Substituted benzoylcyclohexanediones, herbicide agent based on thereof, parent compound

FIELD: organic chemistry, herbicides, agriculture.

SUBSTANCE: invention describes substituted benzoylcyclohexanediones of the general formula (I):

wherein m = 0 or 1; n = 0 or 1; A means a single bond or alkanediyl (alkylene) with 1-4 carbon atoms; R1 means hydrogen atom or unsubstituted alkyl with from 1 to 6 carbon atoms; R2 means methyl; R3 means hydrogen atom, nitro-, cyano-group, halogen atom, alkyl with from 1 to 4 carbon atoms substituted with halogen atom, alkoxy-group with from 1 to 4 carbon atoms or alkyl sulfonyl with from 1 to 4 carbon atoms; R4 means nitro-group, halogen atom, unsubstituted alkyl with from 1 to 4 carbon atoms of that substituted with halogen atom; Z means heterocycle, and herbicide agent based on thereof. Also, invention describes substituted derivatives of benzoic acid of the general formula (III):

wherein values n, A, R3, R4 and Z are given above. These compounds represent the parent substances used for preparing compound of the formula (I). Compounds of the formula (I) elicit high and selective herbicide activity.

EFFECT: valuable properties of compounds.

7 cl, 8 tbl, 7 ex

 

The invention relates to new substituted benzoylecgonine, method of their production and use as herbicides.

It is already known that certain substituted benzoylecgonine have a weed-killing properties (see European patent application EP-090262 AND-135191 AND 186118 AND 186119 AND 186120, AND-319075, international application WO-96/26200 And 97/46530 And 99/07688). However, the effectiveness of these compounds does not meet all necessary requirements.

Now found new substituted benzoylecgonine General formula (I),

in which

m is 0, 1, 2 or 3,

n is 0, 1, 2 or 3,

And is a simple bond or Alcantara (alkylene),

R1is hydrogen or substituted by alkyl or alkoxycarbonyl,

R2is substituted by alkyl, or together with R1is Alcantara (alkylene), and in this case, m is 1, and R1and R2from one carbon atom (“seminally”) or at two adjacent carbon atoms (“vicinal”),

R3is hydrogen, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, or substituted by alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfonyl, alkylamino, dialkylamino or dialkylaminoalkyl,

R4is nitro, cyano, carboxy, carbamoyl, thiocarbamoyl is m, halogen, or substituted by alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfonyl, alkylamino, dialkylamino or dialkylaminoalkyl,

Z is substituted 4-12 membered saturated or unsaturated, monocyclic or bicyclic, heterocyclic group which contains 1-4 heteroatom (up to 4 nitrogen atoms and an alternative or addition of one oxygen atom or one sulfur atom or one group or SO one group SO2), and optionally 1 to 3 oxo group (=O) and/or group thioxo (C=S) as part of a heterocycle, including all possible tautomeric forms of the compounds of General formula (I) and the possible salts of compounds of General formula (I).

The hydrocarbon chain, for example, alkyl or alcander - also in combination with heteroatoms, for example, in alkoxy - are straight or branched.

In addition to the compounds of General formula (I) can also be offered corresponding tautomeric forms, as shown below.

Preferred substituents of the radicals of the above formula have the following meanings:

m is preferably 0, 1 or 2,

n preferably is 0, 1 or 2,

And preferably is a simple bond or Alcantara (alkylene) with 1-4 carbon atoms,

R1preferably is hydrogen; and the and alkyl with 1-6 carbon atoms, substituted by halogen, alkoxy with 1-4 carbon atoms, alkylthio with 1-4 carbon atoms, alkylsulfonyl with 1-4 carbon atoms or alkylsulphonyl with 1-4 carbon atoms; or alkoxycarbonyl, which has up to 6 carbon atoms,

R2preferably is alkyl with 1-6 carbon atoms, substituted with halogen, or together with R1is Alcantara (alkylene) with 2-5 carbon atoms, and in this case, m is 1, and R1and R2from one carbon atom (“seminally”) or at two adjacent carbon atoms (“vicinal”),

R3preferably is hydrogen, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen; or alkyl, alkoxy, alkylthio, alkylsulfonyl or alkylsulfonyl, which has up to 4 carbon atoms in the alkyl groups substituted by halogen, alkoxy with 1-4 carbon atoms, alkylthio with 1-4 carbon atoms, alkylsulfonyl with 1-4 carbon atoms or alkylsulphonyl with 1-4 carbon atoms; or is alkylamino, dialkylamino or dialkylaminoalkyl, which has up to 4 carbon atoms in the alkyl groups,

R4preferably is nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen; or alkyl, alkoxy, alkylthio, alkylsulfonyl or alkylsulfonyl, which has up to 4 carbon atoms in the alkyl groups, substituted what alogena, alkoxy with 1-4 carbon atoms, alkylthio with 1-4 carbon atoms, alkylsulfonyl with 1-4 carbon atoms or alkylsulphonyl with 1-4 carbon atoms; or is alkylamino, dialkylamino or dialkylaminoalkyl, which has up to 4 carbon atoms in the alkyl groups,

Z is preferably the following heterocyclic groups

the connection drawn strokes, is a simple bond or a double bond,

Q is oxygen or sulphur,

R5is hydrogen, hydroxy, mercapto, cyano, halogen; or alkyl, alkylcarboxylic, alkoxy, alkoxycarbonyl, alkylthio, alkylsulfonyl or alkylsulfonyl with up to 6 carbon atoms in the alkyl groups, substituted by cyano, halogen, alkoxy with 1-4 carbon atoms, alkylthio with 1-4 carbon atoms, alkylsulfonyl with 1-4 carbon atoms or alkylsulphonyl with 1-4 carbon atoms; or probationally; or alkylamino or dialkylamino with up to 6 carbon atoms in the alkyl groups, substituted with halogen; or alkenyl, and what kidilam, alkenylacyl, alkanity or alkenylamine with up to 6 carbon atoms in the groups alkenyl or quinil, substituted with halogen; or cycloalkyl, cycloalkane, cycloalkene, cycloalkylation, cyclooctylamine, cycloalkylation, cycloalkylation or cycloalkylation with 3-6 carbon atoms in the groups cycloalkyl and, in this case, with up to 4 carbon atoms in the portion of the alkyl substituted by halogen; or phenyl, phenyloxy, phenylthio, phenylamino, benzyl, benzyloxy, benzylthio or benzylamino, substituted with halogen, alkyl with 1-4 carbon atoms or alkoxy with 1-4 carbon atoms; or pyrrolidino, piperidino or morpholino; or in that case, if two adjacent radicals R5and R5are the double bond together with the adjacent radical R5is also a benzo grouping, and

R6is hydrogen, hydroxy, amino , alkylamino with up to 4 carbon atoms; or alkyl, alkoxy, alkylamino, dialkylamino or alkanolamine with up to 6 carbon atoms in the alkyl groups, substituted with halogen or alkoxy with 1-4 carbon atoms; or alkenyl, quinil or alkenylamine with up to 6 carbon atoms in the groups alkenyl or quinil, substituted with halogen; or cycloalkyl, cycloalkylation or cyclooctylamino with 3-6 carbon atoms in the groups cycloalkyl and, in this case, with up to 3 carbon atoms in the portion of the alkyl, W is displaced by halogen; or phenyl or benzyl substituted by halogen, alkyl with 1-4 carbon atoms or alkoxy with 1-4 carbon atoms; or together with the adjacent radical R5or R6is Alcantara with 3-5 carbon atoms, substituted with halogen or alkyl with 1-4 carbon atoms,

moreover, the individual radicals R5and R6which are connected at the same heterocyclic groups can have identical or different meanings within the above definition.

