Bloomeria (Blumeria), for example, Blumeria graminis; species of the genus Podosphaera, such as, for example, Podosphaera leucotricha; species of the genus Sphaerotheca, such as, for example, Sphaerotheca fuliginea; species of the genus Uncinula, such as, for example, Uncinula necator; diseases caused by rust pathogens such as, for example, species of the genus Gymnosporangium, such as, for example, Gymnosporangium sabinae; species of the genus Hemileia (Hemileia), such as, for example, Hemileia vastatrix; species of the genus Phakopsora (Phakopsora), such as, for example, Phakopsora pachyrhizi and Phakopsora meibomiae; species of the genus Puccinia, such as, for example, Puccinia recondita or Puccinia triticina; species of the genus Uromyces, such as, for example, Uromyces appendiculatus; diseases caused by pathogens from the group of oomycetes (Oomyceten), such as, for example, species of the genus Bremia, such as, for example, Bremia lactucae; species of the genus Peronospora (Peronospora), such as, for example, Peronospora pisi or P. brassicae; species of the genus Phytophthora (Phytophthora), such as, for example, Phytophthora infestans; species of the genus Plasmopara (Plasmopara), such as, for example, Plasmopara viticola; species of the genus Pseudoperonospora, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis; species of the genus Pythium, such as, for example, Pythium ultimum; diseases leading to the formation of spots on the leaves, which cause, for example, leaf species of the genus and withering of Alternaria (Alternaria), such as, for example, Alternaria solani; species of the genus Cercospora, such as, for example, Cercospora beticola; species of the genus Cladosporium, such as, for example, Cladosporium cucumerinum; species of the genus Cochliobolus, such as, for example, Cochliobolus sativus (conidial form: Drexler, syn: Helminthosporium); species of the genus Colletotrichum such as, for example, Colletotrichum lindemuthanium; species of the genus Cycloconium, such as, for example, Cycloconium oleaginum; species of the genus Diaporte (Diaporthe), such as, for example, Diaporthe citri; species of the genus Elsinoe, such as, for example, Elsinoe fawcettii; species of the genus Gloeosporium (Gloeosporium), such as, for example, Gloeosporium laeticolor; species of the genus Glomerella (Glomerella), such as, for example, Glomerella cingulata; species of the genus Guignardia (Guignardia), such as, for example, Guignardia bidwelli; species of the genus Leptosphaeria, such as, for example, Leptosphaeria maculans; species of the genus Magnaporte (Magnaporthe), such as, for example, Magnaporthe grisea; species of the genus Microdochium (Microdochium), such as, for example, Microdochium nivale; species of the genus Mycosphaerella such as, for example, Mycosphaerelle graminicola and M. fijiensis; species of the genus Phaeosphaeria, such as, for example, Phaeosphaeria nodomm; species of the genus Pyrenophora, such as, for example, Pyrenophora teres; species of the genus Ramularia, such as, for example, Ramularia collo-cygni; species of the genus Rhynchosporium, such as, for example, Rhynchosporium secalis; species of the genus Septoria (Septoria), such as, for example, Septoria apii; species of the genus Typhula, such as, for example, Typhula incamata; species of the genus Venturia, such as, for example, Venturia inaequalis; root and stem diseases caused, for example, by species of the genus Corticium, such as, for example, Corticium graminearum; species of the genus Fusarium (Fusarium), such as, for example, Fusarium oxysporum; species of the genus Gaeumannomyces, such as, for example, Gaeumannomyces graminis; species of the genus Rhizoctonia (Rhizoctonia), such

- 32 040946 such as Rhizoctonia solani; species of the genus Tapesia, such as, for example, Tapesia acuformis; species of the genus Thielaviopsis, such as, for example, Thielaviopsis basicola; diseases of ears and panicles (including heads of corn), which are caused, for example, by species of the genus Alternaria (Alternaria), such as, for example, Alternaria spp.; species of the genus Aspergillus, such as, for example, Aspergillus flavus; species of the genus Cladosporium, such as, for example, Cladosporium cladosporioides; species of the genus Claviceps, such as, for example, Claviceps purpurea; species of the genus Fusarium (Fusarium), such as, for example, Fusarium culmorum; species of the genus Gibberella, such as, for example, Gibberella zeae; species of the genus Monographella, such as, for example, Monographella nivalis; species of the genus Septoria (Septoria), such as, for example, Septoria nodorum; diseases caused by smut fungi, such as, for example, species of the genus Sphacelotheca, such as, for example, Sphacelotheca reiliana; species of the genus Tilletia, such as, for example, Tilletia caries, T. controversa; species of the genus Urocystis, such as, for example, Urocystis occulta; species of the genus Ustilago, such as, for example, Ustilago nuda, U. nuda tritici; rotting of fruit, which is caused, for example, by species of the genus Aspergillus (Aspergillus), such as, for example, Aspergillus flavus; species of the genus Botrytis, such as, for example, Botrytis cinerea; species of the genus Penicillium such as, for example, Penicillium expansum and P. purpurogenum; species of the genus Sclerotinia, such as, for example, Sclerotinia sclerotiorum; species of the genus Verticilium, such as, for example, Verticilium alboatrum; seedling and soil-derived seedling rot diseases that cause Fusarium, such as, for example, wilts, such as Fusarium culmorum species; also genus species of the genus Phytophthora (Phytophthora), such as, for example, Phytophthora cactorum; species of the genus Pythium, such as, for example, Pythium ultimum; species of the genus Rhizoctonia, such as, for example, Rhizoctonia solani; species of the genus Sclerotium, such as, for example, Sclerotium rolfsii; cancers, galls (growths) and witch's panicles, which are caused, for example, by species of the genus Nectria, such as, for example, Nectria galligena; wilt diseases which are caused, for example, by species of the genus Monilinia, such as, for example, Monilinia laxa; deformations of leaves, inflorescences and fruits, which are caused, for example, by species of the genus Taphrin (Taphrina), such as, for example, Taphrina deformans; degenerative diseases of woody plants, which are caused, for example, by species of the genus Esca, such as, for example, Phaemoniella clamydospora, Phaeoacremonium aleophilum and Fomitiporia mediterranea; diseases of flowers and seeds, which are caused, for example, by species of the genus Botrytis (Botrytis), such as, for example, Botrytis cinerea; diseases of plant tubers, which are caused, for example, by species of the genus Rhizoctonia (Rhizoctonia), such as, for example, Rhizoctonia solani; species of the genus Helminthosporium, such as, for example, Helminthosporium solani; diseases that are caused by bacterial pathogens, for example, species of the genus Xanthomonas (Xanthomonas), such as, for example, Xanthomonas campestris pv. oryzae; species of the genus Pseudomonas, such as, for example, Pseudomonas syringae pv. lachrymans; species of the genus Erwinia, such as, for example, Erwinia amylovora;

Preferably, the following soybean diseases can be controlled:

fungal diseases of leaves, stems, pods and seeds, which cause, for example, leaf spots caused by Alternaria spec. atrans tenuissima, Anthracnose (Colletotrichum gloeosporoides dematium var. truncatum), brown spots (Septoria glycines) , leaf spots and leaf wilt caused by a species of the genus Cercospora (Cercospora kikuchii), leaf wilt caused by a species of the genus Choanephora (Choanephora infundibulifera trispora (syn.)), leaf spots caused by a species of the genus Dactuliophora glycines, downy mold, caused by a species of the genus Peronospora (Peronospora manshurica), wilting caused by a species of the genus Drexlera (Drechslera glycini), banded leaf spots caused by a species of the genus Cercospora (Cercospora sojina), spots on the leaves caused by a species of the genus Leptospherulina (Leptosphaerulina trifolii), spots on the leaves caused by a species of the genus Phyllosticta (Phyllosticta sojaecola), wilting of pods and stems caused by a species of the genus f homopsis (Phomopsis sojae), powdery mildew caused by a species of the genus Microsphere (Microsphaera diffusa), leaf spots caused by a species of the genus Pyrenochaeta (Pyrenochaeta glycines), withering of above-ground parts, foliage and plant tissues caused by a species of the genus Rhizoctonia (Rhizoctonia solani), rust, smut caused by species of the genus Phakopsora (Phakopsora pachyrhizi, Phakopsora meibomiae), crusty spots caused by a species of the genus Sphaceloma (Sphaceloma glycines), leaf wilt caused by a species of the genus Stemphylium (Stemphylium botryosum), spot spots caused by a species of the genus Corynespora (Corynespora cassiicola ).

Fungal diseases on roots and stems that cause, for example, black root rot caused by a species of the genus Calonectria (Calonectria crotalariae), carbonaceous rot caused by a species of the genus Macrophomina (Macrophomina phaseolina), wilting or drooping, root and crown and pod rot caused by species genus Fusarium (Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti), root rot caused by species of the genus Mycoleptodiscus terrestris, neocosmospore (Neocosmopspora vasinfecta), wilting of the crown and stems caused by a species of the genus Diaporte (Diaporthe phaseolorum), stem ulcer 33 040946 matum, Pythium irregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), root rot, destruction stem blight and downy mildew caused by Rhizoctonia solani, stem blight caused by Sclerotinia sclerotiorum, southern wilt caused by Sclerotinia rolfsii, root rot caused by Thielaviopsis basicola ).

Microorganisms that can cause degradation or alteration of technical materials include, for example, bacteria, fungi, yeasts, algae and slime organisms. Advantageously, the active substances according to the invention act on fungi, in particular moulds, wood-staining and wood-destroying fungi (basidiomycetes), as well as slime organisms and algae. It is necessary to name, for example, microorganisms of the following genera: Alternaria (Alternaria), species such as Alternaria tenuis; aspergillus (Aspergillus), species such as Aspergillus niger; hetomium (Chaetomium), species such as Chaetomium globosum; coniophora (Coniophora), species such as Coniophora puetana; lentinus (Lentinus), species such as Lentinus tigrinus; penicillium (Penicillium), species such as Penicillium glaucum; polyporus (Polyporus), species such as Polyporus versicolor; aureobasidium (Aureobasidium), species such as Aureobasidium pullulans; sclerophoma, species such as Sclerophoma pityophila; trichoderma (Trichoderma), species such as Trichoderma viride; escherichia (Escherichia), species such as Escherichia coli; pseudomonas (Pseudomonas), species such as Pseudomonas aeruginosa; staphylococcus (Staphylococcus), species such as Staphylococcus aureus.

Along with this, the biologically active substances according to this invention show a very good antimycotic effect. They have a very broad antimycotic spectrum, in particular against dermatophytes and shoot fungi, molds and diphasic fungi (for example, against Candida species such as Candida albicans, Candida glabrata), as well as Epidermophyton floccosum, Aspergillus species, such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species such as Trichophyton mentagrophytes, Microsporon species such as Microsporon canis and audouinii. The listing of these fungi is by no means a limitation of the mycotic spectrum covered, but is for explanatory purposes only.

Biologically active substances can therefore be used for both medical and non-medical applications.

The compounds according to the invention can be used as herbicides, preservatives, plant growth regulators or plant improvers, or as microbicides, for example, as fungicides, antimycotics, bactericides, viricides (including anti-viroid agents) or anti-MLO (mycoplasma-like organisms) and RLO (Rickettsia-like organisms). If necessary, they can be used as intermediate and precursor products for the synthesis of other biologically active substances.

A. Chemical examples.

The NMR data of the published examples are presented either in the classical form (δ-values, multiplicity, number of H-atoms) or in the form of so-called lists of NMR peaks. NMR peak listing methods list the NMR data of selected examples as lists of NMR peaks, with each signal peak first given a δ value in parts per thousand (ppm) and then the signal intensity separately separated by a space character. The data pair δ-value-signal intensity of the various signal peaks is separated from each other by a semicolon.

Therefore, the list of sample peaks is of the form:

δι (intensity); 62 (intensity);........; 5i (intensity);......; 5 _P (intensity)

The intensity of clear signals is in correlation with the height of the signals in the printed example of the NMR spectrum in cm and shows the actual ratio of the signal intensity. In wide signals, there may be several peaks or the middle of the signal and its relative intensity compared to the most intense signal in the spectrum.

To calibrate the chemical shift of ^{the 1} H-NMR spectra, we used tetramethylsilane and/or the chemical shift of the solvent, in particular in the case of spectra that are measured in DMSO. Therefore, tetramethylsilane may occur at the peak of the NMR lists, but this is optional.

The ^1H -NMR peak lists are similar to the classic 1H-NMR printed lists and usually contain all the peaks that mention the classic NMR interpretations.

In addition, they can, like the classic ¹ H-NMR printed lists, show signals from solvents, stereoisomers of desired compounds that are also the subject of the invention, and/or impurity peaks.

The compound signals in the delta region of solvents and/or water in our ¹ H-NMR peaks show the usual solvent peaks, eg DMSO peaks in DMSO-D ₆ and the water peak, which on average usually exhibit high intensity.

Peaks of stereoisomers of target compounds and/or peaks of impurities usually have a lower intensity than peaks of desired compounds (eg >90% purity).

Such stereoisomers and/or impurities may be representative of the respective preparation methods. Thus, their peaks can help in recognizing the reproduction of our by-product fingerprinting process.

An expert who evaluates the peaks of the desired compounds using known methods (MestreC, ACD modeling, or empirically derived, analyzed expected values) can isolate the peaks of the desired compounds as needed, applying an additional intensity filter if necessary. Such an isolation would be similar to the aforementioned peak mapping in the classical ¹ H-NMR interpretation.

Further details of the 'H-NMR peak listings can be taken from Research Disclosure Database No. 564025.

The following examples explain the invention in more detail.

Intermediate 1.

Preparation of 3,5-difluoro-N-hydroxybenzenecarboximidoyl chloride.

By analogy with the prescription in WO 2012/130798 for 3,5-dichloro-Nhydroxybenzenecarboximidoyl chloride, 3,5-difluoro-M-hydroxybenzenecarboximidoyl chloride was prepared from 3,5-difluorobenzaldehyde in two steps.

Intermediate 2.

Preparation of 3-(3,5-difluorophenyl)-5-methyl-4H-isoxazole-5-carboxylic acid methyl ester.

By analogy with the prescription in WO 2012/130798 for 3-(3,5-difluorophenyl)-5methyl-4H-isoxazole-5-carboxylic acid methyl ester, 3-(3,5-difluorophenyl)-5-methyl-4H-isoxazole was obtained -5carboxylic acid methyl ester from 3,5-difluorobenzaldehyde in three steps.

Intermediate 3.

Preparation of 3-(3,5-difluorophenyl)-5-vinyl-4H-isoxazole-5-carboxylic acid.

By analogy with the prescription in WO 2012/130798 for 3-(3,5-dichlorophenyl)-5-methyl-4H-isoxazole-5-carboxylic acid, 3-(3,5-difluorophenyl)-5-methyl-4H-isoxazole-5 -carboxylic acid by saponification of 3-(3,5-difluorophenyl)-5-methyl-4H-isoxazole-5-carboxylic acid methyl ester.

Intermediate 4.

Preparation of 3-(3,5-difluorophenyl)-5-methyl-4H-isoxazole-5-carboxylic acid chloride.

By analogy with the prescription in WO 2012/130798 for N-tert-butyl-3-(3,5-dichlorophenyl)-5-methyl-4,5dihydro-1,2-oxazole-5-carboxamide from 3-(3,5- difluorophenyl)-5-methyl-4H-isoxazole-5-carboxylic acid by reaction with oxalyl chloride gave 3-(3,5-difluorophenyl)-5-methyl-4H-isoxazole-5-carboxylic acid chloride and used as starting product without further purification.

Intermediate 5.

Obtaining 3-(3,5-difluorophenyl)-5-(1-hydroxyethyl)-4H-isoxazole-5-methyl carboxylic acid ester.

19.9 g (104 mmol) of 3,5-difluoro-N-hydroxybenzimidoyl chloride (s. intermediate 1) was dissolved in 330 ml of 2-propanol and mixed with 15.0 g (104 mmol) of 3-hydroxy-2-methylenebutanoic acid methyl ester. After addition of 43.8 g (522 mmol) of sodium bicarbonate, the suspension was heated to 50°C and the temperature was maintained for 2 h until complete conversion of the starting material. The suspension was filtered and the filtrate was thickened in vacuo. The residue obtained is taken up in dichloromethane, then washed with saturated sodium chloride solution, the organic phase is dried over sodium sulfate and, after filtration, evaporated under vacuum. The crude product thus obtained was taken up in toluene and crystallized by adding n-heptane. 25.5 g (86%) of 3-(3,5-difluorophenyl)-5-(1-hydroxyethyl)-4H-isoxazole-5-methyl carboxylic acid ester were thus obtained in the form of colorless crystals.

Diastereoisomer 1: ¹ H NMR (CDCl ₃ ): δ = 1.20 (d, 3H), 2.36 (d, 1H), 3.52 (d, 1H), 3.72 (d, 1H), 3.83 (s, 3H), 4.34 ( m, 1H), 6.88 (m, 1H), 7.20 (m, 2H).

Diastereoisomer 2: ¹ H NMR (CDCl ₃ ): δ = 1.29 (d, 3H), 2.12 (d, 1H), 3.58 (d, 1H), 3.68 (d, 1H), 3.83 (s, 3H), 4.23 ( m, 1H), 6.88 (m, 1H), 7.20 (m, 2H).

Intermediate 6.

Preparation of 3-(3,5-difluorophenyl)-5-[1-(trifluoromethylsulfonyloxy)ethyl]-4H-isoxazole-5-methyl carboxylic acid ester.

29.9 (105 mmol) of 3-(3,5-difluorophenyl)-5-(1-hydroxyethyl)-4H-isoxazole-5-methyl ester of carboxylic acid in 660 ml of dichloromethane was cooled to 0°C and mixed with 16.3 g (210 mmol ) pyridine. Then a solution of 38.6 g (137 mmol) of trifluoromethanesulfonic acid anhydride in 80 ml of dichloromethane was slowly added. After 30 minutes at 0° C., it is mixed with 300 ml of dichloromethane and the organic phase is washed three times with 200 ml of a solution of saturated sodium chloride solution and 1 N hydrochloric acid (3:1). Then the organic phase was washed twice with saturated sodium chloride solution, dried over sodium sulfate, and the solvent was removed in vacuo. The starting material thus obtained was used in the next step without further purification.

- 35 040946

Diastereoisomer 1: 1Н NMR (CDCl ₃ ): δ = 1.54 (d, 3H), 3.44 (d, 1H), 3.89 (s, 3H), 3.94 (d, 1H), 5.49 (q,

1H), 6.91 (m, 1H), 7.20 (m, 2H).

Diastereoisomer 2: 1Н NMR (CDCl ₃ ): δ = 1.59 (d, 3H), 3.53 (d, 1H), 3.89 (s, 3H), 3.90 (d, 1H), 5.57 (q, 1H), 6.91 (m , 1H), 7.20 (m, 2H).

Intermediate 7.

Preparation of 3-(3,5-difluorophenyl)-5-vinyl-4H-isoxazole-5-methyl carboxylic acid ester.

43.0 g (103 mmol) of the crude product of the last step (3-(3,5-difluorophenyl)-5-[1(trifluoromethylsulfonyloxy)ethyl]-4H-isoxazole-5-methyl carboxylic acid ester) was dissolved in 500 ml of dimethylacetamide and dropwise for 20 min mixed with a solution of 18.8 g (124 mmol) DBU in 50 ml of dimethylacetamide. The reaction mixture was stirred at room temperature for 2 hours, then glacial 2N hydrochloric acid was added to 1 liter and extracted twice with 500 ml of diethyl ether. The combined organic phases were dried over sodium sulfate, filtered and evaporated in vacuo. After chromatography on silica gel with dichloromethane as eluent, the starting material was recrystallized from cyclohexane. Thus, 23.4 g (85%) of colorless crystals were obtained.

1H NMR (CDCl3): δ = 3.34 (d, 1H), 3.84 (s, 3H), 3.93 (d, 1H), 5.38 (d, 1H), 5.55 (d, 1H), 6.14 (dd, 1H), 6.88 (m, 1H), 7.19 (m, 2H).

Intermediate 8.

Preparation of 3-(3,5-difluorophenyl)-5-vinyl-4H-isoxazole-5-carboxylic acid.

7.5 g (28.0 mmol) of 3-(3,5-difluorophenyl)-5-vinyl-4H-isoxazole-5-methyl ester of carboxylic acid was mixed with 21 ml of 2N sodium hydroxide and heated for 8 h under reflux. After cooling, the reaction mixture was washed with ethyl acetate, the aqueous phase was adjusted to pH 1 with 2N hydrochloric acid, the colorless precipitate was filtered off and dried in air. The yield was 6.8 g (96%).

1H NMR (CDCl3): δ = 3.40 (d, 1H), 3.92 (d, 1H), 5.00 (dd, 1H), 5.45 (d, 1H), 5.63 (d, 1H), 6.16 (dd, 1H ), 6.87-6.93 (m, 1H), 7.16-7.21 (m, 2H).

