Substituted derivatives of pyrazolylborate and their use as herbicides

 

(57) Abstract:

The invention relates to new substituted pyrazolylborate General formula (I) in which R1-R6have the meanings given in the description of the invention. These compounds possess herbicide action. The proposed tools with herbicide action on the basis of these new compounds. Effect: increase of herbicide action. 2 S. and 2 C.p. f-crystals, 2 PL.

The invention relates to new substituted pyrazolylborate, the way they are received, as well as intermediate products for their preparation and to their use as tools with herbicide action.

It has long been known that pyrazoles have a weed-killing properties (international patent application 94/08999).

From U.S. patent 5405829 known pyrazolylborate with the unsubstituted amino group as compounds with herbicide activity.

In the international patent application 94/08999 describes among other things pyrazolylborate with substituted amino group with a weed-killing activity.

From international patent application 96/09303 also known substituted pyrazolylborate with herbicide properties is appropriate herbicide action arise related to selectivity problems in respect of major crops.

The objective of the presented invention to provide new substituted pyrazolylborate who are deprived of such a defect and that its biological properties superior to previously known compounds.

It was found that herbicide activity exceeds the activity of the known compounds, have substituted pyrazolylborate General formula I

< / BR>
in which R1means alkyl with 1-4 carbon atoms,

R2means alkyl with 1-4 carbon atoms, alkylthiols with 1-4 carbon atoms in the alkyl, alkylation with 1-4 carbon atoms in the alkyl, alkylsulfonyl with 1 to 4 carbon atoms in the alkyl, alkoxygroup with 1-4 carbon atoms or one or several times substituted by halogen alkyl with 1-4 carbon atoms, alkylthiols with 1-4 carbon atoms, alkylsulfonyl with 1 to 4 carbon atoms in the alkyl or alkoxygroup with 1-4 carbon atoms,

R1and R2together form a group -(CH2)m-,

R3means hydrogen or halogen,

R4means hydrogen or alkyl with 1-4 carbon atoms,

R5means hydrogen, a nitrogroup, langroup, -COOR7group

< / BR>
or

< / BR>
R6means one of the groups

< / BR>
< / BR>
R8and R9together with the adjacent nitrogen atom form a 5 - or 6-membered saturated a heterocycle,

R10denotes hydrogen, alkyl with 1-4 carbon atoms, substituted one or more times by halogen alkyl with 1-4 carbon atoms,

R11means alkyl with 5 to 8 carbon atoms, cycloalkyl with 3-6 carbon atoms, alkenyl with 2-6 carbon atoms, quinil with 3-6 carbon atoms, one or more times, identically or differently substituted with halogen, langroup, a hydroxyl group or alkoxygroup with 1-4 carbon atoms, alkyl with 1-6 carbon atoms, cycloalkyl with 3-6 carbon atoms, alkenyl with 2-6 carbon atoms or quinil with 3-6 carbon atoms, containing one or more oxygen atoms in the chain alkyl of 2-8 carbon atoms, cycloalkyl with 3-8 carbon atoms, (C3-C8-cycloalkyl-(C1-C4)-alkyl, alkenyl with 3-8 carbon atoms or quinil with 3-8 carbon atoms, (C1-C4-alkoxycarbonyl-(C1-C4)-alkyl, which may optionally be substituted with halogen, or (C1-C4-alkoxycarbonyl-(C2-C4)-alkenyl, which is optionally substituted by halogen, or is likely to mean the group -(CH2)p-NR8R9,

Rvolumes of carbon quinil with 3-4 carbon atoms or alkoxygroup with 1-4 carbon atoms, one or more times, identically or differently substituted with halogen, langroup, a carboxyl group, a hydroxyl group, alkoxygroup with 1-4 carbon atoms or alkoxycarbonyl with 1-4 carbon atoms in the alkyl alkyl with 1-4 carbon atoms, alkenyl with 2-4 carbon atoms or quinil with 3-4 carbon atoms,

And means langroup,

< / BR>
or

< / BR>
R14and R15independently of one another denote hydrogen, alkyl with 1-6 carbon atoms, cycloalkyl with 3-6 carbon atoms, alkenyl with 2-6 carbon atoms or quinil with 3-6 carbon atoms, one or more times, identically or differently substituted with halogen, langroup, a hydroxyl group or alkoxygroup with 1-4 carbon atoms, alkyl with 1-6 carbon atoms, cycloalkyl with 3-6 carbon atoms, alkenyl with 2-6 carbon atoms or quinil with 3-6 carbon atoms, containing one or more oxygen atoms in the chain alkyl of 2-8 carbon atoms, cycloalkyl with 3-8 carbon atoms, alkenyl with 2-8 carbon atoms or quinil with 3-8 carbon atoms, (C1-C4-alkoxycarbonyl-(C1-C4)-alkyl, which may optionally be substituted with halogen, (
R14and R15together with the nitrogen atom form a saturated a heterocycle with 3-6 carbon atoms in the ring which may contain one or more oxygen atoms or sulfur,