Most preferably:

And is a simple bond, methylene, ethylidene (ethane-1,1-deylam) or dimethylene (ethane-1,2-deylam),

R1is hydrogen; or stands, ethyl, n - or isopropyl, n-, ISO - or sec.- bootrom substituted by fluorine, chlorine, methoxy, ethoxy, n - or isopropoxy, methylthio, ethylthio, n - or isopropylthio, methylsulfinyl, ethylsulfinyl, n - or isopropylphenyl, methylsulfonyl, ethylsulfonyl, n - or isopropylammonium; or methoxycarbonyl, etoxycarbonyl, n - or isopropoxycarbonyl,

R2is stands, ethyl, n - or isopropyl, or together with R1is methylene, ethane-1,1-di sludge (ethylidene, -CH(CH3)-), ethane-1,2-deylam (dimethylene, -CH2CH2-), propane-1,3-deylam (trimethylene, -CH2CH2-CH2-), butane-1,4-deylam (tetramethylene, -CH2CH2CH2SN 2-) or pentane-1,5-deylam (pentamethylene, -CH2CH2CH2CH2CH2-), and in this case, m is 1, and R1and R2from one carbon atom (“seminally”) or at two adjacent carbon atoms (“vicinal”),

R3is hydrogen, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, iodine; or stands, ethyl, n - or isopropyl, n-, ISO-, sec.- or tert.-bootrom substituted by fluorine and/or chlorine, methoxy, ethoxy, n - or isopropoxy, methylthio, ethylthio, n - or isopropylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl; or methoxy, ethoxy, n - or isopropoxy substituted by fluorine and/or chlorine, methoxy, ethoxy, n - or isopropoxy; or methylthio, ethylthio, n - or isopropylthio, methylsulfinyl, ethylsulfinyl, n - or isopropylphenyl, methylsulfonyl, ethylsulfonyl, n - or isopropylammonium substituted by fluorine and/or chlorine; or methylamino, ethylamino, n - or isopropylamino, dimethylamino, diethylamino, dimethylaminomethyl or diethylaminosulfur,

R4is nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine; or stands, ethyl, n - or isopropyl, n-, ISO-, sec.- or tert.-bootrom substituted by fluorine and/or chlorine, methoxy, ethoxy, n - or isopropoxy, methylthio, utilty is, n - or isopropylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl; or methoxy, ethoxy, n - or isopropoxy substituted by fluorine and/or chlorine, methoxy, ethoxy, n - or isopropoxy; or methylthio, ethylthio, n - or isopropylthio, methylsulfinyl, ethylsulfinyl, n - or isopropylphenyl, methylsulfonyl, ethylsulfonyl, n - or isopropylammonium substituted by fluorine and/or chlorine; or methylamino, ethylamino, n - or isopropylamino, dimethylamino, diethylamino, dimethylaminomethyl or diethylaminosulfur,

Z is below heterocyclic group

R5is hydrogen, hydroxy, mercapto, cyano, fluorine, chlorine, bromine, iodine; stands, ethyl, n - or isopropyl, n-, ISO-, sec.- or tert.-bootrom, methoxy, ethoxy, n - or isopropoxy, n-, ISO-, sec.- or tert.-butoxy, methylthio, ethylthio, n - or isopropylthio, n-, ISO-, sec.- or tert.-butylthio, methylsulfinyl, ethylsulfinyl, n - or isopropylphenyl, methylsulfonyl, ethylsulfonyl, n - or isopropylammonium substituted by fluorine, chlorine, ethoxy, methoxy, n - or isopropoxy, n-, ISO-, sec.- or tert.-butoxy, methylthio, ethylthio, n - or isopropylthio, n-, ISO-, sec.- or tert.-butylthio, methylsulfinyl, ethylsulfinyl, n - or isopropylphenyl, methylsulfonyl, ethylal what fonila, n - or isopropylammonium; or methylamino, ethylamino, n - or isopropylamino, n-, ISO-, sec.- or tert.-butylamino, dimethylamino, diethylamino, di-n-propylamino or di-ISO-propylamino; or atenilol, propanolol, butanediol, atenolol, PROPYNYL, butanolom, propenyloxy, butenyloxy, property, butylthio, propanolamine or butenylamine substituted by fluorine and/or chlorine; or cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylamine, cyclobutylamine, cyclopentyloxy, cyclohexyloxy, cyclopropylethyl, cyclobutyl, cyclopentyl, cyclohexylthio, cyclopropylamino, cyclobutylamine, cyclopentylamine, cyclohexylamine, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethoxy, cyclopropylmethyl cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropanemethylamine, cyclobutanemethanamine, cyclopentylmethyl or cyclohexylethylamine substituted by fluorine and/or chlorine; or phenyl, phenyloxy, phenylthio, phenylamino, benzyl, benzyloxy, benzylthio or benzylamino substituted by fluorine, chlorine, stands, ethyl, n - or isopropyl, n-, ISO-, sec.- or tert.-bootrom, methoxy, ethoxy, n - or isopropoxy; or - in the case that two adjacent radicals R5and R5N. what was the double bond - together with the adjacent radical R5also is the benzo group,

R6is hydrogen, hydroxy, amino; or stands, ethyl, n - or isopropyl, n-, ISO-, sec.- or tert.-bootrom, methoxy, ethoxy, n - or isopropoxy, methylamino, ethylamino or dimethylamino substituted by fluorine and/or chlorine, methoxy or ethoxy; or atenilol, propanolol, atenolol, PROPYNYL or propenyloxy substituted by fluorine and/or chlorine; or cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl substituted by fluorine and/or chlorine; or phenyl or benzyl substituted by fluorine, chlorine, stands, ethyl, n - or isopropyl, n-, ISO-, sec.- or tert.-bootrom, methoxy, ethoxy, n - or isopropoxy; or together with the adjacent radical R5or R6is propane-1,3-deylam (trimethylene), butane-1,4-deylam (tetramethylene) or pentane-1,5-deylam (pentamethylene), substituted stands and/or ethyl,

moreover, the individual radicals R5and R6which are connected at the same heterocyclic groups can have identical or different meanings within the above definition.

Brand preferred:

And is a simple bond or a methylene,

R1is hydrogen, stands, ethyl, n - or isopropyl,

R2is what etiam,

R3is hydrogen, nitro, cyano, fluorine, chlorine, bromine, iodine, stands, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfonylmethyl, methylsulfonylmethyl, methoxy, ethoxy, deformedarse, triptoreline, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl or dimethylaminoethanol,

R4is nitro, cyano, fluorine, chlorine, bromine, stands, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfonylmethyl, methylsulfonylmethyl, methoxy, ethoxy, deformedarse, triptoreline, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl or dimethylaminoethanol,

R5is hydrogen, hydroxy, chlorine, bromine, stands, ethyl, n - or isopropyl, n-, ISO-, sec.- or tert.-bootrom, deformation, dikhlormetil, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, fertilisation, FORATOM, chloroethyl, defloration, defloration, fluorine-n-propylene, fluorine-ISO-propylene, chlorine-n-propylene, chlorine-ISO-propylene, methoxymethyl, ethoxymethyl, methoxyethyl, amoxicillon, methoxy, ethoxy, n - or isopropoxy, n-, ISO-, sec.- or tert.-butoxy, floratone, chloroethoxy, diflorasone, dichlorethane, triptoreline, trichlorethane, halftracks, Hortiflorexpo, ferrichloride and, methylthio, ethylthio, n - or isopropylthio, foretelling, chloroethylthio, deperately, dichloracetic, chlorpropramide, chlortetracycline, fertilitiy, methylsulfinyl, ethylsulfinyl, n - or isopropylphenyl, methylsulfonyl, ethylsulfonyl, n - or isopropylammonium, dimethylamino, property, butylthio, propylthio, butylthio, cyclopropyl, cyclopropylmethyl, cyclopropylmethoxy, phenyl or phenoxy,

R6is amino, stands, ethyl, n - or isopropyl, n-, ISO-, sec.- or tert.-bootrom, methoxy, ethoxy, methylamino, dimethylamino, cyclopropyl or cyclopropylmethyl; or together with R5is propane-1,3-deylam (trimethylene), butane-1,4-deylam (tetramethylene) or pentane-1,5-deylam (pentamethylene),

As is usually the methylene.

The subject of this invention are preferably salts of sodium, potassium, magnesium, calcium, ammonium, With1-C4-alkyl-ammonium, di-(C1-C4-alkyl)-ammonium, tri-(C1-C4-alkyl)-ammonium, Tetra-(C1-C4-alkyl)-ammonium, tri-(C1-C4-alkyl)-sulfone,5- or6-cycloalkyl-ammonium and di-(C1-C2-alkyl)-benzyl-ammonium compounds of the formula (I), in which values of m, n, A, R1, R2, R3, R4and Z such as described above.

According to the invention is preferred which raised the compounds of formula (I), in which the proposed combination of the above preferred values.

According to the invention, the most preferred are the compounds of formula (I), which proposed a combination of the above preferred values.

