New substituted derivatives of pyrazole, method for their preparing and herbicide compositions comprising these derivatives

FIELD: organic chemistry, chemical technology, herbicides.

SUBSTANCE: invention describes new substituted derivatives of pyrazole of the general formula (I): wherein n = 0 or 1; group A represents independently hydrogen atom, alkyl group with 1-4 carbon atoms, halogenalkyl group with 1-4 carbon atoms, cycloalkyl group with 3-6 carbon atoms or phenyl group having substituting groups optionally; group D represents hydrogen atom, alkyl group with 1-4 carbon atoms, halogenalkyl group with 1-4 carbon atoms, alkenyl group with 2-4 carbon atoms, alkoxy-group with 1-4 carbon atoms, cycloalkyl group with 3-6 carbon atoms, halogen atom, alkoxycarbonyl group with 1-4 carbon atoms, alkylsulfonyl group with 1-4 carbon atoms or phenyl group; group E represents hydrogen atom, halogen atom or phenyl group; groups R1 and R2 both represent halogen atom; group R3 represents hydrogen atom, alkyl group with 1-4 carbon atoms, halogenalkyl group with 1-4 carbon atoms, alkenyl group with 2-4 carbon atoms, alkynyl group with 2-4 carbon atoms or benzyl group; groups R4 and R5 are similar or different and each represents hydrogen atom, alkyl group with 1-4 carbon atoms, halogenalkyl group with 1-4 carbon atoms, cycloalkyl group with 3-8 carbon atoms that can be substituted with alkyl group with 1-4 carbon atoms, alkenyl group with 2-4 carbon atoms, alkynyl group with 2-4 carbon atoms, cyanomethyl group or phenyl group; or each R4 and R5 group means benzyl group; or each R4 and R5 group represents α- or β-phenethyl group having substituting groups at benzyl ring optionally. Indicated substituting groups represent alkoxy-groups with 1-4 carbon atoms wherein indicated substituting groups substitute hydrogen atom at the arbitrary positions 0-2 of the benzyl ring; or groups R4 and R5 form in common 5-membered or 6-membered aliphatic ring wherein the indicated ring can be substituted with alkyl groups with 1-4 carbon atoms and indicated ring can comprise one or two heteroatoms chosen from nitrogen oxygen and sulfur atom, and a method for their preparing. Also, invention describes herbicide compositions based on compound of the formula (I). Invention provides preparing herbicide compositions showing the strong herbicide effect and broad herbicide spectrum of their effect.

EFFECT: improved preparing method, valuable properties of derivatives and compositions.

7 cl, 6 tbl, 3 ex

 

The SCOPE of the INVENTION

The present invention relates to new substituted derivatives of pyrazole, method of production thereof and herbicide compositions containing this derivative(s) as active ingredient(s). More specifically the invention relates to substituted derivatives of pyrazole, useful as herbicides, method of production thereof and herbicide compositions containing the derivative(s) as active ingredient(s). They are applicable in the chemical industry and agriculture, especially in the field of manufacturing agricultural chemicals.

BACKGROUND of the INVENTION

Developed and used herbicides are very numerous. However, there are many weed species whose growth is to be controlled, and the emergence of weeds lasts for a long period of time. Therefore, none of the many herbicide funds may not meet all requirements in respect of, for example, herbicide activity, herbicide spectrum, selectivity to crops, and safety for humans and for the environment.

When cultivation is especially important cereal crops such as wheat, corn, soy, and rice, the required herbicide that is effective herbicide activity even in a small dose, broad spectrum herbicide, sufficient residual efficiency and prevoshodnoy selectivity to crops.

Attempts to detect pyrazoles with herbicide activity for use in herbicides, were not successful. The present applicant disclosed substituted pyrazole derivatives as fungicides and method of production thereof (patent documents 1-3). However, these documents do not have any description regarding herbicide activity of these derivatives.

Patent document 1: JP-A-H10-130106

Patent document 2: JP-A-H10-158107

Patent document 3: EP 00945437 A1

DISCLOSURE of INVENTIONS

Applicants have synthesized new substituted pyrazole derivatives represented by the following formula (1), and conducted various tests. In the result it was found that derivatives have excellent herbicide action on a wide range of weeds, including uncontrolled weeds, and show adequate security for some important crops. Based on these results, it was made the present invention.

The aim of the present invention is to provide new compounds that are safe for crops and have high herbicide action. The task of the invention to provide new substituted derivatives of pyrazole following formula (1) (hereinafter "compounds of the invention") and herbicide compositions containing this proizvodi is e(s) as active ingredient(s).

The invention consists in the following.

The connection according to the invention represents a substituted derivative of pyrazole with herbicide activity and represented by the formula (1):

in which

n is 0 or 1; independently

group a represents a hydrogen atom, a branched or unbranched alkyl group with 1-4 carbon atoms, branched or unbranched halogenating group with 1-4 carbon atoms, cycloalkyl group with 3-6 carbon atoms or phenyl group, optionally having a substituting group;

moreover, these substituting groups are the same or different from each other and are selected from branched or unbranched alkyl groups with 1-4 carbon atoms, branched or unbranched halogenating groups with 1-4 carbon atoms, branched or unbranched alkoxygroup with 1-4 carbon atoms, a hydroxyl group, a branched or unbranched halogenlamp with 1-4 carbon atoms, branched or unbranched alkylcarboxylic with 1-4 carbon atoms, branched or unbranched dialkylaminoalkyl with 1-4 carbon atoms, branched or unbranched dialkylaminoalkyl with 1-4 carbon atoms, branched or closely evlendi of alkylthio with 1-4 carbon atoms, branched or unbranched halogenation with 1-4 carbon atoms, branched or unbranched alkylsulfonyl groups with 1-4 carbon atoms,

atoms of halogen, ceanography, nitro, phenyl group, phenoxy group and benzyloxy;

these replacement group replaces the hydrogen atom in 0-3 arbitrary positions of the phenyl group;

group D represents a hydrogen atom, a branched or unbranched alkyl group with 1-4 carbon atoms, branched or unbranched halogenating group with 1-4 carbon atoms, alkenylphenol group with 2-4 carbon atoms, branched or

nonbranched alkoxygroup with 1-4 carbon atoms, cycloalkyl group with 3-6 carbon atoms, a halogen atom, a branched or unbranched alkoxycarbonyl group with 1-4 carbon atoms, branched or unbranched alkylsulfonyl group with 1-4 carbon atoms or phenyl group.

group R1and R2both represent a halogen atom;

the group R3represents a hydrogen atom, a branched or unbranched alkyl group with 1-4 carbon atoms, branched or unbranched halogenating group with 1-4 carbon atoms, alkenylphenol group with 2-4 carbon atoms, alkylamino group with 2-4 carbon atoms or benzil the th group;

group R4and R5are the same or different and each represents a hydrogen atom, a branched or unbranched alkyl group with 1-4 carbon atoms, branched or unbranched halogenating group with 1-4 carbon atoms, cycloalkyl group with 3-8 carbon atoms which may be substituted by branched or unbranched alkyl group with 1-4 carbon atoms, alkenylphenol group with 2-4 carbon atoms, alkylamino group with 2-4 carbon atoms, cyanomethyl group or phenyl group;

or R4and R5each is a benzyl group;

or R4and R5each is a αor β-fenetylline group, not necessarily with substitute groups on the benzene ring, these substituting groups are branched or non-branched alkoxycarbonyl with 1-4 carbon atoms, where these

replacing group replacing a hydrogen atom in 0-2 arbitrary positions of the benzene ring;

or groups of R4and R5together form a five-membered or six-membered aliphatic ring, in which the indicated ring may be substituted by branched or unbranched alkyl groups with 1-4 carbon atoms, and this ring may contain one or two heteroatoms.

Substituted p is osvitnye of pyrazole, have a weed-killing activity, according to the present invention have the above formula (1)in which R4represents a hydrogen atom and R5represents a substituted an amino group N(R11,R12), and has the following formula (4):

where n is 0 or 1;

Rather it represents a phenyl; E, R1and R2represent a hydrogen atom;

D and R3independently represent a branched or unbranched alkyl group with 1-4 carbon atoms; and

group R11and R12are the same or different and each denotes a hydrogen atom, a branched or unbranched alkyl group with 1-4 carbon atoms, branched or unbranched alkoxycarbonyl group with 1-4 carbon atoms.

The method of obtaining substituted derivatives of pyrazole of the formula (1) involves the reaction of pyrazole derivative of the formula (5) with ether derivative halogenatom formulas (6) to obtain the ether derivative of pyrazole of the formula (7):

and hydrolysis of the ether group of an ester derivative of pyrazole of the formula (7) in the presence of a base, getting a carboxylic acid derivative of the formula (8) and the reaction of the carboxylic acid derivative with an amine R4-NH-R5in the presence of a condensing agent:

where in formulas (5)-(8) n is 0 or 1, the group Z represents a halogen atom, a group R13represents a methyl or ethyl group, and each group A, D, E, R1, R2, R3, R4and R5means independently the same replacement group for formula (1).

Herbicide composition in accordance with the present invention includes a compound selected from substituted derivatives of pyrazole of the formula (1) as an active ingredient.

Herbicide composition according to the present invention includes a compound selected from substituted derivatives of pyrazole of the formula (4) as an active ingredient.

The connection according to the invention represents a substituted derivative of pyrazole with herbicide activity, preferably represented by the following formula (1)

where n is 0 or 1; independently

group a represents a hydrogen atom, a branched or unbranched alkyl group with 1-4 carbon atoms, branched or unbranched halogenating group with 1-4 carbon atoms, cycloalkyl group with 3-6 carbon atoms or a phenyl group substituted by 0-3 substitute groups (0 substituting groups means unsubstituted phenyl group);

these substituting groups are dinasovymi or different from each other and are selected from alkyl groups with 1-4 carbon atoms, halogenating groups with 1-4 carbon atoms, alkoxygroup with 1-4 carbon atoms, halogenlamp with 1-4 carbon atoms, alkylcarboxylic with 1-4 carbon atoms, dialkylaminoalkyl with 1-4 carbon atoms, alkylthio with 1-4 carbon atoms, halogenation with 1-4 carbon atoms, halogen atoms, hydroxyl group, cyanopropyl, phenyl group, fenoxaprop and benzyloxy;

group D represents a hydrogen atom, a halogen atom, a branched or unbranched alkyl group with 1-4 carbon atoms, branched or unbranched halogenating group with 1-4 carbon atoms, alkylamino group with 2-4 carbon atoms, branched or unbranched alkoxygroup with 1-4

carbon atoms, alkoxycarbonyl group with 1-4 carbon atoms, or phenyl group;

group E represents a hydrogen atom, halogen atom or phenyl group;

the group R1and R2both represent a hydrogen atom;

the group R3represents a hydrogen atom, a branched or unbranched alkyl group with 1-4 carbon atoms, alkylamino group with 2-4 carbon atoms, formeterol group or a benzene group;

group R4and R5together form a five-membered or six-membered aliphatic ring, which may contain the 1 or 2 heteroatoms and which may be substituted by an alkyl group with 1-4 carbon atoms, or independently

the group R4represents a hydrogen atom or a branched or unbranched alkyl group with 1-4 carbon atoms, and

the group R5represents a hydrogen atom, a branched or unbranched alkyl group with 1-4 carbon atoms, branched or unbranched halogenating group with 1-4 carbon atoms, branched or unbranched cyanoaniline group with 1-4 carbon atoms, cycloalkyl group with 3-6 carbon atoms that may be substituted by branched or unbranched alkyl group with 1-4 carbon atoms, alkenylphenol group with 2-4 carbon atoms, alkenylphenol group with 2-4 carbon atoms, phenyl group, benzyl group or αor β-fenetylline group optionally having a (branched or unbranched) alkoxygroup with 1-4 carbon atoms in a benzene ring.

Herbicide composition according to the present invention includes a compound selected from the above-mentioned substituted pyrazoles preferably as an active ingredient.

Herbicide composition according to the present invention includes one or more kinds of substituted derivatives of pyrazole as active ingredients.

DETAILED description of the INVENTION

Substituted pyrazole derivatives (also called "the unity of the invention") are new compounds, exhibiting sufficient security for important crops and having excellent herbicide activity and having the structure represented by formula (1) or (4). They have a common fragment consisting of substituted pyrazol ring and N-oxime acid amide. Substituted pyrazole derivative of the formula (4) is a derivative of the compound of formula (1). Compounds according to the invention are presented below as compounds having a specific group, but not limited to.