R16means hydrogen or alkyl with 1-4 carbon atoms,

R17denotes hydrogen, alkyl with 1-4 carbon atoms or substituted by halogen alkyl with 1-4 carbon atoms,

R18, R19, R20, R21, R22and R24mean independently from each other hydrogen, halogen, alkyl with 1-4 carbon atoms, alkenyl with 2-4 carbon atoms or quinil with 3-4 carbon atoms, carboxyl group, or alkoxycarbonyl with 1-4 carbon atoms in the alkyl, one or more times, identically or differently substituted with halogen, langroup, a nitro-group, a hydroxyl group or alkoxygroup with 1-4 carbon atoms, alkyl with 1-4 carbon atoms, alkenyl with 2 to 4 carbon atoms or quinil with 3-4 carbon atoms,

R23and R25mean hydrogen, halogen, alkyl with 1-4 carbon atoms, alkenyl with 2-4 carbon atoms or quinil with 3-4 carbon atoms or

R23and R25together form a saturated or unsaturated 3-8-membered ring containing at UP>31
denotes hydrogen, alkyl with 1-4 carbon atoms, alkyl with 5 to 8 carbon atoms, cycloalkyl with 3-6 carbon atoms, alkenyl with 2-6 carbon atoms, quinil with 3-6 carbon atoms, one or more times, identically or differently substituted with halogen, langroup, a hydroxyl group or alkoxygroup with 1-4 carbon atoms, alkyl with 1-6 carbon atoms, cycloalkyl with 3-6 carbon atoms, alkenyl with 2-6 carbon atoms or quinil with 3-6 carbon atoms, containing one or more oxygen atoms in the chain alkyl with 2 to 8 carbon atoms, cycloalkyl with 3-8 carbon atoms, (C3-C8-cycloalkyl-(C1-C4)-alkyl, alkenyl with 2-8 carbon atoms or quinil with 3-8 carbon atoms, (C1-C4-alkoxycarbonyl-(C1-C4)-alkyl, which may optionally be substituted with halogen, (C1-C4-alkoxycarbonyl-(C2-C4)-alkenyl, which optionally may be substituted with halogen or the group -(CH2)p-NR8R9indicating that, if R12and R31mean hydrogen or R12means hydrogen and R31means alkyl with 1-4 carbon atoms, R13cannot be hydrogen or halogen,

R32means vodor the Mami carbon one or more times, identically or differently substituted with halogen, langroup, a hydroxyl group or alkoxygroup with 1-4 carbon atoms in the alkyl alkyl with 1-6 carbon atoms, cycloalkyl with 3-6 carbon atoms, alkenyl with 2-6 carbon atoms or quinil with 3-6 carbon atoms, containing one or more oxygen atoms in the chain alkyl of 2-8 carbon atoms, cycloalkyl with 3-8 carbon atoms, alkenyl with 2-8 carbon atoms or quinil with 3-8 carbon atoms, (C1-C4-alkoxycarbonyl-(C1-C4)-alkyl, which may optionally be substituted with halogen, (C1-C4-alkoxycarbonyl-(C2-C4)-alkenyl, which optionally may be substituted with halogen,

m means 3 or 4,

n means 0, 1, 2 or 3,

means 1, 2 or 3,

p represents 2, 3 or 4 and

X is oxygen or sulfur.

The designation of the halogen comprises fluorine, chlorine, bromine and iodine.

The designation "alkyl", "alkenyl" or "quinil covers the remains of hydrocarbons, which may be straight or branched chain.

Preferred such substituted pyrazolylborate General formula I,

in which

R1means methyl,

R2oznacza the means chlorine or bromine,

R4means hydrogen,

R5means nitrogroup or langroup,

R6means one of the groups

< / BR>
< / BR>
< / BR>
< / BR>
or

< / BR>
R11means alkyl with 5 to 8 carbon atoms, cycloalkyl with 3-6 carbon atoms, alkenyl with 2-6 carbon atoms, quinil with 3-6 carbon atoms, containing one or more oxygen atoms in the chain alkyl of 2-8 carbon atoms, cycloalkyl with 3-8 carbon atoms, alkenyl with 3-8 carbon atoms or quinil with 3-8 carbon atoms,