According to the invention is absolutely preferred are the compounds of formula (I), which proposed a combination of the above preferred brand values.

Preferred are proposed compounds of the following General formulas (IA), (IB) and (IB):

in which

R5is hydrogen, hydroxy, chlorine, bromine, stands, ethyl, n - or isopropyl, n-, ISO-, sec.- or tert.-bootrom, deformation, dikhlormetil, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, fertilisation, FORATOM, chloroethyl, defloration, defloration, fluorine-n-propylene, fluorine-ISO-propylene, chlorine-n-propylene, chlorine-ISO-propylene, methoxymethyl, ethoxymethyl, methoxyethyl, amoxicillon, methoxy, ethoxy, n - or isopropoxy,

n-, ISO-, sec.- or tert.-butoxy, floratone, chloroethoxy, diflorasone, dichlorethane, triptoreline, trichlorethane, halftracks, Hortiflorexpo, ferrichloride, methylthio, ethylthio, n - or isopropylthio, foretelling, PI is retentio, deperately, dichloracetic, chlorpropramide, chlortetracycline, fertilitiy, methylsulfinyl, ethylsulfinyl, n - or isopropylphenyl, methylsulfonyl, ethylsulfonyl, n - or isopropylammonium, dimethylamino, property, butylthio, propylthio, butylthio, cyclopropyl, cyclopropylmethyl, cyclopropylmethoxy, phenyl or phenoxy,

R6is amino, stands, ethyl, n - or isopropyl, n-, ISO-, sec.- or tert.-bootrom, methoxy, ethoxy, methylamino, dimethylamino, cyclopropyl or cyclopropylmethyl, or together with R5is propane-1,3-deylam (trimethylene), butane-1,4-deylam (tetramethylene) or pentane-1,5-deylam (pentamethylene).

The compounds of formula (IA)in which a is a methylene, are most preferred.

The abovementioned General or preferred definitions of radicals are the end products of the formula (I), and accordingly necessary for obtaining the original or intermediate products. These definitions of radicals can be combined among themselves and with the preferred definitions.

Examples of the proposed compounds of General formula (I) are described in the following groups.

Group 1

Moreover, the values of R3, (R4)n, R5and R6lead, for example, the table 1.

Table 1.

R3(position) (R4)nR5R6
N-CF3CH3
F-CF3CH3
CL-CF3CH3
VG-CF3CH3
I-CF3CH3
NO2-CF3CH3
CN-CF3CH3
CH3-CF3CH3
Och3-CF3CH3
CF3-CF3CH3
OCHF2-CF3CH3
CF3-CF3CH3
SO2CHC-CF3SN 3
N-Och3CH3
F-Och3CH3
CL-Och3CH3
Br-Och3CH3
I-Och3CH3
NO2-Och3CH3
CN-Och3CH3
CH3-Och3CH3
Och3-Och3CH3
CF3-Och3CH3
OCHF2-Och3CH3
CF3-Och3CH3
SO2CH3-Och3CH3
N-Och3CH3
F- Och3CH3
CL-Och3CH3
Br-Och3CH3
I-Och3CH3
NO2-Och3CH3
CN-Och3CH3
CH3-Och3CH3
Och3-Och3CH3
CF3-Och3CH3
OCHF2-Och3CH3
CF3-Och3CH3
SO2CH3-Och3CH3
N-OC2H5CH3
F-OC2H5CH3
CL-OC2H5CH3/sub>
Br-OC2H5CH3
I-OC2H5CH3
NO2-OC2H5CH3
CN-OC2H5CH3
CH3-OC2H5CH3
Och3-OC2H5CH3
CF3-OC2H5CH3
OCHF3-OS2H5CH3
F3-OS2H5CH3
SO2CH3-OS2H5CH3
N-N(CH3)2CH3
F-N(CH3)2CH3
CL-N(CH3)2CH3
VG- N(CH3)2CH3
I-N(CH3)2CH3
NO2-N(CH3)2CH3
CN-N(CH3)2CH3
CH3-N(CH3)2CH3
Och3-N(CH3)2CH3
CF3-N(CH3)2CH3
OCHF2-N(CH3)2CH3
F3-N(CH3)2CH3
SO3CH3-N(CH3)2CH3
N-Och3
F-Och3
CL-Och3
VG-The CH 3
I-Och3
NO2-Och3
CN-Och3
CH3-Och3
Och3-Och3
CF3-Och3
OCHF2-Och3
F3-Och3
SO2CH3-Och3
N(3-)CLCF3CH3
F(3-)CLCH3CH3
CL(3-)CLOch3 CH3
VG(3-)CLVG
CL(3-)CLCF3CH3
NO2(3-)CLCH3CH3
CL(3-)CLS3CH3
CH3(3-)CLCLCH3
Och3(3-)CLOch3CH3
CF3(3-)CLCF3CH3
OCHF2(3-)CLCH3CH3
F3(3-)CLCH3CH3
SO2CH3(3-)CLOch3CH3

Group 2

Moreover, the values of R3, (R4)n, R5and R6lead, for example, in table 2.

Group 3

Moreover, the values of R3, (R4)n, R5and R6such as described above in group 1.

Group 4

Moreover, the values of R3, (R4)n, R5and R6such as described above in group 1.

New substituted benzoylecgonine General formula (I) have a high and selective herbicide efficiency.

New substituted benzoylecgonine General formula (I) are obtained by reacting 1,3-cyclohexandione or its derivative of General formula (II)

in which

the values of m, R1and R2such as above,

with substituted benzoic acids of General formula (III),

in which

the values of n, A, R3, R4and Z are, as indicated above,

in the presence of a dehydration agent, if necessary, in the presence of one or more reactive additives and, if necessary, in the presence of a diluent, and, if necessary, the obtained compound of formula (I) transform in the usual way in salt, or in the usual way spend electrophilic or nucleophilic oxidation or reduction reactions.

The compounds of formula (I) can be converted by conventional methods into other compounds of formula (I) according to the above definition, for example, by nucleophilic substitution (e.g., R5: Cl→ OC2H5, SCH3) or by oxidation (for example, R5: CH2SC3CH2S(O)CH3).

Compounds of General formula (I) can also be principally synthesized, as is schematically represented below.

Make cyclohexandione or its derivative of General formula (II) - see above, with a reactive derivative of the substituted benzoic acids of General formula (III) above is preferably suitable for the sponding chlorides of carboxylic acids, anhydrides of carboxylic acids, cyanides, carboxylic acid, a complex of methyl or ethyl esters of carboxylic acids, if necessary, in the presence of reactive additives, for example, triethylamine ( and, if necessary, in addition to zinc chloride), and, if necessary, in the presence of a diluent, such as methylene chloride:

(Y is, for example, cyano, chlorine).

When carrying out the above transformations to obtain the compounds of formula (I) along with preferred With the benzoylation of cyclohexandione also hold O-benzoylation - see the following formula scheme (see Synthesis 1978, 925-927; Tetrahedron Lett. 37 (1996), 1007-1009, international application WO A-91/05469). Educated in this connection, O-benzyl subjected to isomerization under the reaction conditions of the proposed method to obtain the corresponding compounds With-benzoyl of the formula (I).

As starting substances are used, for example, 1,3-cyclohexanedione and 2-(3-carboxy-5-fluoro-benzyl)-5-ethyl-4-methoxy-2,4-dihydro-3H-1,2,4-triazole-3-one, thus, for the reaction at carrying out of the proposed method is possible as shown in the following diagram:

Cyclohexandione used as starting substances in the proposed pic is the be of obtaining compounds of formula (I) in General defined in the formula (II). In the formula (II) values of m, R1and R2preferably such, as already indicated above in the description of the proposed compounds of formula (I) as the preferred, most preferred and preferred brand values of m, R1and R2.

The original substance of General formula (II) are known and/or can be obtained according to known methods.

Substituted benzoic acid, used as the other starting substances, in General, defined in the formula (III). In the formula (III) values of n And R3, R4and Z is preferably such, as already indicated above in the description of the proposed compounds of formula (I) as the preferred, most preferred and preferred brand values of n, A, R3, R4and Z.