Intermediate 9.

Preparation of 3-(3,5-difluorophenyl)-5-methyl-4H-isoxazole-5-carboxylic acid chloride.

2.70 g (10.6 mmol) of 3-(3,5-difluorophenyl)-5-vinyl-4H-isoxazole-5-carboxylic acid was added in 45 ml of dichloromethane, then three drops of dimethylformamide (DMF) were added and then 2.03 g (15.9 mmol) oxalyl chloride. Active gas formation was observed. The mixture was stirred for 6 hours at room temperature and then the solvent and excess oxalyl chloride were evaporated in vacuo. The starting material thus obtained was used in the next step without further purification.

Intermediate 10.

Preparation of 4-aminotetrahydrofuran-3-methyl carboxylic acid ester.

The 4-aminotetrahydrofuran-3-methyl carboxylic acid ester can be prepared as described in G.R. Ott et al.; Bioorg. Med. Chem. Lett. 2008, 694-699 methods.

Intermediate 11.

Preparation of cis-4-aminotetrahydrofuran-2-methyl ester of carboxylic acid hydrochloride.

Cis-4-aminotetrahydrofuran-2-methyl carboxylic acid ester hydrochloride can be prepared as described in DP. Walker et al., Synthesis 2011, 1113-1119 methods.

Intermediate 12.

Preparation of [cis-4-aminotetrahydrofuran-2-yl](pyrrolidin-1-yl)methanone hydrochloride.

To 100 mg (0.55 mmol) of cis-4-aminotetrahydrofuran-2-methyl ester of carboxylic acid hydrochloride was added 1.15 ml (13.7 mmol) of pyrrolidine and stirred for 3 days at room temperature. The reaction mixture was then evaporated in vacuo. The title compound was thus obtained as a crude product which was used without further purification in the next step.

Intermediate 13.

Preparation of cis-4-amino-N-cyclopropyltetrahydrofuran-2-carboxamide hydrochloride.

To 100 mg (0.55 mmol) of cis-4-aminotetrahydrofuran-2-methyl ester of carboxylic acid hydrochloride was added 0.95 ml (13.7 mmol) of cyclopropylamine and stirred for 3 days at room temperature. The reaction mixture was then evaporated in vacuo. The title compound was thus obtained as a crude product which was used without further purification in the next step.

Intermediate 14.

Preparation of cis-4-amino-N-methyltetrahydrofuran-2-carboxamide hydrochloride.

To 100 mg (0.55 mmol) of cis-4-aminotetrahydrofuran-2-methyl carboxylic acid ester hydrochloride in 2.5 mL of methanol was added 0.20 mL (2.75 mmol) of a 40% solution of methylamine in methanol, and the mixture was stirred for 3 days at room temperature. The reaction mixture was then evaporated in vacuo. The title compound was thus obtained as a crude product, which was used

- 36 040946 without further purification in the next step.

Intermediate 15.

Preparation of cis-4-[[3-(3,5-difluorophenyl)-5-vinyl-4H-isoxazole-5-carbonyl]amino]tetrahydrofuran-2-methyl carboxylic acid ester.

To 601 mg (4.14 mmol) of cis-4-aminotetrahydrofuran-2-methyl carboxylic acid hydrochloride in 12.5 ml of dichloromethane was added 1.15 ml of triethylamine, then 750 mg (2.76 mmol) of carboxylic acid chloride was added at 0°C to Intermediate 9 in 12.5 ml of dichloromethane, stirred for 6 h while warming to room temperature and then added water. The organic phase was separated, dried over sodium sulfate and evaporated in vacuo. Chromatography of the evaporated residue on silica gel gave 1.00 g (91%) of cis-4-[[3-(3,5-difluorophenyl)-5-vinyl-4-nisoxazole-5-carbonyl]amino]tetrahydrofuran-2-carboxylic acid methyl ester.

Intermediate 16.

Preparation of cis-4-[[3-(3,5-difluorophenyl)-5-methyl-4H-isoxazole-5-carbonyl]amino]tetrahydrofuran-2-methyl carboxylic acid ester.

To 262 mg (1.44 mmol) of intermediate 14 in 5 ml of dichloromethane was added 292 mg (2.88 mmol) of triethylamine, then 250 mg (0.96 mmol) of carboxylic acid chloride (intermediate 4) in 6 ml of dichloromethane was added at 0°C, for 6 hours while warming to room temperature, and then water was added. The organic phase was separated, dried over sodium sulfate and evaporated in vacuo. Chromatography of the evaporated residue on silica gel gave 75 mg (21%) of cis-4-[[3-(3,5-difluorophenyl)-5-methyl-4H-isoxazole-5-carbonyl]amino]tetrahydrofuran-2-carboxylic acid methyl ester.

Intermediate 17.

Preparation of cis-4-[[(5S)-3-(3,5-difluorophenyl)-5-vinyl-4H-isoxazole-5-carbonyl]amino]tetrahydrofuran-2-methyl carboxylic acid ester.

By analogy with the preparation of intermediate 9, the corresponding carboxylic acid chloride was first prepared and converted, analogously to intermediate 15, to the title compound.

Thus, from 246 mg (1.35 mmol) of cis-4-aminotetrahydrofuran-2-methyl carboxylic acid hydrochloride and 228 mg (0.90 mmol) of carboxylic acid chloride, 110 mg (31%) of cis-4-[[(5S)-3 -(3,5-difluorophenyl)-5-vinyl-4H-isoxazole-5-carbonyl]amino]tetrahydrofuran-2-methyl carboxylic acid ester.

Intermediate 18.

Preparation of cis-4-[[3-(3-fluorophenyl)-5-methyl-4H-isoxazole-5-carbonyl]amino]tetrahydrofuran-2-methyl carboxylic acid ester.

By analogy with the preparation of intermediate compound 4, the corresponding carboxylic acid chloride was first obtained, which, analogously to intermediate compound 16, was converted to the target compound. Thus, from 169 mg (0.93 mmol) of cis-4-aminotetrahydrofuran-2-methyl carboxylic acid hydrochloride and 150 mg (0.62 mmol) of carboxylic acid chloride, 171 mg (75%) of cis-4-[[3-(3- fluorophenyl)-5-methyl-4H-isoxazole-5-carbonyl]amino]tetrahydrofuran-2-methyl carboxylic acid ester.

Intermediate 19.

Preparation of cis-4-[[3-(3-fluorophenyl)-5-methyl-4H-isoxazole-5-carbonyl]amino]tetrahydrofuran-2carboxylic acid.

mg (0.24 mmol) cis-4-[[3-(3-fluorophenyl)-5-methyl-4H-isoxazole-5carbonyl]amino]tetrahydrofuran-2-methyl ester of carboxylic acid was mixed with 1 ml of 2N hydrochloric acid and left for 3 days at room temperature. The reaction mixture was then evaporated on a rotary evaporator. 33 mg (40%) of cis-4-[[3-(3-fluorophenyl)-5-methyl-4-nisoxazole-5-carbonyl]amino]tetrahydrofuran-2-carboxylic acid was thus obtained.

Intermediate 20.

Preparation of 3-[[3-(3,5-difluorophenyl)-5-methyl-4H-isoxazole-5-carbonyl]amino]tetrahydrofuran-3-methyl carboxylic acid ester and 3-[[3-(3,5-difluorophenyl)- 5-methyl-4H-isoxazole-5carbonyl]amino]tetrahydrofuran-3-carboxylic acid.

First, the carboxylic acid chloride intermediate 4 was prepared, which was converted analogously to intermediate 16 to the title compound.

Thus, from 787 mg (4.33 mmol) of 3-aminotetrahydrofuran-3-methyl ester of carboxylic acid - hydrochloride and 750 mg (2.88 mmol) of carboxylic acid chloride, after processing and chromatography on silica gel, 223 mg (21%) of 3-[[3- (3,5-difluorophenyl)-5-methyl-4H-isoxazole-5carbonyl]amino]tetrahydrofuran-3-methyl ester of carboxylic acid and 535 mg (47%) 3-[[3-(3,5difluorophenyl)-5-methyl -4H-isoxazole-5-carbonyl]amino]-tetrahydrofuran-3-carboxylic acid.

Intermediate 21.

Preparation of 4-[[3-(3,5-difluorophenyl)-5-methyl-4H-isoxazole-5-carbonyl]amino]tetrahydrofuran-3methyl carboxylic acid ester.

- 37 040946

First, the corresponding carboxylic acid chloride was prepared, which was converted analogously to the preparation of intermediate 16 with 4-aminotetrahydrofuran-3-methyl carboxylic acid ester to the title compound.

Thus, from 419 mg (8.66 mmol) of 4-aminotetrahydrofuran-3-methyl carboxylic acid ester and 500 mg (1.92 mmol) of carboxylic acid chloride, 657 mg (91%) of 4-[[3-(3,5difluorophenyl)-5- methyl 4H-isoxazole-5-carbonyl]amino]tetrahydrofuran-3-methyl carboxylic acid ester.

Intermediate 22.

Preparation of cis-4-[[(5S)-3-(3,5-difluorophenyl)-5-vinyl-4H-isoxazole-5-carbonyl]amino]tetrahydrofuran-2-carboxylic acid.

0.52 g of methyl ester was dissolved in 8 ml of tetrahydrofuran and cooled to 0°C. To this solution was added dropwise with stirring a solution of 98 mg of lithium hydroxide in 4 ml of water. The reaction mixture was brought to room temperature with stirring for 1 hour. The reaction mixture was diluted with water, acidified with 0.5 M aqueous hydrochloric acid, and extracted with ethyl acetate. The ethyl acetate phase thus obtained was then dried and concentrated in vacuo.

The starting product for further processing was placed in 2 M aqueous sodium hydroxide solution and washed with ethyl acetate. Thereafter, the aqueous phase was acidified with 2M aqueous hydrochloric acid and extracted with dichloromethane. The dichloromethane phase was dried and thickened. Received 0.53 g of carboxylic acid (84% yield).

Analytical data of intermediate compounds.

Intermediate No. NMR Intermediate - 16 ¹ H-NMR(400.0 MHz, CDC13): δ= 7.518(1.0);7.260(181.8);7.171(1.8);7.166(2.2);7.162(1.3);7.155(1.2);7.151(2.2); 7.146(1.8);6.996(1.0);6.898(0.6);6.883(0.7);6.882(0.7);6.878(1.2);6.876(1.2);6.870(0.6);6.854(0.6);4.578(1.1); 4.573(0.7);4.569(1.1);4.560(0.5);4.554(1.6);4.545(1.3);4. 530(1.0);4.521(0.8);4.065(0.8);4.052(0.8);4.042(1.3);4.029(1.7);4.017(0.8);4.006(1.1);3.993(1.0);3.967(0.7 );3.962(0.7);3.900(0.6);3.896(0.6);3.834(14.5);3.785(16.0);3.773(2.0);3.756(1.8);3.730(2.2);3.712(2.0);3.190 (1.9);3.182(2.0);3.146(1.6);3.138(1.8);2.558(0.7);2.541(0.9);2.524(0.8);2.506(0.5);2.019(0.5);1.710(11.3) ;1.687(10.3); 1.541(35.4);0.008(2.1);0.000(68.8);-0.008(1.9) Intermediate - 17 ¹ H-NMR(400.0 MHz, CDC13): δ= 7.262(28.6);7.180(2.2);7.174(2.6);7.171(1.5);7.163(1.5);7.160(2.6);7.154(2.1);6.

- 38 040946

903(0.8);6.887(0.9);6.882(1.6);6.876(0.8);6.860(0.8);6.176(2.0);6.150(2.3);6.133(2.4);6.106(2.5);5.560(1.8 );5.558(1.8);5.544(1.7);5.543(1.7);5.517(1.5);5.515(1.5);5.501(1.5);5.500(1.4);5.357(1.6);5.356(1.6);5.343( 1.5);5.342(1.5);5.330(1.5);5.329(1.5);5.316(1.4);5.315(1.4);5.299(9.2);4.603(0.5);4.596(0.6);4.591(0.6);4.585( 0.6);4.579(0.6);4.574(1.1);4.565(1.2);4.558(1.1);4.550(1.4);4.542(0.9);4.534(0.9);4.525(0.8); 4.056(0.8);4.043(0.9);4.041(0.9);4.033(1.3);4.028(0.8);4.020(1.3);4.017(1.4);4.004(1.1);3.950(0.7);3.946(0.7); 3.944(0.7);3.929(1.1);3.922(2.7);3.905(0.5);3.899(2.3);3. 878(2.2);3.856(2.2);3.814(15.9);3.800(16.0);3.322(1.9);3.313(1.9);3.279(1.6);3.270(1.7);2.566(0.5);2.564(0.5); 2.555(0.6);2.549(0.5);2.546(0.5);2.540(0.6);2.538(0.6) ;2.531(0.6);2.529(0.6);2.514(0.5);2.511(0.6);2.094(0.6 );2.060(0.5);2.052(0.5);2.044(0.6); ^1.577 (5.9);0.000(11.4) );7.310(0.7);7.268(1.5);7.265(3.0);7.259(207.2);7.253(1.0);7.252(0.8);7.251(0.6);7.145(0.8);7.140( 0.6);7.130( 1.0);7.121(0.9);7.113(0.6);7.110(0.6);6.995(1.2);4.577(1.2);4.567(1.1);4. intermediate 557(0.6);4.553(1.2);4.550(1.2);4.544(1.0);4.540(1.1);4.526(0.9);4.517(0.8);4.072(0. connection - 18 8);4.059(0.8);4.048(1.3);4.035(1.6);4.021(0.8);4.010(1.1);3.997(0.9);3.966(0.7);3.961(0.8);3.896(0.6);3.890 (0.6);3.835(14.3);3.800(2.0);3.785(2.1);3.778(16.0);3.762(0.6);3.757(2.3);3.742(2.1);3.223(1.9);3.215(2.1);3.180 (1.7);3.172(1.9);2.561(0.8);2. 549(0.5);2.543(0.9);2.526(0.9);2.520(0.5);2.509(0.5);2.503(0.5);2.018(0.6);1.983(0.5);1.725(0.6);1.714(1.4 );1.708(11.3);1.697(0.7);1.686(10.3);1.666(0.6);1.606(2.7);0.008(2.2);0.000(86.6);-0.008(2.6) ¹ H-NMR(400.0 MHz, d ₆ -DMSO): δ= 8.147(0.6);8.130(0.6);8.087(0.6);8.069(0.6);7.526(2.2);7.524(2.3);7.517(3.2);7.5 12( 2.2);7.498(2.4);7.469(1.1);7.465(0.9);7.349(0.6);7.341(0.6);7.334(0.7);7.326(1.0 );7.322(0.9);7.315(0.6);7.308( 0.6);7.303(0.7);5.756(5.0);4.380(0.6);4.365(1.4);4.35 intermediate 9(0.8);4.349(1.0);4.343(1.5);4.327(0.9);4.318(0.8);4.303(0.8);3.911(0.7);3.895(0.7); connection - 19 3.889(0.9);3.873(0.8);3.868(0.7);3.853(0.7);3.847(0.8);3.831(0.7);3.761(1.3);3.740(1.5);3.717(1.6);3.696(1.9); 3.678(0.8);3.671(0.7);3.660(0.8);3.647(0.7);3.638(0.6);3. 625(0.6);3.390(1.8);3.385(1.7);3.346(1.9);3.341(2.0);3.322(43.8);2.670(0.6) ;2.544(0.8);2.524(1.3);2.519(2.0); 2.510(32.8);2.506(72.0);2.501(100.7);2.497(70.3);2.492(31.4);2.468(0.8);2.456(1.2);2.451(1.0);2.447(1.1);2.436(0.5); 2.425(0.7);2.328(0.6); 2.048(0.5);1.979(0.6);1.963(0.6);1.947(0.6 ⁾ ;1.567(1.4);1.534(16.0);0.000(1.8) );7.217(0.8);7.186(1.3);7.181(2.3);7.178(1.4);7.175(1.5);7.171(1.1);7. 167(1.6);7.164(1.3);7.161(2.3);7.155(1.1);6.919(0.5);6.913(0.9);6.897(1.1);6.891(1.1). intermediate 8);6.886(0.9);6.876(0.5);6.870(0.9);4.239(1.7);4.215(2.1);4.203(1.6);4.179(1.9);4.0 connection - 20 12(1.6);4.002(2.5);3.996(1.5);3.993(2.0);3.988(1.1);3.982(2.1);3.977(2.8);3.968(0.9);3.964(0.9);3.946(1.3); 3.922(1.1);3.769(1.9);3.760(1.7);3.724(14.8);3.716(2.1);3.706(16.0);3.208(3.1);3.165(2.8);2.624(0.6);2.603(0.5) ;2.590(0.9);2.584(0.6);2.570(0.6);2.551(0.8);2.252(0.6);2.236(0.5);2.219(0.5);2.190(0.6);2.174(0.6);1.723( 14.0);1. 547(5.9);0.008(0.7);0.000(23.6);-0.008(0.7) ¹ H-NMR(400.0 MHz, CDC13): δ= 7.263(33.4);7.258(0.6);7.179(0.5);7.174(1.4);7.168(1.8);7.165(2.3);7.159(2.1);7. 157(1.5);7.154(2.0);7.148(2.2);7.145(1.7);7.140(1.3);7.040(0.7);7.021(0.7);6.916(0.8);6.910(0.8);6.900(0.8 );6.894(1.7);6.888(1.5);6.882(0.6);6.879(0.7);6.872(1.0);6.866(0.8);4.715(0.8);4.710(0.6);4.706(0.8);4.700( 0.6);4.696(0.8);4.690(0.5);4.225(0.7 intermediate );4.203(1.7);4.181(1.8);4.159(0.9);4.149(0.6);4.131(1.6);4.113(1.6);4.095(0.6);4.03 connection - 21 8(0.9);4.023(0.9);4.014(1.8);4.000(1.8);3.991(1.0);3.976(1.1);3.950(1.0);3.934(1.0); 3.927(0.9);3.922(1.0);3.911(0.9);3.907(1.1);3.899(0.9);3.884(0.9);3.792(2.0);3.780(2.0);3.774(0.6);3.772(0.5); 3.757(0.9);3.746(16.0);3.741(1.2);3.737(6.0);3.731(1.2); 3.725(1.0);3.710(0.6);3.704(0.6);3.691(16.0);3.680(1.1);3.665(0.9);3.656(0.8);3.54 1(3.0);3.211(2.8);3.188(0.6);3.168(2.4);3.145(0.5);3.007(1.0);2.045(7.1);1.722(10.8 );1.715(13.2);1.688(2.5); 1.277(2.6);1.264(1.8);1.260(5.3);1.242(2.3);0.899(0.9);0.882(3.1);0.864(1.2);0.000(13.7)

- 39 040946

Intermediate - 22 Ή-ΝΜΚ(400.0 MHz, CDC13): δ= 7.520(1.5);7.343(1.5);7.322(1.6);7.305(1.7);7.284(1.9);7.261(268.6);7.179(1.2); 7.177(1.2);7.166(5.7);7.164(8.0);7.161(9.1);7.158(8.3);7.147(8.5);7.144(8.8);7.141(7.4);7.139(5.1);7.129(1.0); 6.997(1.5);6.906(1.3);6.900(2.2);6.896(1.6);6.890(2.3);6. 884(3.3);6.878(4.5);6.874(3.2);6.869(4.3);6.863(3.1);6.857(2.3);6.853(1.6);6.847(2.1);6.841(0.9);6.168(4.3 );6.156(4.4);6.141(4.9);6.130(5.1);6.124(5.4);6.113(5.2);6.098(5.5);6.086(5.4);5.544(7.8);5.543(6.8 );5.532(7.5);5.531(6.8);5.501(6.8);5.500(6.0);5.489(6.7);5.355(7.2);5.346(7.0);5.328(6.8);5.319(6.4);5.299(16.0 );4.609(3.9);4.598(7.8);4.588(5.5);4.585(6.1);4.575(8.8);4.565(5.7);4.553(2.3);4.546(2.1);4.540(1.5 );4.527( 1.2);4.380(0.5);4.150(1.0);4.132(2.6);4.115(2.7);4.103(3.0);4.097(1.2);4.09 0(3.0);4.079(7.4);4.066(7.2);4.056 (4.9);4.042(4.5);4.012(3.1);4.007(3.1);3.988(2.1); 3.983(4.6);3.976(3.1);3.958(1.9);3.952(1.8);3.926(7.3);3.915(7.6);3.884(8.4);3.872(8.6);3.698(0.6);3.332(7.6); 3.325(7.6);3.289(6.6);3.282(6.7);2.681(1.5);2.664(1.6) ;2. 657(1.6);2.646(2.1);2.640(3.3);2.629(2.0);2.623(3.4);2.616(1.7);2.605(3.7);2.599(1.8);2.588(1.8);2.582 (1.8);2.564(1.6);2.226(1.3);2.219(2.1);2.210(1.3);2.192(1.2);2.184(3.0);2.176(3.1);2.167(1.4);2.150(1.1); 2.141(1.8);2.133(1.1);2.116(4.1);2.046(10.8);1.432(3.6);1.304(1.2);1.277(5.0);1.265(5.9);1.259(10.0);1.242(3.6 );0.899(3.2);0. 882(11.0);0.864(4.2);0.008(2.5);0.000(95.7);-0.008(2.8)

Example I-01.