Scope of the present invention also includes other claimed compounds with herbicide activity, namely derivatives of the compounds according to the invention having different substitute groups, salts (e.g. sodium salt, potassium salts, magnesium salts, calcium salts, aluminum salts, zinc salts), hydrates, solvate and crystalline polymorphs of the compounds. Further possible stereoisomers, when the compounds according to the invention contain an asymmetric carbon (for example, when R1and R2in the formula (1) or (4) are different from each other). Compounds according to the invention include all possible isomers and mixtures containing two or more isomers in any proportions.

The following describes in order the detailed structure of the compounds according to the invention (1)and (4), methods of preparation, herbicide steps, the compositions and methods of use thereof.

Substituted derivatives of pyrazole

Compounds according to the invention are substituted derivatives of pyrazole, including substituted pyrazol ring and N-oxime acid amide, as indicated in the formula (1), and its derivatives (represented by formula (4)). In formulas

(1) and (4) n is 0 or 1. In any case, acid amides (1) and hydrazide derivatives (4) of the present invention may contain a hydrogen atom and the other groups described below as a substitute groups A, D, E, R1-R5, R11and R12.

Group a in the formula (1) represents a hydrogen atom, a branched or unbranched alkyl group with 1-4 carbon atoms, branched or unbranched halogenating group with 1-4 carbon atoms, cycloalkyl group with 3-6 carbon atoms or phenyl group, optionally having one or more substituting groups represented below.

Substitute group of the phenyl groups may be the same or different from each other and are selected from branched or unbranched alkyl groups with 1-4 carbon atoms, branched or unbranched halogenating groups with 1-4 carbon atoms, branched or unbranched alkoxygroup with 1-4 carbon atoms, branched or Neretva the run of halogenlamp with 1-4 carbon atoms, branched or unbranched alkylcarboxylic with 1-4 carbon atoms, branched or unbranched dialkylaminoalkyl with 1-4 carbon atoms, branched or unbranched dialkylaminoalkyl with 1-4 carbon atoms, branched or unbranched alkylthio with 1-4 carbon atoms, branched or unbranched halogenation with 1-4 carbon atoms, branched or unbranched alkylsulfonyl groups with 1-4 carbon atoms, halogen atoms, hydroxyl group, ceanography, phenoxy group and benzyloxy.

These approximate replacement group can replace a hydrogen atom in 0-3 arbitrary positions of the phenyl group.

Specific examples of the above groups are presented below without limiting the scope of the invention.

Branched or unbranched alkyl groups with 1-4 carbon atoms include methyl, ethyl, sawn and boutelou group and isomeric groups.

Branched or unbranched halogenoalkane group with 1-4 carbon atoms include formeterol, deformational, triptorelin, dichlorethylene and bromopropyl group and isomeric groups.

Cycloalkyl group with 3-6 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl and tsiklogeksilnogo group.

"Fenil the th group, optionally have one or more substitutional groups", presented as an approximate group a in the formula (1), refers to a phenyl group substituted by the same or different substitute groups 0-5 in arbitrary positions. Examples of substituting groups include branched or unbranched alkyl groups with 1-4 carbon atoms, branched or unbranched halogenoalkane group with 1-4 carbon atoms, branched or unbranched of alkoxygroup with 1-4 carbon atoms, branched or unbranched of halogenlampe with 1-4 carbon atoms, branched or unbranched of alkylcarboxylic with 1-4 carbon atoms, branched or unbranched of dialkylaminoalkyl with 1-4 carbon atoms, branched or unbranched of dialkylaminoalkyl with 1-4 carbon atoms, branched or unbranched of ancilliary with 1-4 carbon atoms, branched or unbranched of halogenation with 1-4 carbon atoms. branched or unbranched alkylsulfonyl group with 1-4 carbon atoms, halogen atoms, hydroxyl group, cyano. Specific examples of alkyl groups and halogenating groups include, but are not limited to, the group described above.

Branched or unbranched of alkoxygroup with 1-4 ATO the AMI carbon include methoxy, ethoxy, propoxy, butoxy group and isomeric groups.

Branched or unbranched of halogenlampe with 1-4 carbon atoms include monitorless, chloropropoxy group and isomeric groups.

Branched or unbranched of alkylcarboxylic with 1-4 carbon atoms include methylcarbonate, ethylcarbonate, propylmalonate, BUTYLCARBAMATE group.

Branched or unbranched of dialkylaminoalkyl with 1-4 carbon atoms include dimethylaminocarbonylmethyl, diethylaminocarbonylmethyl group.

Branched or unbranched of dialkylaminoalkyl with 1-4 carbon atoms include dimethylaminomethylene, diethylaminoethoxy group.

Branched or unbranched of ancilliary with 1-4 carbon atoms include methylthio, ethylthio, propylthio, butylthio group and isomeric groups.

Branched or unbranched of halogenation with 1-4 carbon atoms include monochromacity, triptoreline group.

Branched or unbranched alkylsulfonyl group with 1-4 carbon atoms include methylsulfonyl, ethylsulfonyl, propylsulfonyl and butylsulfonyl group and isomeric groups.

The halogen atoms include fluorine atoms, chlorine, bromine and iodine.

Arbitrary is a replacement group in the phenyl group, each may represent a phenyl group, not necessarily having the next one or more substitutional groups (these substituting groups are the same as the above-mentioned replacement group), phenoxy group, optionally having one or more substituting groups in the benzene ring (these substituting groups are the same as the above-mentioned replacement group) or benzyloxy, optionally having one or more substituting groups in the benzene ring (these substituting groups are the same as the above-mentioned replacement group). Specific examples of such substituted phenyl groups having one or more substituting groups in the benzene ring) include methylphenylene group, chloraniline group, dichloraniline group, 3-(1-(chlorobenzylamino)-ethyl)phenyl group, 3-(benzyloxy)phenyl group, 3-(methylendioxy)phenyl group, 3-(Chlorobenzilate)phenyl group, 3-(cyanobenzyl)phenyl group, 3-(dimethylsiloxy)phenyl group, 3-(DICHLOROSILANE)phenyl group, 3-(pyridyloxy)phenyl group, 3-(benzoyloxy)phenyl group, 3-(chlorobenzoyloxy)phenyl group, benzyl group, phenoxymethyl group, methylpenicillin group, phenylthiomethyl group, methylphenylthiomethylannui group, 1-Phenoxyethanol group, 1-(methylphenoxy)ethyl group, 1-phenylthiomethyl group, 1-(methylphenylthio)ethyl group, is exigrep, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2-chlorophenoxy, 3-chlorophenoxy, 4-chlorophenoxy, 2-triftormetilfosfinov, 2,5-dimethylphenoxy, 2,5-dichlorophenoxy, 2-chloro-5-triftormetilfosfinov, phenylthiourea, 2-methylphenylthio, benzyloxy, 2-methylbenzylamine, 3-methylbenzylamino, 4-methylbenzylamine, 2-chlorobenzoyloxy,3-chlorobenzylamino, 4-chlorobenzoyloxy, 2-triftormetilfullerenov, 2,5-dimethylbenzaldehyde, 2,5-dichlorobenzaldehyde, 2-chloro-5-triftormetilfullerenov, menzilcioglu, 2-methylbenzaldehyde, benzoyloxymethyl group, 2-methylbenzyloxycarbonyl group, 3-methylbenzyloxycarbonyl group and 4-methylbenzyloxycarbonyl group.

Branched or unbranched alkyl groups with 1-4 carbon atoms to the above-mentioned groups (R6, R7, R8, R9and R10) include alkyl groups mentioned above, but are not limited to.

For the above group of especially preferred are hydrogen atom, methyl group, ethyl group, n-sawn group, ISO-sawn group, n-bucilina group, tert-bucilina group, triptorelin group, cyclopropyl group, cyclobutyl group, cyclopentenone group, cyclo is exilda group, phenyl group, 2-Fortunella group, 3-Fortunella group, 4-Fortunella group, 2-chloraniline group, 3-chloraniline group, 4-chloraniline group, 2-bratinella group, 3-bratinella group, 4-bratinella group, 2,3-diferencia group, 2,4-diferencia group, 2,5-diferencia group, 2,6-diferencia group, 3,4-diferencia group, 3,5-diferencia group, 2,5-dichloraniline group, 2-fluoro-4-chloraniline group, 3-fluoro-4-chloraniline group, 4-fluoro-2-chloraniline group, 4-fluoro-3-bratinella group, 4-cyanoaniline group, 2-methylphenylene group, 3-methylphenylene group, 4-methylphenylene group, 3,4-dimethylaniline group, 3-fluoro-4-methylphenylene group, 4-fluoro-3-methylphenylene group, 2-fluoro-3-triftormetilfullerenov group, 2-fluoro-4-triftormetilfullerenov group, 2-fluoro-5-triftormetilfullerenov group, 3-fluoro-4-triftormetilfullerenov group, 3-fluoro-5-triftormetilfullerenov group, 4-fluoro-2-triftormetilfullerenov group, 4-fluoro-3-triftormetilfullerenov group, 4-isopropylphenyl group, 4-triftormetilfullerenov group, 4-hydroxyproline group, 4-acetoacetanilide group, dimethylaminocarbonylmethyl group, dimethylaminocarbonylmethyl group, 4-methylthiophenyl group, 4-methylsulfinylphenyl group, 4-triptorelin ilen group, 4-methoxyphenyl the Naya group, 2,3-dimethoxyphenyl group, 3-fluoro-4-metoksifenilny group, 4-fluoro-3-metoksifenilny group, 2-chloro-4-metoksifenilny group, 3-chloro-4-metoksifenilny group, 4-deformationally group, 4-triphtalocyaninine group, 4-(2,1,1-triptoreline)phenyl group, 2-deformedarse-4-metoksifenilny group, 3,5-debtor-4-metoksifenilny group, 4-phenylphenolate group, 3-phenoxyphenyl group, 4-phenoxyphenyl group, 4-benzyloxyaniline group 4-(N-hydroxyimino)phenyl group, 4-(N-methoxyimino)phenyl group and 4-(N,N-dimethylaminomethylene)phenyl group.

Group D in the formula (1) represents a hydrogen atom, a branched or unbranched alkyl group with 1-4 carbon atoms, branched or unbranched halogenating group with 1-4 carbon atoms, alkenylphenol group with 2-4 carbon atoms, branched or unbranched alkoxygroup with 1-4 carbon atoms, cycloalkyl group with 3-6 carbon atoms, a halogen atom, a branched or unbranched alkoxycarbonyl group with 1-4 carbon atoms,

branched or unbranched alkylsulfonyl group with 1-4 carbon atoms or phenyl group.

Alkeneamine group with 2-4 carbon atoms include vinyl, propanolol and butenyloxy group. For the latter two groups of possible isomeric groups on the new double bond.

Branched or unbranched alkoxycarbonyl group with 1-4 carbon atoms include methoxycarbonyl, ethoxycarbonyl and propoxycarbonyl group.

Specific examples of other groups for the group D include the above-mentioned groups, but are not limited to.

For the above-mentioned groups D preferred are hydrogen atom, chlorine atom, methyl group, ethyl group, etinilnoy group, triptorelin group, methylsulfinyl group, ethoxycarbonyl group and phenyl group.

Group E in the formula (1) represents a hydrogen atom, halogen atom or phenyl group. Specific examples of these groups include the above-mentioned groups, but are not limited to.

For the above groups E preferred are a hydrogen atom, a halogen atom and phenyl group.

Group R1and R2both represent a halogen atom. Specific examples of these groups include the groups mentioned above, but are not limited to.

The group R3represents a hydrogen atom, a branched or unbranched alkyl group with 1-4 carbon atoms, branched or unbranched halogenating group with 1-4 carbon atoms, alkenylphenol group with 2-4 carbon atoms, alkylamino group with 2-4 carbon atoms or benzyl group. A specific example is s of these groups described above, but not limited to. For groups of R3preferred are a hydrogen atom, a branched or unbranched alkyl group with 1-4 carbon atoms, Alchemilla group with 2-4 carbon atoms, Alchemilla group with 2-4 carbon atoms.

Group R4and R5may be the same or different from each other and each denotes a hydrogen atom, a branched or unbranched alkyl group with 1-4 carbon atoms, branched or unbranched halogenating group with 1-4 carbon atoms, cycloalkyl group with 3-8 carbon atoms which may be substituted by branched or unbranched alkyl group with 1-4 carbon atoms, alkenylphenol group with 2-4 carbon atoms, alkenylphenol group with 2-4 carbon atoms, cyanomethylene group or phenyl group substituted by 0-5 arbitrary placeholder groups specified above.

In addition, the group R4and R5each can be αor β-fenetylline group, optionally having one or more substituting groups in the benzene ring. Substituting group selected from branched or unbranched alkoxygroup with 1-4 carbon atoms. Approximate replacement group may substitute the hydrogen atom 0-2 in arbitrary positions of the benzene ring αor β-fenetylline group.