R12means hydrogen or methyl,

R13means hydrogen or methyl,

R16means hydrogen,

R17means hydrogen,

R18, R19, R20, R21, R22, R23, R24and R25independently of one another denote hydrogen, halogen or alkyl with 1-3 carbon atoms,

R23and R25together form a three-membered cycle containing an oxygen atom,

R29means hydrogen or halogen,

R31denotes hydrogen, alkyl with 1-4 carbon atoms, alkyl with 5 to 8 carbon atoms, cycloalkyl with 3-6 carbon atoms, alkenyl with 2-6 carbon atoms, quinil with 3-6 carbon atoms, one or more times, identically or differently substituted allogenically with 3-6 carbon atoms, alkenyl with 2-6 carbon atoms or quinil with 3-6 carbon atoms, indicating that, if R12and R31mean hydrogen or R12means hydrogen and R31is an alkyl with 1-4 carbon atoms, R13cannot be hydrogen,

X means oxygen and

n means 0, and

means 1 or 2.

Compounds according to the invention of General formula I get when, for example,

A) compound of General formula II

< / BR>
where R1, R2and R3have the meanings mentioned for the General formula I, is subjected to reaction with a compound of General formula III

< / BR>
where R5means a group-COOR7or

< / BR>
and R7, R8and R9have the meanings mentioned for the General formula I, and X means oxygen,

and means group OR26or

< / BR>
and R26, R27and R28independently of one another denote alkyl with 1-4 carbon atoms, or

B) if R6means a group -(CH2)about-A,

moreover, And means langroup and has the values stated for the General formula I, the compound of General formula Ia

< / BR>
in which R1, R2, R3, R4and R5have the meanings mentioned for the General formula I, and In means easy La, or

C) if R3means halogen, the compound of General formula IB

< / BR>
in which R1, R2, R4, R5and R6have the above for General formula I value, is subjected to reaction with a suitable halogenation agent, or

G) if R6means one of the groups

< / BR>
or

< / BR>
in which R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, n and X have the meanings mentioned for the General formula I, the compound of General formula IB or Iك

< / BR>
< / BR>
in which R1, R2, R3, R4, R5, R16, R17and n have the meanings mentioned for the General formula I, and R30means alkyl with 1-4 carbon atoms, is subjected to reaction with a compound of General formula IV or V

< / BR>
< / BR>
where R18, R19, R20, R21, R22, R23, R24, R25and X have the meanings mentioned for the General formula I, or

D) if R6mean group

< / BR>
in which R12, R13and R31have the meanings mentioned for the General formula I, and R29means chlorine or bromine, a compound of General formula Ia

< / BR>
in which R1, R2, R3, R4and R5have these for about the/SUP>, R3, R4and R5have the above for General formula I value, is subjected to reaction with Michael acceptor of the General formula VI

< / BR>
where R12, R13and R31have the meanings mentioned for the General formula I, or

(E) if R6mean group

< / BR>
in which R11, R12and R13have the above for General formula I values, the compound of General formula If

< / BR>
in which R1, R2, R3, R4, R5, R11, R12and R13have the above for General formula I, values and R29means chlorine or bromine, is treated with a suitable base, or

G) the compound of General formula Z or AI

< / BR>
< / BR>
where R1, R2, R3, R4, R5, R12, R13and R29are indicated for the formula I, values and R33means a hydroxyl group, chlorine, bromine or alkoxygroup with 1-4 carbon atoms, are subjected to interaction with alcohol of General formula VII or with the amine of General formula VIII

R11-OH (VII) R14R15NH (VIII)

in which R11, R14and R15have the above for General formula I values.

Known to be used as feedstock compounds of General formula II according varinia according to the invention of General formula I, in which5means a group-COOR7or-C(=X)NR8R9(A) the production method, receiving method, described Bisagni and others in Tetrahedron 29, 435 (1973).

Variant B) method of obtaining it is advisable to carry out so that the original substance of General formula Ia can be reacted with the salt of hydrocyanic acid in a suitable solvent at a temperature of 20oWith up to 180oC.

As suitable solvents should, for example, to call a simple ether, such as diethyl ether, tetrahydrofuran or 1,4-dioxane, amides, such as dimethylformamide, dimethylacetamide or N-an organic, aromatic hydrocarbons, such as benzene, toluene or xylene, or sulfoxidov, such as dimethylsulfoxide. As a suitable cyanide should mention cyanide lithium, sodium and potassium.

Compounds of General formula Ia are used as starting substances are known. Obtaining them are described in the international patent application 94/08999.

Halogenoalkane according to variant B) method of obtaining is suggested according to the known methods of halogenation of heterocyclic aromatic compounds, such as, for example, described in the book. Gubina-Vashem inert solvent.