Preparation of N-[3-(cyclopropylcarbamoyl)tetrahydrofuran-3-yl]-3-(3,5-difluorophenyl)-5-methyl-4Nisoxazole-5-carboxamide.

100 mg (0.28 mmol) 3-[[3-(3,5-difluorophenyl)-5-methyl-4H-isoxazole-5carbonyl]amino]tetrahydrofuran-3-carboxylic acid, 20 mg (0.35 mmol) cyclopropylamine, 11.4 mg ( 0.08 mmol) of 1-hydroxy-1I-benzotriazole and 65 mg (0.33 mmol) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride were added at room temperature in 5 ml of dichloromethane. Then, 41 mg (0.35 mmol) of N,N-diethylisopropylamine was added, and the reaction mixture was stirred at room temperature for 16 h. Then again 2 ml of dichloromethane, 20 mg (0.35 mmol) of cyclopropylamine, 11.4 mg (0.08 mmol) of 1-hydroxy-1H-benzotriazole and 65 mg (0.33 mmol) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride were added and stirred for 16 h at room temperature. Then the reaction mixture was mixed with water, the organic phase was separated, dried over sodium sulfate and evaporated in vacuum. The evaporated residue was purified by silica gel chromatography (solvent: ethyl acetate/n-heptane). 91 mg (82%) of the title compound was thus obtained.

Example I-02.

Preparation of 3-(3,5-difluorophenyl)-K-[cis-5-(methylcarbamoyl)tetrahydrofuran-3-yl]-5-vinyl-4Nisoxazole-5-carboxamide.

100 mg (0.26 mmol) of the carboxylic acid methyl ester of intermediate compound 15 in 2 ml of methanol was mixed with 0.47 ml (6.57 mmol) of a 40% solution of methylamine in methanol and stirred at room temperature for 16 h. The reaction mixture was then evaporated in vacuo. In this way 73 mg (72%) of the title compound was obtained.

Example I-03.

Preparation of 3-(3,5-difluorophenyl)-5-methyl-N-[cis-5-(pyrrolidine-1-carbonyl)tetrahydrofuran-3yl]-4H-isoxazole-5-carboxamide.

To 100 mg (0.38 mmol) of carboxylic acid chloride intermediate 4 in 8 ml of dichloromethane was added 106 mg (0.57 mmol) of carboxylic acid amide intermediate 12, then 117 mg (1.15 mmol) of triethylamine was added at 0°C and stirred for 6 h when heated to room temperature. The reaction mixture was evaporated in vacuo and the resulting residue was purified by silica gel chromatography (eluent n-heptane/ethyl acetate). 96 mg (61%) of 3-(3,5-difluorophenyl)-5-methyl-N-[cis-5-(pyrrolidin-1-carbonyl)tetrahydrofuran-3-yl]-4H-isoxazole-5carboxamide was thus obtained.

Example I-04.

Preparation of N-[cis-5-(cyclopropylcarbamoyl)tetrahydrofuran-3-yl]-3-(3,5-difluorophenyl)-5-methyl4H-isoxazole-5-carboxamide.

To 100 mg (0.38 mmol) of carboxylic acid chloride intermediate compound 4 in 8 ml of dichloromethane was added 98 mg (0.57 mmol) of carboxylic acid amide intermediate compound 13, then 117 mg (1.15 mmol) of triethylamine was added at 0°C and stirred for 6 h when heated to room temperature. The reaction mixture was evaporated in vacuo and the resulting residue was purified by silica gel chromatography (eluent n-heptane/ethyl acetate). 101 mg (65%) of N-[cis-5-(cyclopropylcarbamoyl)tetrahydrofuran-3-yl]-3-(3,5-difluorophenyl)-5-methyl-4-nisoxazole-5-carboxamide was thus obtained.

- 40 040946

Example I-05.

Preparation of 3-(3,5-difluorophenyl)-5-methyl-N-[cis-5-(methylcarbamoyl)tetrahydrofuran-3-yl]-4Nisoxazol-5-carboxamide.

To 100 mg (0.38 mmol) of carboxylic acid chloride intermediate compound 4 in 8 ml of dichloromethane was added 83 mg (0.57 mmol) of carboxylic acid amide intermediate compound 14, then 117 mg (1.15 mmol) of triethylamine was added at 0°C and stirred for 6 h when heated to room temperature. The reaction mixture was evaporated in vacuo and the resulting residue was purified by silica gel chromatography (eluent n-heptane/ethyl acetate). 50 mg (34%) of 3-(3,5-difluorophenyl)-5-methyl-N-[cis-5-(methylcarbamoyl)tetrahydrofuran-3-yl]-4H-isoxazole-5carboxamide was thus obtained.

Example I-06.

Preparation of 3-(3,5-difluorophenyl)-N-[cis-5-(pyrrolidin-1-carbonyl)tetrahydrofuran-3-yl]-5 vinyl-4H-isoxazole-5-carboxamide.

100 mg (0.26 mmol) of the carboxylic acid methyl ester of intermediate 15 was mixed with 0.52 ml (6.57 mmol) of pyrrolidine and stirred at room temperature for 16 h. The reaction mixture was then evaporated in vacuo and the resulting residue was purified by silica gel chromatography (eluent n-heptane/ethyl acetate). 57 mg (48%) of the title compound was thus obtained.

Example I-07.

Preparation of 3-(3,5-difluorophenyl)-5-methyl-N-[4-(methylcarbamoyl)tetrahydrofuran-3-yl]-4Nisoxazol-5-carboxamide.

To 150 mg (0.40 mmol) of the carboxylic acid methyl ester of intermediate compound 21 in 5 mL of methanol was added 0.15 mL (2.00 mmol) of a 40% solution of methylamine in methanol and stirred for 3 days at room temperature. The reaction mixture was then evaporated in vacuo. 125 mg (84%) of the crude title compound was thus obtained.

Example I-08.

Preparation of N-[4-(cyclopropylcarbamoyl)tetrahydrofuran-3-yl]-3-(3,5-difluorophenyl)-5-methyl-4Nisoxazole-5-carboxamide.

150 mg (0.40 mmol) of the carboxylic acid methyl ester of intermediate 21 was mixed with 0.51 ml (6.10 mmol) of cyclopropylamine and stirred for 3 days at room temperature. The reaction mixture was then evaporated in vacuo. 193 mg of the crude title compound was thus obtained.

Example I-09.

Preparation of 3-(3,5-difluorophenyl)-5-methyl-K-[4-(pyrrolidine-1-carbonyl)tetrahydrofuran-3-yl]-4Nisoxazole-5-carboxamide.

150 mg (0.40 mmol) of the carboxylic acid methyl ester of intermediate 21 was mixed with 0.51 ml (6.10 mmol) of pyrrolidine and stirred for 3 days at room temperature. The reaction mixture was then evaporated in vacuo and the resulting residue was purified by silica gel chromatography (eluent n-heptane/ethyl acetate). 58 mg (34%) of the title compound was thus obtained.

Example I-10.

Preparation of 3-(3-fluorophenyl)-N-[cis-5-(methoxycarbamoyl)tetrahydrofuran-3-yl]-5-methyl-4Nisoxazole-5-carboxamide.

0.11 g of carboxylic acid intermediate 19 and 30 mg of (aminooxy)metahydrochloride were dissolved in dichloromethane and mixed in turn with 0.08 g of triethylamine and 0.28 g of a solution of propylphosphonic acid anhydride (50%) in tetrahydrofuran. The reaction mixture was stirred for 2.5 h at room temperature. The reaction mixture was then washed with saturated aqueous sodium hydrogen carbonate, dried and concentrated in vacuo. The starting material was purified by silica gel chromatography. In this way, 0.10 g (86%) of the hydroxamic acid ester was obtained.

Example I-11.

Preparation of (5S)-3-(3,5-difluorophenyl)-N-[cis-5-(methoxycarbamoyl)tetrahydrofuran-3-yl]-5-vinyl4H-isoxazole-5-carboxamide.

100 mg of carboxylic acid intermediate 22 and 27 mg of (aminooxy)metahydrochloride were dissolved in dichloromethane and mixed in turn with 0.08 g of triethylamine and 0.26 g of a solution of propylphosphonic anhydride (50%) in tetrahydrofuran. The reaction mixture was stirred for 3 hours at room temperature. The reaction mixture was then washed with saturated aqueous sodium hydrogen carbonate, dried and concentrated in vacuo. The starting material was purified by silica gel chromatography. 96 mg of hydroxamic acid ester were obtained (89% yield).

Example I-12.

Preparation of (5S)-3-(3,5-difluorophenyl)-N-[cis-5-(ethoxycarbamoyl)tetrahydrofuran-3-yl]-5-vinyl4H-isoxazole-5-carboxamide.

- 41 040946 mg of carboxylic acid intermediate 22 and 26 mg of (aminooxy)ethane hydrochloride were dissolved in dichloromethane and mixed in turn with 0.07 g of triethylamine and 0.21 g of a solution of propylphosphonic acid anhydride (50%) in tetrahydrofuran. The reaction mixture was stirred for 3 hours at room temperature. The reaction mixture was then washed with saturated aqueous sodium hydrogen carbonate, dried and concentrated in vacuo. The starting material was purified by silica gel chromatography. Received 87 mg of hydroxamic acid ester (98% yield).

Example I-13.

Preparation of (5S)-3-(3,5-difluorophenyl)-N-[cis-5-(isopropoxycarbamoyl)tetrahydrofuran-3-yl]-5vinyl-4H-isoxazole-5-carboxamide.

mg of carboxylic acid intermediate 22 and 29 mg of 2(aminooxy)propane hydrochloride were dissolved in dichloromethane and mixed in turn with 0.07 g of triethylamine and 0.21 g of a solution of propylphosphonic anhydride (50%) in tetrahydrofuran. The reaction mixture was stirred for 3 hours at room temperature. The reaction mixture was then washed with saturated aqueous sodium hydrogen carbonate, dried and concentrated in vacuo. The starting material was purified by silica gel chromatography. 95 mg of hydroxamic acid ester were obtained (86% yield).

Example I-14.

Preparation of (5S)-3-(3,5-difluorophenyl)-N-[cis-5-(trifluoromethylsulfonylcarbamoyl)tetrahydrofuran-3-yl]-5-vinyl-4H-isoxazole-5-carboxamide.

0.11 g of carboxylic acid intermediate 22 and 6 mg of 4-dimethylaminopyridine were dissolved in 5 ml of dichloromethane. Then, while stirring at room temperature, 65 mg of 1(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride per 0.17 g of 1,1,1-trifluoromethanesulfonamide was added, and the reaction mixture was left for 2 h at room temperature and then stirred for another 3 days at this temperature. The reaction mixture was washed with 0.5 M aqueous hydrochloric acid, dried, and concentrated in vacuo. The starting material was purified by silica gel chromatography. Received 94 mg acylsulfonamide (81% yield).

Example I-15.

Preparation of (5S)-3-(3,5-difluorophenyl)-N-[cis-5-(dimethylaminocarbamoyl)tetrahydrofuran-3-yl]-5 vinyl-4H-isoxazole-5-carboxamide and Example I-16.

Preparation of (5S)-3-(3,5-difluorophenyl)-N-[cis-5-(methylsulfonylcarbamoyl)tetrahydrofuran-3yl]-5-vinyl-4H-isoxazole-5-carboxamide.

0.12 g of carboxylic acid intermediate 22 and 94 mg of 1-hydroxybenzotriazole 86% were dissolved in 3 ml of dichloromethane and slowly stirred at room temperature for 15 min. Then 0.16 g of methanesulfonamide was added, followed by a solution of 94 mg of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 0.09 g of N-ethyl-N-isopropylpropan-2-amine in 3 ml of dichloromethane. The reaction mixture was stirred for 0.5 h at room temperature and left for 2 days. The reaction mixture was then washed with 0.5 M aqueous hydrochloric acid, dried, and concentrated in vacuo. The starting material was purified by silica gel chromatography. Received 43 mg acylsulfonamide (29% yield).

Example I-17.

Preparation of (5S)-3-(3,5-difluorophenyl)-N-[cis-5-(dimethylcarbamoyl)tetrahydrofuran-3-yl]-5-vinyl4H-isoxazole-5-carboxamide.

mg of carboxylic acid intermediate 22 and 24 mg of 1,1-dimethylhydrazine were dissolved in 5 ml of dichloromethane. Then, with stirring at room temperature, 80 mg of triethylamine was added per 0.51 g of a solution of propylphosphonic acid anhydride (50%) in tetrahydrofuran, and then the reaction mixture was stirred for 4 h at room temperature. The reaction mixture was then washed with saturated aqueous sodium hydrogen carbonate, dried and concentrated in vacuo. The starting material was purified by silica gel chromatography. 0.08 g of dimethylhydrazide I15 (73% yield) and 0.01 g of dimethylamide I-17 (9% yield) were obtained.

Example I-18.

Preparation of (5S)-N-[Cis-5-(cyclopropylcarbamoyl)tetrahydrofuran-3-yl]-3-(3,5-difluorophenyl)-5vinyl-4H-isoxazole-5-carboxamide.

mg of carboxylic acid intermediate 22 and 17 mg of cyclopropylamine were dissolved in 5 ml of dichloromethane. Then, with stirring at room temperature, 77 mg of triethylamine was added per 0.48 g of a solution of propylphosphonic acid anhydride (50%) in tetrahydrofuran, and then the reaction mixture was stirred for 2.5 h at room temperature. The reaction mixture was then washed with saturated aqueous sodium hydrogen carbonate, dried and concentrated in vacuo. The starting material was purified by silica gel chromatography. 95 mg of cyclopropylamide were obtained (91% yield).

Example I-19.

Preparation of tert-butyl N-[[cis-4-[[(5S)-3-(3,5-difluorophenyl)-5-vinyl-4H-isoxazole-5

- 42 040946 carbonyl]amino]tetrahydrofuran-2-carbonyl]amino]carbamate.

0.18 g of carboxylic acid intermediate 22 and 84 mg of 1-hydroxybenzotriazole (86%) were dissolved in 8 ml of dichloromethane and stirred at room temperature for 30 min. Then 77 mg of tert-butyl hydrazinecarboxylate was added, followed by a solution of 141 mg of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 95 mg of N-ethyl-N-isopropylpropan-2-amine in 4 ml of dichloromethane. The reaction mixture was stirred for 0.5 h at room temperature, left overnight, and stirred again for another 6 h at room temperature. Then the reaction mixture was washed with 0.5 M aqueous hydrochloric acid, dried and concentrated in vacuo. The starting material was purified by silica gel chromatography. Received 112 mg of product (47% yield).

Examples I-20 - I-30 of the table. 1.

The preparation was carried out similarly to the above named preparation examples.

Analytical data of examples I-01 - I-30.

1-01 ¹ H-NMR(400.0 MHz, CDC13): δ= 7.717(1.5);7.519(1.0);7.260(176.6);7.193(0.5);7.181(2.9);7.178(1.9);7.175(3.2); 7.172(1.8); 7.164(1.7);7.161(3.3);7.155(2.8);7.143(0.5);6.996(1.0);6.908(0.5);6.904(0.6);6.902(0.9);6.889(0.7);6.886(1.0); 6.883(1.2);6.880(1.7);6.877(0.7);6.875(0.8);6.864(0.5);6.861(0.6);6.859(0.9);6. 483(0.5);6.466(0.7);5.299(5.5);4.073(2.4);4.060(2.0);4.049(5.0);4.039(2.9);4.032(2.4);4.026(1.2);4.022(1.3 );4.016(0.9);4.014(1.0);3.991(2.7);3.988(3.6);3.967(1.6);3.964(2.1);3.768(2.8);3.758(1.9);3.725(3.3);3.715( 2.2);3.201(2.9);3.192(2.0);3.158(2.6);3.149(1.8);2.719(0.6);2.709(1.1 );2.699(1.2);2.691(1.3);2.682(0.9);2.414( 1.0);2.399(2.0);2.388(1.0);2.383(2.1);2.379(1.6);2.368(2.0);2.360(0.8);2.347(0.8);2.335(0.6);1.720(10.9);1.709 (16.0);1.545(3.5);1.259(0.6);0.790(0.6);0.785(0.8);0.781(1.2);0.778(1.9);0.774(1.7);0.772(2.7);0.768(1.6) ;0.764(1.6);0.760(2.0);0.7 57(2.0);0.754(2.2);0.750(1.0);0.743(0.6);0.739(0.6);0.464(0.6);0.461(1.0);0.454(1.2 );0.451(2.4 );0.448(2.6);0.444(2.4);0.441(1.9);0.438(2.5);0.435(1.8);0.430(1.0);0.421(0.6);0.008(2.4);0.00 0( 80.2);-0.008(2.1) 1-02 Ή-ΝΜΚ(400.0 MHz, CDC13): δ= 7.264(29.0);7.174(1.0);7.170(1.6);7.168(1.6);7.165(1.6);7.162(0.8);7.157(0.8);7.154(1.6);7. 151(1.6);7.148(1.4);7.145(1.0);6.924(0.6);6.918(0.7);6.913(0.9);6.907(0.9);6.902(0.8);6.897(0.9);6.891(0.9 );6.886(1.0);6.880(0.6);6.186(0.9);6.159(1.0);6.142(1.1);6.128(0.8);6.116(1.1);6.101(0.9);6.085(0.9);6.058( 1.0);5.532(1.4);5.531(1.5);5.521(1.3);5.519(1.3);5.489(1.3);5.488(1.2);5.478(1.2);5.476(1.2);5.367(1.2);5.340( 2.2);5.315(1.1);5.313(1.2);5.300(16.0);4.460(0.6);4.449(0.8);4.437(1.3);4.426(1.2);4.414(0.7);4.403(0.5);4.027 (0.7);4.015(0.7);4.004(1.0);3.991(1.0 );3.987(0.6);3.975(0.6);3.963(0.9);3.951(0.8);3.934(1.4);3.908(0.5);3.904 (0.6);3.891(1.6);3.87 0(1.6);3.826(2.0);3.322(1.5);3.303(1.3);3.278(1.3);3.260(1.1);2.900(3.4);2.899(3.4 );2.888(3.4); 2.887(3.3);2.854(3.9);2.853(4.0);2.848(1.0);2.847(1.0);2.841(4.0);2.840(3.8);2.836(1.0);2.835(0.9);2.812(1.5); 2.811(1.6);2.799(1.5);2.575(0.5);2.198(0.6);1.978(3.0);0.000(12.6) 1-03 The two diastereoisomers are presented in a mixture, the indication of the sum of the signals is indicated with rounding. Ή-ΝΜΗ^ΟΟ.Ο MHz, CDC13): δ= 8.51 - 8.39 (br, 1 Η), 7.21 - 7.14 (m, 2 Η), 6.88 - 6.82 (m, 1 Η), 4.72 - 4.69 (m, 1 Η), 4.63 4.54 (m, 1 Η) , 4.02 - 3.93 (m, 1 Η), 3.89 - 3.67 (m, 3 Η), 3.58 - 3.44 (m, 3 Η), 3.16 - 2.88 (m, 2 Η), 2.34 - 2.20 (m, 2 Η), 2.01 - 1.80 (m, 3 Η), 1.72 - 1.70 (m, 3 Η). 1-04 The two diastereoisomers are presented in a mixture, the indication of the sum of the signals is indicated with rounding. ¹ H-NMR(400.0 MHz, CDC13):