Examples except the run or unbranched alkenyl groups with 2-4 carbon atoms, etkinlik groups with 2-4 carbon atoms, branched or unbranched alkoxyalkyl groups with 1-4 carbon atoms, branched or unbranched halogenating groups with 1-4 carbon atoms, halogen atoms and substituted phenyl groups include the groups described above, but are not limited to.

Examples of the substituted or unsubstituted amino group include amino group and substituted amino groups, such as dimethylaminopropyl, diethylaminopropyl, dipropylamino, dibutylamino, ethylmethylamino, diphenylamino, belinograph, anisidino, phenetidines, toluidine, xylidine, methoxycarbonylamino, cyclopropylamino and itinerating.

Examples cycloalkyl group with 3-8 carbon atoms which may be substituted by branched or unbranched alkyl group with 1-4 carbon atoms, include cyclopropyl group, cyclobutyl group, cyclopentyl group, tsiklogeksilnogo group, cycloheptyl group, cyclooctyl group and the same acyclic groups, substituted branched or unbranched alkyl group with 1-4 carbon atoms.

For the above groups of R4preferred are a hydrogen atom, methyl group and ethyl group. For the above groups of R5preferred is entrusted are a hydrogen atom, branched or unbranched alkyl group with 1-4 carbon atoms, branched or unbranched halogenation group with 1-4 carbon atoms, branched or unbranched cyanoaniline group with 1-4 carbon atoms, cycloalkyl group with 3-6 carbon atoms that may be substituted by an alkyl group, a substituted or unsubstituted phenyl group, substituted or unsubstituted benzyl group and a substituted or unsubstituted fenetylline group.

In addition, the group R4and R5may together form a five-membered or six-membered aliphatic ring. The ring can moderate one or two heteroatoms. Heteroatoms in the aliphatic ring include nitrogen, oxygen, sulfur, phosphorus and arsenic. Five-membered or six-membered ring may be substituted by a group selected from alkyl groups with 1-4 carbon atoms, branched or unbranched halogenating groups with 1-4 carbon atoms, branched or unbranched alkoxygroup with 1-4 carbon atoms, halogenlamp with 1-4 carbon atoms, halogen atoms, ceanography and nitro-group.

In a particularly preferred embodiment of the compounds according to the invention R4and R5together form heteroalicyclic group, such as five-membered or six-membered ring containing one nitrogen atom, or sestic the military ring containing one nitrogen atom and one oxygen atom or sulfur (for example, connection 118-122 in Table 1 of the following Examples).

Specific examples of the group-N(R4R5in the formula (1) below, including cases where R4and R5together form a five-membered or six-membered aliphatic ring, a substituted alkyl group with 1-4 carbon atoms, etc. In the following formulas, Me, Et, Pr, Bu, i, t, pen and hex denotes methyl, ethyl, propyl, butyl, ISO-, tert-, pentyl and hexyl, respectively.

The PREFERRED EMBODIMENT of the INVENTION

Table 1 presents the connections 1-124, synthesized in Examples (described later) as typical examples of substituted derivatives of pyrazole of the formula (1) according to the present invention. However, the compounds according to the invention is not limited to them.

When R4represents a hydrogen atom and R5is substituted by the amino group-N(R11,R12in the formula (1), in particular the connection according to the invention represents a substituted hydrazide derivative of pyrazole represented by the formula (4):

where n is 0 or 1;

Rather it represents a phenyl; E, R1and R2represent a hydrogen atom;

D and R3regardless of oznachaet branched or unbranched alkyl group with 1-4 carbon atoms; and

group R11and R12may be the same or different and each denotes a hydrogen atom, a branched or unbranched alkyl group with 1-4 carbon atoms, branched or unbranched alkoxycarbonyl group with 1-4 carbon atoms.

Specific examples of the aforementioned groups described above, but are not limited to.

In substituted derivatives of pyrazole of the formula (4) preferably, the group represented a phenyl group substituted by 0-3 substitute groups (0 substituting groups means unsubstituted phenyl group), the group D is a group selected from branched or unbranched alkyl groups with 1-4 carbon atoms, cycloalkyl group with 3-6 carbon atoms and halogen atoms, E represents a hydrogen atom, a group R1and R2both represent a halogen atom, a group R3represents a group selected from branched or unbranched alkyl groups with 1-4 carbon atoms, alkenyl groups with 2-4 carbon atoms, etkinlik groups with 2-4 carbon atoms and groups of R11and R12would be the same or different and selected from a hydrogen atom, a branched or unbranched alkyl groups with 1-4 carbon atoms.

Connections 123 and 124, are presented in Table 1 Examples (listed on the over), are typical examples of substituted derivatives of pyrazole of the formula (4). However, the compounds according to the invention are not limited to.

The method of obtaining substituted derivatives of pyrazole

The following describes the method of obtaining the compounds according to the invention. To obtain compounds according to the invention (1) must meet the following reaction stages:

Stage (a): a Derivative of pyrazole of the formula (5) is reacted with the ether derivative halogenosilanes (i.e. derived oxime halogenerator) formula (6) in the presence of a base to obtain the ether derivative of the formula (7):

Stage (a):

where Z represents a halogen atom and R13represents a methyl or ethyl group.

Stage (b): Ethereal group ethereal derivative (formula 7) hydrolyzing the reason for obtaining a carboxylic acid derivative represented by the formula (8).

Stage (C): carboxylic acid Derivative reacts with the amine R4-NH-R5in the presence of a condensing agent to obtain compounds according to the invention (formula 1):

1):

Stage (b):

where R4and R4represent the same groups as described above.

Approximate condensing agents for use in Stage (C) include carbonyldiimidazole, conidiomata is, decarboxylation hydrochloride and 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide.

Some types of amines can affect the ether derivative of the formula (7) for the direct synthesis of compounds according to the invention of formula (1).

Approximate base used in the reaction between the derivative of pyrazole of the formula (5) and ether derivative halogenosilanes formula (6)include inorganic bases such as sodium hydride, sodium bicarbonate, sodium carbonate, potassium carbonate and cesium carbonate, and organic bases such as triethylamine and 1,8-diazabicyclo(5,4,0)-undeca-7-ene (DBU).

Regarding the amounts of reagents subjected to the reaction, usually about 1-5 equivalents, preferably 1-3 equivalents of ether derivative halogenosilanes formula (6), and about 1-5 equivalents, preferably 1-3 equivalents of base per equivalent of the pyrazole derivative represented by the formula (5).

In the above reaction is commonly used solvent. Suitable solvents include ethers, such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, ethylene oxide and 1,4-dioxane; acid amides such as N,N-dimethylformamide and N-organic; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; and acetonitrile.

The reaction temperature and reaction time on the stage (a) accounted for the amount usually from about 0 to 150° C, preferably from 10 to 100°and from 10 minutes to 24 hours, respectively. The reaction may be accompanied by the usual methods of processing and purification of column chromatography, recrystallization, etc. that is required to obtain the final compounds.

Exemplary bases used in stage (b)include lithium hydroxide, potassium hydroxide and sodium hydroxide.

Relative to the amount of the condensing agent under reaction used approximately 1-5 equivalents, preferably 1-3 equivalents, as well as about 1-5 equivalents, preferably 1-3 equivalents of base are used per equivalent of the ether derivative represented by the formula (7).

In the above reaction is usually a mixture of water and an alcoholic solvent. Suitable solvents include methanol, ethanol, propanol and butanol. The solvent and water are used in equal amounts.

After the reaction, the reaction mixture can be processed in the usual method, and the reaction product can be isolated column chromatography, recrystallization, etc.

The reaction temperature and reaction time on the stage (C) is usually from about 0 to 100°C, preferably from 10 to 80°and from 10 minutes to 24 hours, respectively.

Substituted pyrazol ring, represented by formula (5), may SinTe aromatica of various derivatives of pyrazole, with the replacement group. Exemplary methods of synthesis are given below for pyrazol ring, in which groups D and E are hydrogen atoms or is substituted, or in which the group D is a halogen atom.

Substituted pyrazol ring of formula (5)in which E represents a hydrogen atom, can be obtained by the reaction of α-formication the following formula (9) with hydrazinehydrate (stage (d)). It is also obtained by the reaction raminosoa derivative of the formula (10) with hydrazinehydrate (stage (e)).

Regarding the amounts of reagents under reaction used approximately 1-5 equivalents of hydrazine hydrate is added to the equivalent of α-formication formula (9) or raminosoa derivative of the formula (10).

In the above reaction is commonly used solvent. Suitable solvents include ethers, such as diethyl ether, 1,2-dimethoxyethane and tetrahydrofuran; acid amides such as N,N-dimethylformamide and N-organic; alcohols such as methanol and ethanol; organic acids such as acetic acid, and aromatic hydrocarbons such as benzene and toluene.

The reaction temperature and reaction time on the stage (d) is usually from about 0 to 150°and from 10 minutes to 24 hours, respectively. The reaction may be accompanied by normal SP the ways of processing and purification of column chromatography, by recrystallization, etc. that is required to obtain the final compounds.

α-Formication represented by the formula (9)can be obtained by condensation of Clausena between the derivative of the ketone of the formula (11) and format HCOOR14(where R14represents a methyl or ethyl group) in the presence of a base (stage (f)).

Stage (f):

Approximate base used in the above reaction include sodium hydride, sodium methylate and sodium ethylate.

Regarding the amounts of reagents under reaction used approximately 1-20 equivalents format and approximately 1-2 equivalents of base per equivalent of the derived ketone represented by the formula (11).

In the above reaction is commonly used solvent. Suitable solvents include formats. The solvent may be optionally diluted with ether, such as diethyl ether, 1,2-dimethoxyethane or tetrahydrofuran.

The reaction temperature and reaction time on the stage (f) is usually from about 0 to 100°and from 10 minutes to 24 hours, respectively. The reaction may be accompanied by the usual methods of processing and purification of column chromatography, recrystallization, etc. that is required to obtain the final compounds.

Eminova derivative of the formula (10) can the be obtained by the reaction of a derivative of a ketone of the formula (11) with N,N-dimethylformamidine (stage (g)).

Stage (g):

Regarding the amounts of reagents under reaction used 1-10 equivalents of N,N-dimethylformamidine equivalent to the derived ketone represented by the formula (11).

In the above reaction is commonly used solvent. Exemplary solvents include aromatic hydrocarbons such as benzene and toluene, and ethers such as 1,2-dimethoxyethane and tetrahydrofuran.

The reaction temperature and reaction time on the stage (g) is usually from about 0 to 150°and from 10 minutes to 24 hours, respectively. The reaction may be accompanied by the usual methods of processing and purification of column chromatography, recrystallization, etc. that is required to obtain the final compounds.

Substituted pyrazol ring of formula (5)in which E is a proxy group, can be obtained by the reaction of diketone derivative of the following formula (12) with hydrazinehydrate (stage (h)).

Stage (h):

Regarding the amounts of reagents under reaction used 1-5 equivalents of hydrazine hydrate is added to the equivalent derived ketone of the formula (12).

In the above reaction is commonly used solvent. Suitable solvents include ethers, such as diethyl ether, 1,2-dimethoxyethane is tetrahydrofuran; acid amides such as N,N-dimethylformamide and N-organic; alcohols such as methanol and ethanol; organic acids such as acetic acid; and aromatic hydrocarbons such as benzene and toluene.

The reaction temperature and reaction time on the stage (h) is usually from about 0 to 150°and from 10 minutes to 24 hours, respectively. The reaction may be accompanied by the usual methods of processing and purification of column chromatography, recrystallization, etc. that is required to obtain the final compounds.

The derived ketone represented by the formula (12)can be obtained by condensation of Clausena between the derivative of the ketone of the formula (11) and carboxylate in the presence of a base (stage (i)). R15represents a C1-4alkyl group.

Stage (i):

Approximate base used in the above reaction include sodium hydride, sodium methylate and sodium ethylate.

Regarding the amounts of reagents under reaction used approximately 1-20 equivalents of carboxylate and about 1-2 equivalents of base per equivalent of the derived ketone represented by the formula (11).

In the above reaction is commonly used solvent. Exemplary solvents include ethers, such as diethyl ether, 1,2-dimethoxy the Academy of Sciences and tetrahydrofuran; and acid amides such as N,N-dimethylformamide and N-organic.

The reaction temperature and reaction time on stage (i) is usually from about 0 to 100°and from 10 minutes to 24 hours, respectively. The reaction may be accompanied by the usual methods of processing and purification of column chromatography, recrystallization, etc. that is required to obtain the final compounds.