As halogenation means can for example be used sulfurylchloride, sodium hypochlorite, N-chlorosuccinimide, N-bromosuccinimide, chlorine or bromine.

Acetals or ketals receive option D) of the method of receiving according to the methods described in the book. T. W. Greene "Protective groups in organic synthesis", 1980, pp. 116 et seq. page

Known used as starting substances, the compounds of General formula IB and Iك. Obtaining them are described in the international patent application 94/08999.

The compounds according to variant D) method of obtaining can be synthesized are presented in U.S. patent 5250504 way.

Known compounds of General formula Ia, used as starting materials. Obtaining them are described in the international patent application 94/08999.

The compounds according to variant E) method of obtaining can be obtained well-known for elimination method, as described in the book. J. March "Modern organic chemistry", 2nd edition, 1977, page 895 et seq. p. and in the literature cited therein.

The esterification according to the stage W) way of getting known and can be carried out by conventional methods, for example, described in the book. Gubina-Weyl, volume E5, page 659 and A-Weyl, volume E5, page 934 et seq. p. (1985).

Separate stages of a method of obtaining can be carried out in a solvent or without solvent, and if necessary use such solvents and diluents which are inert with respect to the corresponding reagents. For example, such solvents or diluents are aliphatic, alicyclic and aromatic hydrocarbons, which respectively optionally can be prochlorperazine, as, for example, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, telengard, trichloroethylene and chlorobenzene, ethers, such as diethyl ether, metaliteracy ether, methyl tert-butyl ether, diisopropyl ether, disutility ether, dioxane and tetrahydrofuran, ketones, such as acetone, methyl ethyl ketone, methylisobutylketone and methyl isobutyl ketone, NITRILES, such as acetonitrile and propionitrile, alcohols, such as methanol, ethanol, isopropyl alcohol, butyl alcohol, tert-butyl alcohol, tert-amyl alcohol and ethylene glycol, esters, such as ethyl acetate and amylacetate, acid amides, such as dimethylformamide and dime is, for example, pyridine and triethylamine, carboxylic acids, such as acetic acid, and mineral acids such as sulfuric acid and hydrochloric acid.

Treatment of compounds according to the invention carry out the usual well-known ways. Purification is carried out by crystallization or column chromatography.

Compounds according to the invention are generally colorless or slightly yellow crystalline substance or a viscous liquid substances which, in part, highly soluble in chlorinated hydrocarbons, such as methylene chloride or chloroform, ethers, such as diethyl ether or tetrahydrofuran, alcohols, such as methanol or ethanol, ketones, such as acetone or butanone, Amidah, as, for example, dimethylformamide, or in sulfoxidov, such as dimethyl sulfoxide.

Compounds according to the invention show a good herbicide activity against broadleaf weeds and grasses. Possible selective use for different crops, for example in the case of rape, root crops, soybeans, cotton, rice, corn, barley, wheat and other cereals. Individual compounds are also suitable as selective weed control in the case of perennial crops, for example afforestations, decorative forest plantations, planting fruits, grapes, citrus fruits, nuts, bananas, coffee, tea, and rubber plantations, plantations of oil palm, cocoa, berries and hops.

Compounds according to the invention can, for example, be applied against the following species of plants:

dicotyledonous weed species, such as Sinapis, Lepidium, Galium Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Brassica, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbaniia, Ambrosia, Cirsium, Sonchus, Solanum, Lamium, Veronica, Abuliton, Datura, Viola, Galeopsis, Papaver, Centaurea and Chrysanthemum;

monocotyledonous weed species such as Avena, Alopecurus, Echinochloa, Setaria, Panicum, Digitaria, Poa, Eleusine, Brachiaria, Lolium, Bromus, Cyperus, Elymus, Sagittaria, Monochoria, Fimbristylis, Eleocharis, Ischaemum and Apera.

Spent amount varies depending on the method of application to germination and post germination is between 0.001 and 5 kg/ha

The required intensity of the action and speed of action can, for example, be achieved through a synergistic effect of additives, such as organic solvents, wetting means and oils. Such supplements help so if you need to reduce the dosage of the current beginning.

It is advisable to use existing start according to the invention or mixtures thereof in the form of hothouses, adding liquid and/or particulate fillers or diluents and, if necessary, enhance the adhesion, wetting, emulsifying and/or dispersing AIDS.

Suitable liquid excipients are, for example, aliphatic and aromatic hydrocarbons, for example benzene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulfoxide, dimethylformamide, then fractions of mineral oils and vegetable oils.

As solid fillers suitable minerals, such as bentonite, silica gel, talc, kaolin, attapulgite, limestone and vegetable products, such as flour.