- 43 040946

δ= 7.20 - 7.13 (m, 2 Η), 6.92 - 6.85 (m, 1 Η), 6.77 - 6.69 (br, 1 Η), 4.49 - 4.34 (m, 2 Η), 4.02 3.93 (m, 1 Η) , 3.88 - 3.69 (m, 2 Η), 3.20 - 3.05 (m, 1 Η), 2.99 - 2.65 (m, 2 Η), 2.62 - 2.48 (m, 1 Η), 2.26 - 2.08 (m, 1 Η) , 1.71 - 1.69 (m, 3 Η), 0.88 - 0.73 (m, 2 Η), 0.65 - 0.47 (m, 2 Η). 1-05 ¹ H-NMR(499.9 MHz, d ₆ -DMSO): δ= 7.483(3.5);7.469(4.2);7.294(4.8);7.269(11.7);7.254(8.5);7.240(6.2);7.219(14.9) ;7.205(6.8);4.9 62(2.7);4.946(2.8);4.830(2.2);4.800(3.5);4.776(2.4);4.551(4.7);4.542(9.5);4.536(6.4);4.526(7.7 ); 4.519(10.5);4.499(2.9);4.457(3.7);4.423(5.8);4.392(3.1);4.111(2.9);4.077(2.4);3.750(4.0);3.714(3.6);3.368(2.0 );3.344(3.1);3.320(2.0);3.298(50.8);3.276(0.4);2.923(1.6);2.898(4.4);2.875(7.2);2.844(8.7);2.814(7.7);2.806( 7.5);2.784(16.0);2.776(7.7);2.760(2.3);2.753(3.0);2.744(1.3);2.616(2.0); 2.502(12.6);2.499(17.3);2.496(13.3);2.084(0.5);1.706(9.0);1.676(9.6);1.647(12.4);1.403(6.2);1.384(5.6);1.352(7.1) ;1.335(8.5);1.315(8.2);1.298(5.5);1.179(3.5);1.174(3.5);0.000(8.4) 1-06 ¹ H-NMR(400.0 MHz, CDC13): δ= 7.265(29.8);7.200(1.0);7.197(0.7);7.194(1.2);7.191(0.7);7.183(0.7);7.180(1.8);7.178( 1.2);7. 174(1.7);7.164(0.6);7.160(1.0);7.155(0.8);6.877(0.8);6.861(0.9);6.855(1.6);6.849(0.8);6.833(0.8);6.215(0.8 );6.188(1.0);6.186(1.0);6.172(1.0);6.159(1.0);6.145(1.1);6.142(1.1);6.116(1.1);5.593(1.2);5.591(1.2);5.562( 1.4);5.560(1.5);5.550(1.1);5.548(1.1);5.519(1.3);5.517(1.3);5.335(1.0 );5.333(ll);5.324(1.2);5.323(1.2);5.308( l.l);5.306(1.2);5.300(16.0);5.298(2.0);5.296(1.4);4.7 15(1.0);4.707(0.8);4.694(0.7);4.687(1.0);4.601(0.5) ;4.014(0.7);4.001(0.7);3.991(1.0);3.982(0.8 );3.978(1.0);3.969(0.7);3.959(1.0);3.951(0.5);3.946(0.9);3.942(1.7) ;3.900(1.9);3.888(1.3);3.87 2(0.6);3.867(0.6);3.845(1.8);3.810(0.5);3.805(0.6);3.712(0.6);3.687(0.8);3.539(1 .l);3.534(0.7); 3.529(0.6);3.520(1.4);3.514(ll);3.503(0.8);3.494(0.9);3.480(0.8);3.476(0.7);3.467(0.6);3.462(0.6);3.455(0.6); 3.298(1.4);3.294(1.6);3.267(0.6);3.256(1.3);3.251(1.5);2.956(1.1);2.321(0.6);2. 313(0.7);2.303(1.5);2.291(1.0);2.284(0.6);2.280(0.6);2.250(0.6);2.050(1.5);2.014(0.7);1.991(0.6);1.987(0.6) );1.979(0.8);1.971(0.8);1.964(1.1);1.957(0.8);1.954(0.8);1.950(1.1);1.933(0.7);1.898(0.8);1.882(1.2);1.866( 1.2);1.847(0.8);1.778(0.6);1.769(0.7);1.761(1.4);1.753(0.7);1.744(0.5 );0.000(12.3) 1-07 ¹ H-NMR(400.0 MHz, d ₆ -DMSO): δ=8.328(1.3);8.314(1.6);8.310(1.6);8.296(1.2);7.910(0.6);7.899(0.8);7.888(0.9) ;7.864(0.6);7.8 55(0.8);7.844(0.8);7.419(1.9);7.414(3.9);7.410(2.2);7.405(4.3);7.400(5.6);7.396(6.0);7.388(4.2 );7.384(2.0);7.380(4.0);7.377(3.5);7.370(0.9);5.756(16.0);4.467(0.6);4.453(1.4);4.439(1.8);4.4 35(1.6);4.426( 0.9);4.422(1.3);4.418(0.9);4.023(1.1);4.016(1.2);4.002(2.5);3.996(2.6);3.981(1.3 );3.975(1.4);3.910(0.7);3.902( 0.7);3.875(0.5);3.871(0.5);3.856(1.7);3.850(0.8);3.843(0.7);3.84 0(1.5);3.835(2.0);3.824(1.4);3.818(1.5);3.806 (1.6);3.802(1.6);3.793(0.6);3.784(3.6);3.775(2.7); 3.747(0.8);3.740(3.1);3.731(3.2);3.703(0.8);3.669(1.6);3.661(0.7);3.653(1.6);3.648(1.5);3.644(1.7);3.632(1.6 );3.628(1.8);3.623(1.6);3.617(0.9);3.607(1.8);3.588(1.5);3.575(1.5);3.566(1.3);3. 558(0.6);3.553(1.3);3.507(1.4);3.494(1.4);3.486(1.3);3.472(1.2);3.420(0.7);3.404(0.8);3.389(3.

- 44 040946

1);3.380(2.9);3.359(0.8);3.345(2.8);3.336(3.0);3.320(19.5);3.006(0.6);2.989(0.8);2.985(0.8);2. 976(0.8);2.972(0.9);2.954(0.9);2.941(0.7);2.938(0.8);2.933(0.8);2.925(0.8);2.920(0.8);2.917(0. 7);2.904(0.6);2.602(0.6) ;2.594(2.7);2.586(10.1);2.583(3.8);2.574(9.8);2.538(10.5);2.526(11.0); 2.520(2.0);2.512(23.8);2.507(53.0);2.502(74.2);2.498(51.2);2.493(22.4);2.452(0.6) ;2.394(2.3); 2.383(2.4);2.366(4.0);2.150(1.1);1.553(15.0);l.541(15.0);l.514(3.7);1.235(1.0);0.000(6.6) 1-08 ¹ H-NMR(400.0 MHz, d ₆ -DMSO): δ= 8.293(1.4);8.025(1.0);7.958(1.2);7.839(1.0);7.412(3.2);7.403(4.8);7.397(5.0) ;7.387(3.7);7.3 78(3.0);4.534(1.3);4.521(3.l);4.508(1.5);4.440(1.3);4.426(1.9);4.408(ll);3.999(1.0);3.993 (ll );3.979(2.1);3.972(2.3);3.958(1.1);3.951(1.2);3.894(0.9);3.857(1.6);3.840(1.6);3.835(1.9);3.819(2.3); 3.798(1.4);3.782(2.5);3.756(2.4);3.738(2.5);3.712(3.0);3.700(0.9);3.670(1.4);3.654(1.5); 3.643(1.6);3.632(1.8);3.626(1.6);3.622(1.7);3.605(1.5);3.599(2.0);3.583(3.3);3.570(3.3);3.566(2.0);3.560(1.6); 3.553(2.3);3.538(1.2);3.509(1.1);3.494(1.3);3.487(1.2);3.473(1.2);3.436(1.1);3. 430(1.3);3.394(3.2);3.378(2.7);3.367(1.5);3.349(2.4);3.333(4.5);3.316(477.3);3.266(2.6);2.909(0.8);2.892(0.9); 2.847(0.9);2.675(3.0);2.670(4.3);2.665(3.0);2.615(2.0);2.606(1.5);2.592(1.6);2.583(1.l);2.574(1.8);2.564 (1.7);2.556(2.2);2.546(2.4);2.536(1.5);2.523(10.9);2.519(15.3);2.510(219.7);2.505(486.3);2.501(679.4);2.496(468.6); 2.492(204.7) ;2.455(3.4);2.451(4.1);2.446(3.1 );2.401(1.2);2.332(2.7);2.328(4.1);2.323(2.8);2.177(2.9);2.161(5.6 );2.144(2.6) ;2.074(1.2);2.00 9(0.8);1.990(0.9);1.741(11.8);1.560(3.5);1.549(11.6);1.538(16.0);1.236(1.0);0.980( 1.2);0.961(2.4);0.942(1.2);0.614(1.2);0.604(2.0);0.600(2.8);0.588(3.2);0.584(4.7);0.579(3.4);0.571(3.1);0. 566(4.0);0.554(2.7);0.549(2.l);0.543(1.7);0.536(1.8);0.530(1.6);0.526(1.5);0.380(1.4);0.368(3.4);0.363 (3.5);0.358(4.0);0.346(2.3);0.341(2.3);0.314(0.9);0.301(2.3);0.296(2.5);0.292(2.6);0.286(2.1);0.242(0.8); 0.008(ll);0.000(51.9);-0.008(1.6)

- 45 040946

1-09 ¹ H-NMR(400.0 MHz, CDC13): δ= 7.520(1.8);7.280(0.5);7.278(0.6);7.277(0.6);7.276(0.8);7.275(0.8);7.274(0.9);7.274( ll);7.2 73(1.2);7.272(1.2);7.271(1.4);7.271(1.4);7.270(1.5);7.269(2.0);7.268(2.4);7.267(2.8);7.266(3.3);7.266 (4.0);7.265(5.4);7.264(7.3);7.261(310.2);7.258(4.3);7.257(2.6);7.256(2.1);7.255(1.5);7. 254(1.2);7.254(0.9);7.253(0.8);7.252(0.9);7.251(0.7);7.250(0.5);7.227(0.5);7.211(1.2);7.184(0.8);7.176(2.3 );7.170(2.3);7.164(2.9);7.158(3.4);7.150(2.2);7.148(2.5);7.144(3.1);7.138(2.6);7.1 25(1.0);7.094(0.5);6.997( 1.8);6.925(0.8);6.919(0.7);6.913(0.8);6.909(0.9);6.904(1.5);6.897(1.6 );6.892(1.7);6.886(0.9);6.882(0.9);6.875( 1.2);6.870(1.l);4.652(0.5);4.645(0.6);4.639(0.6);4.572(0.8);4.567(0.7);4.246(0.6);4.239(0.8);4.227(0.7) ;4.218(1.6);4.205(1.0);4.197(1.0);4.184(1.5); 4.163(0.9);4.083(0.6);4.077(0.5);4.062(1.5);4.054(0.7);4.040(ll);4.027(1.0);4.021(0.5);4.014(1.5);4.005(1.7); 3.991(1.8);3.981(1.3);3.968(1.2);3.947(1.1);3.932(1.2);3.926(1.0);3.915(1.2);3. 910(1.2);3.899(1.2);3.893(1.0);3.877(1.0);3.833(0.9);3.828(1.0);3.809(0.8);3.804(0.8);3.791(1.1):3.782(3 .l);3.767(3.4);3.742(1.8);3.739(3.1);3.733(0.9);3.729(1.5);3.724(3.5);3.710(1.0);3.699(2.4);3.686(1.9); 3.669(0.8);3.652(0.6);3.551(0.9);3.538(1.2);3.520(2.0);3.509(1.l);3.503(1.5 );3.483(1.4);3.468(1.8);3.450 (2.0);3434(1.0);3.422(1.4);3.404(1.4);3.389(0.9);3.382(1.0);3.372(1.0);3.353(0.9);3.332(0.6);3.313( 0.8);3.306(0.7);3.288(0.6);3.220(2.7);3.212(2.6);3.177(2.5); 3.169(2.5);3.166(1.7);3.152(1.3);3.123(1.6);3.109(1.8);3.036(0.5);3.031(0.7);2.022(0.6);2.005(1.4);1.990(1.7); 1.973(1.4);1.957(0.6);1.927(0.8);1.910(1.3);1.891(1.9);1.874(1.9);1.868(1.8);1. 860(2.1);1.842(1.2);1.825(0.6);1.718(15.5);1.715(16.0);1.698(6.4);l.652(6.8);1.255(0.6);0.008(4.0);0.006(1.3 );0.005(1.5);0.004(2.1);0.000(138.3);-0.005(1.2);-0.006(1.0);-0.007(0.8);0.008(3.7):-0.050(0.6) 1-10 ¹ H-NMR(400.6 MHz, CDC13): δ= 9.764(1.2);9.707(1.3);7.404(1.4);7.397(1.6);7.393(1.6);7.390(1.7);7.384(2.l); 7.379(2.0);7.369(3.1);7.365(4.8);7.360(6.5);7.356(6.0);7.352(4.6);7.346(2.0);7.340(3.2);7.310(1.3);7.148(0.6) ;7.142(1.1);7.136(1.1);7.129(1.1);7.127(1.1);7.121(1.7);7.115(1.2);7.112(1.2);7.106(1.0);7.098(1.0);4.532(0.7 );4.521(0.9);4.508(1.2);4.498(1.8);4.488(1.7);4.477(1.8);4.465(1.5);4.026(0.7); 4.013(0.8);4.002(1.2);3.989(1.1);3.973(0.7);3.960(0.7);3.949(1.3);3.943(1.4);3.936(2.0);3.920(0.8);3.912(0.7); 3.890(1.2);3.885(1.l);3.866(0.8);3.861(0.8);3.840(3.0);3.834(12.0);3.808(1.2); 3.803(1.5);3.797(2.3);3.790(2.3);3.781(1.2);3.778(1.5);3.774(0.9);3.758(0.7);3.743(15.7);3.335(0.8);3.316(0.8) ;3.274(0.9);3.271(0.9);3.240(2.5);3.227(2.5);3.197(2.2);3.184(2.2);2.627(0.5); 2.622(0.7);2.610(0.7);2.605(0.8);2.594(0.8);2.588(0.9);2.570(0.9);2.327(0.6);2.317(0.7);2.284(0.5);2.239(0.6); l.713(1.l);1.707(2.2);l.702(1.9);1.693(15.1);1.689(16.0);1.287(0.6);1.259(2.8) ;0.000(0.9) 1-11 ¹ H-NMR(400.0 MHz, CDC1 ₃ ): δ= 8.80 (br d, J=4.13 Hz, 1 H), 7.20 - 7.13 (m, 2 H), 7.00 - 6.93 (m, 1 H), 6.92 - 6.85 (m, 1 H), 6.19 - 6.06 (m, 1 H), 5.51 (dd, J=17.17, 1.91 Hz, 1 H), 5.34 (dd, J=10.65, 8.42 Hz, 1 H), 4.54 -

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4.41 (m, 2 Η), 4.18 (sept, J=6.04 Hz, 1 H), 4.05 - 3.96 (m, 1 H), 3.93 - 3.77 (m, 2 H), 3.34 - 3.26 (m, 1 H) , 2.71 - 2.58 (m, 1 H), 2.22 - 2.13 (m, 1 H), 1.32 - 1.22 (m, 6 H) 1-12 ¹ H-NMR(400.0 MHz, CDC1 ₃ ): 5= 8.93 (br d, J=7.31 Hz, 1 H), 7.20 - 7.13 (m, 2 H), 7.00 - 6.93 (m, 1 H), 6.93 - 6.85 (m, 1 H), 6.20 - 6.06 (m, 1 H), 5.51 (dd, J=17.32, 3.66 Hz, 1 H), 5.34 (dd, J=10.33, 8.42 Hz, 1 H), 4.54 4.41 (m, 2 H), 4.08 - 3.95 (m, 3 H), 3.93 - 3.79 (m, 2 H), 3.34 - 3.27 (m, 1 H), 2.69 - 2.56 (m, 1 H), 2.25 - 2.17 (m, 1H), 1.34 - 1.24 (m, 3H) 1-13 ¹ H-NMR(400.0 MHz, CDC1 ₃ ): 5= 9.01 (br d, 1=10.49 Hz, 1 H), 7.20 - 7.12 (m, 2 H), 7.02 - 6.94 (m, 1 H), 6.93 - 6.85 (m, 1 H), 6.19 - 6.07 (m, 1 H), 5.51 (dd, 1=17.33, 4.29 Hz, 1 H), 5.35 (dd, 1=10.65, 8.11 Hz, 1 H), 4.55 4.41 (m, 2 H), 4.03 - 3.95 (m, 1 H), 3.94 - 3.79 (m, 5 H), 3.34 - 3.26 (m, 1 H), 2.68 - 2.55 (m, 1 H), 2.27-2.19 (m, 1H). 1-14 ¹ H-NMR(400.0 MHz, d ₆ -DMSO): δ=8.339(1.3);8.319(1.5);8.313(1.7);8.293(1.5);7.445(0.8);7.428(5.5);7.422(3.9) ;7.416(3.3);7.4 10(5.0);7.406(5.3);7.392(2.0);7.386(3.2);7.381(2.l);7.369(0.7);7.364(1.3);7.358(0.9);6.158 (2.0 );6.152(2.6);6.132(2.3);6.126(2.9);6.115(2.3);6.109(3.1);6.088(2.3);6.082(3.0);5.753(3.3);5.41 1(3.4 );5.408(3.6);5.404(2.9);5.402(3.0);5.368(3.0);5.365(3.2);5.361(2.5);5.358(2.7);5.316(0.7); 5.304(2.7);5.301(2.8);5.298(3.4);5.296(3.2);5.289(0.7);5.277(2.6);5.275(2.6);5.271(3.2);5.269(3.0);4.346(1.2); 4.326(1.l);4.313(1.0);4.306(1.0);4.292(0.8);4.171(1.7);4.158(2.5);4.149(2.3);4. 146(2.0);4.136(2.1);4.125(1.4);3.893(15.9);3.881(16.0);3.864(9.4);3.836(7.4);3.820(5.8);3.814(4.7);3.800(3.8); 3.793(2.9);3.778(2.3);3.666(0.6);3.646(0.5);3.633(2.0);3.627(1.8);3.622(1.8);3.614(1.9);3.606(1.4);3.601(1.5 );3.594(1.2);3.574(1.0);3.558(5.2);3.529(0.7);3.514(4.0);2.674(1.9);2.670(2.6);2.665(1.8);2.661(0.9) ;2.523(11.0);2.519(15.3);2.510(144.2);2.505(295.0);2.501(402.4);2.496(275.2);2.492(123.6);2.387(1.0);2.366(0.9);2.354(0.9) ;2.347(0.9);2.337(1.8);2.332(2.7);2.328(3.2);2.323(2.0);2.314(0.8);2.308(0.9);2.288(0.5);l.827(0.6);1.813( 1.5);1.800(1.8);1.780(1.4);l.767(1.5);1.755(0.6);1.236(1.0);0.008(3.1);0.000(95.5);-0.008(2.9) 1-15 ¹ H-NMR(400.0 MHz, CDC13): δ= 7.263(36.9);7.174(0.5);7.170(1.1);7.162(1.5);7.156(1.4);7.153(1.3);7.150(1.3);7.144( 1.3);7. 142(1.3);7.137(1.0);6.921(0.7);6.915(0.8);6.912(0.7);6.906(0.8);6.900(0.8);6.894(0.8);6.890(0.7);6.884(0.9 );6.878(0.6);6.182(0.8);6.155(0.9);6.138(1.0);6.128(0.7);6.112(1.0);6.102(0.7);6.0 85(0.8);6.058(0.8);5.529( 1.2);5.528(1.3);5.517(1.5);5.486(1.1);5.485(1.1);5.474(1.2);5.370(1.3);5.344(1.8);5.319(1.l);4.456(0.7); 4.443(ll);4.432(1.0);4.429(ll);4.419(1.0);4.405(0.7);4.148(0.6);4.131(1.9);4.113(1.9);4.095(0.6);4.020(0.7) ;4.007(0.7);3.996(0.9);3.983(ll);3.972(0.6); 3.961(0.8);3.948(0.8);3.937(1.3);3.894(1.6);3.882(1.9);3.839(1.6);3.834(0.6);3.327(1.4);3.314(1.3);3.284(1.2); 3.271(1.1);2.668(0.5);2.654(15.4);2.645(1.2);2.634(16.0);2.621(0.5);2.610(0.7)