Substituted pyrazol ring of formula (5)in which D and E are both hydrogen atoms, can be obtained by the reaction of the derived enamine following formula (13) with hydrazinehydrate (stage (j)) to obtain the pyrazole derivative of the formula (5)in which D and E are both hydrogen atoms.

Stage (j):

Regarding the amounts of reagents under reaction used approximately 1-5 equivalents of hydrazine hydrate is added to the equivalent derived enamine of the formula (13).

In the above reaction is commonly used solvent. Suitable solvents include ethers, such as diethyl ether, 1,2-dimethoxyethane and tetrahydrofuran; acid amides such as N,N-dimethylformamide and N-organic;

alcohols, such as methanol and ethanol; organic acids such as acetic acid; and aromatic hydrocarbons such as benzene and toluene.

The reaction temperature and time to implement the tion stage (j) is usually from about 0 to 150° With and from 10 minutes to 24 hours, respectively. The reaction may be accompanied by the usual methods of processing and purification of column chromatography, recrystallization, etc. that is required to obtain the final compounds.

Substituted pyrazol ring of formula (5)in which D is a hydrogen atom, can be obtained by the reaction of diketone derivative of the following formula (14) with hydrazinehydrate (stage (k)).

Phase (k):

Regarding the amounts of reagents under reaction used approximately 1-5 equivalents of hydrazine hydrate is added to the equivalent of diketone derivative of the formula (14).

In the above reaction is commonly used solvent. Suitable solvents include ethers, such as diethyl ether, 1,2-dimethoxyethane and tetrahydrofuran; acid amides such as N,N-dimethylformamide and N-organic; and aromatic hydrocarbons such as benzene and toluene.

The reaction temperature and reaction time on the stage (k) is usually from about 0 to 150°and from 10 minutes to 24 hours, respectively. The reaction may be accompanied by the usual methods of processing and purification of column chromatography, recrystallization, etc. that is required to obtain the final compounds.

Derived diketone represented by the formula (14)can be obtained to what ntensities of Clausena between the derivative of the ketone of formula (15) and carboxylate in the presence of a base (stage (1)). R16is1-4alkyl group.

Stage (1)

Regarding the amounts of reagents under reaction used approximately 1-20 equivalents of carboxylate and about 1-2 equivalents of base per equivalent of the derived ketone represented by the formula (14).

Examples of bases that are applicable in the above reaction include sodium hydride, sodium methylate and sodium ethylate.

In the above reaction is commonly used solvent. Suitable solvents include ethers, such as diethyl ether, 1,2-dimethoxyethane and tetrahydrofuran; and acid amides such as N,N-dimethylformamide and N-organic.

The reaction temperature and reaction time on the stage (1) is usually from about 0 to 100°and from 10 minutes to 24 hours, respectively. The reaction may be accompanied by the usual methods of processing and purification of column chromatography, recrystallization, etc. that you want to restore the final connection.

Substituted pyrazol ring of formula (5)in which D is a halogen atom (X), can be obtained by the reaction of halogenation agent with a pyrazole derivative of the following formula (16) (stage (m)). X represents a chlorine atom, bromine or iodine.

Stage (m):

Relative activities is but quantities of reagents, subjected to the reaction, are used 1-10 equivalents of halogenation agent on the equivalent of a pyrazole derivative of the formula (16).

Approximate halogenation agents include chlorine gas, N-chlorosuccinimide, 1,5-dichloro-5,5-dimethylhydantoin, bromine, N-bromosuccinimide and 1,5-dibromo-5,5-dimethylhydantoin.

In the above reaction is commonly used solvent. Suitable solvents include halogenated solvents such as dichloromethane, chloroform, carbon tetrachloride and 1,2-dichloroethane.

The reaction temperature and reaction time on the stage (m) is usually from about 0 to 30°and from 10 minutes to 24 hours, respectively. The reaction may be accompanied by the usual methods of processing and purification of column chromatography, recrystallization, etc. that is required to obtain the final connection.

Ether derived halogenosilanes represented by the formula (6)can be obtained by the reaction of the hydroxylamine derivative of the formula (19) with a derivative of halogenerator formula (18) (stage (n)).

Stage (n):

Regarding the amounts of reagents under reaction used 1-3 equivalents, preferably 1-1 .5 equivalents of hydroxylamine of the formula (19) is equivalent to the derived halogenerator formula (18).

In the above reactions are usually the use of a solvent. Suitable solvents include alcohols, such as methanol, ethanol, normal propanol, isopropanol, normal butanol and benzyl alcohol; and aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene and ethylbenzene. Of them, preferred are methanol, ethanol, benzene and toluene.

The reaction may be accompanied by the usual methods of processing and the final reaction product may be subjected to the next reaction without purification.

The reaction temperature and reaction time on the above stages are usually from about 0 to 150°C, preferably from 20 to 100°and from 10 minutes to 24 hours, respectively. The reaction may be accompanied by normal processing and the final reaction product may be subjected to the next reaction without purification.

Compounds according to the invention (4) can be obtained according to such aforementioned method synthesis step (C). In this synthesis of the carboxylic acid derivative of the formula (8) is condensed with a substituted hydrazine having the replacement group, R11and R12(i.e. H2NNR11R12instead Amin R4-NH-R5. Reaction conditions are the same as for stage (C). Some species of hydrazine derivatives can interact with the ether derivative of the formula (7) for the direct synthesis of the compounds according to the invention.

Gerbil the basic steps

Herbicide range (mountainous region)

Some compounds according to the invention are useful as a herbicide for upland areas and raw land. They in any solid tillage, integrated cultivation and processing of the leaves can have a small high doses of herbicide action on different types of field weeds. Control weeds are, for example, broadleaf weeds, including Solanaceae weeds such as Solanum nigrum and Datura stramonium, Malvaceae weeds such as Abutilon theophrasti and Sida spinosa, weeds Convolvulaceae, such as Ipomoea PPPs. (for example, Ipomoea purpurea) and Calystegia PPPs., weeds Amaranthaceae, such as Amaranthus lividus and Amaranthus retroflexus, Compositae weeds, such as Xanthium pensylvanicum, Ambrosia artemisiaefolia, Helianthus annuus, Galinsoga ciliata, Cirsium arvenser, Senecio vulgaris and Erigeron annus, weeds Cruciferae, such as Rorippa indica, Sinapis arvensis and Capsella Bursapastoris, weeds Polygonaceae, such as Polygonum Blumei and Polygonum convolvulus, weeds Portulacaceae, such as Portulaca oleracea, Cher. weeds Chenopodiaceae, such as Chenopodium album, Chenopodium ficifolium and Kochia scoparia, weeds Caryophyllaceae, such as Stellaria media, weeds Scrophulariaceae, such as Veronica persica, weeds Commelinaceae, such as Commelina communis, Gramineae weeds, such as Lamium amplexicaule and Lamium purpureum, weeds Euphorbiaceae, such as Euphorbia supina and Euphorbia maculata, weeds Rubiaceae, such as Galium spurium and Rubia akane, weeds Violaceae, such as Viola mandshurica and herbaceous weeds such as Sesbania exaltata and Cassia obtusifolia; and other weeds on the tea cereal weeds, such as Sorghum bicolor Panicum dichotomiflorun, Sorghum halepense, Echinochloa crus-galli var. crus-galli, Echinochloa crus-galli var. praticola, Echinochloa utilis, Digitaria adscendens, Avenafatua, Eleusine indica, Setaria viridis, Alopecurus aegualis and ROA Appia, and Cyperaceous weeds such as Cyperus rotundus (Cyperus esculentus).

Further compounds according to the invention can suppress widespread weeds such as weeds appearing on the harvest fields, fallow lands, land under permanent crops, pastures, lawns, on both sides of the railway, playgrounds, vacant land, forests, agricultural lands, dams and other uncultivated lands.

The selectivity to crops (upland area)

Some compounds according to the invention do not affect the growth of major crops, such as Orysa sativa, Triticum aestivum, Hordeum vulgare, Sorghum bicolor, Arachis hypogaea, Zea mays, Glycine max, Gossypium spp. and Beat vulgaris, lawn grasses, such as Zoysia japonica and Zoysia matrella, and horticultural crops, such as flowers, ornamental plants and vegetable crops, including Raphanus sativus and Brassica napus.

Herbicide spectrum (rice fields)

Some compounds according to the invention are useful as herbicides rice fields. They in any treatment as water and foliage are able to give a small dose of high herbicide action on different varieties of rice weeds. Weeds such, for example, weeds Alismatceae, such as Alisma canaliculatum, Sagittaria trifolia and Sagittaria pygmaea, ornate Cyperaceous, such as Cyperus difformis, Cyperus serotinus, Scirpus juncoides, Eleocharis kuroguwai and Eleocharis acicularis, weeds Scrophulariaceae, such as Lindernia pyxidaria, weeds Pontederiaceae such as Monochoria vaginalis, weeds Potamogetonaceae, such as Potamogeton distinctus, weeds Umbelliferae such as Oenanthe javanica, weeds Lythraceae such as Rotala indica and Ammannia multiflora, weeds Elatinaceae, such as Elatine triandra and Graminaceous weeds such as Echinochloa oryzicola, Echinochloa crus-galli var. formosensis and Echinochloa crus-galli. Var. crus-galli.

The selectivity to crops (rice fields)

Compounds according to the invention do not exhibit significant chemical hazards when transplanting rice or direct planting of rice.

Actions on aquatic plants

Compounds according to the invention have an effect on the algae, such as blue-green algae and aquatic weeds, such as Eichnomia crassipes, which appear in streams, channels, lakes, swamps, ponds and water basins.

Structures

Herbicide composition according to the present invention contain one or more kinds of the compounds according to the invention as active ingredients. In the compositions the active ingredient(s) combined with solid or liquid carrier and optionally a surface active substance and other adjuvant, and the mixture is prepared in conventional forms of agricultural chemicals, such as wet powders, powders, granules, beads, concentrated liquids, aerosols is, water-soluble powders, concentrates, emulsions, concentrated suspensions, fluid substances and briquettes. In particular, for use in rice fields herbicide composition preferably is made into pellets and packaged in water-soluble polymer film, as will be described later.

To obtain herbicide compositions can be used with any method commonly used to obtain agricultural chemicals. If necessary, the active ingredients for agricultural chemicals can finely sprayed in advance air mill or impact mill and mixed with a carrier, a surface-active agent, etc. To obtain compositions is not in the form of powders may be appropriate processing depending on the final composition. In the case of granular formulations, for example, the ingredients can be mixed, crushed and granulated to the desired size using the extruder according to the General method of granulation of agricultural chemicals. To obtain the suspension formulations of the active ingredient(s) may be dispersed in water containing a carrier and a surfactant as a wetting agent, dispersing agent and suspensory agent, and suspended particles can be prop is disposed through a wet mill, such as DYNO-Mill, or sand mill, and optionally mixed with adjuvant, etc. water-Soluble powders and wet powders can be dissolved or suspended in water for application. Concentrates of emulsions can be obtained by mixing the active ingredient(s) with the appropriate emulsification agent using a homogenizer, emulsifier under pressure or DYNO-Mill.

Supplements

In the practical application of the compounds according to the invention compounds can be used separately. They can also be used in compositions in combination with useful additives commonly used for compounds such as carriers, surfactants, solvents and adjuvants, effective to improve dispersion and to improve other properties of the active ingredients (for example, filling agents, these antifreeze agents, anti-foam agents, antiseptic agents, stabilizing agents and dyes).

Examples of the solid carriers or diluents include finely ground powders or granules vegetable substances, fibrous materials, synthetic plastic powders, clays (such as kaolin, bentonite, in ground clay, diatomaceous earth and clay Fubasami), talc, inorganic materials (pumice, sulfur powder, activated carbon and calcium carbonate) and production of the mini-fertilizers (such as ammonium sulfate, the ammonium phosphate and urea). Examples of liquid carriers or diluents include water, alcohols, ketones, esters, aromatic hydrocarbons, aliphatic hydrocarbons, esters, NITRILES, amides (N,N-dimethylformamide, dimethyl sulfoxide), and halogenated hydrocarbons.

Examples of surfactants include alkyl esters of sulfuric acid, alkyl sulphonates, alkylarylsulphonates acid, alcylaryl ethers, esters of glycol ethers polyhydrogenated alcohols and derivatives of alcohols sugars.

Examples of scattering or dispersing agents include casein, gelatin, starch powder, carboxymethylcellulose, gum Arabic, alginic acid, lignin, bentonite, polyvinyl alcohol, palm oil, molasses, agar, etc.

Examples of the stabilizers include a mixture of isopropylacetate, tricresylphosphate, higher oil epoxidase, surface-active agents, fatty acids and their esters. As will be described hereinafter, the compositions according to the present invention can contain other fungicides, insecticides, herbicides or fertilizers in addition to the above ingredients.