The original substance of General formula (III) are not yet known in the literature, except 2-(5-carboxy-2,4-dichloro-phenyl)-4-deformity-5-methyl-2,4-dihydro-3H-1,2,4-triazole-3-one, he 2,4-dichloro-5-(4-deformity-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazole-1-yl)-benzoic acid (CAS-Reg.- No. 90208-77-8) and 2-(5-carboxy-2,4-dichloro-phenyl)-4,5-dimethyl-2,4-dihydro-3H-1,2,4-triazole-3-one, he 2,4-dichloro-5-(4,5-dihydro-3,4-dimethyl-5-oxo-1H-1,2,4-triazole-1-yl)-benzoic acid (CAS Reg. No. 90208-76-7). The original substance of General formula (III) are the subject of the proposed invention as new substances, except 2-(5-carboxy-2,4-dichl the R-phenyl)-4-deformity-5-methyl-2,4-dihydro-3H-1,2,4-triazole-3-one and 2-(5-carboxy-2,4-dichloro-phenyl)-4,5-dimethyl-2,4-dihydro-3H-1,2,4-triazole-3-one (see the Japan patent JP-58225070 is described in Chem. Abstracts 100:209881, the Japan patent JP-02015069 is described in Chem. Abstracts 113:23929).

New substituted benzoic acid of General formula (III) are obtained by reacting a derivative of benzoic acid of General formula (IV)

in which

the values of n, A, R3, R4and Z such as described above, and

Y is cyano, carbamoyl, halogenocarboxylic or alkoxycarbonyl,

with water, if necessary, in the presence of hydrolytic additives, for example, sulfuric acid, at temperatures between 50° 120° With (see receipt).

Derivatives of benzoic acid of General formula (IV)required as intermediates are known and/or can be obtained according to known methods (see German patent application DE-A-3839480, AND DE-4239296, European patent application EP-597360, ER AND-609734, German patent application DE-A-4303676, European patent application EP-617026, German patent application DE-A-4405614, U.S. patent US-A-5378681).

New substituted benzoic acid of General formula (III) are obtained by reacting a halogen(alkyl)benzoic acids of General formula (V),

in which

the values of n, A, R3and R4such as above, and

X is halogen (preferably chlorine, fluorine or bromine),

with Conn what changes the General formula (VI)

in which

the Z value is, as mentioned above,

if necessary, in the presence of reactive additives, for example, triethylamine or potassium carbonate, and, if necessary, in the presence of a diluent, for example acetone, acetonitrile, N,N-dimethyl-formamide or N,N-dimethyl-ndimethylacetamide, at a temperature between 50° 200° With (see receipt).

Instead halogen(alkyl)benzoic acids of General formula (V) is also possible similarly to the above-described methods, the interaction of the corresponding NITRILES, amides and esters, preferably complex methyl or ethyl esters with compounds of General formula (VI). By subsequent hydrolysis by conventional methods, for example, by reacting with a solution of caustic potash in water and ethanol, you may receive the corresponding substituted benzoic acids.

Halogen(alkyl)benzoic acid of General formula (V) or the corresponding NITRILES or esters is required as the floor products are known and/or can be obtained according to known methods (see European patent application EP-90369, ER AND-93488, ER AND-399732, ER AND-480641, ER AND-609798, ER AND-763524, German patent application DE-2126720, international application WO A-93/03722, WO A-97/38977, U.S. patent USA-3978127, USA-4837333).

Other compounds of General formula (VI)required as the e intermediates are known and/or can be obtained according to known methods.

The proposed method of obtaining new substituted benzoylecgonine General formula (I) is carried out using a dehydration agent. It makes possible the use of conventional chemicals, suitable for connection with the water.

You can use, for example, dicyclohexylcarbodiimide and carbonyl-bis-imidazole.

The most preferred agent dehydration is dicyclohexylcarbodiimide.

The proposed method of obtaining new substituted benzoylecgonine General formula (I) is carried out using a reactive additives.

Use, for example, sodium cyanide, potassium cyanide, cyanhydrin acetone, 2-cyano-2-(trimethylsilyloxy)-propane and trimethylsilylacetamide.

The most preferred reactive additive is trimethylsilane.

The proposed method of obtaining new substituted benzoylecgonine General formula (I) is conducted using other reactive additives. Other reactive additives in the proposed method are usually basic organic nitrogen compounds, such as trimethylamine, triethylamine, Tripropylamine, tributylamine, ethyl-Diisopropylamine, N,N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl dicyclohexylamine, N,N-dimethyl-aniline, N,N-dimethyl-Ben is ylamine, the pyridine, 2-methyl-pyridine, 3-methyl-pyridine, 4-methyl-pyridine, 2,4-dimethyl-pyridine, 2,6-di-methyl-pyridine, 3,4-dimethyl-pyridine and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethyl-amino-pyridine, N-methyl-piperidine, 1,4-diaza-bicyclo[2,2,2]-octane, 1,5-diazabicyclo[4,3,0]-non-5-ene or 1,8-diazabicyclo[5,4,0]-undec-7-ene.

As a diluent when carrying out the proposed method, first of all inert organic solvents, for example, preferably aliphatic, alicyclic or aromatic, if necessary, halogenated hydrocarbons, such as benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, simple, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride or 1,2-dichloro-ethane; ethers, for example, a simple diethyl ether, simple, diisopropyl ether, dioxane, tetrahydrofuran, simple etilenglikolevye or etilenglikolevye ether; ketones, such as acetone, butanone or methyl isobutyl-ketone; NITRILES, such as acetonitrile, propionitrile or butyronitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or triamide hexamethylphosphoric acid; esters, for example, methyl ester acetic acid or complex ethyl ester of acetic acid; sulfoxidov, for example, dimethyl sulfoxide.

When carrying out the proposed method, the reaction temperature can be varied within wide limits. The reaction temperature is usually between 0° 150° C, preferably between 10° 120° C.

The proposed method is carried out usually under normal pressure. However, it is also possible to conduct the proposed method at elevated or reduced pressure is normally between 0.1 bar and 10 bar.

When carrying out the proposed method, the original substance is usually used in approximately equimolar amounts. However, it is also possible to use one of the components in excess. The interaction is usually carried out in a suitable diluent in the presence of a dehydration agent, and the reaction mixture is stirred for several hours at the required temperature. The processing carried out by the usual methods (see receipt).

The proposed active substances can be used as defoliants, desicants, agents inhibit the growth of grasses and preferably as agents for the destruction of weeds. Under the weeds understood all plants which grow in places where they are unwanted. Proposed substances as primary or selective herbicides depends mainly on their usage levels.

The proposed active substances can be used in the following plants.

Dicotyledonous weed species: mustard,peppergrass, bedstraw, starwort, Matricaria, Popovka, galinsoga, pigweed, nettles, Ragwort, amaranth, purslane, cocklebur, bindweed, morning glory, Highlander, sesbania, ragweed, Thistle, Thistle, sow Thistle, nightshade, Rorippa, rotala, lindernia, dead-nettle, Veronica, abutilon, dope, violet, galeopsis, poppy, cornflower, clover, Buttercup, dandelion.

Dicotyledonous cultivated plants species: cotton, soybeans, beets, carrots, beans, peas, nightshade, flax, morning glory, Vic, tobacco, tomato, peanuts, cabbage, lettuce, cucumber, pumpkin.

Monocotyledonous weeds: barnyard grass, spickle, millet, weed, Timothy, bluegrass, fescue, Eleusis, brachiaria, ryegrass, brome, oat, syt, sorghum, wheat grass, cynodon, Monochoria, arrowheads, bolotnitsa, reed, buckwheat, bent grass, Alopecurus.

Dicotyledonous cultivated plants species: rice, tea, wheat, barley, oats, rye, sorghum, millet, sugarcane, pineapple, asparagus, onions.

Application of the proposed active substances is in no way limited to these species, and also equally apply to other plants.

Depending on the concentration of the compounds are suitable for the complete destruction of weeds, for example, industrial equipment and rail tracks, roads and squares with or without the presence of trees. You can also use compounds for combating weeds in perennial cultures, for example, if p is a CORF wood, ornamental, fruit, wine, citrus, walnut, banana, coffee, tea, rubber, oil-palm, cocoa, fruit and hop crops, ornamental lawns and sports fields, pastures, and for the selective combating of weeds in annual crops.

The proposed compounds of formula (I) are most suitable for the selective combating of monocotyledonous and dicotyledonous weeds in monocotyledonous cultivated plants before the shoot and after the shoot of the plants.

The active substance is processed in the usual formulations, such as solutions, emulsions, wettable powders, suspensions, powders, pollinating agents, pastes, soluble powders, granulated products, concentrates, emulsions and suspensions, natural and synthetic substances impregnated with active ingredient, as well as micro-capsules in polymeric substances.