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;2.548(1.0);2.532(0.5);2.044(8.4);1.603(1.0);1.277(2.4);1.259(5.6);l.241(2.3);0.008(0.5);0.OOO (13.7) 1-16 ¹ H-NMR(400.0 MHz, CDC13): δ=8.922(0.9);7.518(2.7);7.295(0.5);7.260(481.5);7.208(1.0);7.181(1.5);7.176(1.8);7.162( 2.2); 7.144(1.7);7.138(1.4);6.996(2.6);6.919(0.9);6.914(0.7);6.903(0.8);6.897(1.6);6.892(1.5);6.876(0.8);6.870(0.7); 6.800(1.0);6.170(1.2);6.143(2.4);6.127(1.3);6.116(1.3);6.100(2.9);6.073(1.6);5. 540(2.0);5.527(2.2);5.497(1.7);5.483(2.0);5.379(3.7);5.352(3.5);4.541(1.0);4.529(1.2);4.518(l. 6);4.508(1.2 );4.496(0.9);4.434(0.7);4.092(0.9);4.079(0.9);4.067(1.9);4.054(1.7);4.042(1.4);4.0 29(1.2);3.978(0.9);3.969( 0.8);3.954(0.6);3.931(0.8);3.925(0.9);3.916(2.2);3.899(2.5);3.873(2.4 );3.856(2.3);3.492(1.7);3.376(16.0);3.350( 14.7);3.331(2.2);3.328(2.2);3.288(2.0);3.284(1.9);2. 699(0.6);2.682(0.7);2.661(0.7);2.641(0.8);2.621(0.6);2.314(0.7);2.261(0.6);2.225(0.5);1.548(l 3.3);1.256(1.3) ;1.242(0.6);0.008(5.3);0.000(176.6);-0.008(5.2);-0.150(0.6) 1-17 ¹ H-NMR(400.6 MHz, CDC13): δ=8.303(0.5);8.282(0.9);8.261(0.5);7.271(4.1);7.205(1.4);7.199(1.7);7.188(1.2);7.185( 1.9);7.1 79(2.8);7.174(2.0);7.162(1.2);7.160(1.8);7.154(1.4);6.888(0.7);6.883(1.2);6.877(0.6);6.867(1.4);6.861 (2.3);6.855(1.2);6.845(0.7);6.839(1.2);6.833(0.6);6.213(1.2);6.186(1.4);6.180(1.2);6.170(1.4);6.153(1.3); 6.143(1.5);6.137(1.4);6.110(1.4);5.594(1.9);5.593(2.0);5.551(3.6);5.510(1.6); 5.508(1.6);5.342(2.0);5.341(2.0);5.323(1.8);5.322(1.8);5.316(1.8);5.314(1.8);5.297(1.6);5.296(1.6);4.850(1.7); 4.843(1.6);4.829(2.0);4.822(1.7);4.586(0.7);4.581(0.7);4.573(0.8);4.568(1.1);4. 562(0.9);4.555(0.8);4.549(0.7);4.010(1.0);3.998(ll);3.988(2.2);3.975(2.2);3.965(1.4);3.952(l. 4);3.941(2.1 );3.898(2.4);3.883(2.2);3.845(1.1);3.840(3.4);3.822(0.7);3.818(0.7);3.793(1.0);3.788(0.9);3.770(0.8); 3.765(0.7);3.304(4.4);3.261(3.8);3.137(14.7);3.133(16.0);3.027(0.5);3.002(14.1);2.992(13.2);2.357(0.8);2.352(1.3); 2.331(0.8);2.322(0.8);2.314(1.8);2.311(1.7);2.308(1.5) ;2.293(ll);2.291(1.2);2.288(1.0);2.270(0.8);2.045(2.1); 1.853(1.0);1.334(0.9);1.286(1.5);1.277(1.0);1.256(4.5);1.242(0.9);0.880(0.8);0.000(3.1)

- 48 040946

1-18 Ή-ΝΜΚ^ΟΟ.Ο MHz, CDC13): δ= 7.519(2.5);7.315(0.8);7.260(401.6);7.258(381.2);7.170(16.6);7.155(17.2);6.996(2.3);6.883( 6.9);6.863(9.3);6.845(7.2);6.719(4.5);6.693(5.1);6.180(3.8);6.153(4.1);6.135(7.3);6.108(7.9);6. 089(4.4);6.064(4.4);5.532(12.0);5.489(10.4);5.372(8.6);5.346(13.4);5.322(8.8);4.448(3.4);4.42 2(7.0);4.405(8.8) ;4.399(9.3);4.371(4.7);4.002(3.8);3.990(3.8);3.978(5.9);3.966(9.0);3.954(4.3); 3.942(5.4);3.927(9.7);3.879(16.0);3.859(4.3);3.835(9.4);3.812(5.4);3.790(4.0);3.322(9.3);3.307(8.8); 3.278(7.9);3.264(7.7);2.786(2.8);2.776(4.0);2.768(4.6);2.760(4.5);2.752(4.6);2.744(4.8); 2.735(4.7);2.727(3.1);2.632(1.9);2.615(4.1);2.597(5.1);2.591(5.0);2.581(5.3);2.574(5.4);2.55 5.0);2.538(2.4);2.196(3.5);2.161(6.4);2.125(3.3);1.548(100.8);1.333(1.1);1.283(1.5);1.256(4.6) ;0.879(1.6);0.843( 3.0);0.827(9.9);0.808(13.3);0.787(8.2);0.617(11.2);0.601(4.7);0.591(6.6);0.581(5.7);0.563(5.8);0.000(138.7);- 0.002(131.1);-0.152(0.8) 1-19 ¹ H-NMR(400.0 MHz, CDC13): δ=8.214(1.2);8.106(1.4);7.518(2.9);7.293(1.2);7.260(529.3);7.227(1.7);7.221(2.0);7.208( 2.6); 7.188(2.3);7.182(2.6);7.168(2.6);7.163(2.2);6.996(3.2);6.916(1.7);6.900(1.8);6.895(3.0);6.888(1.6);6.873(1.5); 6.171(1.7);6.158(1.5);6.145(2.0);6.128(2.2);6.115(1.8);6.101(1.9);6.088(1.8);5. 538(3.0);5.529(3.3);5.494(2.6);5.487(2.8);5.359(4.2);5.332(3.8);4.580(1.4);4.437(1.5);4.049(0.9);4.037(0.9 );4.025(1.9);4.013(2.0);3.997(2.1);3.984(2.1);3.968(2.5);3.928(3.1);3.924(3.3);3.885(3.0);3.324(2.9 );3.295(2.8);3.281(2.6);3.252(2.6);2.553(0.7);2.447(1.1);2.424(0.9);2.410(0.8 );2.364(1.1);2.044(1.5);1.541(30.8 );1.507(52.0);1.500(32.6);1.464(1.0);1.266(9.4);0.899(4.9);0.882(16.0);0.864(6.2);0.146(1.0);0.008(6.7);0.000 (193.0);-0.008(6.3) 1-20 ¹ H-NMR(400.0 MHz, CDC13): δ= 7.5193 (0.6); 7.2604(100.9); 7.1884 (0.7); 7.1762(1.8); 7.1698(2.6); 7.1635(2.2); 7.1601(2.0); 7.1565(2.2); 7.1503(2.4); 7.1438(1.6); 7.0179 (1.0); 6.9965 (1.4); 6.9101 (0.9); 6.9045 (0.9); 6.8940 (0.8); 6.8884 (1.9); 6.8829 (1.8); 6.8773 (0.7); 6.8667 (0.9); 6.8611 (0.9); 6.1799(1.2); 6.1531(1.3); 6.1367(1.5); 6.1321(1.2); 6.1100 (1.5); 6.1053 (1.4); 6.0889 (1.4); 6.0621 (1.5); 5.5268 (2.0); 5.5255 (2.0); 5.5113 (2.3); 5.4837 (1.8); 5.4824 (1.7); 5.4680(1.9); 5.3594(2.1); 5.3440 (1.9); 5.3326 (2.0); 5.3173 (1.8); 4.4620 (0.9); 4.4432(1.6); 4.4327 (1.3); 4.4199 (1.7); 4.4091 (1.8); 4.3969 (1.0); 4.3858 (0.8); 4.0356 (0.9); 4.0228 (0.9); 4.0117 (1.4); 4.0034(1.1); 3.9990 (1.3); 3.9909 (0.9); 3.9794 (1.4); 3.9669 (1.2); 3.9270 (2.1); 3.9098 (0.9); 3.9031 (0.9); 3.8840 (3.2); 3.8778 (3.5); 3.8522 (0.6); 3.8478 (0.6); 3.8348 (2.5); 3.7243 (16.0); 3.7111 (15.6); 3.6112 (1.2); 3.6027 (0.5); 3.5953 (1.3); 3.5871 (1.4); 3.5716 (1.8); 3.5609 (1.1); 3.5562 (1.3); 3.5463 (1.0); 3.5385 (0.8); 3.3163 (2.2); 3.3043(2.2); 3.2733 (1.9); 3.2613(1.9); 2.6165 (2.4); 2.6103 (1.4); 2.6011(4.7); 2.5938 (2.6); 2.5860 (2.3); 2.5787(1.4); 2.5639 (0.7); 2.5592 (0.9); 2.5536 (0.7); 2.5418 (0.8); 2.5363 (0.7); 2.2238 (0.6); 2.1888 (0.5); 2.1623 (0.6); 2.1280 (0.5); 1.5572 (6.4); 1.2563 (1.1); 0.0079 (1.2); -0.0002 (33.7); -0.0085 (1.1) 1-21 ¹ H-NMR(400.0 MHz, CDC13):

- 49 040946

δ= 7.2608 (68.6); 7.1807 (0.5); 7.1751 (0.8); 7.1685(2.1); 7.1626(3.6); 7.1571(3.1); 7.1529(2.8); 7.1484(3.0); 7.1428(4.0); 7.1371(2.4); 7.1245 (0.8); 7.0700 (0.6); 7.0533 (0.6); 7.0156 (0.6); 6.9967 (0.9); 6.9102 (0.9); 6.9049 (0.9); 6.8938 (0.8); 6.8885 (1.8); 6.8832 (1.7); 6.8777 (0.7); 6.8668 (0.9); 6.8616 (0.9); 6.1800 (1.2); 6.1532(1.3); 6.1368 (1.5); 6.1325(1.3); 6.1100 (1.6); 6.1057 (1.4); 6.0893 (1.4); 6.0625 (1.5); 5.5114 (2.2); 5.5018 (2.4); 5.4690 (1.9); 5.4588 (2.1); 5.3527 (2.3); 5.3259(4.2); 5.2990(1.9); 4.5138 (0.9); 4.5037 (1.0); 4.4891 (1.5); 4.4783 (1.9); 4.4710 (0.7); 4.4646(1.7); 4.4607(1.2); 4.4541(2.0); 4.4479 (1.2); 4.4420 (1.0); 4.4367 (0.8); 4.4307 (0.6); 4.1635 (0.8); 4.1487 (0.8); 4.1380 (1.8); 4.1242(1.8); 4.1176(1.6); 4.1092 (1.7); 4.1027 (1.6); 4.0953(1.7); 4.0798 (1.0); 4.0669 (1.0); 4.0557 (1.5); 4.0497 (0.6); 4.0428 (1.4); 4.0174 (1.8); 4.0044 (1.6); 3.9944 (1.6); 3.9823 (1.6); 3.9700 (1.6); 3.9580 (0.8); 3.9502 (0.7); 3.9409 (2.5); 3.9288 (1.0); 3.9250 (1.0); 3.8979 (2.9); 3.8705 (2.2); 3.8275 (2.6); 3.8001 (16.0); 3.7868(15.7); 3.3070 (2.4); 3.2866(2.3); 3.2639 (2.0); 3.2436 (2.0); 2.6322 (0.5); 2.6156 (0.5); 2.6087 (0.5); 2.5978 (0.7); 2.5917 (0.6); 2.5808 (0.6); 2.5739 (0.7); 2.5569 (0.7); 2.5539 (0.6); 2.5472 (0.5); 2.5360 (0.7); 2.5305 (0.6); 2.5192 (0.6); 2.5127 (0.6); 2.4959 (0.6); 2.2739 (1.1); 2.2666(1.2); 2.2392 (0.9); 2.2321 (0.9); 1.5678 (1.1); 1.2583 (0.9); 0.0079 (0.9); -0.0002 (22.3); -0.0085 (0.6) 1-22 ¹ H-NMR(400.0 MHz, CDC13): δ= 7.5193 (0.6); 7.2605(104.8); 7.2594 (101.9); 7.2228(2.2); 7.2086(1.5); 7.1842(2.0); 7.1701(4.3); 7.1659(4.7); 7.1520(7.7); 7.1384(4.6); 6.9958 (0.6); 6.9514 (1.3); 6.9334 (1.4); 6.8996 (1.4); 6.8922 (1.8); 6.8861 (2.4); 6.8822 (2.4); 6.8777 (2.4); 6.8717 (1.8); 6.8653 (1.4); 6.1851(1.6); 6.1589(1.7); 6.1424(1.8); 6.1300 (1.6); 6.1156 (2.0); 6.1034 (1.8); 6.0871 (1.9); 6.0601 (2.0); 5.5101 (4.2); 5.5046(4.2); 5.4669(3.6); 5.4615 (3.8); 5.3541(3.6); 5.3266(6.0); 5.2986(3.5); 4.4793 (2.3); 4.4734 (2.1); 4.4671 (2.0); 4.4120 (1.8); 4.4009 (2.5); 4.3947(2.5); 4.3886 (3.0); 4.3776(3.1); 4.3711(3.7); 4.3527(2.3); 4.3353(1.9); 4.3187 (0.9); 4.2141 (0.9); 4.2043(1.2); 4.1967(2.6); 4.1858(4.2); 4.1790(3.2); 4.1680(7.4); 4.1502(6.0); 4.1324 (2.0); 4.0309 (1.2); 4.0173 (1.3); 4.0072 (3.8); 3.9945 (3.7); 3.9842 (2.3); 3.9713 (2.1); 3.9575 (2.4); 3.9521 (2.4); 3.9337 (1.4); 3.9209 (3.4); 3.8839 (3.5); 3.8778 (4.1); 3.8415 (5.4); 3.8249 (1.5); 3.8186 (1.5); 3.3108 (5.7); 3.2676(4.9); 2.6780 (1.2); 2.6649 (1.3); 2.6401 (2.4); 2.6273 (2.3); 2.6194 (1.2); 2.6139 (1.3); 2.6029 (1.3); 2.5955 (1.3); 2.5845 (2.0); 2.5736 (1.5); 2.5553 (7.3); 2.5416 (6.4); 2.5297 (3.3); 2.5150 (2.5); 2.4914 (1.5); 2.4772 (1.4); 2.1670(2.1); 2.1415 (1.9); 2.1330 (2.0); 1.9583 (0.9); 1.5574 (5.4); 1.3281 (9.5); 1.3104 (14.3); 1.2918 (12.0); 1.2850 (8.0); 1.2729 (7.6); 1.2671 (12.9); 1.2493 (16.0); 1.2326 (10.6); -0.0002 (38.6); -0.0015 (37.8) 1-23 ¹ H-NMR(400.0 MHz, CDC13): δ= 8.9621 (1.0); 7.5207 (2.6); 7.2955 (0.6); 7.2862 (0.8); 7.2619 (459.9); 7.1725(1.8); 7.1668(2.2); 7.1527(2.6); 7.1471(2.1); 7.1352 (0.7); 6.9978 (2.5); 6.9156 (0.8); 6.8995 (0.8); 6.8939 (1.5); 6.8721 (1.1); 6.8525 (0.7); 4.5515 (1.0); 4.5405 (1.0); 4.5285 (1.1); 4.5168 (1.1); 4.4210

- 50 040946

(0.8); 4.4138 (0.8); 4.0623 (1.0); 4.0489 (0.9); 4.0378 (1.3); 4.0249 (1.3); 3.9220 (0.9); 3.9143 (0.9); 3.8967 (0.7); 3.8904 (0.7); 3.7760 (2.6); 3.7591 (0.5); 3.7327 (3.0); 3.7157 (0.7); 3.3935(13.3); 3.3551 (3.1); 3.2023(3.1); 3.1589(2.7); 2.6827 (0.6); 2.6663 (0.6); 2.6590 (0.6); 2.6481 (0.7); 2.6429 (0.7); 2.6315 (0.6); 2.6247 (0.7); 2.6082 (0.6); 2.3659 (0.8); 2.3307 (0.6); 1.7042 (4.1); 1.6963 (16.0); 1.5537 (39.0); 1.3330 (1.6); 1.2844 (2.4); 1.2541 (6.3); 0.8799 (0.9); 0.1458 (0.6); 0.0080 (5.5); -0.0002 (199.1); -0.0085 (6.8); -0.1498 (0.6) 1-24 ¹ H-NMR(400.6 MHz, CDC13): 5=9.5455 (1.6); 9.4925 (1.5); 7.2954(2.3); 7.2765 (0.9); 7.2510 (0.7); 7.1743 (0.5); 7.1618(2.9); 7.1564(3.8); 7.1420(3.8); 7.1367(3.0); 7.1302 (0.6); 7.1243 (0.6); 6.9029 (0.9); 6.8969 (0.9); 6.8872 (0.8); 6.8812(1.8); 6.8753 (1.8); 6.8693 (0.8); 6.8658 (0.6); 6.8595 (1.0); 6.8536 (0.9); 4.5375 (0.6); 4.5267 (0.8); 4.5138 (0.9); 4.5039 (1.4); 4.4931 (1.3); 4.4819(1.5); 4.4705 (1.5); 4.0333 (0.7); 4.0204 (0.8); 4.0097 (1.1); 3.9968 (1.0); 3.9845 (0.7); 3.9717 (0.7); 3.9606 (1.1); 3.9479 (1.0); 3.9325 (1.0); 3.9258 (1.0); 3.9090 (0.6); 3.9022 (0.6); 3.8828 (1.0); 3.8776 (1.0); 3.8589 (0.8); 3.8523 (0.9); 3.8420 (11.4); 3.8184 (1.8); 3.7751 (2.1); 3.7668 (2.8); 3.7608(16.0); 3.7237 (2.2); 3.2105 (2.2); 3.1989(2.6); 3.1671(1.9); 3.1556(2.3); 2.6245 (0.5); 2.6141 (0.6); 2.6080 (0.6); 2.5978 (0.8); 2.5900 (0.7); 2.5732 (0.6); 2.3252 (0.6); 2.2563 (0.6); 2.0502 (0.9); 1.6956 (15.4); 1.6893 (15.1); 1.2612 (1.4); 1.2572 (1.9); -0.0002 (0.8) 1-25 ¹ H-NMR(400.6 MHz, CDC13): 5=7.2724 (4.6); 7.2001 (1.3); 7.1944(1.6); 7.1912 (0.9); 7.1838(1.1); 7.1800 (1.7); 7.1742(1.6); 7.1720(1.7); 7.1662(1.8); 7.1629(1.2); 7.1550(1.0); 7.1518(1.7); 7.1462(1.4); 6.8826 (0.7); 6.8768 (1.2); 6.8710 (0.6); 6.8609 (1.3); 6.8551 (2.3); 6.8492 (1.2); 6.8391 (0.7); 6.8333 (1.2); 6.8275 (0.6); 4.8488 (1.8); 4.8418 (1.6); 4.8284 (1.8); 4.8211 (1.8); 4.5763 (0.5); 4.5692 (0.5); 4.5628 (0.7); 4.5566 (0.7); 4.5500 (0.6); 4.5439 (0.7); 4.1485 (0.6); 4.1307(1.8); 4.1128 (1.8); 4.0950 (0.6); 4.0199 (1.0); 4.0074 (1.1); 3.9970 (1.4); 3.9845 (1.3); 3.9751 (1.1); 3.9623 (1.1); 3.9520 (1.4); 3.9393 (1.3); 3.8636 (0.9); 3.8584 (0.8); 3.8407 (0.7); 3.8355 (0.6); 3.8049(2.2); 3.7621(3.1); 3.7472 (2.4); 3.7427 (0.8); 3.7368 (0.7); 3.7044 (2.6); 3.1654(2.6); 3.1615(2.7); 3.1415(14.8); 3.1346(16.0); 3.1225(2.4); 3.1187(2.4); 2.9966(15.0); 2.9905(14.2); 2.3855 (0.6); 2.3809 (0.9); 2.3765 (0.6); 2.3427 (0.8); 2.3247 (0.8); 2.3220 (0.8); 2.3091(1.1); 2.3018 (2.0); 2.2964 (0.7); 2.2912 (0.6); 2.2878 (0.6); 2.2849 (1.0); 2.2822 (1.0); 2.2649 (0.8); 2.1269 (0.7); 2.1252 (0.7); 2.0455 (8.6); 1.7186 (13.2); 1.6887(12.7); 1.4304 (0.6); 1.4163 (0.6); 1.3345 (0.5); 1.2856 (0.8); 1.2776 (2.7); 1.2598 (6.6); 1.2420 (2.5); 0.8802 (0.6); -0.0002 (3.0)