As surface-active substances should be called, for example, cellulosolvens, simple polyetheleneterftalate ether, naphthalenesulfonate and their salts, phenolsulfonic and their salts, formaldehyde, esters of fatty alcohols with sulfuric acid, and substituted benzosulfimide and their salts.

The share of beginning of the current or active principles in different finish forms may vary within wide limits. For example, funds contain about 10 to 90 wt.% acting early, from about 90 to 10 wt.% liquid or solid fillers, and t is th usual way, for example, with water as a carrier in the form of a solution for spraying in amounts from about 100 to 1000 l/ha Use of the so-called low-volume or ultra-low volume method is also possible, as is their application in the form of so-called microgranulates.

The preparation of these ready-made forms can be carried out in a known ways to do this, for example by grinding and mixing. If desired finished shape of the individual components can be first quickly mixed before applying them, as, for example, do in practice when the so-called method using containers for mixing.

The following examples illustrate the formation of compounds according to the invention.

Example 1 (method D)

1-(4-Bromo-5-deformedarse-1-methyl-3 - pyrazolyl)-5-(4,7-dihydro-1,3-doxepin-2-yl)-1H-pyrazole-4-carbonitrile

In 50 ml of toluene was dissolved 3.0 g (7.1 mmole) of 1-(4-bromo-5-deformedarse-1-methyl-3-pyrazolyl)-5-(1,1-diatexite)-1H - pyrazole-4-carbonitrile and then added 6.3 g (71 mmol) of CIS-2,3-butene-1,4-diol and a catalytic amount of p-toluenesulfonic acid. Boil for half an hour with water separator, washed with chilled solution of sodium chloride, dried over magnesium sulfate and close the>/P>So pl.: 90-91oC.

Example 2 (method E)

Methyl ester 1-(4-chloro-5-deformedarse-1-methyl-3-pyrazolyl)-4-cyan-5 - pyrazolyl-3-(2-chloro-2-methyl)propionic acid

Pre-load of 1.5 g (13 mmol) of tert-butylnitrite, 15 ml of methyl ester of methacrylic acid and 1.0 g of copper chloride (II) in 15 ml of acetonitrile and added in three doses of 2.55 g (10 mmol) 5-amino-1-(4-chloro-5-deformedarse-1-methyl-3-pyrazolyl)-4 - pyrazolecarboxylate. Stirred for 2 hours at room temperature, add 50 ml of 2n. hydrochloric acid and extracted three times with dichloromethane, dried over magnesium sulfate and concentrated. The cleaning is performed using column chromatography in the mixtures of hexane/ ethyl acetate. Output: 1,65 g, which is 46% of theory.

So pl.: 65oC.

Example 3 (method E)

Methyl ester 1-(4-chloro-5-deformedarse-1-methyl-3-pyrazolyl)-4-cyan-5 - pyrazolyl-3-(2-methyl)prop-2-ene acid

Preloads 73 mg (of 2.45 mmole) of sodium hydride (80%) in 20 ml of absolute dimethylformamide and added 1.0 g (of 2.45 mmole) of methyl ester 1-(4-chloro-5-deformedarse-1-methyl-3 - pyrazolyl)-4-cyan-5-pyrazolyl-3-(2-chloro-2-methyl) propionic acid. Stirred for 2 hours at 60oWith, the solvent is removed and estatoe.

So pl.: 88oC.

Example 4 (method W)

2,2-Dimethoxyethoxy ether (E)-3-[1-(4-chloro-5-deformedarse-1-methyl-3-pyrazolyl) -4-cyan-5-pyrazolyl]acrylic acid

Pre-load 1 g (was 2.76 mmole) of the acid chloride of 1-(4-chloro-5-deformedarse-1-methyl-3-pyrazolyl)-4-cyan-5 - pyrazolyl-3-propionic acid in 20 ml of dichloromethane and at room temperature was added 0.28 g (was 2.76 mmole) of triethylamine and 0.29 grams (was 2.76 mmole) of dimethylacetal glycolic aldehyde. Stirred for 2 hours at room temperature, the solvent is removed and the residue purified via chromatography on a column in mixtures of hexane/ ethyl acetate. Output: 0,80 g, which is 67% of theory.

So pl.: 92oC.

Similarly receive the following compounds of formula I according to the invention, and R4equally means hydrogen and "TRANS" over a double bond indicates the TRANS-configuration of this double bond.

The following examples explain the invention:

Examples of applications:

these symbols

ALOMY for Alopecurus myosuroides

AGRRE for Elymus repens

AVEFA for Avena fatua

SETVI for Setaria viridis

PANSS for Panicum sp.