These compounds get in a known manner, for example by mixing the active substances with solvents, for example, liquid solvents and/or solid fillers, if necessary, using surfactants, such as emulsifiers and/or dispersants and/or foam.

If the diluent is water, you can use, for example, organic solvent as an auxiliary solvent. In the operation of liquid solvents, mainly use: aromatic hydrocarbons, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons, e.g. cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethylsulfoxide, and water.

As particulate fillers are used: for example ammonium salts and natural mineral powder, for example, kaolin, alumina, talc, chalk, attapulgite, montmorillonite or diatomaceous earth, and synthetic mineral powder, for example, highly dispersed silicic acid, alumina and silicates; as fillers granular products used: for example, crushed and fractionated natural rocks such as calcite, marble, pumice, thick, dolomite, and also synthetic granulated products of inorganic and organic powder and granular products of the organic material is, for example, sawdust, coconut kernel, corn cobs and stalks of tobacco; as emulsifiers and foaming agents are used: for example nonionic and anionic emulsifiers, for example, esters of polyoxyethylene and fatty acids, simple ether and polyoxyethylene fatty alcohol, for example, a simple alkylarylsulphonates ether, alkyl sulphonates, alkyl sulphates, arylsulfonate, and also protein hydrolysates; as dispersant use: for example lignin-sulphite lye and methylcellulose.

The compositions may contain adhesive agents, such as carboxymethylcellulose, natural and synthetic polymers in the form of powder, granules or latex, for example, gum Arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as Catalina and lecithins, and synthetic phospholipids. Other additives can be mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide, Prussian blue, and organic dyes, for example, alizarin dyes, azo dyes and metallophthalocyanine dyes and coloring of nutrients, for example, salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The compositions usually contain 0.1 to 95 wt. -%, preferably 0.5 to 90 wt%. AK is active substances.

The proposed active substances can be used as such or in part, and in a mixture with known herbicides, which are used for pest control, and it is possible to use the finished composition or mixing in the tank.

For mixing use a known herbicides, for example,

acetochlor, alfthan(-sodium), klonipin, alachlor, aloxide(-sodium), ametrine, amithlon, amidosulfuron, anilofos, Azul, atrazine, azafenidin, azimsulfuron, benazolin(-ethyl), benvenisty, encultured(-methyl), bentazon, benzefoam, benzoylperoxy(-ethyl), bialaphos, bifenox, bispyribac(-sodium), bromobutyl, bromophenoxy, bromoxynil, butachlor, butoxide, butylate, catastropy, galaxidi, carbetamide, carfentrazone(-ethyl), chlorethoxyfos, chloramben, ozone chloride, chlorimuron(-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinidon(-ethyl), cinmetacin, kinokultura, clethodim, clodinafop(-propargyl), clomazone, clomipram, clopyralid, cloperastine(-methyl), karasulu(-methyl), cumyluron, cyanazine, cybutryne, cycloate, cycloaliphatic, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), dicloflam, diacetyl(-ethyl), difenzoquat, diflufenican, diflubenzuron, dimefuron, gameparty, dimethachlor, deltamethrin, dimethenamid, Dimexidum, d is nitramine, diphenamid, Diquat, dithiopyr, Diuron, damron, apoprotein, ARTS, asbroker, ethalfluralin, atomiculture(-methyl), ethofumesate, idoxifene, ethoxysulfuron, etamesonic, fenoxaprop(-P-ethyl), planrep(-isopropyl), planrep(-isopropyl-L), planrep(-methyl), flazasulfuron, fluazifop(-P-butyl), plazoleta, flucarbazone, flufenacet, flumetsulam, flumiclorac(pencil), flumioxazin, flubiprofen, flumetsulam, fluometuron, verkleiden, foreglimpse(-ethyl), flupoxam, flypaper, flupyrsulfuron(-methyl-sodium), flurenol(-butyl), fluridone, fluroxypyr(-meptyl), flurried, flurtamone, fluthiacet(-methyl), flutamide, fomesafen, glufosinate(-ammonium), glyphosate(-isopropylammonium), galasoft, haloxyfop(-ethoxyethyl), haloxyfop(P-methyl), hexazinone, imazamethabenz(-methyl), imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron, ioxynil, isopropylene, Isoproturon, Sauron, isoxaben, isoxaflutole, isoxaflutole, isocaporate, lactofen, lenacil, linuron, MSRA, MSR, mefenacet, mesotrione, metamitron, metazachlor, methabenzthiazuron, metaventure, metobromuron, (alpha)metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron, nitroanilide, napropamide, neburon, nicosulfuron, norflurazon, arrancars, oryzalin, oxadiargyl, oxadiazon, ACS is sulfuron, oxacyclobutane, oxilorphan, paraquat, pelargonia acid, pendimethalin, phenoxazone, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), procarbazine, prometryn, propachlor, propanil, propaquizafop, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraflufen(-ethyl), pyrazolate, pyrazosulfuron(-ethyl), paradoxien, perbenzoic, perimutter, pyridate, Perminova(-methyl), pyrithiobac(-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop(-P-ethyl), quizalofop(-R-tefuryl), rimsulfuron sethoxydim, Simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron-(methyl), sulfosate, sulfosulfuron, tabulam, tebuthiuron, tepraloxydim, terbutylazine, terbutryn, tanishlar, leflunamide, thiazopyr, thidiazuron, thifensulfuron(-methyl), thiobencarb, thiocarbonyl, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and triflusulfuron.

Also is it possible mixing with other active substances, for example, fungicides, insecticides, acaricides, nematicides, protective substances from damage by birds, nutrients and agents for improving soil structure.

The active substance can be used in the form of a composition or with the addition of a diluent, such as, for example, ready-to-use solutions, suspensions, emulsions, powders, the asty and granular products. The introduction of active substances is carried out in the usual way, for example, by spraying, atomizing, irrigating, spilling.

The proposed active substances can be introduced both before and after germination of the plants. Also the active substances can be introduced into the soil before sowing.

The used quantity of active substances may vary within wide limits, basically, it depends on the desired effect. The amount used is usually 1 g-10 kg of active substance per hectare of land area, preferably 5 g to 5 kg per hectare

Receipt and use of the proposed active substances result in the following examples.

Examples retrieve

Example 1

1.2 g (3,48 mmol) 5-ethoxy-4-methyl-2-(carboxy-5-trifluoromethyl-benzyl)-2,4-dihydro-3H-1,2,4-triazole-3-it is placed in 30 ml of acetonitrile and added 0.39 g (3,48 mmol) of 1,3-cyclohexandione and 0,76 g (3.7 mmol) of DICYCLOHEXYL-carbodiimide at room temperature (about 20°). The reaction mixture was stirred overnight (about 15 hours) at room temperature and then mixed with 1.0 ml (7.0 mmol) of triethylamine and 0.10 ml (1,39 mmol) trimethylsilylacetamide and incubated for 3 hours at room temperature. The mixture is then stirred with 100 ml of 5%sodium carbonate solution, which is then removed with DICYCLOHEXYL eveny, and the alkaline aqueous phase is repeatedly extracted with ethyl acetate. Then in the aqueous phase adjust pH 2 by adding 35%hydrochloric acid, and the aqueous phase is repeatedly extracted with methylene chloride. The methylene chloride phase is dried over sodium sulfate and concentrate.

As an amorphous residue obtain 0.8 g (52% of theory) 5-ethoxy-4-methyl-2-[2-(2,6-dioxo-cyclohexyl-carbonyl)-5-trifluoromethyl-benzyl]-2,4-dihydro-3H-1,2,4-triazole-3-one.

logP (determined at pH=2): 2,70.

Example 2

To a suspension of 2.15 g (6.5 mmol) of 2-(4-carboxy-3-chloro-phenyl)-4-methyl-5-trifluoromethyl-2,4-dihydro-3H-1,2,4-triazole-3-one, or 0.83 g (7.2 mmol) of 1,3-cyclo-hexanedione and 40 ml of acetone is added a solution of 1.5 g (7.2 mmol) dicyclo-hexylcaine in 40 ml of acetone, and the reaction mixture is heated for 16 hours at a temperature of 20° C. Then added to the mixture of 1.3 g (13 mmol) of triethylamine and 0.26 g (2.6 mmol) of trimethylsilylacetamide, and the reaction mixture is stirred for 4 hours at a temperature of 20° C. the mixture is Then mixed with 180 ml of 2%solution of sodium carbonate and filtered. The mother liquor is extracted with a complex ester of acetic acid. Then the aqueous phase is acidified with 2N-hydrochloric acid and extracted with methylene chloride. The organic phase is dried, concentrated in a water jet vacuum and digeridoo with simple diethyl and petroleum ether is m Precipitated crystalline product is isolated via filtration.