- 51 040946

1-26 Ή-ΝΜΚ^ΟΟ.ό MHz, CDC13): δ= 7.3193 (0.9); 7.1666(1.1); 7.1605(1.9); 7.1572(1.5); 7.1547(1.6); 7.1511(1.3); 7.1466(1.4); 7.1441(1.4); 7.1407(2.0); 7.1349(1.2); 7.0893 (0.6); 6.9034 (0.6); 6.8957 (0.5); 6.8896 (0.8); 6.8818 (1.0); 6.8757 (0.6); 6.8600 (0.5); 4.4759 (0.9); 4.4644 (1.0); 4.4523 (0.9); 4.4434 (1.0); 4.4413 (1.0); 4.4307 (0.8); 4.4206 (0.7); 4.4075 (0.6); 4.1305(1.3); 4.1127(1.3); 4.0416 (0.6); 4.0285 (0.7); 4.0180 (1.0); 4.0049 (0.8); 3.9932 (0.6); 3.9804 (0.6); 3.9693 (0.8); 3.9566 (0.8); 3.9046 (0.5); 3.8976 (0.5); 3.8144 (1.5); 3.7711 (1.4); 3.7617 (1.4); 3.7184 (1.6); 3.2169 (1.5); 3.2000 (1.3); 3.1735 (1.5); 3.1567(1.1); 2.6648(14.5); 2.6486 (0.6); 2.6363 (16.0); 2.6143 (0.6); 2.6108 (0.5); 2.6081 (0.6); 2.5741 (1.7); 2.5497 (0.6); 2.1183 (0.5); 2.0718 (0.6); 2.0470 (6.1); 1.6956 (13.2); 1.2782 (1.8); 1.2604 (4.0); 1.2425 (1.7); -0.0002 (0.5) 1-27 ¹ H-NMR(400.6 MHz, CDC13): δ= 8.8097 (1.6); 8.8075 (1.6); 8.7461 (1.5); 8.7438 (1.5); 8.0732 (0.8); 8.0589 (0.9); 7.9541 (1.8); 7.9503(1.9); 7.9374 (1.6); 7.9336 (1.6); 7.2999 (1.3); 7.1780 (0.9); 7.1718 (0.9); 7.1604(1.0); 7.1145(1.4); 7.1089 (1.8); 7.1059(1.1); 7.0979 (1.0); 7.0947 (1.8); 7.0891 (1.5); 6.9942 (1.2); 6.9886 (1.6); 6.9855 (1.0); 6.9777 (0.9); 6.9745 (1.6); 6.9689 (1.3); 6.8962 (0.6); 6.8803 (0.7); 6.8745 (1.2); 6.8687 (0.6); 6.8588 (0.5); 6.8531 (0.9); 6.8387 (0.7); 6.8329 (1.1); 6.8271 (0.5); 6.8112 (0.6); 4.8504 (0.7); 4.8364 (0.8); 4.7851 (0.7); 4.7715 (0.7); 4.7592 (0.7); 4.7478 (0.7); 4.6661 (0.7); 4.6553 (0.8); 4.6033 (0.8); 4.5945 (0.9); 4.5794 (0.8); 4.5709 (0.8); 4.5595 (0.8); 4.5498 (0.9); 4.5359 (0.9); 4.5262 (0.9); 4.5050 (0.6); 4.4993 (0.5); 4.4942 (0.6); 4.4877 (0.6); 4.4788 (0.6); 4.4734 (0.6); 4.4684 (0.5); 4.4621 (0.5); 4.1468(1.2); 4.1290(3.6); 4.1112 (3.6); 4.1028 (2.0); 4.0917 (3.2); 4.0848 (1.5); 4.0567 (1.7); 4.0454 (1.8); 4.0364 (1.2); 3.7225 (2.0); 3.7118 (2.3); 3.6793 (2.3); 3.6686 (2.6); 3.1364(2.4); 3.0967 (2.3); 3.0932 (2.4); 3.0535 (1.9); 2.6157 (0.6); 2.5998 (0.9); 2.5950 (0.6); 2.5921 (0.6); 2.5840 (0.7); 2.5812 (0.8); 2.5760 (0.9); 2.5644 (0.7); 2.5605 (0.7); 2.5577 (0.7); 2.5409 (0.5); 2.4130 (0.7); 2.3006 (0.6); 2.2661 (0.5); 2.1363 (0.9); 2.1075 (0.6); 2.0440 (16.0); 1.6123 (11.4); 1.5944(12.6); 1.2769 (4.5); 1.2591 (9.7); 1.2412(4.3); -0.0002 (0.7) 1-28 ¹ H-NMR(400.0 MHz, CDC13): δ= 7.5186 (1.7); 7.3091(1.1); 7.2917 (0.6); 7.2870 (0.5); 7.2719 (1.4); 7.2597(290.5); 7.2108 (0.8); 7.1834 (0.6); 7.1774 (0.7); 7.1708(1.8); 7.1652(3.4); 7.1598(3.0); 7.1553(2.0); 7.1508(2.6); 7.1454(3.3); 7.1398(1.8); 7.1331 (0.7); 7.1273 (0.5); 6.9957 (1.8); 6.9048 (1.1); 6.8859 (2.2); 6.8830 (2.1); 6.8772 (1.4); 6.8701 (1.3); 6.8640 (1.6); 6.8614 (1.5); 4.5156 (1.1); 4.5020 (1.6); 4.4927(1.3); 4.4862 (1.3); 4.4788 (1.8); 4.4635(1.2); 4.4239 (1.0); 4.4149 (1.0); 4.1207(1.0); 4.1064 (1.0); 4.0966 (1.4); 4.0825 (1.2); 4.0733 (1.1); 4.0596 (1.0); 4.0492 (1.4); 4.0354 (1.2); 3.9396 (0.9); 3.9295 (0.9); 3.9153 (0.8); 3.9057 (0.8); 3.8876 (0.9); 3.8807 (0.9); 3.8646 (0.8); 3.8554 (0.8); 3.7763 (2.4); 3.7593 (2.3); 3.7331 (2.8); 3.7161 (2.7); 3.5188 (0.6); 3.5007 (1.3); 3.4897 (1.2); 3.4825 (1.8); 3.4793 (2.0); 3.4720 (1.6); 3.4653 (2.7); 3.4616(2.4); 3.4506

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(1.3); 3.4472 (1.3); 3.4431 (1.8); 3.4260 (1.0); 3.1963(2.8); 3.1936(3.0); 3.1531 (2.5); 3.1504 (2.7); 2.7050 (0.5); 2.6998 (0.6); 2.6868 (0.6); 2.6828 (1.0); 2.6767 (0.6); 2.6708 (0.7); 2.6649 (1.2); 2.6597 (0.7); 2.6482 (1.2); 2.6424 (0.7); 2.6301 (0.6); 2.6253 (0.7); 2.3054 (0.8); 2.2925 (0.7); 2.2837 (1.0); 2.2709 (0.7); 2.2604 (0.9); 2.2466 (1.5); 2.1944(2.8); 2.1809 (0.7); 2.1470 (0.6); 2.1326 (0.6); 1.9610 (0.6); 1.9506 (0.8); 1.9401 (1.1); 1.9321 (1.6); 1.9207 (1.4); 1.9135 (1.9); 1.8926(1.4); 1.8741 (0.9); 1.7018(14.9); 1.6984(16.0); 1.5592(1.1); 1.5035 (0.9); 1.3329 (0.6); 1.2843 (1.0); 1.2562 (3.6); 1.2133 (0.7); 1.1942 (0.5); 1.1206 (4.0); 1.1144 (4.0); 1.1020 (8.3); 1.0958 (8.0); 1.0833 (3.8); 1.0771 (3.7); 0.9470 (0.6); 0.9284 (1.2); 0.9101 (0.6); 0.8802 (0.9); 0.0079 (3.7); -0.0002 (132.2); -0.0085 (4.6) 1-29 ¹ H-NMR(400.0 MHz, CDC13): δ= 7.5188 (1.6); 7.3096 (0.8); 7.2599(281.0); 7.2101 (0.8); 7.1813(2.0); 7.1731(3.2); 7.1672(3.1); 7.1619(3.1); 7.1562(3.3); 7.1480(2.1); 6.9959 (2.0); 6.9141 (1.1); 6.9086 (1.2); 6.8981 (1.1); 6.8926 (2.2); 6.8871 (2.1); 6.8817 (1.0); 6.8767 (0.8); 6.8708 (1.4); 6.8655 (1.4); 6.8596 (1.1); 6.8305 (1.3); 6.1736(1.3); 6.1472(2.0); 6.1305(1.6); 6.1218(1.4); 6.1041(2.2); 6.0786 (1.5); 5.5442 (2.3); 5.5356 (2.9); 5.5011 (2.1); 5.4925 (2.5); 5.3800 (2.5); 5.3728 (2.3); 5.3534 (2.4); 5.3460 (2.2); 4.5082 (1.1); 4.5019(1.1); 4.4943 (1.5); 4.4860 (1.9); 4.4792 (1.5); 4.4713 (1.6); 4.4651 (1.8); 4.4517 (1.0); 4.4394 (0.9); 4.1486(1.1); 4.1307(3.4); 4.1128(3.5); 4.1025 (1.0); 4.0950 (1.4); 4.0888 (1.0); 4.0783 (2.2); 4.0644 (2.0); 4.0539 (1.4); 4.0398 (1.2); 3.9349 (1.1); 3.9253 (1.2); 3.9181 (2.6); 3.8997 (2.9); 3.8869 (1.2); 3.8750 (2.9); 3.8567 (2.5); 3.7302 (0.6); 3.7180 (0.6); 3.5469 (1.2); 3.5381 (0.9); 3.5350 (1.3); 3.5237 (1.0); 3.4990 (1.2); 3.4930 (1.0); 3.4825 (2.4); 3.4761 (1.9); 3.4659 (1.9); 3.4586 (1.9); 3.4538 (2.0); 3.4417 (1.4); 3.4372 (1.9); 3.4205 (1.0); 3.4019 (0.5); 3.3281 (4.2); 3.2850 (3.8); 2.7233 (0.5); 2.7124 (0.5); 2.7060 (0.6); 2.7005 (0.6); 2.6890 (1.2); 2.6832 (0.7); 2.6775 (0.8); 2.6713 (1.2); 2.6659 (0.8); 2.6599 (0.8); 2.6481 (0.6); 2.6373 (0.6); 2.2910 (0.7); 2.2840 (1.3); 2.2606(1.1); 2.2466 (3.0); 2.2271(1.2); 2.2184 (0.8); 2.2036 (1.3); 2.1944(5.5); 2.1741 (0.5); 2.1671 (0.7); 2.1305 (0.9); 2.1011 (0.7); 2.0438 (16.0); 1.9565 (0.8); 1.9502 (0.8); 1.9385 (1.6); 1.9315 (1.6); 1.9147 (2.0); 1.8986 (1.7); 1.8926 (1.6); 1.8805 (1.0); 1.8748 (1.0); 1.8567 (0.5); 1.6134 (0.9); 1.5964 (1.2); 1.5798 (1.3); 1.5602 (1.2); 1.5436 (0.9); 1.5039 (0.8); 1.4094 (0.6); 1.3908 (0.8); 1.3709 (0.8); 1.3531 (0.6); 1.3331 (1.0); 1.2844 (1.6); 1.2766 (5.4); 1.2587 (13.8); 1.2409 (5.0); 1.2324 (1.0); 1.2133 (1.4); 1.1943(1.1); 1.1231 (3.8); 1.1172 (3.8); 1.1045 (7.7); 1.0986 (7.3); 1.0858 (3.8); 1.0800 (3.6); 0.9468 (1.6); 0.9284 (3.1); 0.9100 (1.4); 0.8968 (0.6); 0.8801 (1.5); 0.8625 (0.7); 0.0080 (3.4); -0.0002 (116.8); -0.0085 (3.9) 1-30 Ή-ΝΜΚ(400.0 MHz, CDC13): 0=7.5185 (2.5); 7.3218 (0.5); 7.3181 (0.6); 7.3094 (0.9); 7.3021 (0.5); 7.2957 (0.6); 7.2941 (0.5); 7.2902 (0.7); 7.2886 (0.7); 7.2862 (0.8); 7.2854 (0.8); 7.2822 (1.0); 7.2790(1.1); 7.2782(1.1); 7.2759(1.4); 7.2750 (1.5); 7.2743(1.6); 7.2734 (1.7); 7.2727 (1.8); 7.2711(2.2); 7.2703(2.3); 7.2694(2.4); 7.2678(3.3); 7.2670(3.6); 7.2596 (455.4); 7.2279 (0.7); 7.2103 (0.6); 7.1464(2.3); 6.9956 (2.7); 6.8685 (1.6); 4.5296 (0.8); 4.1304 (0.8); 4.1125 (0.8); 3.9728 (0.7); 3.7768 (0.5); 3.7375 (0.6); 3.1965(1.0); 3.1528 (0.8); 2.0436 (2.6); 1.6706 (6.3); 1.6102 (16.0); 1.2842 (0.9); 1.2763 (1.1); 1.2584 (3.4); 1.2406 (1.0); 0.8801 (0.6); 0.1460 (0.6); 0.0102 (1.0); 0.0079 (6.0); 0.0063 (2.0); 0.0054 (2.2); 0.0046 (2.6); -0.0002 (201.3); -0.0052 (3.5); -0.0060 (2.7); -0.0068 (2.2); -0.0085 (5.9); -0.0116 (0.6); -0.0124 (0.5); -0.1496 (0.6)

In a similar manner to the above named preparation examples, and given the general data for the manufacture of substituted isoxazoline-carboxamides, the following named compounds can be prepared:

Table 2.1: compounds 2.1-1 - 2.1-390 according to the invention of general formula (I.1), where Z-(C=W)N(R11)-R ¹² has the meaning as defined below.

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Table 2.1

No. R ¹¹ VyL”w No. R ¹¹ VyL” W 2.1-1 ^(Z-1)γΝΗ ₂ ' 0 2.1-2 H Y^’Y^CH, 'o 2.1-3 Η '0 2.1-4 n ^(ζ-η^Ν. o V 2.1-5 CH, γΜγ^ 'o 2.1-6 ' O 2.1-7 ^(Z-I^N^J ' O 2.1-8 Y(Z-1)^Q o 2.1-9 H γ^γ^ΟΗ ' O 2.1-10 n -^(Z-I^N^C^ ABOUT 2.1-11 n γ^γ^ο^οΗ, 'o 2.1-12 n ?* Y^ySA^ 'oh 2.1-13 CH ₃ 'o 2.1-14 n n/iZ-D^N SNz V p A o o o 2.1-15 N (Z-1)..N CF ₃ Y p A 2.1-16 н _v < ^z - ^1, Y ^N gs^ ^CH 3 ' LLC 2.1-17 н if ⁴ ) τ^ζ-υ^Α^ V Τ Λ ' ο Ο Ο 2.1-18 SN ₃ n^(Z-1)^N _v CF ₃ V p A o o o 2.1-19 Η ^AZ-I^N ΝΗ ₂ V π D ^Ί ο Ο Ο 2.1-20 n ?From Y YA ³ o O o 2.1-21 Η γ( ^ζ -ηγ%Η ₂ ' 0 2.1-22 n ^ (r-p ^ u ^ snz o SN ₃ 2.1-23 Η about sleep ₃ 2.1-24 n ? ^Nz γ YN he. 2.1-25 SNz ⁵ ° ^SN SN ₃ 2.1-26 n I? ^Nz 2.1-27 ^(Z-2)γΝΗ ₂ 'O 2.1-28 n Y^Y^CH, 'o 2.1-29 Η _^(Z-2)^N^CH ₃ O 2.1-30 n VYv 2.1-31 CH, oh 2.1-32 ^(Z-ZJ^nC/* ' o 2.1-33 ' ABOUT 2.1-34 τγίΖ-^γ'Ό ' O

- 54 040946

2.1-35 Η (Ζ-^γ^οΗ ' ο 2.1-36 Η (Ζ-^Ν,θ^ ' Ο 2.1-37 Η Y^Y^O^CH, ' ο 2.1-38 Η ΐ· γ^γ^Αα, ' ο 2.1-39 SNz ' O 2.1-40 Η (Z-ZJ.A/Hj Υ π A 'ο θ θ 2.1-41 Η (Z-2)^.Ν^ CF ₃ V π A 2.1-42 Η ,ζ-ζ, ν ^Ί ο Ο ο 2.1-43 Η jf ⁴ ] 5 Π Ά ' OOO 2.1-44 CH3 (g-g^m cf ₃ Υ π A 2.1-45 Η (Ζ-2)^Ν^ ΝΗ ₂ V π A ' ο Ο ο 2.1-46 n ooo 2.1-47 Η γΡ-ΖΙγ^ 0 2.1-48 .^lg-g^u^snz ' about SN ₃ 2.1-49 Η γ ^{(Z 2)} Y%^CH ₃ 2.1-50 Y ^(Z - ²⁾ Y ^K -Ach ₃ O 2.1-51 γ ^(Z-2) Y^N-^CHs sn ₃ 2.1-52 Y^ySA^ 2.1-53 _^(Z-3)γΝΗ ₂ ' 0 2.1-54 n ^ζ-Ίγ^Η, o 2.1-55 Η γ(Ζ 3)γ4/ ^Η 3 ' Ο 2.1-56 n ν'-γ^ν 2.1-57 SNz 'ο 2.1-58 γZ-3)^Ν^ 'O 2.1-59 γζ-3γΐ£^9 ο 2.1-60 (2-3)^^ ' ABOUT

- 55 040946

2.1-61 Η γ'^'γ^ΟΗ ' ο 2.1-62 Η Τ/( ^Ζ -3)γ%^Η ₃ 'o 2.1-63 Η γ^γ'^ΟΗ, ' ο 2.1-64 Η ft γγΛ* 'o 2.1-65 SNz -γχ(Ζ-3)γ ^Ν ^ _ο ^ΟΗ3 ' Ο 2.1-66 Η T> Z-3) ^ N _V CH ₃ V p A ' O o o 2.1-67 Η Τ>Z-3)^Ν CF ₃ V π Α 2.1-68 n γ^γ^^ ^{0 3 Ί} OOO 2.1-69 Η jf ⁴ ] 5 Π ' Ο Ο ο 2.1-70 CH3 (Z^ί^,Ν^ CF ₃ V t A o o o 2.1-71 Η (Ζ-3)^Ν ΝΗ ₂ V π l ' ο Ο Ο 2.1-72 n ooo 2.1-73 Η 0 2.1-74 n ^ yg-z ^ m ^ snz ' about SN ₃ 2.1-75 Η Y<“>Y ⁿ 'n^ch _j ' Ο CHs 2.1-76 n ? ⁿ ' γ γ Ν SNz 2.1-77 Y(Z-3)yN _s p _cHj ° ^sn ₃ 2.1-78 γ,,γΛ,,Ι^ 2.1-79 _^(Z-4)γΝΗ ₂ ' 0 2.1-80 n Y^Y^ch, 'o 2.1-81 Η ^(Z-4)^N^CH ₃ ' Ο 2.1-82 n vv ^ 2.1-83 CH3 γ^γ^ 'o 2.1-84 ^(Z-4)^ί^ '0 2.1-85 f^o γΛΖ-^γΝ^ o 2.1-86 ' O

- 56 040946

2.1-87 Η γ<~>γ% _Η ' ο 2.1-88 Η -γ( ^Ζ - ⁴ )γ ^Ν - _ο ^Η ₃ ' Ο 2.1-89 Η h Π ° ^SNz ' ο 2.1-90 Η Γ* Υ^Υ^Α^ ' ο 2.1-91 CH3 γ^γΝ^^ ο 2.1-92 Η (Z-4)γ^ CH ₃ Υ Υ A ' Ο ο ο 2.1-93 Η (Z-4)γ.Ν^ CF ₃ V π A ' ο Ο ο 2.1-94 Η υ^'υ^^^ ^Ί ο Ο Ο 2.1-95 Η / ⁴ ]' ο Ο ο 2.1-96 SNz (Ζ-4)γ.Ν CF ₃ Υ Υ A ο ο ο 2.1-97 Η -^(Ζ^Ι^Ν ΝΗ ₂ V Υ l ' ο Ο ο 2.1-98 Η V* Υ^'ϊ» ο ο ο 2.1-99 Η γ^Ιγ^ ' ο 2.1-100 Η ν Π 2.1-101 Η T^Y'S^CH, ' 0 An, 2.1-102 Η? ^Η ' Y^Y^rA^ ο 2.1-103 Υ^Υ^Υ^ SNz 2.1-104 Η ϊ Ϊ%Η, 2.1-105 _^(Z-5)γΝΗ ₂ 'Ο 2.1-106 Η Υ^'υ^η. ο 2.1-107 Η -γ(ζ-5)γΝ^0Η ₃ ' ο 2.1-108 Η 2.1-109 γ^'γ^οΗ, 2.1-110 (Z-5)^nC^ 'Ο 2.1-111 γ^γΟ ο 2.1-112 γ(Ζ-5)γθ ^Ί Ο