SORHA for Sorghum halepense

ECHCG for Echinochloa crus-galli

DIGSA for Digitaria sanguitis purpureum

MATCH for Matricaria chamomilla

POLPE for Polygonum sp.

VERPE for Veronica persica

CHEAL for Chenopodium album

AMARE for Amaranthus retroflexus

STEME for Stellaria media

0 = no lesions

1 = 1-24% of lesions

2 = 25-74% of lesions

3 = 75-89% of lesions

4 = 90-100% of lesions

In greenhouse grown plants were treated after germination input connections in the amount of from 0.03 kg of active start/ ha Connection for this purpose is evenly sprayed over the plants in the form of an emulsion with 500 l of water/ha after 2 weeks of treatment the compounds according to the invention showed excellent activity against weeds, which can be seen from the following table.2.

1. Substituted pyrazolylborate General formula I

< / BR>
in which R1means alkyl with 1-4 carbon atoms;

R2means alkyl with 1-4 carbon atoms, alkylthiols with 1-4 carbon atoms in the alkyl, alkylation with 1-4 carbon atoms in the alkyl, alkylsulfonyl with 1 to 4 carbon atoms in the alkyl, alkoxygroup with 1-4 carbon atoms or alkyl with 1-4 carbon atoms, alkylthiols with 1-4 carbon atoms, alkylsulfonyl with 1 to 4 carbon atoms in the alkyl or alkoxygroup with 1-4 carbon atoms, one or several times substituted by halogen;

R1and Rrepresents hydrogen or alkyl with 1-4 carbon atoms;

R5denotes hydrogen, a nitro-group, cyano, -COOR7group

< / BR>
or

< / BR>
R6means one of the groups

< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
-(CH2)about-A,

< / BR>
or

< / BR>
R7, R8and R9independently of one another denote hydrogen or alkyl with 1-4 carbon atoms;

R8and R9together with the adjacent nitrogen atom form a 5 - or 6-membered saturated a heterocycle;

R10denotes hydrogen, alkyl with 1-4 carbon atoms, substituted one or more times by halogen, alkyl with 1-4 carbon atoms;

R11means alkyl with 5 to 8 carbon atoms, cycloalkyl with 3-6 carbon atoms, alkenyl with 2-6 carbon atoms, quinil with 3-6 carbon atoms; alkyl with 1-6 carbon atoms, cycloalkyl with 3-6 carbon atoms, alkenyl with 2-6 carbon atoms or quinil with 3-6 carbon atoms, one or more times, identically or differently substituted with halogen, cyano, hydroxyl group or alkoxygroup with 1-4 carbon atoms; alkyl of 2-8 carbon atoms, cycloalkyl with 3-8 carbon atoms, (C3-C8-cycloalkyl-(C1-C4)-alkyl, alkenyl with 3-8 carbon atoms or quinil with 3-8 carbon atoms, interrupted by one or more atomant substituted with halogen, or (C1-C4-alkoxycarbonyl-(C2-C4)-alkenyl, which is optionally substituted by halogen, or is likely to mean the group -(CH2)p-NR8R9;

R12and R13independently of one another denote hydrogen, halogen, alkyl with 1-4 carbon atoms, alkenyl with 2-4 carbon atoms, quinil with 3-4 carbon atoms or alkoxygroup with 1-4 carbon atoms; alkyl with 1-4 carbon atoms, alkenyl with 2-4 carbon atoms or quinil with 3-4 carbon atoms, one or more times, identically or differently substituted with halogen, cyano, carboxyl group, hydroxyl group, alkoxygroup with 1-4 carbon atoms or alkoxycarbonyl with 1-4 carbon atoms in the alkyl;

And means

< / BR>
R14and R15independently of one another denote hydrogen, alkyl with 1-6 carbon atoms, cycloalkyl with 3-6 carbon atoms, alkenyl with 2-6 carbon atoms or quinil with 3-6 carbon atoms; alkyl with 1-6 carbon atoms, cycloalkyl with 3-6 carbon atoms, alkenyl with 2-6 carbon atoms or quinil with 3-6 carbon atoms, one or more times, identically or differently substituted with halogen, cyano, hydroxyl group or alkoxygroup with 1-4 carbon atoms; alkyl of 2-8 the ode, interrupted by one or more oxygen atoms; and (C1-C4-alkoxycarbonyl-(C1-C4)-alkyl, which may optionally be substituted with halogen, (C1-C4-alkoxycarbonyl-(C2-C4)-alkenyl, which optionally may be substituted with halogen, or alkoxycarbonyl with 1 to 4 carbon atoms in the alkyl;

R14and R15together with the nitrogen atom form a saturated a heterocycle with 3-6 carbon atoms in the ring which may contain one or more oxygen atoms or sulfur;