The concentration of the active ingredients

The concentration of active ingredient in the herbicide compositions according to the invention can vary depending on the type of the above-described composition. In the case of wet powders concentration and the active ingredient is in the range from 5 to 90% and preferably from about 10 to 85%. For concentrates of emulsions, the concentration of active ingredient is in the range from 3 to 70% and preferably from about 5 to 60%. For pellets, the concentration of active ingredient is in the range from 0.01 to 50% and preferably from 0.05 to 40%.

Use (dosage and method of application)

Thus obtained wet powders or concentrates of emulsions can be sprayed or be diluted with water to the desired concentration of the suspension or emulsion before or after expansion of suppressed weeds. Granular formulations may be applied directly or also be entered before or after expansion of suppressed weeds. In the practical application of the herbicide composition according to the invention as a herbicide, it will accordingly be used in such quantities that allow you to obtain not less than 0.1 g of the active ingredient(s) per hectare.

When the connection according to the invention is used as the active ingredient of the herbicide, its amount is usually from 10 g to 8000 g, preferably from 10 g to 2000 g per hectare, although it varies depending on weather conditions, type of composition, time of use, application methods, soil conditions, cultivation of crops suppress weeds, etc. In case emulsifying concentrates, wet powders, to which centrato suspensions, concentrates of emulsions, water soluble granules, liquid compositions and other data number of such compositions usually applied after dilution 10-1000 liters of water (optionally containing adjuvants such as fillers) per hectare. On the other hand, granules and some types of concentrated suspensions and liquid formulations are usually applied without dilution. Examples of adjuvants include surfactants described above, polyoxyethylene fatty acids (esters), ligninsulfonate, abietate, dinaftiletilena and vegetable oils, such as oil concentrate, soy oil, corn oil, cottonseed oil and sunflower oil.

The use of a composition

Herbicide composition according to the invention can be used in a mixture with one or more agents for plant protection, such as fungicides, insecticides, herbicides, nematicides, acaricides, bactericides, plant growth regulators, fertilizers and soil improvers.

Compounds according to the invention can be used in combination with compound(s)that control the growth or regulate activity on valuable plants, such as crops, ornamental plants and fruit trees. Such compounds controlling the growth of a plant include, but are not limited to, ethephon, indoleacetic acid, articleset, closefunc, dichlo the prop, 1-naphthylacetamide, 4-cap, benzylaminopurine, forchlorfenuron, gibberellins, maleic hydrazide, invented, uniconazole-R, chlormequat, paclobutrazol, flurried, meekathara, prohexadione calcium, trihexyphenidyl, daminozide, mefluidide, isoprothiolane sulfate and oxine. They can be used separately or as a mixture of two or more kinds.

Examples of fungicides include, but are not limited to, phtalic, flutolanil, mepronil, S-658, pyroquilon, tricyclazole, provenzal, isoprothiolane, iprobenfos, telital and benomyl. Examples of insecticides include, but are not limited to, isoxathion, trichlorfon, propafol, diazinon, formation, disulfoton, dimethoate, monocrotophos, Arafat, carbofuran, carbosulfan, thiocyclam, cartap, bensultap, benfuracarb, furathiocarb, carbaryl, buprofezin, fenobucarb, metolcarb, propoxur, methomyl, Imidacloprid, nitenpyram, cicloprofen, etofenprox and selflove. They can be used separately or as a mixture of two or more kinds.

Herbicide mixture

The application of the herbicide composition, and then mixed with another herbicide ingredient, causes a reduction of the applied dose and labor to apply. Due to the synergistic effects of such mixed herbicides can be expected over a broad spectrum herbicide and higher herbicide activity described in the s here herbicide compositions. Herbicide composition can be mixed with two or more known herbicides. Such herbicides include atrazine, cyanazine, deltamethrin, metribuzin, prometryn, Simazine, simetryn, chlortoluron, Diuron, dameron, fluometuron, Isoproturon, linuron, methabenzthiazuron, nicarbazin, bromoxynil, ioxynil, ethalfluralin, pendimethalin, trifluralin, acifluorfen, acifluorfen-sodium, bifenox, gametocidal, fomesafen, lactofen, oxadiazon, oxadiargyl, oxyfluorfen, carfentrazone-ethyl, flumiclorac-pentyl, flumioxazin, fluthiacet-methyl, sulfentrazone, thidiazuron, azafenidin, pyraflufen-ethyl, cinidon-ethyl, difenzoquat, Diquat, paraquat, 2,4-D, 2,4-DB, DCPA, MSRA, MSRB, clomipram, clopyralid, dicamba, dithiopyr, fluroxypyr, mecoprop, napleonic, finacial, quinolones, triclopyr, thiazopyr, acetochlor, alachlor, butachlor, detail-ethyl, metolachlor, pretilachlor, propachlor, enculture-methyl, chlorsulfuron, chlorimuron-ethyl, halosulfuron-methyl, metsulfuron-methyl, nicosulfuron, primisulfuron-methyl, pyrazosulfuron-ethyl, sulfometuron-ethyl, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, oxasulfuron, azimsulfuron, florasulam-methyl, cycloaliphatic, flumetsulam, florasulam, flupyrsulfuron, flazasulfuron, imazosulfuron, metosulam, dicloflam, prosulfuron, rimsulfuron, triflusulfuron-methyl, atok sulfuron, sulfosulfuron, flucarbazone sodium, procarbazine-sodium (MKN-6561), imazamethabenz-methyl, imazapyr, imazaquin, imazethapyr, mazamet, imazamox, bispyribac sodium, Perminova-methyl, pyrithiobac-sodium, aloxide-sodium, clethodim, sethoxydim, tralkoxydim, tepraloxydim, profoxydim (BAS-625H), diclofop-methyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, fluazifop-butyl, fluazifop-p-butyl, haloxyfop-methyl, quizalofop-p-ethyl, cyhalofop-butyl, clodinafop-propargyl, benzefoam, clomazone, diflufenican, norflurazon, pyrazolate, paradoxien, picolinafen, beflubutamid, flurtamone, isoxaflutole, sulcotrione, benzamycin, mesotrione, glufosinate-ammonium, glyphosate, bentazone, benthiocarb, bromated, butamifos, butyl, timepart, dimethenamid, DSMA, ARTS, asbroker, isoxaben, mefenacet, molinet, MSMA, piperophos, perimutter, prosulfocarb, propanil, peridot, triallate, cafestol, flupoxam, flufenacet, diflubenzuron, triazolam, phenoxazone, indianian, metaventure, oxacyclobutane and phentrazine.

These compounds are described in the catalog of Farm Chemical Handbook (Meister Publishing Company) (1997), SHIBUYA INDEX (8th edition) (1999, The Pesticide Manual, British crop protection council) 12th edition (2000) and Herbicide research conspectus (Hakuyu-sha). The above compounds are given for illustration and not for exceptions. The compounds can be used alone or as a mixture of two or more kinds.

With the appropriate mixing ratio between the compound of the invention and other herbicide(s) can vary depending on the type of active ingredients of additional herbicide(s). However, it is usually in the range from 1:0.01 to 1:10 by weight. When the herbicide composition according to the invention are used with the above-mentioned other herbicides, a method of obtaining a composition is not specifically limited. For example, the connection according to the invention and the other active ingredient(s), such as the aforementioned additional herbicide(s), each is pre-mixed with a solid carrier, liquid carrier, a surface-active substance or other adjuvant to obtain concentrates of emulsions, wet powders, suspension concentrates, water-dispersible granules, water-soluble powders, aqueous solutions, water-dispersible granules or the like, followed by mixing together. It is also possible that the connection according to the invention is pre-mixed with additional herbicide(s) and then the mixture was mixed with a solid carrier, liquid carrier, a surface-active substance or other adjuvant composition to obtain emulsification concentrate, wet powder, suspension concentrate, granules, emulsion concentrate, water soluble granules or the like, the resulting compositions will contain the connection according to the invention and other herbicides as active ingredients in a total amount of from 0.5 to 80% by weight, preferably from 1.5 to 70% by weight.

Method of use

Obtained the oppozitsii of the present invention can be used on plants want to suppress directly or after dilution with water or the like may be carried out according to various methods. Exemplary methods of application include spraying or spreading, use a creamy or paste-like herbicides, the use of steam and applying granular herbicides slow release.

Herbicide composition according to the invention can be applied to plants by direct spraying, spreading or application on the target, or the spread or introduction into the soil around plants, rice fields, etc. In the case of rice fields can be any of the application methods, such as the transfer of the herbicide composition of the agricultural stream of water from a water source, a lower level of the dam in the rice fields and distribution, or making compositions on pereskazyvayuschuyu seedlings of rice machine method, suitable for use with herbicide.

When herbicide composition should be applied on the water surface, the preferred embodiment of the invention, where the herbicide composition is filled and packaged in water soluble or erodible in water tanks for processing and application. When such floating tanks scattered on the flooded field, they float on the water surface and spread far. The investigator is about, active herbicide ingredients can be dispersed on top of or inside the rice fields. It may therefore be achieved by reducing the operating force applied herbicide and phytotoxicity and can be expected to be sustainable action.

In order herbicide composition could float on the water surface, it is necessary that a certain density of the composition was less than 1.0, preferably 0.95 or less, or that the composition contained a surface agent such as carbonate and water-soluble solid acid.

In applying the herbicide composition according to the invention, in which the herbicide composition packaged in a water soluble or erodible in the water tank, the desired goal can be achieved only with the introduction of the composition directly into the waterlogged field in respect of from 3 to 20 containers 10 and. Introduced into the water these tanks are spread on the water surface, plunging once, but not floating on the surface, and spreading on the water surface, or apply again, submerging and surfacing soon, that is, they are immersed, but soon come to the surface and distributed on the water surface again and again. In General floating herbicide compositions of this type, when they are immersed and then emerge, capable of rapid ascent and unlikely to be left on the surface of the soil is. As described above, the compositions of the present invention have an excellent property distribution (diffusion property) and spread evenly over the rice fields. These properties allow you to achieve a homogeneous dispersion compositions even without getting on the rice field and the workforce can be reduced. Accordingly, the above-mentioned floating structures herbicide compositions are the preferred embodiment of the present invention.

EXAMPLES

The present invention is further described by the following examples and test examples, but they must in no way be considered as limiting the invention.

In the following description, the term "part(s)" denotes "part(s) by weight".

Synthesis of pyrazol derivatives

Further detailed examples illustrate the synthesis of compounds according to the invention, represented by formula (1) or (4).

Example obtain 1

Synthesis of ethyl-2-methoxyimino-3-bromopropionate (represented by formula (6) Stage (n), where n is 0, R1and R2both are hydrogen atoms, Z represents a bromine atom, R3represents a methoxy group, and R13represents ethyl.

Ethylbromide (purity 80%), 38.9 g (200 mmol as calculated for purity 100%) was dissolved in 100 ml of ethanol. At room temperature the solution was added 16.6 g (200 mm is l) hydrochloride methoxyamine, further heating by boiling under reflux for 2 hours. After the reaction, the ethanol was evaporated and to the residue was added 200 ml of ethyl acetate. The reaction product was washed successively with a saturated aqueous solution of sodium bicarbonate and an aqueous solution of sodium chloride and then dried over anhydrous magnesium sulfate. After filtration and subsequent distillation to remove solvent received 36,9 g (165 mmol) of ethyl-2-methoxyimino-3-bromopropionate in the form of a light yellow oily substance. The yield was 80%. The synthesized product was subjected to the next reaction without further purification.

Example of getting 2

Synthesis of N-methylamide-2-methoxyimino-3-((4'-methoxyphenyl)-4-methyl-pyrazole)-1-yl-propanoic acid (Compound 41, represented by formula (1)in which n is 0, And represents 4-methoxyphenyl, D represents methyl, E is a hydrogen atom, R1and R2both represent hydrogen atoms, R3represents methyl, R4represents a hydrogen atom and R5represents methyl).

(Stage 1)

10 g (60.9 mmol) of 4'-methoxypropiophenone was dissolved in 100 ml of methylformate. At room temperature the solution was added dropwise 15.3 g (79.2 mmol) of sodium methoxide at a concentration of 28% methanol solution for 30 minutes with the consequences of the decisions by stirring at the same temperature for 6 hours. To the reaction mixture were added 100 ml of water and the pH of the solution was brought to 1 with concentrated hydrochloric acid, then stirring for 1 hour. Next, the reaction mixture three times was extracted with 100 ml of ethyl acetate. The organic phase is washed with saturated aqueous sodium chloride and then dried over anhydrous magnesium sulfate. After filtration and subsequent evaporation to remove solvent was obtained 9.8 g (51.0 mmol) of 2-formyl-4'-methoxypropiophenone in the form of light yellow crystals. The yield was 84%. The synthesized product was subjected to the next reaction without further purification.