Obtain 1.6 g (59% of theory) of 2-[4-(2,6-dioxocyclohexa)-3-trichlorophenyl]-4-methyl-5-trifluoromethyl-2,4-dihydro-3H-1,2,4-triazole-3-one with a melting point (Fp) 182° C.

logP (determined at pH=2):3,13.

Analogously to examples 1 and 2 and in accordance with the General description of the proposed method is also possible, for example, compounds of formula (I) or formula (IA-3), (IB-2), (IB-2) or (Iك), are given in tables 3 and 4.

Educt of the formula (III)

Example (III-1)

4.5 g (15 mmol) of 2-(3-chloro-4-cyano-phenyl)-4-methyl-5-trifluoromethyl-2,4-dihydro-3H-1,2,4-triazole-3-absorb it in 80 ml of 60%sulfuric acid, and the resulting mixture heated for 6 hours in the presence of phlegmy. The mixture is then cooled the ri room temperature and the precipitated crystalline product is isolated via filtration.

Obtain 4.5 g (91% of theory) of 2-(3-carboxy-4-chloro-phenyl)-4-methyl-5-trifluoromethyl-2,4-dihydro-3H-1,2,4-triazole-3-one with a melting point (Fp) 223° C.

Example (III-2)

2 g (4.9 mmol) of 5-bromo-4-methyl-2-(2-etoxycarbonyl-5-trifluoromethyl-benzyl)-2,4-dihydro-3H-1,2,4-triazole-3-one (see example IV-1) dissolved in 30 ml of 10%sodium hydroxide solution with ethanol and heated for 2 hours in the presence of phlegmy. The reaction mixture was concentrated in a water jet vacuum, absorbed in 20 ml of water and acidified with diluted hydrochloric acid. Precipitated solid is filtered and dried.

As a solid product is obtained 1.2 g (71% of theory) 5-ethoxy-4-methyl-2-(2-carboxy-5-trifluoromethyl-benzyl)-2,4-dihydro-3H-1,2,4-triazole-3-one.

logP: 2,18a)

Example (III-3)

13,4 g (35 mmol) of 4-methyl-5-trifluoromethyl-2-(2,6-dichloro-3-methoxycarbonyl-benzyl)-2,4-dihydro-3H-1,2,4-triazole-3-it is placed in 60 ml of 1,4-dioxane and slowly added a solution of 1.54 g (a 38.5 mmol) of sodium hydroxide in 20 ml of water at room temperature. The reaction mixture is stirred for 150 minutes at a temperature of 60° and then concentrated in a water jet vacuum. The residue is dissolved in 100 ml of water, and the solution adjust pH 1 by adding concentrated hydrochloric acid. Fallen in this crystalline powder isolate through which illitracy.

Get 11.7 g (90% of theory) of 4-methyl-5-trifluoromethyl-2-(2,6-dichloro-3-carboxy-benzyl)-2,4-dihydro-3H-1,2,4-triazole-3-one with a melting point (Fp) 207° C.

Analogously to example (III-1)to(III-3) also may receive, for example, compounds of General formula (III), which are given in table 5.

Educt of the formula (IV)

Example (IV-1)

Stage 1

10 g (49 mmol) of 2-methyl-4-trifluoromethyl-benzoic acid are dissolved in 150 ml of ethanol and add 1 ml of concentrated sulfuric acid, then remaut in the presence of phlegmy within 24 hours. The solution is concentrated and placed in methylene chloride and extracted with saturated aqueous sodium bicarbonate. The methylene chloride phase is dried over sodium sulfate and concentrated in a water jet vacuum.

As an amorphous residue receive 9 g (80% of theory) of a compound ethyl ester of 2-methyl-4-trifluoromethyl-benzoic acid.

Stage 2

9 g (39 mmol) of a compound ethyl ester of 2-methyl-4-trifluoromethyl-benzoic acid are dissolved in 200 ml of carbon tetrachloride and add 7 g (39 mmol) of N-bromo-succinimide and 0.1 g of dibenzoylperoxide. The mixture is then heated for 6 hours in the presence of phlegmy, besieged succinimide filtered and the filtrate is concentrated in a water jet vacuum.

Get 12 g of amorphous residue, which in addition to complex ethyl ester 2-methyl bromide-4-trifluoromethyl-benzoic acid further comprises 17% of complex ethyl ester of 2,2-dibromomethyl-4-trifluoromethyl-benzoic acid and 12% of complex ethyl ester of 2-methyl-4-trifluoromethyl-benzoic acid.

Stage 3

4 g complex ethyl ester 2-methyl bromide-4-trifluoromethyl-benzoic acid (about 70%) and 2.28 g (12.8 mmol) of 5-bromo-4-methyl-2,4-dihydro-3H-1,2,4-triazole-3-one are dissolved in 150 ml of acetonitrile, added to 5.3 g (38.4 mmol) of potassium carbonate and the mixture is heated for 2 hours at the intensive mixing in the presence of phlegmy. The reaction mixture is absorbed in water and extracted with methylene chloride. The collected methylene chloride phase is dried over sodium sulfate, concentrated in a water jet vacuum and chromatographic.

As an amorphous product is obtained 2 g (38% of theory) of 5-bromo-4-methyl-2-(2-etoxycarbonyl-5-trifluoromethyl-benzyl)-2,4-dihydro-3H-1,2,4-triazole-3-one.

1H-NMR (nuclear magnetic resonance) (CDCl3that δ ): 5,46 ppm.

Example (IV-2)

6.7 g (40 mmol) of 4-methyl-5-trifluoromethyl-2,4-dihydro-3H-1,2,4-triazole-3-it is placed in 150 ml of acetonitrile and added 11 g (80 mmol) of potassium carbonate. The mixture is then heated at a temperature of 50° and added dropwise to 13.1 g (44 mmol) of a compound methyl ester 3-methyl bromide-2,4-dichloro-benzoic acid in 20 ml of acetonitrile with stirring. Then the reaction mixture is heated for 15 hours under stirring in the presence of phlegmy, concentrated in a water jet vacuum, the residue is absorbed in methylene chloride, washed with 1N-hydrochloric acid, dried with sodium sulfate and filtered. The filtrate is concentrated under reduced pressure, the residue digeridoo with simple petroleum ether and the precipitated crystalline product is isolated via filtration.

Obtain 14.9 g (97% of theory) of 4-methyl-5-trifluoromethyl-2-(2,6-dichloro-3-methoxycarbonyl-benzyl)-2,4-dihydro-3H-1,2,4-triazole-3-the point PL is the exercise (Fp)109° C.

Analogously to example (IV-1 and IV-2) also may receive, for example, compounds of General formula (IVa), which are shown in table 6.

Determination of the logP values specified in the tables, is conducted according to EEC-Directive 78/831 Annex V.A8 through GHUR (liquid chromatography high resolution) on a column with treatment phases (18). Temperature: 43° C.

(a) a solvent for the determination in the acidic environment: 0.1% aqueous phosphoric acid, acetonitrile; linear gradient of 10-90% acetonitrile - the corresponding results measured what I marked in the tables under a).

(b) solvents to determine in a neutral environment: from 0.01 molar aqueous phosphate buffer solution, acetonitrile; linear gradient of 10-90% acetonitrile - the corresponding measurement results are marked in the tables underb).

Examinations carried out using unbranched Alkan-2-ones (with 3 to 16 carbon atoms), in which the logP values are known (determination of the logP values was performed at a certain time through a linear interpolation between two successive alkanoate).

The maximum value of λ determined by the UV spectra of 200 nm - 400 nm at the maximum of the chromatographic signals.

Examples of use

Example

Testing before the shoot of the plant:

solvent: 5% of the mass. acetone

emulsifier: 1% of the mass. simple alkylarylsulphonates ether

1% of the mass. the active substance is mixed with the specified amount of solvent, add the specified amount of emulsifier, and the concentrate is diluted with water to the preferred concentration.

Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is sprayed with the active substance so that the preferred amounts of active substances had on the unit square. The concentration of the composition is determined so that the preferred number of actively what about the substance was in 1000 litres of water per hectare.

Three weeks later analyze the degree of plant damage in % damage in comparison with the growth of the untreated control plants.

0% = result not available (untreated control samples)

100% = total destruction of weeds

In this test the compounds according to examples of the preparation of 1 and 10 demonstrate the high effectiveness against weeds when enough good compatibility with cultivated plants, such as corn.

Table A: testing before the shoot of plants in the greenhouse.
The active substance according to example receivingThe amount used (g l/ha)CornSytAbutilonAmaranthMustard
1000-100100100100
100001009010090

Example B

Testing post-emergent plants:

solvent: 5% of the mass. acetone

emulsifier: 1% of the mass. simple alkylarylsulphonates ether

To obtain the final form of the active substance 1% of the mass. the active substance is mixed with the specified amount of solvent, add the specified amount of emulsifier, and the concentrate is diluted with water to the preferred concentration.

The test plants with a height of 5-15 cm are sprayed with the finished form of the active substance so that the preferred amounts of active substances had on the unit square. The concentration of the composition is determined so that the preferred amount of active substance was in 1000 litres of water per hectare.

Three weeks later analyze the degree of plant damage in % damage in comparison with the growth of the untreated control plants.

0% = result not available (untreated control samples)

100% = total destruction of weeds

In this test the compounds according to examples of the preparation of 1 and 10 demonstrate the high effectiveness against weeds when enough good compatibility with cultivated plants, for example, ku is urusai.

1. Substituted benzoylecgonine General formula (I),

in which

m is 0 or 1,

n is 0 or 1,

A represents a simple bond or alcander (alkylen) with 1-4 carbon atoms,

R1means hydrogen or unsubstituted alkyl with 1-6 carbon atoms,

R2means methyl,

R3means hydrogen, nitro, cyano, halogen, substituted with halogen alkyl with 1-4 carbon atoms; alkoxy with 1-4 carbon atoms, or alkylsulfonyl with 1 to 4 carbon atoms,

R4means nitro, halogen, unsubstituted or substituted with halogen alkyl with 1-4 carbon atoms,

Z means a heterocyclic group of the formula

the connection drawn strokes, is a double bond,

Q denotes an oxygen or sulphur,

R5means hydrogen, halogen; unsubstituted or substituted with halogen alkyl with 1-6 carbon atoms; alkoxy with 1-4 carbon atoms; alkylthio, alkanity, alkylsulfonyl or alkylsulfonyl with 1 to 6 carbon atoms; dialkylamino with 2-8 carbon atoms; or cycloalkyl with 3-6 carbon atoms,

R6means alkyl or alkoxy with 1-4 carbon atoms; or cycloalkyl with 3-6 carbon atoms; or together with the adjacent radical R5means alcander with 3-5 carbon atoms; or

in that case, if two adjacent radicals R5and R5are double bonds, together with the adjacent radical R5also mean anthropo.

2. Substituted benzoylecgonine according to claim 1, characterized in that

m is 0 or 1,

n is 0 or 1,

And is a simple bond or a methylene,

R1means hydrogen; methyl, ethyl, n - or isopropyl, n-, ISO - or sec.- butyl,

R2means methyl,

R3means hydrogen, nitro, cyano, fluorine, chlorine, bromine; methyl, ethyl, n - or isopropyl, optionally substituted by fluorine, methoxy, ethoxy or methylsulphonyl,

R4means nitro, chloro; methyl, ethyl, n - is whether isopropyl, optionally substituted by fluorine,

Z means a heterocyclic group of the formula

the connection drawn strokes, is a double bond,

Q denotes an oxygen or sulphur,

R5means hydrogen, bromine; methyl, ethyl, n - or isopropyl, optionally substituted by fluorine, chlorine; methoxy, ethoxy, n - or isopropoxy; methylthio, ethylthio, n - or isopropylthio; methylsulphonyl, dimethylamino, or

R6means methyl, ethyl, n - or isopropyl; methoxy, ethoxy or cyclopropyl;

or together with the adjacent radical R5means propane-1,3-diyl (trimethylene) or butane-1,4-diyl (tetramethylene); or

in that case, if two adjacent radicals R5and R5are double bonds, together with the adjacent radical R will also mean anthropo.

3. Substituted benzoylecgonine according to claim 1, characterized General formula (IA),

in which

m is the number 0 or 1,

n is the number 0 or 1,

A represents a simple bond or methylene,

Q means oxygen,

R1means hydrogen or methyl,

R2means methyl,

R 3means hydrogen, nitro, cyano, fluorine, chlorine, bromine, trifluoromethyl, methoxy or methylsulphonyl,

R4means nitro, chloro, trifluoromethyl or methyl,

R5means methyl, ethyl, trifluoromethyl; methoxy, ethoxy, optionally substituted by fluorine; n - or isopropoxy, methylthio, methylsulphonyl, dimethylamino or cyclopropyl, and

R6means methyl, methoxy, ethoxy or cyclopropyl.

4. Substituted benzoylecgonine according to claim 1, characterized General formula (1B),

in which

m is the number 0 or 1,

n is the number 0 or 1,

A represents a simple bond or methylene,

Q means oxygen,

R1means hydrogen or methyl,

R2means methyl,

R3means hydrogen, nitro, cyano, fluorine, chlorine, bromine, trifluoromethyl, methoxy or methylsulphonyl,

R4means nitro, chlorine or trifluoromethyl,

R5means methyl, ethyl, trifluoromethyl; methoxy, ethoxy, n - or isopropoxy, methylthio, ethylthio, isopropylthio, methylsulphonyl, dimethylamino or cyclopropyl, and

R6means methyl, ethyl, ethoxy or cyclopropyl.

5. Substituted benzoylecgonine according to claim 1, characterized General formula (IB),

in the cat the swarm

n is the number 0 or 1, a represents a simple bond or methylene, Q means oxygen, R1means hydrogen,

R3means hydrogen, nitro, cyano, fluorine, chlorine, bromine, methoxy or methylsulphonyl,

R4means nitro, chlorine, methyl or trifluoromethyl,

R5means methyl, ethyl, trifluoromethyl, ethoxy, n - or isopropoxy, methylthio, methylsulphonyl or cyclopropyl, and

R6means methyl, ethoxy or cyclopropyl.

6. Substituted benzoic acid of General formula (III)

in which

the values of n, A, R3, R4and Z such as described in one of claims 1 to 5, excluding the compounds 2-(5-carboxy-2,4-dichloro-phenyl)-4-deformity-5-methyl-2,4-dihydro-3H-1,2,4-triazole-3-one and 2-(5-carboxy-2,4-dichloro-phenyl)-4,5-dimethyl-2,4-dihydro-3H-1,2,4-triazole-3-one.

7. Herbicide agent, characterized in that it contains one substituted benzoylchloride according to one of claims 1 to 5, and the usual fillers.



 

Same patents:

The invention relates to organic chemistry, in particular to the compounds representing amide of the formula I:

in which * denotes an asymmetric carbon atom; R1and R2independently from each other represent a hydrogen atom or halogen, amino, hydroxyamino-, nitro-, cyano-, sulfamidihappo, (ness.)alkyl, -OR5, -C(O)OR5, PERFLUORO(ness.)alkyl, (ness.)alkylthio, PERFLUORO(ness.)alkylthio, (ness.)alkylsulfonyl, PERFLUORO(ness.)alkylsulfonyl or (ness.)alkylsulfonyl; R3denotes cycloalkyl containing from 3 to 7 carbon atoms, or (ness.)alkyl containing from 2 to 4 carbon atoms; R4means (O)other40or unsubstituted or monosubstituted five - or six-membered heteroaromatic ring bound ring carbon atom of the amino group, and a five - or six-membered heteroaromatic ring contains from 1 to 3 heteroatoms selected from sulfur atoms, oxygen, and nitrogen, with one heteroatom is a nitrogen atom, which is adjacent to the connecting ring carbon atom; this is monosubstituted heteroaromatic ring monogamist on the ring angle is found (ness.)alkyl, halo-, nitro-, cyano, -(CH2)n-OR6, -(CH2)n-C(O)OR7, -(CH2)n-C(O)OTHER6, -C(O)-C(O)OR8and -(CH2)n-OTHER6or its pharmaceutically acceptable salts

The invention relates to new heterocyclic substituted phenoxyacetamide, methods for their preparation and use as a means protivodiareynogo

The invention relates to new biologically active compounds

The invention relates to new medicines, in particular to the field of synthesis of compounds with antidiuretic activity, and can be applied in medicine, urology

The invention relates to new medicines, namely the synthesis of compounds with antiviral activity, and can be applied in medicine, Virology
The invention relates to the field of heterocyclic chemistry, in particular to an improved method for producing 2-amino-5-chloro-1,3,4-thiadiazole - an intermediate product in the synthesis of dyes, herbicides, fungicides and pharmaceuticals

FIELD: organic chemistry, chemical technology, agriculture, pharmacy.