- 57 040946

2.1-113 Η y^y^ ' ο 2.1-114 n T / (Z-5) ^% yH ₃ ' O 2.1-115 Η 'ο 2.1-116 n P* γ^γΑγ^ ' o 2.1-117 SNz -γΖ-5γΝ^ΟΗ ₃ Ο 2.1-118 n (Z-5)^N^ CH3 V p L ' Ooo 2.1-119 Η (Z-5) h< CF ₃ V π A 2.1-120 n •y (Z 5) 'o o^'o 2.1-121 Η f ⁴ ] (Z-5)^hk ί I ' O O O 2.1-122 CH3 (Ζ-δί^,Ν^ CF ₃ V p A ' o O O 2.1-123 n -, ^ (Z-5) ^ Ν ΝΗ ₂ V π A ' o o o 2.1-124 n V p A ⁴⁸ 'o θ θ 2.1-125 I'm learning™, 'oh 2.1-126 n ^ (Z-SJ ^ N ^ ^ CHj O SN ₃ 2.1-127 n uchuA ^ unit, 0 A 2.1-128 Y^Y^rAc^ o 2.1-129 Y^Y^N-^CHa ° ^CH3 2.1-130 γ^γίίΛ^ 2.1-131 _^(Z-6)γΝΗ ₂ ' 0 2.1-132 n Y^’Y^ch, ’ o 2.1-133 n y(Z-6)yNyH ₃ 'O 2.1-134 n 2.1-135 CH. Υ^'γ^ΟΗ. O 2.1-136 (Z-6)^N^ ' ABOUT 2.1-137 (Z-6)γ*0 'o 2.1-138 γ(Ζ-6)γΟ ' about 2.1-139 I'm learning _oh n' oh 2.1-140 n T / (Z-6) ^% yH ₃ ' o 2.1-141 n Y^’Y^O^CH, 'o 2.1-142 n ? ⁿ ' γ^-βγΝ^θΑ^ ' o 2.1-143 SNz γζ-βγ^θ^ ’ o 2.1-144 n ΤΥ (Z-6) ^ Ν CH ₃ V p A ' O o o 2.1-145 n -,ΛΖ-β^Ν CF ₃ V p A ' o O O 2.1-146 n' o o ^{/ x} o 2.1-147 H A' o o o 2.1-148 CH3 (Z-ej^N CF ₃ ν γ _ο 4 2.1-149 H (Z-6)^Ν ΝΗ ₂ V p l ' o O o 2.1-150 Η? ^Η 3 o o o 2.1-151 I'm learning™, Oh 2.1-152 n TYlZ-eix^N^CHj o SNz

- 58 040946

2.1-153 Η ⁷ About SNz 2.1-154 H? ^N s -y ^'y ^ m ^ snz 2.1-155 ° CH3 2.1-156 γ^γ^A^ 2.1-157 _^(Z-7)γΝΗ ₂ 'O 2.1-158 Η γΙ ^{ζ 7} >γ%Η, ο 2.1-159 H (Z-7) γΝ.---, CH ₃ 'O 2.1-160 Η γ”νΥ 2.1-161 SI. γ^ΙγΎ, 'o 2.1-162 γ^γ^ ο 2.1-163 γ(Z-7)^Ν^ ' O 2.1-164 γ(Z-7)γθ ' Ο 2.1-165 n γΜγ^, 'o 2.1-166 Η -γ(Ζ-7)γΝ^ _ο ,ΟΗ ₃ ' Ο 2.1-167 n Y^Y^O^CHa o 2.1-168 Η Γ tLpukD, ' ο 2.1-169 PPE ' ABOUT 2.1-170 Η τ^ζ-η^Ν snz Υ π Α 'ο ο ο 2.1-171 n T>Z-7)^N CF ₃ Y p A 2.1-172 Η - ₇ ^(Z-7) _x .N^^^CH ₃ Υ π Α ' ο Ο Ο 2.1-173 ⁿ if ⁴ *! γ^Λ^ ' o o o 2.1-174 SNz _{b /} (r-7) _{h /} 'k ^ SR ₃ V Υ Α ο ο ο 2.1-175 n -^(ζ-η^Ν νη ₂ V p A ' o O o 2.1-176 Η? ^Η 3 y ^(z - ⁷⁾ y ⁿ A ^{n ch} 3 ο ο ο 2.1-177 n γ' ^{ζ 7} )γ%„ ₂ ⁷ o 2.1-178 Η -1/(Ζ-7)γ ^Ν ^ _Ν ^ΟΗ ₃ Ο sn ₃ 2.1-179 n 'About SNz 2.1-180 Η? ^Η 3 ->/(Z 7)γγΝ^ γ Υ ίϊ ^sn ' 2.1-181 y|g-7)uM _h ^ _cH3 ° ^CH3 2.1-182 υ^'Ύ^Α^' 2.1-183 _^(Z-8)γΝΗ ₂ 'O 2.1-184 Η γ'^Υ^ΟΗ, ο 2.1-185 n - ^ (Z-8) ^ N.---, CH ₃ 'O 2.1-186 Η -, ^(Z-8)γΝ^ θ'' 2.1-187 SNz ABOUT 2.1-188 γ ^|ζ -'γθ ο 2.1-189 ^(Z-8)γΝ^1 ' O 2.1-190 ι^ζ-β^ίζ^ ο

- 59 040946

2.1-191 Η ABOUT 2.1-192 n Τ/(Z-8)γΝ _Χο ^Η ₃ 'O 2.1-193 Η 'ο 2.1-194 n ? γ^γ^Α^, 'o 2.1-195 PPE ' ABOUT 2.1-196 n (Z-8)^.N^ CH3 V p A ' o θ o 2.1-197 Η Τγ(Ζ-8)^Ν CF ₃ V τ &' o o o 2.1-198 n γ( ^ζ ' ⁸ ) Y ^N ^ _S ^^CH ₃ ' o o'o 2.1-199 n jf ⁴ ] ' 0 o o 2.1-200 SNz τ/ίΖ-βΙγ^Ν^ CF ₃ E Π o O O 2.1-201 n (Z-8)^Ν^ ΝΗ ₂ V π Λ ' o O o 2.1-202 n R* ooo 2.1-203 n γ^'γ^ΝΗ, 'o 2.1-204 n -^(Z-ej^N^CHj O SN ₃ 2.1-205 γ^γϋγ^ ' o sleep, 2.1-206 H? ^N s y ^ A _Ns I ⁿ 2.1-207 n t^^'y'^m-^eiz SNz 2.1-208 Y^Y^AAb 2.1-209 _^(Z-9)γΝΗ ₂ 'O 2.1-210 n Y^Y^ch, o 2.1-211 n ^g^^/Nz 'o 2.1-212 n γ^γ^ 2.1-213 C, γ^γ^οκ, o 2.1-214 ^(Z-9)^nO ' O 2.1-215 (Z-^^ί^Τ ' ABOUT 2.1-216 ^(g-e)^^ ¹ o 2.1-217 n Υ^γΝ-ΟΗ O 2.1-218 n T^(Z-9)^N, _o ,CH3 ' O

- 60 040946

2.1-219 Η 'ο 2.1-220 Η f ο 2.1-221 CH3 y (g-9) y%, CH ₃ ' Ο 2.1-222 Η Τ>Ζ-9)^Ν Sn ₃ Υ π Α ο Ο ο 2.1-223 Η -, MZ-9)^.N CF ₃ V π Α ' ο Ο Ο 2.1-224 Η Τ>Ζ-9)γ%^^ΟΗ ₃ ο ο ^ζ 'ο 2.1-225 Η Γ ⁴ ] (1 η'η ' ο Ο Ο 2.1-226 SNz τ/(Z-9)χ^Ν Cf ₃ Υ π Α ο ο ο 2.1-227 Η (Ζ-9)^Ν^ ΝΗ ₂ V π Α ' ο θ Ο 2.1-228 Η .^(Ζ-ίΟ^Ν Ν Υ π Α ³ ο Ο Ο 2.1-229 Η 'ο 2.1-230 Η T^z-gi^N^CHa O CH3 2.1-231 Η Υ Τ 7 ^CHz 'O CHz 2.1-232 Η? ^Nz (Z-9)^.Ν _χ γ Υ !Υ-· 2.1-233 Η γ ^Ζ -9)γΝ ° ^CH3 2.1-234 Y^ySA^ 2.1-235 _^(Z-10)γΝΗ ₂ ' Ο 2.1-236 Η ο 2.1-237 Η ^(Z-10)^N^CH3 0 2.1-238 Η γ'^'γ^ 2.1-239 SNz (ζ-ιογ^ 'ο 2.1-240 (Z-10)^,nC^ 'ο 2.1-241 (ZdO)^iOj ο 2.1-242 ^(z-ioi^nC^ ο 2.1-243 Η γ<ζ ΐ)γ% _Η ' ο 2.1-244 Η T/(Z-10)^N _Xo ^CH ₃ ' ο 2.1-245 Η (ζαοίγΚθ^^ ' 0 2.1-246 Η _V (Z-10)Y%AcH3 ' ο

- 61 040946

2.1-247 CHz (Z-IO ^ N ^ CHj ' o 2.1-248 Η (Ζ-ΙΟ)^,Ν^ CH ₃ V π Α ' ο Ο Ο 2.1-249 Η (Z-IOJ^N CF ₃ V st 2.1-250 Η (Ζ-10Κ.Ν /^CH3 V Y <Λ 2.1-251 ⁿ ιΡί V π l 'Ο ο ο 2.1-252 CH3 (Ζ-ΙΟ)^,Ν^ CF ₃ V π A 2.1-253 Η (Ζ-10)^Ν ΝΗ ₂ V π Α ' Ο ο ο 2.1-254 Η (Ζ-ΙΟ)^,Ν^ Η V π Α * ο θ Ο 2.1-255 Η <ζ-ιογ>< _ΝΗ! 0 2.1-256 Η ^(Z-IOJ^N^^CHs Ο sn ₃ 2.1-257 Η γ^Ίγ^^οΗ, O CH3 2.1-258 (Z-10) _v N. _n A _c Mon ³ 2.1-259 ⁵ ° Ρη. SNz 2.1-260 'θ Η 2.1-261 ^(Ζ-11)^ΝΗ ₂ 0 2.1-262 Η γ^ΊΊγ^Η, ' Ο 2.1-263 Η ^(Z-ID^N^CHa ' Ο 2.1-264 Η ν'Ύ^ 2.1-265 Ρ* γ^γ^ΟΗ, ' ο 2.1-266 ^(z-id^nC^ ο 2.1-267 Τ^(Z-11)γΝ^χΙ 'Ο 2.1-268 Ο 2.1-269 Η γ^’Ιγ^ΟΗ ' ο 2.1-270 Η T/(Z-11) ^ ^N ^ _o ^ CH ₃ ^Ί Ο 2.1-271 Η γ^Ίγ^Ο^ΟΗ, ' ο 2.1-272 Η 'ο 2.1-273 SNz g^g-p^k^snz ο 2.1-274 Η (Z-ID^N^ CH3 V π Α 'Ο Ο ο

- 62 040946

2.1-275 Η (Z-11)^t< CF ₃ V p A 2.1-276 n ' ooo 2.1-277 ⁿ ' ooo 2.1-278 SNz (Z-11) ^ N ^ CF ₃ V t 0¾ 2.1-279 n _ΛΖ-11)^Ν ΝΗ ₂ V T A ' o O O 2.1-280 Η Υ^”Υ*Χ%“. ' ooo 2.1-281 n Υ< ^ζ - ¹ ”Υ ^ν 'νη _! ' ABOUT 2.1-282 n ^(Z-ID^N^^CHj O SN ₃ 2.1-283 n ' about 1η, 2.1-284 n _ν ^(Ζ - ^ι υγ%Α ^0Η ₃ 2.1-285 ° ^SN W 2.1-286 Y^vSA^ 2.1-287 ^ΛΖ-12)γΝΗ ₂ O 2.1-288 Η γ<ζ ¹² )γ% _Η , ' ο 2.1-289 n ^ (Z-12) ^ N ^ CH ₃ 'O 2.1-290 Η υΎΎ 2.1-291 Siz (Z-I^N^ 'O 2.1-292 _ν "." _)γ ο ο 2.1-293 r^ ⁰ (Ζ-ΙΣί^Ν^ 'O 2.1-294 Τ^(Z-12)^Ν^ Ο 2.1-295 H γ< ^Ζ - «> γ% Η o 2.1-296 Η 'Ο 2.1-297 n Y'z-'Z'yS^ch, 'O 2.1-298 Η _V ( ^Z -1 ² )Y%A _CH3 ' 0 2.1-299 CH3 .^(Z-IZ^N^CHj ' O 2.1-300 Η (Z-12)^.Ν^ SNz Υ π Α 'ο Ο Ο 2.1-301 n (Z-12)γ,Ν ΟΡ ₃ V p A ' o O o 2.1-302 Η 'ο Ο ο

- 63 040946

2.1-303 Q, soy Y sr 2.1-304 SNz (Ζ-ΙΖί^,Ν^ CF ₃ Υ Υ A ο ο ο 2.1-305 Η (Ζ-ΙΖ^Ν ΝΗ ₂ Υ π A ' ο Ο ο 2.1-306 Ηf* ooo 2.1-307 Η <Ζ-12) _γ Ν, _ΝΗι ο 2.1-308 n I^Z-IZ^N^C^ About CH3 2.1-309 Η (Z-12)^Ν^ Υ π 7 ^CHz O CHz 2.1-310 n ? ^Nz gDmgKhHASn YY ^{th sn} 2.1-311 γ ^{(Z 12)} Y^n-*cHj CH3 2.1-312 n N 1% n. γ^'γ^ΑΛ^ 2.1-313 _ _χ (Z-13)γΝΗ ₂ 0 2.1-314 n (Z-13) _Y >k _CHj 'o 2.1-315 Η ^(z-nj^N.—,sn ₃ 'o 2.1-316 n 2.1-317 CH3 γ(ζ-ΐ3)γΝ. _ΟΗ3 about 2.1-318 γζ-ΐ3)γ,Ν^ o 2.1-319 (ζ-ηγίΟ* '0 2.1-320 O 2.1-321 n (Z.13) _γ Κ _οΗ 0 2.1-322 n (Z-13)γ^Ν^ _οΧ ΟΗ3 O 2.1-323 n <z.13) _y ^ _o ^ _cHs ' o 2.1-324 n ' ABOUT 2.1-325 CH3 -γΖ-13)γ,Ν^0Η ₃ o 2.1-326 n (Z-ISJ ^ N ^ SNz Y Y A ' LLC 2.1-327 H (Z-13) ^, N CF ₃ Y p A o o o 2.1-328 n (.-’zu^^n, ~ ooo 2.1-329 N if ⁴ ] _,(Z-13) _x .N^ _s /<Y n Π w ¹ ο Ο ο 2.1-330 CH3 (Z-13) ^^ CF ₃ Υ p A o o o

- 64 040946

2.1-331 Η (Ζ-13)^Ν ΝΗ ₂ V π A ' Ο Ο ο 2.1-332 n Y^W^ o o o 2.1-333 Η 0 2.1-334 n ^JZ-IS^N^CH, o ch ₃ 2.1-335 Η Oh sleep 2.1-336 n (Z-13) ^ N ^ A YY th ^SN Z o 2.1-337 (ζ-13)^^^^ ° ^CH ₃ 2.1-338 2.1-339 ^(Ζ-14)γΝΗ ₂ ' 0 2.1-340 n (Z-14) _Y ^ _cHj o 2.1-341 Η ^(Z-UJ^N^CHs Ο 2.1-342 n _v ™ _y4z 2.1-343 SNz (Z-UyN^ Ο 2.1-344 O 2.1-345 ^(Z-14)γΝ^ ' Ο 2.1-346 -Ι^(Ζ-14)^ί^ O 2.1-347 Η - ₁ /(ζ ΐ4)γ ^Ν ' _ΟΗ ' ο 2.1-348 n (Z-14)^N^ _o ^CH3 O 2.1-349 Η 'ο 2.1-350 Η ΐ· ' O 2.1-351 CH3 -3 / (Z-14) ^ N ^ _o ^ CH ₃ O 2.1-352 n (Z-14)^.Ν^ CH3 V p A ' OOO 2.1-353 Η ΐΛΖ-14)^Ν CF ₃ V π A o O o 2.1-354 n ' ooo 2.1-355 n if ⁴ ] (Z-14)^N^ _S X> V n A ' o O O 2.1-356 SNz Y p A o o O 2.1-357 n (Z-14) ^ N ^ NH ₂ 5 p A o O o 2.1-358 n t* ' OOO

- 65 040946

2.1-359 n (Ζ-Ι^γΚ^ o 2.1-360 n ^(Z-14)γΝ^^Η ₃ O CH ₃ 2.1-361 n about SNz 2.1-362 n ? ⁿ · 2.1-363 ° ^sn ₃ 2.1-364 2.1-365 ^(Z-15)γΝΗ ₂ 'O 2.1-366 Η (Ζ-15)γΧ _0Ηι ο 2.1-367 n (gich^m^snz 'o 2.1-368 Η γ^ΎΑζ 2.1-369 G*o 2.1-370 _^(Z-15)γΝ^ Ο 2.1-371 (Ζ-Ιδ,γί^ ' ABOUT 2.1-372 γ(Z-15)γ£^ Ο 2.1-373 n (Z-15)γM. _0Η ' Oh 2.1-374 Η (Ζ-15)γΝ^ _οΧ ΟΗ3 Ο 2.1-375 n υΎού' o 2.1-376 Η Ρ' ο 2.1-377 CH3 γ(Z-15)γΝ^ _ο ^ΟΗ ₃ O 2.1-378 Η (Ζ-15ΚγΙ< SNz V π A ο ο ο 2.1-379 H (Z-15)yyN CF3 V p A ' ooo 2.1-380 Η ^(Ζ-15) ' o ° ^,x ° 2.1-381 n [A| (ζ-ΐ5)γγΝ t P / o ooo 2.1-382 CH3,(Z-15)^.N^ CF ₃ Υ π A o O O 2.1-383 n (Z-15)γ.Ν^ ΝΗ ₂ V p A ' o o o 2.1-384 Η ?* Υ^Ύ^^ ' OOO 2.1-385 n γ<ζ· ¹⁵ )γ% _Η2 ' o 2.1-386 n γ^(Z-15)γ^Ν^ ΌΗ ₃ ^v У U 2.1-387 n _ν (Z-15) _γ Ν _Χι ^ _{{; Η3} O CH3 2.1-388 n ? ^Nz Υ Υ th ^CH1 2.1-389 SNz 2.1-390 Y^’yA^

Table 2.2: compounds 2.2-1 - 2.2-390 according to the invention of General formula (I.2), where Z-(C=W)N(R11)-R ¹² has the meaning as defined in table. 2.1.

Table 2.3: compounds 2.3-1 - 2.3-390 according to the invention of General formula (I.3), where Z-(C=W)N(R11)-R ¹² has the meaning as defined in table. 2.1.

Table 2.4: compounds 2.4-1 - 2.4-390 according to the invention of General formula (I.4), where Z-(C=W)N(R ⁿ )-R ¹² has the meaning as defined in table. 2.1.

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Table 2.5: compounds 2.5-1 - 2.5-390 according to the invention of General formula (I.5), where Z-(C=W)N(R11)-R ¹² has the meaning as defined in table. 2.1.

Table 2.6: compounds 2.6-1 - 2.6-390 according to the invention of General formula (I.6), where Z-(C=W)N(R ⁿ )-R ¹² has the meaning as defined in table. 2.1.

Table 2.7: compounds 2.7-1 - 2.7-390 according to the invention of general formula (I.7), where Z-(C=W)N(R11)-R ¹² has the meaning as defined in table. 2.1.

Table 2.8: compounds 2.8-1 - 2.8-390 according to the invention of General formula (I.8), where Z-(C=W)N(R11)-R ¹² has the meaning as defined in table. 2.1.

Table 2.9: compounds 2.9-1 - 2.9-390 according to the invention of General formula (I.9), where Z-(C=W)N(R11)-R ¹² has the meaning as defined in table. 2.1.

Table 2.10: compounds 2.10-1 - 2.10-390 according to the invention of general formula (I.10), where Z(C=W)-N(R11)-R ¹² has the meaning as defined in table. 2.1.

Table 2.11: compounds 2.11-1 - 2.11-390 according to the invention of General formula (I.11), where Z(C=W)-N(R11)-R ¹² has the meaning as defined in table. 2.1.

Table 2.12: compounds 2.12-1 - 2.12-390 (C=W)-N(R ¹¹ )-R ¹² is as defined according to the invention of general formula (I.12), where in the table. 2.1.

Z-67 040946

Table 2.13: compounds 2.13-1 - 2.13-390 according to the invention of General formula (I.13), where (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.14: compounds 2.14-1 - 2.14-390 according to the invention of General formula (I.14), where (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.15: compounds 2.15-1 - 2.15-390 according to the invention of general formula (I.15), where (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.16: compounds 2.16-1 - 2.16-390 according to the invention of General formula (I.16), where Z(C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

Table 2.17: compounds 2.17-1 - 2.17-390 according to the invention of General formula (I.17), where Z(C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

0-17),

Table 2.18: compounds 2.18-1 - 2.18-390 according to the invention of General formula (I.18), where (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

Table 2.19: compounds 2.19-1 - 2.19-390 according to the invention of General formula (I.19), where (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

ZZ-

Table 2.20: compounds 2.20-1 - 2.20-390 according to the invention of General formula (I.20), where Z(C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

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Table 2.21: compounds 2.21-1 - 2.21-390 according to the invention of General formula (I.21), where (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.22: compounds 2.22-1 - 2.22-390 according to the invention of General formula (I.22), where (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.23: compounds 2.23-1 - 2.23-390 according to the invention of general formula (I.23), where (C=W)-N(R11)-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.24: compounds 2.24-1 - 2.24-390 according to the invention of General formula (I.24), where (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.25: compounds 2.25-1 - 2.25-390 according to the invention of General formula (I.25), where (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.26: compounds 2.26-1 - 2.26-390 according to the invention of General formula (I.26), where (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.27: compounds 2.27-1 - 2.27-390 according to the invention of General formula (I.27), where (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

Z-

- 69 040946

Table 2.28: compounds 2.28-1 - 2.28-390 according to the invention of General formula (I.28), where (C=W)-N(R ¹¹ )-R ¹² has the meaning, as defined in table. 2.1.