R16means hydrogen or alkyl with 1-4 carbon atoms;

R17denotes hydrogen, alkyl with 1-4 carbon atoms or substituted by halogen alkyl with 1-4 carbon atoms;

R18, R19, R20, R21, R22and R24mean independently from each other hydrogen, halogen, alkyl with 1-4 carbon atoms, alkenyl with 2-4 carbon atoms or quinil with 3-4 carbon atoms, carboxyl group, or alkoxycarbonyl with 1-4 carbon atoms in the alkyl; alkyl with 1-4 carbon atoms, alkenyl with 2-4 carbon atoms or quinil with 3-4 carbon atoms, one or more times, identically or differently substituted with halogen, langroup, a nitro-group, a hydroxyl group or is of Pereda, alkenyl with 2-4 carbon atoms or quinil with 3-4 carbon atoms; or

R23and R25together form a saturated or unsaturated 3-8-membered ring, optionally containing one or more atoms of sulfur or oxygen;

R29means hydrogen or halogen;

R31denotes hydrogen, alkyl with 1-4 carbon atoms, alkyl with 5 to 8 carbon atoms, cycloalkyl with 3-6 carbon atoms, alkenyl with 2-6 carbon atoms, quinil with 3-6 carbon atoms; alkyl with 1-6 carbon atoms, cycloalkyl with 3-6 carbon atoms, alkenyl with 2-6 carbon atoms or quinil with 3-6 carbon atoms, one or more times, identically or differently substituted with halogen, cyano, hydroxyl group or alkoxygroup with 1-4 carbon atoms; alkyl of 2-8 carbon atoms, cycloalkyl with 3-8 carbon atoms, (C3-C8-cycloalkyl-(C1-C4)-alkyl, alkenyl with 2-8 carbon atoms or quinil with 3-8 carbon atoms, interrupted by one or more oxygen atoms; (C1-C4-alkoxycarbonyl-(C1-C4)-alkyl, which may optionally be substituted with halogen, (C1-C4-alkoxycarbonyl-(C2-C4)-alkenyl, which if necessary can be UP> mean hydrogen and R31means hydrogen or alkyl with 1-4 carbon atoms, R29cannot be hydrogen, halogen or alkyl with 1-4 carbon atoms, b) if R12and R29mean hydrogen and R31means hydrogen or alkyl with 1-4 carbon atoms, R13cannot be hydrogen, halogen or alkyl with 1-4 carbon atoms, C) if R12means halogen or alkyl with 1-4 carbon atoms, R13means hydrogen and R31means alkyl with 1-4 carbon atoms, R29cannot be hydrogen, halogen or alkyl with 1-4 carbon atoms, d) if R12means halogen or alkyl with 1-4 carbon atoms, R29means hydrogen and R31means alkyl with 1-4 carbon atoms, R13cannot be hydrogen, halogen or alkyl with 1-4 carbon atoms, d) if R12means hydrogen, R31means alkyl with 1-4 carbon atoms and R13means halogen, R29cannot be an alkyl with 1-4 carbon atoms, (e) if R12means hydrogen, R31means alkyl with 1-4 carbon atoms and R29means halogen, R13cannot be an alkyl with 1-4 carbon atoms;

m means 3 or 4;

n means 0, 1, 2 or 3;

means 1 or 3;

p represents 2, 3 or 4;
1means methyl, R2means dipterocarp, R1and R2together form a group -(CH2)4-, R3means chlorine or bromine, R4means hydrogen, R5means the nitro-group or cyano, R6means one of the groups

< / BR>
< / BR>
< / BR>
< / BR>
or

< / BR>
R11means alkyl with 5 to 8 carbon atoms, cycloalkyl with 3-6 carbon atoms, alkenyl with 2-6 carbon atoms, alkinyl with 3-6 carbon atoms; alkyl of 2-8 carbon atoms, cycloalkyl with 3-8 carbon atoms, alkenyl with 3-8 carbon atoms or quinil with 3-8 carbon atoms, interrupted by one or more oxygen atoms;

R12means hydrogen or methyl;

R13means hydrogen or methyl;

R16means hydrogen;

R17means hydrogen;

R18, R19, R20, R21, R22, R23, R24and R25independently of one another denote hydrogen, halogen or alkyl with 1-3 carbon atoms;

R23and R25together form a saturated, including the oxygen atom of trivalent loop;

R29means hydrogen or halogen;