(Stage 2)

9.8 g (51.0 mmol) of 2-formyl-4'-methoxypropiophenone synthesized in Stage 1, was dissolved in 150 ml of ethanol. At room temperature the solution was added dropwise 3.8 g (61.2 mmol) of 80% hydrazine hydrate is added, then stirring at the same temperature for 1 hour and then heating at boiling under reflux for 2 hours. After the reaction, the reaction mixture was cooled to room temperature and the solvent was evaporated. The result obtained 8.4 g (44.9 mmol) of 3-(4'-methoxyphenyl)-4-methylpyrazole in the form of an orange oily substance. The yield was 88%. The synthesized product was subjected to the next reaction without further purification.

(Stage 3)

1.6 g (8.5 mmol) of 3-(4'-methoxyphenyl)-4-meth is pyrazole, synthesized in Stage 2, was dissolved in 30 ml of N,N-dimethylformamide. At room temperature the solution was sequentially added 1.4 g (10.2 mmol) of sodium carbonate and 2.9 g (10.2 mmol) of ethyl-2-methoxyimino-3-bromopropionate synthesized in the Example of obtaining 1, further heating to 110°With stirring for 4 hours. After the reaction, the reaction mixture was poured into 100 ml of water and extraheavy three times with 50 ml diethyl ether. The organic phase is washed with saturated aqueous sodium chloride and then dried over anhydrous magnesium sulfate. After filtration and subsequent evaporation to remove solvent was obtained 2.6 g (7.4 mmol) of ethyl-2-methoxyimino-3-((4'-methoxyphenyl)-4-methyl-pyrazole)-1-yl-propanoate in a three-neck flask with 100 ml Yield was 87%. The synthesized product was subjected to the next reaction without further purification.

(Stage 4)

1.1 g (3.1 mmol) of ethyl-2-methoxyimino-3-((4'-methoxyphenyl)-4-methyl-pyrazole)-1-yl-propanoate synthesized in Stage 3, were combined with a methanol solution of 40%methylamine, further stirring at room temperature for 4 hours. After the reaction, the solvent was evaporated. The obtained residue was purified by column chromatography on silica gel using chloroform as additionally separated by. Next, the solvent was removed by evaporation, olucha 0.96 g (2.9 mmol) of N-methylamide 2 methoxyimino-3-((4'-methoxyphenyl)-4-methyl-pyrazole)-1-yl-propanoic acid as white crystals. The yield was 94%.

Example for the preparation of 3

Synthesis of N-methylamide 2 methoxyimino-3-((2',6'-differenl)-4-methyl-pyrazole)-1-yl-propanoic acid (Compound 58, represented by formula (1)in which n is 0, And represents a 2,6-differenl, D represents methyl, E is a hydrogen atom, R1and R2are both hydrogen atoms, R3represents methyl, R4represents a hydrogen atom and R5represents methyl).

(Stage 1)

4.9 g (29.0 mmol) of 2,6-diplocraterion was dissolved in 100 ml of toluene. To the solution was added 6.9 g (58.0 mmol) of N,N-dimethylformamidine, further heating by boiling under reflux for 8 hours and then stirring at the same temperature for 6 hours. After the reaction, the toluene and excess N,N-dimethylformamidine was evaporated, obtaining 6.2 g (27.5 mmol) of 1-(2',6'-differenl)-2-methyl-3-N,N-dimethylamino-2-propene in the form of orange resinous substance. The yield was 95%.

(Stage 2)

6.2 g (27.5 mmol) of 1-(2',6'-differenl)-2-methyl-3-N,N-dimethylamino-2-propene, synthesized in Stage 1, was dissolved in 150 ml of ethanol. At room temperature the solution was added dropwise 2.4 g (37.7 mmol) of 80% hydrazine hydrate is added, then stirring at the same temperature for 1 hour and then heating at boiling reverse Kholodilin the com within 2 hours. After the reaction, the reaction mixture was cooled to room temperature and the solvent was evaporated. The result was obtained 4.8 g (24.7 mmol) of 3-(2',6'-differenl)-4-methylpyrazole in the form of an orange oily substance. The yield was 85%. The synthesized product was used in next reaction without further purification.

(Stage 3)

2.0 g (10.0 mmol) 3-(2',6'-differenl)-4-methylpyrazole, synthesized in Stage 2, was dissolved in 40 ml of N,N-dimethylformamide. At room temperature the solution was sequentially added 1.7 g (12.0 mmol) of sodium carbonate and 3.5 g (12.4 mmol) of ethyl-2-methoxyimino-3-bromopropionate synthesized in the Example of obtaining 1, further heating to 110°With stirring for 4 hours. After the reaction, the reaction mixture was poured into 100 ml of water and was extracted three times with 50 ml diethyl ether. The organic phase is washed with saturated aqueous sodium chloride and then dried over anhydrous magnesium sulfate. After filtration and subsequent evaporation to remove solvent was obtained 2.6 g (7.7 mmol) of ethyl-2-methoxyimino-3-((2',6'-differenl)-4-methyl-pyrazole)-1-yl-propanoate. The yield was 62%. The synthesized product was used in next reaction without further purification.

(Stage 4)

2.6 g (7.7 mmol) of ethyl-2-methoxyimino-3-((2',6'-differenl)-4-methyl-pyrazole)-1-yl-disappear is oata, synthesized in Stage 3, were combined with 30 ml of a methanol solution of 40%methylamine, and then stirring at room temperature for 4 hours. After the reaction, the solvent was evaporated. The residue was purified by column chromatography on silica gel using chloroform as additionally separated by. Next, the solvent was removed by evaporation, obtaining 2.0 g (6.2 mmol) of N-methylamide 2 methoxyimino-3-((2',6'-differenl)-4-methyl-pyrazole)-1-yl-propanoic acid as white crystals. The yield was 81%.

Example 4

Synthesis of N-cyclopropylamine 3-(phenyl-4-methyl-pyrazole)-1-yl-propanoic acid (Compound 21, represented by the formula (1)in which n is 0, And represents phenyl, D is methyl, E is a hydrogen atom, R1and R2both represent a hydrogen atom, R3represents methyl, R4represents a hydrogen atom and R5is cyclopropyl).

(Stage 1)

5.0 g (37.3 mmol) of propiophenone was dissolved in 100 ml of methylformate. At room temperature the solution was added dropwise 8.6 g (44.7 mmol) of methanol solution of 28% sodium methoxide in 30 minutes, then stirring at the same temperature for 6 hours. To the reaction mixture were added 100 ml of water and the pH of the solution was brought to 1 with concentrated hydrochloric KIS is the notes, further stirring for 1 hour. After that the reaction mixture three times was extracted with 100 ml of ethyl acetate. The organic phase is washed with saturated aqueous solution of hydrochloride of sodium and then dried over anhydrous magnesium sulfate. After filtration and subsequent evaporation to remove solvent was obtained 5.7 g (35.4 mmol) of 2-formylpyridine in the form of light yellow crystals. The yield was 95%. The synthesized product was used in next reaction without further purification.

(Stage 2)

5.7 g (35.4 mmol) of 2-formylpyridine synthesized in Stage 1, was dissolved in 150 ml of ethanol. At room temperature the solution was added dropwise 2.4 g (37.7 mmol) of 80% hydrazine hydrate is added, then stirring at the same temperature for 1 hour and then heating at boiling under reflux for 2 hours. After the reaction, the reaction mixture was cooled to room temperature and the solvent was evaporated. The result was obtained 5.2 g (33.2 mmol) of 3-phenyl-4-methylpyrazole in the form of white crystals. The yield was 88%. The synthesized product was used in next reaction without further purification.

(Stage 3)

2.0 g (12.7 mmol) of 3-phenyl-4-methylpyrazole, synthesized in Stage 2, was dissolved in 40 ml of N,N-dimethylformamide. At room temperature the solution was sequentially added to the 2.1 g (15.2 mmol) of sodium carbonate and 3.4 g (15.2 mmol) of ethyl-2-methoxyimino-3-bromopropionate, synthesized in the Example of obtaining 1, further heating to 110°With stirring for 4 hours. After the reaction, the reaction mixture was poured into 100 ml of water and was extracted three times with 50 ml diethyl ether. The organic phase was washed with a saturated aqueous solution of hydrochloride of sodium and then dried over anhydrous magnesium sulfate. After filtration and subsequent evaporation to remove solvent was obtained 2.9 g (9.6 mmol) of ethyl-2-methoxyimino-3-(phenyl-4-methyl-pyrazole)-1-yl-propanoate. The yield was 63%. The synthesized product was used in next reaction without further purification.

(Stage 4)

2.9 g (9.6 mmol) of ethyl-2-methoxyimino-(3-phenyl-4-methyl-pyrazole)-1-yl-propanoate synthesized in Stage 3, was dissolved in a mixture solvent consisting of 20 ml ethanol and 20 ml of water. At room temperature the solution was added 0.5 g (9.6 mmol) of powdered sodium hydroxide (85%), followed by stirring at the same temperature for 1 hour. After the reaction the pH of the reaction mixture is brought up to 1 using concentrated hydrochloric acid. After the reaction mixture was extracted with three times 50 ml of ethyl acetate. The organic phase was washed with a saturated aqueous solution of hydrochloride of sodium and then dried over anhydrous magnesium sulfate. After filtration and subsequent evaporation for removal the Oia solvent was obtained 2.6 g (9.5 mmol) of 2-methoxyimino-3-(phenyl-4-methylpyrazole)-1-yl-propanoic acid. The yield was 99%. The synthesized product was used in next reaction without further purification.

(Stage 5)

2.1 g (7.7 mmol) of 2-methoxyimino-3-(phenyl-4-methylpyrazole)-1-yl-propanoic acid, synthesized in Stage 4, was dissolved in 30 ml of tetrahydrofuran. At room temperature the solution was added 1.9 g (11.5 mmol) of carbonyldiimidazole, further stirring at the same temperature for 30 minutes. Then was added 1.3 g (23,1 mmol) cyclopropylamine and the mixture was stirred at the same temperature for 2 hours. After the reaction, the reaction mixture was poured into 50 ml of water and was extracted three times with 50 ml diethyl ether. The organic phase was dried over anhydrous magnesium sulfate, followed by filtration and evaporation to remove solvent. The residue was purified column chromatography on silica gel using chloroform as additionally separated by. Subsequently, the solvent was removed by evaporation, receiving 1.0 g (3.2 mmol) of N-cyclopropylamine 3-(phenyl-4-methyl-pyrazole)-1-yl-propanoic acid as white crystals. The yield was 42%.

Compounds 1-20, 22-40, 42-57 and 59-124, are presented in table 1, next get by analogy with the formation of compounds 41 (an Example of obtaining 2), 58 (Example obtaining 3) and 21 (Example 4). They were synthesized using the methodologies presented in the Examples get 1-4, excluded the eat the connections of the source materials are groups corresponding to the groups of target compounds. These NMR spectrum and physical properties of these compounds are presented in tables 2 and 3, respectively.

Table 1 Ph, Me, Et, Bn, Pr, Bu, Pen, Hex, l, and t denote phenyl, methyl, ethyl, benzyl, propyl, butyl, pentyl, hexyl linear, cyclic and tertiary, respectively.