Z-

Table 2.29: compounds 2.29-1 - 2.29-390 according to the invention of General formula (I.29), where (C=W)-N(R11)-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.30: compounds 2.30-1 - 2.30-390 according to the invention of General formula (I.30), where (C=W)-N(R11)-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.31: compounds 2.31-1 - 2.31-390 according to the invention of General formula (I.31), where (C=W)-N(R11)-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.32: compounds 2.32-1 - 2.32-390 according to the invention of General formula (I.32), where (C=W)-N(R11)-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.33: compounds 2.33-1 - 2.33-390 according to the invention of General formula (I.33), where (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.34: compounds 2.34-1 - 2.34-390 according to the invention of General formula (I.34), where (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.35: compounds 2.35-1 - 2.35-390 according to the invention of General formula (I.35), where (C=W)-N(R ¹¹ )-R ¹² has the meaning, as defined in table. 2.1.

Z-70 040946

Table 2.36: compounds 2.36-1 - 2.36-390 according to the invention of General formula (I.36), where (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.37: compounds 2.37-1 - 2.37-390 according to the invention of General formula (I.37), where (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.38: compounds 2.38-1 - 2.38-390 according to the invention of General formula (I.38), where (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.39: compounds 2.39-1 - 2.39-390 according to the invention of General formula (I.39), where (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.40: compounds 2.40-1 - 2.40-390 (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

according to the invention of the general formula (I.40), where

Z-

Table 2.41: compounds 2.41-1 - 2.41-390 according to the invention of General formula (I.41), where (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.42: compounds 2.42-1 - 2.42-390 according to the invention of General formula (I.42), where (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

Z-71 040946

Table 2.43: compounds 2.43-1 - 2.43-390 according to the invention of General formula (I.43), where (C=W)-N(R ⁿ )-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.44: compounds 2.44-1 - 2.44-390 according to the invention of general formula (I.44), where (C=W)-N(R11)-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.45: compounds 2.45-1 - 2.45-390 according to the invention of General formula (I.45), where (C=W)-N(R11)-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.46: compounds 2.46-1 - 2.46-390 according to the invention of General formula (I.46), where (C=W)-N(R11)-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.47: compounds 2.47 - 2.47-390 according to the invention of General formula (I.47), where (C=W)-N(R11)-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.48: compounds 2.48-1 - 2.48-390 according to the invention of General formula (I.48), where (C=W)-N(R11)-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.49: compounds 2.49-1 - 2.49-390 according to the invention of General formula (I.49), where (C=W)-N(R11)-R ¹² has the meaning as defined in table. 2.1.

Z-

- 72 040946

Table 2.50: compounds 2.50-1 - 2.50-390 according to the invention of General formula (I.50), where (C=W)-N(R ⁿ )-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.51: compounds 2.51-1 - 2.51-390 according to the invention of General formula (I.51), where (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.52: compounds 2.52-1 - 2.52-390 according to the invention of General formula (I.52), where (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.53: compounds 2.53-1 - 2.53-390 according to the invention of General formula (I.53), where (C=W)-N(R ¹¹ )-R ¹² has the meaning, as defined in table. 2.1.

Z-

Table 2.54: compounds 2.54-1 - 2.54-390 according to the invention of General formula (I.54), where (C=W)-N(R ¹¹ )-R ¹² has the meaning as defined in table. 2.1.

Z-

Table 2.55: compounds 2.55-1 - 2.55-390 according to the invention of General formula (I.55), where (C=W)-N(R ¹¹ )-R ¹² has the meaning, as defined in table. 2.1.

Z-

Table 2.56: compounds 2.56-1 - 2.56-390 according to the invention of General formula (I.56), where (C=W)-N(R ¹¹ )-R ¹² has the meaning, as defined in table. 2.1.

Z-

B. Formulation Examples.

1. Means for pollination.

Pollinator can be obtained by mixing 10 wt.h. compounds of General formula (I) and 90 wt.h. talc as an inert substance and grinding in a hammer mill.

2. Dispersible powder.

A water-dispersible, wettable powder is obtained by mixing 25 wt.h. connections

- 73 040946 of the general formula (I), 64 wt.h. containing kaolin quartz as an inert substance, 10 wt.h. ligninsulfonic acid potassium and 1 wt.h. sodium oleoylmethyltaurine as a wetting agent and dispersant and ground in a pin crusher.

3. Dispersion concentrate.

Easily dispersible in water dispersion concentrate is obtained by mixing 20 wt.h. compounds of General formula (I), 6 wt.h. alkylphenol polyglycol ether (© Triton X 207), 3 wt.h. isotridecanolpolyglycol ether (8 EO) and 71 wt.h. paraffinic mineral oil (boiling range, for example, about 255-277°C) and grinding in a ball grinder to a fineness of grinding of 5 μm.

4. Emulsifiable concentrate.

The emulsifiable concentrate is obtained from 15 wt.h. compounds of general formula (I), 75 wt.h. cyclohexanone as a solvent and 10 wt.h. oxoethylated nonylphenol as an emulsifier.

5. Water-dispersible granulate.

Water-dispersible granules are obtained by grinding wt.h. compounds of formula (I), calcium lignin sulfonic acid, sodium lauryl sulfate, polyvinyl alcohol and kaolin, in a pin crusher and granulating the powder in a fluidized bed by spraying water as the granulating liquid.

Also get a water-dispersible granulate, in which 25 wt.h. compounds of formula (I),

sodium 2,2-dinaphthylmethane-6,6-disulfonic acid, sodium oleoylmethyltaurine acid, polyvinyl alcohol, calcium carbonate and water, are homogenized in a colloid mill and pre-crushed, then pulverized in a bead mill, and the suspension thus obtained is sprayed both in a scrubber and with mononozzle and dry.

C. Biological examples.

Description of experiences.

1. Herbicidal action against harmful plants and compatibility with cultivated plants in the pre-emergence period.

Seeds of mono- or dicotyledonous weeds or cultivated plants were placed in plastic pots or wood fiber pots and covered with earth. The compounds of the invention were applied to the surface of the earth as a wetting powder (WP) or an emulsion concentrate (EC) in the form of an aqueous suspension or emulsion with the addition of 0.5% additives at a water rate calculated as 600 l/ha. After treatment, the pots were placed in a greenhouse and good growth conditions were created for the test plants. Approximately 3 weeks visually assessed the effect of drugs, compared with the untreated control group in percentage terms. For example, 100% action = plants died, 0% action = like control plants.

The following abbreviations have been used in the following table: unwanted plants/weeds:

ABUTH: Abutilon theophrasti ALOMY: Alopecurus myosuroides AMARE: Amaranthus retroflexus AVEFA: Avena fatua CYPES: Cyperus esculentus ECHCG: Echinochloa crus-galli HORMU: Hordeum murinum LOLRI: Lolium rigidum PHBPU: Pharbitis purpurea POLCO: Polygonum convolvulus SETVI: Setaria viridis STEME: Stellar ia media VERPE: Veronica persica VIOTR: Viola tricolor

- 74 040946

Table C1

Herbicidal action in % in the pre-emergence period against ALOMY

Example No. Dosage [g/ha] ALOMY 1-17 80 90 1-11 80 100 1-16 80 100 1-18 80 100 1-12 80 100 1-13 80 100 1-23 80 100 1-24 80 100 1-14 80 100 1-15 80 100 1-21 80 100 1-26 80 100 1-25 80 100 1-20 80 100 1-22 80 100 1-10 80 100 1-02 80 90 1-27 80 90 1-08 80 90 1-04 80 80

Table C2

Herbicidal activity in % pre-emergence against AVEVA

Example No. Dosage [g/ha] AVEFA 1-17 80 100 1-11 80 100 1-16 80 100 1-18 80 90 1-12 80 100 1-13 80 100 1-23 80 100 1-24 80 100 1-14 80 90 1-15 80 90 1-21 80 100 1-26 80 90 1-25 80 90 1-20 80 100 1-22 80 100 1-10 80 80 1-19 80 90 1-02 80 100 1-05 80 100 1-27 80 80

- 75 040946

Table C3

- 76 040946

Table C6

- 77 040946

Table C9

- 78 040946

Table C11

- 79 040946

Table C13

As the results show, the compounds according to the invention, such as compounds No. I-02 and other compounds from the table. (I-05, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, I-18, I-19, I-20, I -21, I-22, I-23, I-24, I-25, I-26, I-27, I-28, I-29) show very good efficacy (80-100% herbicidal action) against harmful plants such as Abutilon theophrasti, Alopecurus myosuroides, Amaranthus retroflexus, Avena fatua, Cyperus esculentus, Echinochloa crus-galli, Hordeum murinum, Lolium rigidum, Pharbitis purpurea, Polygonum convolvulus, Setaria viridis, Stellaria media, Veronica persica and Viola tricolor at an application rate of 0.08 kg of active ingredient or less per hectare.

2. Herbicidal action against harmful plants and compatibility with cultivated plants in the post-emergence period.

Seeds of mono- or dicotyledonous weeds or cultivated plants were placed in plastic or wooden pots in sandy loam, covered with earth and grown in a greenhouse under controlled growth conditions. 2-3 weeks after sowing, the test plants were treated at the first leaf stage. The green parts of the plants were sprayed with the compounds according to the invention, represented by a powder for

- 80 040946 wetting (WP) or emulsion concentrate (EC), in the form of an aqueous suspension or emulsion with the addition of 0.5% additives with a water consumption rate calculated as 600 l/ha. Approximately 3 weeks, the test plants were in the greenhouse, in optimal growth conditions, visually assessed the effect of the drugs, compared with the untreated control group. For example, 100% action = plants died, 0% action = like control plants.

Table C15

Herbicidal activity in % in the post-emergence period against ALOMY

Example No. Dosage [g/ha] ALOMY 1-23 320 90 1-19 320 90 1-18 320 90 1-20 320 100 1-12 320 90 1-21 320 90 1-28 320 90 1-24 320 100 1-29 320 90 1-22 320 100 1-26 320 100 1-16 320 90 1-13 320 90 1-14 320 90 1-15 320 100 1-05 320 90 1-17 320 90 1-27 320 90 1-11 320 90 1-25 320 100 1-10 320 100 1-04 320 90 1-02 320 100 1-03 320 80 1-06 320 90 1-08 320 90

- 81 040946

Table C16

Herbicidal activity in % post-emergence against AVEFA

Example No. Dosage [g/ha] AVEFA 1-23 320 100 1-19 320 90 1-18 320 90 1-20 320 100 1-12 320 100 1-21 320 100 1-28 320 100 1-24 320 100 1-29 320 90 1-22 320 100 1-26 320 100 1-13 320 90 1-14 320 80 1-15 320 100 1-05 320 80 1-17 320 90 1-27 320 100 1-11 320 90 1-25 320 90 1-10 320 90 1-04 320 100 1-02 320 90 1-03 320 90 1-06 320 90 1-08 320 80

- 82 040946

Table C17

Herbicidal activity in % post-emergence against ECHCG

- 83 040946

Table C19

Herbicidal activity in % post-emergence against SETVI

Example No. Dosage [g/ha] SETVI 1-23 320 80 1-19 320 90 1-18 320 90 1-20 320 90 1-21 320 90 1-28 320 90 1-24 320 80 1-29 320 90 1-22 320 90 1-26 320 80 1-16 320 80 1-13 320 90 1-15 320 80 1-05 320 80 1-17 320 90 1-27 320 80 1-11 320 90 1-25 320 80 1-10 320 90 1-04 320 90 1-02 320 90 1-03 320 90 1-06 320 80

Table C20

Herbicidal activity in % post-emergence against ABUTH

Example No. Dosage [g/ha] ABUTH 1-23 320 80 1-19 320 90 1-18 320 90 1-20 320 80 1-12 320 80 1-21 320 90 1-28 320 80 1-24 320 80 1-29 320 90 1-22 320 80 1-26 320 80 1-16 320 80 1-13 320 80 1-14 320 90 1-15 320 80 1-05 320 80 1-11 320 80 1-25 320 80 1-02 320 80

- 84 040946

Table C21

- 85 040946

1-27 320 90 1-11 320 80 1-25 320 90 1-10 320 90 1-04 320 80 1-02 320 90 1-03 320 80 1-06 320 80 1-08 320 80 1-07 320 80 1-09 320 80

Table C23

Herbicidal activity in % post-emergence against POLCO

Example No. Dosage [g/ha] POLCO 1-23 320 90 1-19 320 90 1-18 320 90 1-20 320 80 1-12 320 80 1-21 320 90 1-28 320 80 1-24 320 80 1-29 320 90 1-22 320 80 1-26 320 80 1-13 320 80 1-14 320 80 1-15 320 90 1-05 320 80 1-17 320 80 1-27 320 80 1-11 320 80 1-25 320 80 1-04 320 80 1-03 320 80 1-06 320 80 1-08 320 80 1-07 320 80

- 86 040946

Table C24

Herbicidal activity in % post-emergence against STEME

Example No. Dosage [g/ha] STEM 1-23 320 90 1-19 320 90 1-18 320 90 1-20 320 80 1-12 320 90 1-21 320 90 1-28 320 90 1-24 320 100 1-29 320 90 1-22 320 80 1-26 320 100 1-16 320 90 1-13 320 90 1-14 320 90 1-15 320 90 1-05 320 80 1-17 320 90 1-27 320 90 1-11 320 90 1-25 320 90 1-10 320 80 1-04 320 80 1-02 320 90 1-03 320 90 1-06 320 80

- 87 040946

Table C25

Herbicidal activity in % post-emergence against VIOTR

Example No. Dosage [g/ha] VIOTR 1-23 320 80 1-19 320 90 1-18 320 80 1-20 320 80 1-12 320 80 1-21 320 90 1-28 320 90 1-24 320 90 1-29 320 90 1-22 320 80 1-26 320 90 1-16 320 80 1-13 320 80 1-14 320 100 1-15 320 80 1-05 320 80 1-17 320 80 1-27 320 80 1-11 320 80 1-04 320 80 1-02 320 80 1-03 320 80

- 88 040946

Table C26

Herbicidal activity in % in the post-emergence period against VERPE

Example No. Dosage [g/ha] VERPE 1-23 320 80 1-19 320 80 1-18 320 80 1-20 320 80 1-12 320 80 1-21 320 80 1-28 320 90 1-24 320 80 1-29 320 90 1-22 320 80 1-26 320 80 1-16 320 80 1-13 320 80 1-14 320 90 1-15 320 80 1-05 320 80 1-17 320 80 1-27 320 80 1-11 320 80 1-25 320 80 1-10 320 80 1-04 320 80 1-02 320 80 1-03 320 90 1-06 320 80 1-08 320 80

-

Claims (12)

Table C27 Herbicidal activity in % in the post-emergence period against HORMU Example No. Dosage [g/ha] HORMU 1-23 320 100 1-19 320 90 1-18 320 90 1-20 320 100 1-12 320 90 1-21 320 100 1-28 320 90 1-24 320 100 1-29 320 90 1-22 320 100 1-26 320 100 1-16 320 80 1-13 320 90 1-14 320 80 1-15 320 90 1-17 320 80 1-27 320 100 1-25 320 90 1-10 320 90 As the results show, compounds according to the invention, such as compounds No. I-02 and other compounds from the table (I-04, I-10, I-15, I-18, I-19, I-20, I-21 , I-21, I-22, I-23, I-24, I-26, I-27, I-28, I-29) when treated in the post-emergence period, they show very good efficiency (80-100% herbicidal effect) against harmful plants such as Abutilon theophrasti, Alopecurus myosuroides, Amaranthus retroflexus, Avena fatua, Echinochloa crus-galli, Hordeum murinum, Lolium rigidum, Pharbitis purpurea, Polygonum convolvulus, Setaria viridis, Stellaria media, Veronica persica and Viola tricolor at a rate of 0.32 kg active ingredient or less per hectare. CLAIM 1. 3-Phenylisoxazoline-5-carboxamide of general formula (I) and its agrochemically acceptable salts, in which R ¹ and R ² are respectively hydrogen; R ³ means (C ₁ -C ₃ )alkyl, (C ₃ -C ₄ )cycloalkyl, (C ₂ -C ₃ )alkenyl, (C ₂ -C ₃ )alkynyl or (C ₁ -C ₃ )alkoxy which are substituted m residues selected from the group consisting of fluorine, chlorine, bromine, cyano, (C ₁ C ₂ )alkoxy and hydroxy; Y means oxygen; W is oxygen; Z means a group selected from Z-1 to Z-4, where Z-1 to Z-4 have the following meaning: Z-1 Z-2 Z-3 Z-4 wherein the arrow denotes, respectively, a bond with the C=W group of the formula (I); R ¹¹ means hydrogen, or (C ₁ -C ₃ )alkyl or (C ₃ -C ₆ )cycloalkyl, which are substituted by m residues selected from the group consisting of fluorine and chlorine; - 90 040946 R ¹² is hydrogen or cyano, or OR ⁷ , S(O)nR ⁵ , NR ⁶ R ⁸ , NR ⁶ CO2R ⁸ , (C1-C ₆ )alkyl, (C ₃ -C ₆ )cycloalkyl, (C ₂ -C ₃ )alkenyl or (C ₂ C ₃ ) alkynyl which are substituted with m residues selected from the group consisting of fluorine, chlorine, bromine, cyano and hydroxy; or R ¹¹ and R ¹² together with the nitrogen atom to which they are attached form a saturated, partially or fully unsaturated five- or six-membered ring which, in addition to the said nitrogen atom, contains g carbon atoms, η oxygen atoms and p elements from the group consisting of NR ⁷ and NCOR ⁷ as ring atoms, the carbon atom bearing p oxo groups; X ² , X ⁴ and X ⁶ mean independently of each other, respectively, hydrogen or fluorine; X ³ and X ⁵ mean independently of each other hydrogen, fluorine, chlorine, bromine, hydroxy or cyano, or (C ₃ -C ₃ )alkyl, (C1-C ₃ )alkoxy, (C ₃ -C ₄ )cycloalkyl, ( C ₂ -C ₃ )alkenyl or (C ₂ -C ₃ )alkynyl which are substituted with m residues selected from the group consisting of fluorine, chlorine and bromine; R ⁵ means (C 1 -C ₆ )alkyl, (C ₃ -C ₆ )cycloalkyl or phenyl, which are substituted by m residues from the group consisting of fluorine, chlorine and hydroxy; R ⁶ is hydrogen or R ⁵ ; R ⁷ means hydrogen, or (C1-Ce)alkyl or (C ₃ -Ce)cycloalkyl, which are substituted by m residues selected from the group consisting of fluorine, chlorine and (C1-C ₂ )alkoxy; R ⁸ means hydrogen, or (C1-C ₆ )alkyl, (C ₃ -C ₆ )cycloalkyl or phenyl, which are substituted by m residues selected from the group consisting of fluorine, chlorine and (C1-C ₂ )alkoxy; m is equal to ordinal 0, 1, 2 or 3; η is equal to the ordinal number 0, 1 or 2; p is equal to the ordinal number 0 or 1; and r is equal to the ordinal number 3, 4, or 5. 2. A compound according to claim 1, characterized in that R ¹² is hydroxy. 3. A plant growth regulator, characterized in that it contains one or more compounds of general formula (I) or their salts according to claim 1 or 2. 4. Herbicidal agent, characterized in that it contains one or more compounds of general formula (I) or their salts according to claim 1 or 2. 5. The herbicidal agent of claim 4, which further comprises a formulation aid. 6. Herbicidal product according to claim 4 or 5, containing at least one additional biologically active substance from the group of insecticides, acaricides, herbicides, fungicides, protective agents and/or plant growth regulators. 7. Herbicidal agent according to one of claims 4 to 6, containing a protective agent. 8. Herbicidal agent according to claim 7, wherein the protective agent is selected from the group consisting of mefenpyr-diethyl, cyprosulfamide, isoxadifen-ethyl, cloquintoset-mexil, benoxacor and dichloramide. 9. A method for controlling unwanted plants, characterized in that the effective amount of at least one compound of formula (I) at π. 1 or 2 or one herbicidal agent according to one of claims 4 to 8 is applied to the unwanted plants or to the locus where the unwanted plants grow. 10. Use of a compound of formula (I) according to claim 1 or 2 or a herbicidal agent according to one of claims 4 to 8 for controlling unwanted plants. 11. Use according to claim 10, characterized in that the compound of formula (I) is used to control unwanted plants in crops of useful plants. 12. Use according to claim 11, characterized in that the beneficial plants are transgenic beneficial plants. Kommersant Eurasian Patent Organization, EAPO Russia, 109012, Moscow, Maly Cherkassky per., 2