R31denotes hydrogen, alkyl with 1-4 carbon atoms, alkyl with 5 to 8 carbon atoms, cycloate, cycloalkyl with 3-6 carbon atoms, alkenyl with 2-6 carbon atoms or quinil with 3-6 carbon atoms, one or more times, identically or differently substituted with halogen, cyano, hydroxyl group or alkoxygroup with 1-4 carbon atoms, provided that (a) if R12and R13mean hydrogen and R31means hydrogen or alkyl with 1-4 carbon atoms, R29cannot be hydrogen or halogen, b) if R12and R29mean hydrogen and R31means hydrogen or alkyl with 1-4 carbon atoms, R13cannot be hydrogen or stands, in) if R12means methyl, R13means hydrogen and R31means alkyl with 1-4 carbon atoms, R29cannot be hydrogen or halogen, g) if R12means methyl, R29means hydrogen and R31means alkyl with 1-4 carbon atoms, R13cannot be hydrogen or stands, d) if R12means hydrogen, R31means alkyl with 1-4 carbon atoms and R29means halogen, R13may not be the stands;

X is oxygen;

n means 0;

means 1.

3. Means having a weed-killing effect, characterized in that they contain at least one connection on p. 1 the implementing agents.

 

Same patents:

The invention relates to a technology for 1,4,3,6-dianhydro-D-sorbitol dinitrate, which is the substance of the medicinal product "nitrosorbid"

The invention relates to a new method of obtaining the previously described connections of a number of dibenzo[b, e]pyrano[3,2-b]-1-benzopirilievyh salts of General formula (I),

< / BR>
where X 0;

R1a hydrogen atom;

R2-R4the atom of hydrogen or halogen, C1-C6alkyl or C1-C6alkoxygroup, the nitro-group;

R5, R6, R7the atom of hydrogen or C1-C6alkyl,

that exhibit fluorescent properties and are used as dyes for dyeing films and aminomethylating fibers (DOS 2942931 (1980), BASF, Erf

The invention relates to 1,4-disubstituted the piperazines of General formula I, the method of production thereof, containing compositions and their use for the clinical treatment of painful conditions, increased pain sensitivity and/or inflammatory conditions in which the pathophysiological role of C-fibers, causing neurogenic pain or inflammation

The invention relates to piperazine derivatives of General formula I, in which R1denotes pyridyl or phenyl, unsubstituted or once substituted Ph or 2 - or 3-Tiepolo, R2indicates Ph1or Het
The invention relates to an anhydrous crystalline form of the hydrochloride R(-)-M-(4,4-di(3-methyltin-2-yl)but-3-enyl)-nicotinebuy acid, free from associated organic solvent (1), which is nephroscopes and thermally stable under normal storage conditions

The invention relates to the derivatives of thiophene of the General formula I, in which R1is the formula A1- X1- R3; R2is perhaps the formula A2- X2- R4; ring b is 4-10-membered nitrogen-containing cycloalkyl ring or 5 - or 6-membered nitrogen-containing unsaturated heterocycle; Ar represents an aryl ring or heteroaryl ring; A1, A2and A3may be the same or different and each represents a bond or lower alkylenes group; X1and X2may be the same or different and each represents a bond or a formula-O-, -S-; R3and R4may be the same or different, and each represents a hydrogen atom, cyclic aminogroup or a lower alkyl group, aryl group or aracelio group, or its pharmaceutically acceptable salt

The invention relates to benzothiadiazine General formula I, in which X represents hydrogen or halogen, Y represents-CN or-NR1R2where l denotes an integer of 1 or 2, m represents an integer of 0, 1 or 2, n denotes an integer equal to 2, 3 or 4, except for the case when Y - SP, n may be equal to 1, R1denotes hydrogen, (C1-C6)alkyl or alkoxycarbonyl, R2denotes hydrogen, (C1-C10)alkylsulphonyl, (C3-C12)cycloalkylcarbonyl, hydroxy(C1-C6)alkylsulphonyl, phenylcarbinol, possibly substituted with halogen, cryptomaterial, thienylboronic or benzotriazolyl, or R1and R2together with the nitrogen atom to which they are bound, form a loop formula II, where a denotes C=0 or CH2In stands WITH a= 0, SNON, CH2or CH2CH2and Z represents hydrogen, and their pharmaceutically acceptable additive salts of acids, provided that when X=N, n can be 4, and R1and R2cannot be both hydrogen

The invention relates to new nitrogen-containing heterocyclic compounds with biological activity, in particular to substituted derivatives of pyrazole and means of having a weed-killing activity

The invention relates to piperazine derivatives of the formula I, in which R1denotes a substituted radicals CN or Hal indole-3-ilen residue, R2denotes unsubstituted 2-oxo-2H-1-benzopyran-6-yl or 2-oxo-2H-1-benzopyran-4-yl
Up!