Table 1-2
Cyclic amines
NoADER1, R2R3R4-R5n
118PhMeHHMeG10
119PhMeHHMeG20
120PhMe HHMeG30
121PhMeHHMeG40
122PhMeHHMeG50
Table 1-3
No.AndDER1R2R3R11R12n
123PhMeHHHMeHCO2Me0
124PhMeHH HMeMeMe0
Table 2-1
δ value (ppm, solvent: COCl3, internal standard: tetramethylsilane was)
12.03(3H,s),2.89(3H,d),4.01(3H,s),5.17(2H,s),6.62(1H,bs),7.22(1H,s)
111.00-2.20(11H,m),1.99(3H,s),2.89(3H,d),4.00(3H,s),5.03(2H,s),6.97(1H,bs),7.18(1H,s)
132.89(3H,d),4.02(3H,s),5.27(2H,s),6.49(1H,d),7.24-7.82(5H,m)
142.87(3H,d),4.01(3H,s),5.20(2H,s),6.70(1H,bs),7.22-7.91(6H,m)
152.88(3H,d),3.14(1H,s),4.05(3H,s),5.20(2H,s),6.67(1H,bs),7.07(2H,t),7.73(1H,s),8.03(2H,dd)
162.20(3H,s),4.07(3H,s),5.18(2H,s),5.43(1H,bs),6.67(1H,bs),7.20-7.73(6H,m)
172.17(3H,s),4.07(3H,s),5.17(2H,s),6.60(2H,bs),7.25-7.64(5H,m)
182.21 (3H,s),2.84(3H,d),5.18(2H,s),6.74(1H,bs),7.24-7,66(6H,m)
191.15(3H,t),2.19(3H,s),3.35(2H,q),4.06(3H,s),5.17(2H,s),6.72(1H,bs),7.27-7.65(6H,m)
202.27(3H,s),2.58(6H,s),4.00(3H,s),5.17(2H,s),7.21-7.70(7H,m)
21 0.61-0.89(4H,m),2.14(3H,s),2.62-2.85(1H,m),4.02(3H,s),5.19(2H,s),6.89(1H,s),7.38-7.69(6H,m)
221.38(9H,s),2.10(3H,s),4.04(2H,s),5.16(2H,s),6.57(1H,bs),7.25-7.65(6H,m)
231.21-2.06(8H,m),2.18(3H,s),3.86-4.29(1H,m),4.02(3H,s),5.17(2H,s),6.65(1H,bs),7.21-7.58(6H,m)
241.16-1.94(10H,m),2.18(3H,s),3.65-4.08(1H,m),4.04(3H,s),5.17(2H,s),6.52(1H,bs),7.25-7.67(6H,m)
250.84-2.03( 13H,m),2.20(3H,s),4.02(3H,s),5.20(2H,s),5.20(2H,s),6.49(1H,bs),7.21-7.70(7H,m)
262.19(3H,s),4.03(3H,s),5.20(2H,s),5.06-5.30(4H,m),5.63-6.07(1H,m),6.82(1H,m),7.22-7.70(6H,m)
272.19(3H,s),2.21(1H,s),4.08(3H,s),4.17(2H,d),5.18(2H,s),6.99(1H,bs),7.23-7.72(6H,m)
282.10(3H,s),3.35-4.19(4H,m),4.51(1H,t),5.20(2H,s),6.90(1H,bs),7.25-7.70(7H,m)
292.28(3H,s),4.21(3H,s),4.51,5.30(2H,s),7.00-7.85(11H,m),8.21(1H,bs)
302.20(3H,s),4.00(3H,s),4.50(2H,d),5.21(2H,s),6.95-7.70(12H,m)
311.50(3H,d),2.19(3H,s),4.01(3H,s),5.19(2H,s),7.01(1H,d),7.34-7.71(12H,m)
322.18(3H,s),2.69(2H,t),3.53(2H,q),3.82(6H,s),4.00(3H,s),5.18(2H,s),6.68-7.70(10H,m)
33342.19(3H,s),3.78-4.14(2H,m),4.09(3H,s),5.20(2H,s),7.07(1H,bs),7.24-7.65(6H,m)

351.93(3H,s),2.22(3H,s),2.87(3H,d),4.00(3H,s),5,20(2H,s),6.70(1H,bs),7.10-7.25(4H,m),7.37(1H,s)
362.18(3H,s),2.37(3H,s),2.87(3H,d),4.03(3H,s),5.20(2H,s),6.75(1H,bs),7.00-7.53(5H,m)
372.14(3H,s),2.38(3H,s),2.90(3H,d),4.05(3H,s),5.19(2H,s),6.78(1H,bs),7.14-7.78(5H,m)
381.28(6H,s),2.00(1H,m),2.00(3H,s),2.90(3H,d),4.01(3H,s),5.19(2H,s),6.56-7.80(6H,m)
392.21(3H,s),2.86(3H,d),4.02(3H,s),5.20(2H,s),6.48-7.92(l1H,m)
402.22(3H,s),2.88(3H,d),4.04(3H,s),5.21(2H,s),6.70(1H,bs),7.37(1H,s),7.68(4H,q)
412.16(3H,s),2.85(3H,d),3.79(3H,s),4.05(3H,s),5.18(2H,s),6.91(1H,bs),6.85-7.62(5H,m)
422.04(3H,d),2.84(3H,d),4.00(3H,s),5.19(2H,s),6.75(1H,bs),6.97-7.56(5H,m)
432.20(3H,s),2.90(3H,d),4.03(3H,s),5.20(2H,s),6.60-7.13(2H,m),7.20-7.60(4H,m)
442.17(3H,s),2.88(3H,d),4.02(3H,s),5.20(2H,s),6.70(1H,bs),6.90-7.70(5H,m)
451.98(3H,s),2.85(3H,d),4.00(3H,s),5.20(2H,s),6.41-7.80(6H,m)
462.20(3H,s),2.88(3H,d),4.02(3H,s),5.19(2H,s),6.37-8.20(6H,m)
472.17(3H,s),4.03(3H,s),5.18(2H,s),6.75(1H,bs),7.23-764(5H,m)
481.97(3H,s),2.87(3H,d),4.01(3H,s),5.20(2H,s),6.32-7.99(6H,m)
492.20(3H,s),2.87(3H,d),4.03(3H,s),5.20(2H,s),6.38-8.09(6H,m
502.18(3H,s),2.89(3H,d),4.02(3H,s),5.18(2H,s),6.49-7.82(6H,m)
512.20(3H,s),2.87(3H,d),4.03(3H,s),5.20(2H,s),6.80(1H,bs),7.40(1H,s),7.60(2H,d),7.80(2H,d)
522.13(3H,s),2.85(3H,d),4.00(3H,s),5.17(2H,s),6.72(1H,bs),6.83-7.47(10H,m)
532.18(3H,s),2.86(3H,d),4.04(3H,s),5.19(2H,s),6.72(1H,bs),6.95-7.70(10H,m)
542.18(3H,s),2.85(3H,d),4.00(3H,s),5.08(2H,s),5.18(2H,s),6.56-7.31(11H,m)
551.98(3H,s),2.85(3H,d),4.00(3H,s),5.21(2H,s),6.68(1H,bs),7.00-7.39(4H,m)
562.01(3H,s),2.90(3H,d),4.02(3H,s),5.21(2H,s),6.71-7.59(5H,m)
572.01(3H,d),2.98(3H,d),4.05(3H,s),5.19(2H,s),6.70(1H,bs),6.91-7.39(4H,m)
581.95(3H,s),2.85(3H,d),3.83(3H,s),5.01(2H,s),6.62(1H,bs),6.92-7.55(5H,m)
592.10(3H,s),2.90(3H,d),4.03(3H,s),5.19(2H,s),6.67(1H,bs),6.95-7.63(4H,m)
602.10(3H,s),2.88(3H,d),4.05(3H,s),5.18(2H,s),6.32-7.36(4H,m),8.01(1H,bs)
612.13(3H,s),2.90(3H,d),4.01 (3H,s),5.19(2H,s),6.40-7.62(6H,m)
622.19(3H,s),2.29(3H,s),4.01 (3H,s),5.18(2H,s),6.50-7.80(6H,m)
632.12(3H,s),2.83(3H,d),3.68(3H,s),4.01(3H,s),5.19(2H,s),6.62-7.70(6H,m)
652.20(3H,s),2.90(3H,d),4.10(3H,s),5.20(2H,s),6.50(1H,t),6.60-6.90(1H,m),7.25(1H,s),7.40(4H,q)
662.20(3H,s),2.90(3H,d),4.05(3H,s),5.20(2H,s),6.50-6.95(1H,m),7.21(1H,s),7.38(1H,s),7.80(2H,s)
672.20(3H,s),2.90(3H,d),4.05(3H,s),5.20(2H,s),5.90(1H,t),6.60-6.80(1H,m),7.25(1H,s),7.50(4H,q)
68 2.20(3H,s),2.50(3H,s),2.90(3H,d),4.00(3H,s),5.20(2H,s),6.60-6.80(1H,m),7.20(1H,s),7.40(4H,q)
692.20(3H,s),2.90(3H,d),3.00(3H,s),4.05(3H,s),5.20(2H,s),6.60-6.80(1H,m),7.40(1H,s),7.80-7.90(4H,bs)
702.18(3H,s),2.85(3H,d),4.03(3H,s),5.18(2H,s),6.70(1H,bs),7,35-to 7.84(5H,m)
712.18(3H,s),2.30(6H,s),2.89(3H,d),4.03(3H,s),5.18(2H,s),6.53-7.57(6H,m)
722.02(3H,s),2.90(3H,d),3.59(3H,s),3.90(3H,s),5.22(2H,s),6.73(1H,bs),6.85-7.36(4H,m)
732.00(3H,s),2.90(3H,d),4.15(3H,s),5.21(2H,s),6.70(1H,bs),7.18-7.41(4H,m)
742.16(3H,s),2.29(3H,s),2.82(3H,d),4.00(3H,s),5.18(2H,s),6.50-7.59(5H,m)
752.17(3H,s),2.35(3H,d),2.86(2H,d),4.05(3H,s),5.19(2H,s),6.70(1H,bs),6.84-7.51(4H,m)
762.10(3H,s),2.90(3H,d),3.90(3H,s),4.00(3H,s),5.20(2H,s),6.60-6.80(1H,m),7.25(1H,s),7.20-7.50(3H,m)
772.20(3H,s),2.82(3H,d),3.90(3H,s),4.00(3H,s),5.20(2H,s),6.60-6.80(1H,m),7.00-7.25(3H,m),7.30(1H,s)
782.10(3H,s),2.90(3H,d),3.90(3H,s),4.00(3H,s),5.20(2H,s),6.60-7.00(2H,m),7.25(1H,s),7.40-7.90(2H,m)
791.90(3H,s),2.80(3H,d),3.80(3H,s),4.00(3H,s),5.20(2H,s),6.60-7.00(2H,m),7.18(1H,s),7.20-7.40(2H,m)
802.20(3H,s),2.88(3H,d),4.04(3H,s),5.19(2H,s),6.66(1H,bs),7.25-7.55(4H,m)
812.00-2.10(3H,m),2.85(3H,d),4.05(3H,s),5.20(2H,s),7.20(1H,s),7.00-7.50(3H,m)
821.90(3H,s),2.85(3H,d),4.00(3H,s),5.20(2H,s),6.60-6.80(1H,m),7.15(1H,s),6.90-7.40(3H,m)
832.20(3H,s),2.90(3H,d),4.06(3H,s),5.20(2H,s),5.25(2H,s),6.70(1H,bs),7.00-7.88(4H,m)
842.04(3H,s),2.89(3H,d),.02(3H,s),5.20(2H,s),6.41-7.89(5H,m)
852.01(3H,s),2.90(3H,d),4.01(3H,s),5.22(2H,s),6.44-7.98(5H,m)
862.23(3H,s),2.90(3H,d),4.01 (3H,s),5.21 (2H,s).6.37-8.10(5H,m)
872.21(3H,s),2.90(3H,d),4.05(3H,s),5.20(2H,s),6.40-8.01(5H,m)
882.20(3H,s),2.88(3H,d),4.00(3H,s),5.20(2H,s),6.37-8.23(5H,m)
891.83(3H,s),2.90(3H,d),3.99(3H,s),5.19(2H,s),6.41-7.79(5H,m)
902.43(3H,s),3.20(3H,d),4.52(3H,s),5.75(2H,s),7.40(1H,bs),7.82-8.57(4H,m)
912.20(3H,s),2.85(3H,d),3.85(3H,s),4.08(3H,s),5.20(2H,s),6.60(1H,t),7.00(1H,s),7.22(1H,s),7.28-7.50(2H,m)
922.17(3H,s),2.87(3H,d),4.00(3H,s),4.05(3H,s),5.17(2H,s),6.70(1H,bs),7.27(1H,s),7.35(1H,s)
932.19(3H,s),2.64(3H.s),2.81(3H,s),3.99(3H,s),5.20(2H,s),6.90-7.65(5H,m)