SUBSTANCE: invention relates to a method for preparing chlorobenzoxazoles of the formula (I):

wherein R1, R2 and R3 are determined as in cl. 1; in the case (a) R3 means hydrogen, halogen atom, cyano-, nitro-group, halogenalkyl with 1-5 carbon atoms, halogenalkoxy-group with 1-5 carbon atoms, alkyl with 1-5 carbon atoms, alkoxy-group with 1-5 carbon atoms, phenyl or phenoxy-group; or in the case (b) R3 means chlorine atom. Method involves interaction of benzoxazoles of the formula (II) given in the invention description with chlorinating agent in the presence of acid catalyst to form the monochlorinated product (I), or in the case (b) with excess of chlorinating agent to form dichlorinated product (I) wherein R3 means chlorine atom. Chlorobenzoxazoles are used as intermediate substances for synthesis of biologically active compounds, agents for protection of plants and pharmaceuticals preparations. Invention provides selective synthesis of chlorobenzoxazoles with high yields.

EFFECT: improved preparing method.

10 cl, 7 ex

The invention relates to certain new compounds, to a method for producing these compounds, to pharmaceutical compositions containing such compounds and for using such compounds and compositions in medicine

The invention relates to new chemical substances, which have valuable pharmacological properties, more particularly to a nitrogen-containing heterocyclic compounds of General formula I

< / BR>
where X is oxygen or sulfur;

Y is carbon or nitrogen;

Z is carbon or nitrogen, and Y and Z are not simultaneously mean nitrogen;

R1and R2independent from each other and denote hydrogen, alkyl with 1 to 6 carbon atoms, halogen, trifluoromethyl, nitrile, alkoxy with 1 to 6 carbon atoms, a group of CO2R7where R7means hydrogen or alkyl with 1 to 6 carbon atoms, group-C(O)NR8R9where R8and R9not dependent from each other and denote hydrogen, alkyl with 1 to 3 carbon atoms, methoxy or together with the nitrogen form a morpholine, pyrrolidine or piperidine-NR10R11where R10and R11denote hydrogen or alkyl with 1 to 6 carbon atoms, group-C(O)R12where R12means alkyl with 1 to 6 carbon atoms, group-SO2R12where R12has the specified value, -NHC(O)R12where R12has the specified value, -NHSO2R12where R12has a specified value, and-SO2NR13R14where R13and R142R12where R12has the specified value, -NHC(O)R12where R12has the specified value, -NHSO2R12where R12has the specified value, -SO2NR13R14where R13and R14have a specified value, a nitrogroup, 1-piperidinyl, 2-, 3 - or 4-pyridine, morpholine, thiomorpholine, pyrrolidine, imidazole, unsubstituted or substituted at the nitrogen by alkyl with 1 to 4 carbon atoms, 2-thiazole, 2-methyl-4-thiazole, dialkylamino with 1 to 4 carbon atoms in each alkyl group, or alkilany ether with 1 to 4 carbon atoms;

R4an ester of formula-CO2R16where R16means alkyl with 1 to 4 carbon atoms, the amide of formula C(O)NR17R18where R17and R18independent from each other and denote hydrogen, alkyl with 1 to 2 carbon atoms, methoxy or together with the nitrogen form a morpholine, piperidine or pyrrolidine, phenyl, unsubstituted or substituted by residues from the group comprising halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, 3-methyl-1,2,4-oxadiazol-5-yl, 2 - or 3-thienyl, 2-, 3 - or 4-pyridyl, 4-pyrazolylborate 4 stands, the ketone of the formula C(O)R19'where R19means alkyl with 1 to 3 carbon atoms, phenyl or 1-Mei-2-yl, a simple ester of the formula-CH2OR20where R20means alkyl with 1 to 3 carbon atoms, thioether formula-CH2SR20where R20has the specified value, the group CH2SO2CH3amines of the formula-CH2N(R20)2where R20has the specified value, the remainder of the formula-CH2NHC(O)R21where R21means methyl, amino or methylamino - group-CH2NHSO2Me2where Me denotes methyl carbamate of the formula CH2OC(O)NHCH3;

R5and R6independent from each other and denote hydrogen or methyl;

n is 0,1 or 2,

Provided that the substituents are not simultaneously have the following meanings: Y and Z is carbon, R1or R2hydrogen, halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, cyano, nitro, trifluoromethyl, R3unsubstituted phenyl and R4group-C(O)OR16'where R16'means hydrogen, alkyl, alkenyl or quinil, group-C(O)N(R18')(R19'), where R18'and R19'denote hydrogen, alkyl with 1 to 6 carbon atoms, phenyl, alkoxy or together with the nitrogen form pyrrolidine, piperidine or morpholine, cyanotic, unsubstituted phenyl and 4-imidazole,

in the form of a racemate or an individual enantiomers and their salts, are inhibitors of leukotriene biosynthesis

The invention relates to benzoxazolinone, more specifically to certain benzoxazolinone, substituted not only in position 6 amine side chain, but also in the provisions of 4,5 or 7 of the benzene ring

The invention relates to a method for 4,5,6-trichloroanisole-2, which finds application as an antiseptic

The invention relates to androidiani carboxanilides, compositions based on them and the way to deal with arteriotomy and can be used in agriculture

FIELD: organic chemistry, herbicides, agriculture.

SUBSTANCE: invention relates to new substituted benzoylketones of the general formula (I): , all possible tautomeric forms and possible salts that can represent active substance as a component of herbicide agent. In the formula (I) A means (C1-C4)-alkyl; R1 means cyclo-(C3-C6)-alkyl; R2 means hydrogen atom (H), cyano-group (CN); R3 means hydrogen atom (H), halogen atom, CF3, (C1-C4)-alkylsulfonyl; R4 means halogen atom; X means groups: or wherein R5 means (C1-C4)-alkyl, (C1-C4)-alkoxy-group, (C1-C4)-alkylthio-group, di-(C1-C6-alkyl)-amino-group; R6 means (C1-C4)-alkyl, (C1-C4)-alkoxy-group, cyclo-(C3-C6)-alkyl; n = 0 or 1 including all possible tautomeric forms and possible salts. Compounds of the formula (I) elicit herbicide activity and can be used in herbicide composition.

EFFECT: valuable properties of compounds.

3 cl, 1 sch, 3 tbl, 13 ex

The invention relates to new substituted phenyl derivatives, which are strong blockers chlorine ion channels and as such are useful in the treatment of sickle cell anemia, cerebral edema that accompanies ischemia or tumor, diarrhea, hypertension (diuretic), osteoporosis and to reduce the intraocular pressure for the treatment of disorders such as glaucoma

The invention relates to new amide derivatives of General formula (I) or their salts, where a means thiazolidin, imidazoline, triazoline, benzimidazolyl, benzothiazolyl, thiadiazolyl, imidazopyridine or imidazothiazole; X is a bond, -NR5-, -NR5CO-, -NR5CONH-, NR5SO2-, -NR5C(= NH)NH-; R1means H, lower alkyl, aryl, pyridyl, thienyl, furyl, thiazolyl, benzimidazolyl, imidazopyridine, triazolyl, thiadiazolyl, imidazolyl, imidazothiazoles, benzothiazolyl, cyclohexyl, which may be optionally substituted with halogen, lower alkyl, -OH, -CN, -NO2, -CF3, -NH2, -O-lower alkyl, and the Deputy of the lower alkyl may be substituted by phenyl, naphthyl, fullam, tanila or pyridium;2a, R2bmean H or lower alkyl; R3means hydrogen or lower alkyl; R4a, R4bmean H or HE, or taken together form a group =O or =N-O-lower alkyl; R5means H or lower alkyl
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