940.82(3H,t),1.05(3H,t),2.17(3H,s),3.26(4H,q),5.20(2H,s),7.22-7.68(6H,m)
951.27(3H,t),2.90(3H,d),4.05(3H,s),4.21(2H,q),6.67(1H,bs),7.22-8.07(6H,m)
962.80(3H,s),2.84-2.87(3H,d),4.10(3H,s),5.25(2H,s),6.64(1H,bs),7.40-7.95(5H,m),8.10(1H,s)
972.97(3H,d),3.80(3H,s),3.83(3H,s),5.16(2H,s),6.65(1H,s),7.20-8.00(5H,m)
981.19(3H,d),2.61(2H,q),4.01 (3H,s),5.20(2H,s),6.76(1H,bs),7.21-7.68(6H,m)
992.90(5H,d),4.02(3H,s),5.22(2H,s),6.71(1H,bs),7.10-7.70(11H,m)
1002.90(3H,d),4.00(3H,s),5.20(2H,s),6.37-8.04(7H,m)
1012.82(3H,d),3.89(3H,s),5.19(2H,s),6.71(1H,bs),7.71-7.81(11H,m)
2.24(3H,s),2.83(3H,d),3.12(1H,bs),5.26(2H,s),6.81-7.68(6H,m)
1032.22(3H,s),2.91(3H,d),5.24(2H,s),5.75(2H,d),6.70(1H,bs),7.24-7.90(6H,m)
1042.18(3H,s),2.90(3H,d),5.24(2H,s),5.75(2H,d),6.70(1H,bs),6.92-7.70(5H,m)
1052.18(3H,s),2.83(3H,d),2.67(2H,m),5.16-5.38(2H,m),5.19(2H,s),6.82(1H,bs),7.26-7.64(6H,m)
1062.18(3H,s),2.83(3H,d),5.23(2H,s),5.25(2H,s),6.66(1H,bs),7.30-7.62(l1H,m)
1072.17(3H,s),2.51(1H,t),2.85(3H,d),4.78(2H,d),5.21(2H,s),6.80(1H,bs),7.25-7.70(6H,m)
1082.41(3H,s),2.84(3H,d),4.05(3H,s),5.16(2H,s),6.77( 1H,bs),7.19-7.65(6H,m)
1092.08(3H,s),2.10(2H,t),2.89(3H,d),3.99(3H,s),4.02(2H,t),7.18-7.96(6H,m)
1102.20(3H,s),2.88(3H,d),4.03(3H,s),5.20(2H,s),5.60(1H,bs),7.37(1H,s),7.47-7.80(4H,m),8.13(1H,s)
1112.20(3H,s),2.85(3H,d),3.97(3H,s),4.03(3H,s),5.17(2H,s),6.77(1H,bs),7.35(1H,s),7.40-7.80(4H,m),8.05(1H,s)
1122.20(3H,s),2.85(9H,m),4.05(3H,s),5.20(2H,s),6.60-6.80(1H,m),7.20(1H,s),7.25(1H,s),7.35-7.95(4H,m)
1181.62-1.99(4H,m),2.10(3H,s),3.10(2H,t),3.37(2H,t),3.99(3H,s),5.21 (2H,s),7.22-7.68(6H,m)
1191.18-1.61(5H,m),2.20(3H,s),3.00-3.43(4H,m),3.98(3H,s),5.21 (2H,s),7.21-7.70(6H,m)
1202.21(3H,s),3.18-3-78(4H,m),3.97(3H,s),5.21(2H,s),7.22-7.68(6H,m)
1210.92(3H,d),1.10(3H,d),2.20(3H,s),2.00-to 3.38(6H,m),3.98(3H,s),5.05(2H,s),7.21-7.72(6H,m)
1222.18(3H,s),2.35-2.55(4H,m),3.70-3.80(4H,m),3.94(3H,s),5.20(2H,s),7.25-7.67(6H,m)
1232.18(3H,s),3.78(3H,s),4.02(3H,s),5.09(2H,s),6.2(1H,bs),7.22-7.77(6H,m),8.48(1H,bs)
1242.27(3H,s),2.58(6H,s),4.00(3H,s),5.17(2H,s),7.21-7.70(7H,m)

Table 3-1Table 3-2
ConnectionPropertiesConnectionProperties
No.No.
1TPL 117-118°66TPL 91-92°
11TPL 90-92°67TPL 108-109°
13Oily68TPL 136-137°
14TPL-119°69TPL 118-119°
15TPL 81-82°70TPL 103-104°
16TPL 167-168°71TPL 140-141°
17TPL>200°72TPL 134-135
18TPL 139-140°73TPL 139-140°
19Oily74TPL 93-94°
20TPL 81-82°75TPL 86-87°
21TPL 95-96°76TPL 96-97°
22Oily77TPL 99-100°
23TPL>200°78TPL 117-118°
24Resinous substance79TPL 112-113°
25Resinous substance80TPL 135-136°
26Oily81TPL 81-82°
27TPL 40-4 1°82TPL 115-116°
28Oily83TPL 94-95°
29TPL 170-171°84TPL-119°
30TPL 93-94°85TPL 101-103°
31Resinous substance86TPL-121°
32Oily87TPL 108-109°
33TPL 85-86°88TPL 110-111°
34TPL 102-103°89TPL 140-142°
35TPL 128-129°90TPL 121-122°
36Resinous substance91TPL 109-110°
37TPL 99-100°92TPL 117-118°
38TPL 100-101°93Oily
39TPL 124-125°94Oily
40TPL 128-129°95TPL 118-119°
41TPL 99-100°96TPL-112°
42TPL 102-103°97TPL 182-183°
43TPL 118-119°98TPL 49-50°
44TPL 84-85°99TPL 112-113°
45TPL 108-111°100TPL 103-104°
46TPL 76-78°101Resinous substance
47TPL 119-121°102TPL 151-152°
48Oily103TPL 98-99°
49TPL 94-96°104Resinous substance
50TPL-112°105Resinous substance
51TPL 133-134°106Oily
52Resinous substance107Resinous substance
53Oily108TPL 154-155°
54TPL 122-123°109Oily
55TPL-116°110Oily
56TPL 113-114°111Resinous substance
57TPL-134°112TPL 64-65°
58TPL 131-132°118Oily
59TPL 77-78°119Oil is NISTO
60TPL-110°120Oily
61TPL 161-162°121Oily
62TPL 115-116°122Oily
63TPL 156-157°123TPL 166-167°
65TPL 140-141°124Oily

Structures

Example composition 1

Getting wet powder

Mixed 10 parts of each of compounds shown in Table 1 (Compounds 11-124), 83 parts clay, 2 parts of white carbon black, 2 parts ligninsulfonate acid soda and 3 parts alkylnaphthalenes acid soda and sprayed to obtain a wet powder.

Example composition 2

Obtaining granules

Mixing 2.5 parts of each of compounds shown in Table 1 (Compounds 11-124), 28 parts of bentonite, 52 parts of talc, 2 parts dodecylbenzenesulfonic acid soda and 2 parts ligninsulfonate acid soda. To the mixture was added 13.5 parts of water. The resulting mixture was mixed, granulated in a granulator and then vysushila and was molded to obtain a pellet.

An example of a structure of 3

Receive floating substances

Well mix 5 parts of each of compounds shown in Table 1 (Compounds 11-124), 11 parts of propylene glycol, 3 parts of SORPOL 7290P (trade mark, available from TOHO Chemical Industry Co., Ltd.), 0.1 part TOXANONE N100 (trade mark, available from Sanyo Chemical Industries, Ltd.), 0.2 parts of ANTIFOAM E-20 (trademark, available from KAO Corporation), 1.5 parts of KUNIPIA F (trade mark, available from Kunimine Industries Co,. Ltd.) and 79.2 parts of water. The mixture was sprayed wet spraying until the particle size of 5 μm or less. Thus gained the floating substance.

Example of part 4

Obtaining emulsion concentrate

5 parts of each of compounds shown in Table 1 (Compounds 11-124), was dissolved in 50.5 parts of N-methylpyrrolidone. The solution was combined with 24.5 parts of SAS 296 (trade mark, available from NIPPON PETROCHEMICALS COMPANY, LTD.) and 20 parts of SORPOL 3880L (trade mark, available from TOHO Chemical Industry Co., Ltd.). The mixture was stirred to obtain a homogeneous solution. Thus obtained emulsion concentrate.

Test for herbicide action

Examples of testing herbicide herbicide action of the compositions according to the invention are given below, but it should be noted that the invention is in no way limited to these test examples.

Test example 1

Processing leaves of upland fields

Plastic tank 130 is m 2filled Nagorno soil. Subsequently sown and covered with soil of a thickness of approximately 1 cm weed seeds Setaria viridis, Digitaria adscendens, Chenopodium album and Stellaria media, seeds of soybean (Glycine max) and wheat (Triticum aestivum). On the 14th day after sowing, the wet powder obtained in Example 1, was diluted with water so that the amount of active ingredient was 1 kg per hectare, and then uniformly applied to the surface of the leaves of the plant. At the 21st day after application conducted monitoring and evaluation according to the following criteria.

The results are presented in Table 4.

Test example 2

Processing upland soils

Plastic tank 130 cm2filled Nagorno soil. Subsequently sown and covered with soil of a thickness of approximately 1 cm weed seeds Setaria viridis, Digitaria adscendens, Chenopodium album and Stellaria media, seeds of soybean (Glycine max) and wheat (Triticum aestivum). The next day after sowing, the wet powder obtained in Example 1, was diluted with water so that the amount of active ingredient was 1 kg per hectare, and then uniformly applied to the surface of the soil. At the 21st day after application conducted monitoring and evaluation according to the above criteria.

The results are presented in Table 5.

Test example 3

Processing of rice fields

Plastic tank 130 cm2the floor is Yali soil with rice and ground regulated to a depth of 4 see Subsequently sown the seeds of Echinochloa crusgalli, Monochoria vaginalis, Ammannia multiflora and Scirpus juncoides and transplanted rice (Oryza sative, variety: Koshihikari) at the age of two leaves at 2 plants rice 1 capacity to a depth of 3 see On the 10th day after transplantation, the wet powder obtained in Example 1, was dissolved in the water so that the amount of active ingredient was 1 kg per hectare, and then throw it on the water surface. At the 21st day after the dispersion of the conducted monitoring and evaluation according to the above criteria.

The results are presented in Table 6.

Evaluation criteria

Herbicide activity was evaluated on the basis of the following criteria:

Index: 0-5

5: herbicide action not less than 90% or phytotoxicity 90% or more;

4: herbicide action is not less than 70% and less than 90% or phytotoxicity 70% or more and less than 90%;

3: herbicide action not less than 50% and less than 70% or phytotoxicity 50% or more and less than 70%;

2: herbicide action not less than 30%and less than 50% or phytotoxicity 30% or more and less than 50%;

1: herbicide action not less than 10% and less than 30% or phytotoxicity 10% or more and less than 30%;

0: herbicide action is not less than 0% and less than 10% or phytotoxicity 0% or more and less than 10%;

3
Table 4-1Table 4-2
Connection # Herbicide activityConnection # Herbicide activity
SDSGTSDSGT
VAndAndMMAndVAndAndMMAnd
1135530057555500
1334440059555500
1455550065555500
1755550067455400
1855550070455400
1955550074555500
2023550075555500
21555500773553 00
2333440081555500
2443440082354400
2645550083354400
2755550085445500
2833430086354400
303440088455500
3345440092555500
3445440094335500
3645540098344400
37555500103345500
41555510104 345500
42555500105655500
43555500106333300
44555500111445500
46555500118344500
47555500120445400
53455400122444400
54454400124334400
5655550057555500
SV: Setaria viridis
DA: Digitaria adscendens
CA: Chenopodium album
SM Stellaria media
GM: Soybean (Glycine max)
TA: Wheat (Triticum aestivum)

5
Table 5-1Table 5-2
Connection # Herbicide activityConnection # Herbicide activity
SDSGTSDSGT
VAndAndMMAndVAndAndMMAnd
1344550056555510
1455551057555500
1744440059555500
1855550065555500
1955550067445500
2034340070334400
2144550074455510
2344540075445510
24435400774555 00
2645550081555510
2755551082454500
2834430083555500
3043430086455510
3345550088445500
344550092555500
3644551094335400
3755550098344500
41555510103455500
43555510104455500
44555500105 444400
46555510106344400
47555500111445500
51444400118334400
53354400120344400
54345500122334400
55555500124335400
SV: Setaria viridis
DA: Digitaria adscendens
CA: Chenopodium album
SM: Stellaria media
GM: Soybean (Glycine max)
TA: Wheat (Triticum aestivum)

td align="center"> 5
Table 6-1Table 6-2
Connection # Herbicide activityConnection # Herbicide activity
ESMAndAboutESMAndAbout
JVMSJVMS
1155515555550
14555515655550
17445505755550
18555505855551
19555505955550
20545406055550
2155550 6555550
23445506755540
24445407354540
26555507655550
27555507755550
30445408155550
31345408654550
33545508755550
34555519054550
35544409154550
37555519255550
38555509854540
4055550 10355550
415555010544550
425555011155550
435555111834440
445555111933440
475555012033440
4955551122 43440
535555012333440
EC: Echinochloa crusgalli
SJ: Scirpus juncoides
MV: Monochoria vagynalis
AM: Ammannia multiflora
OS: Rice (Oryza saliva)

As shown in Tables 4-6, the wet powder herbicides containing compound according to the invention of formula (1) or (4), provides excellent weed-killing effect on various weeds in upland fields or weeds of rice fields. They show no significant phytotoxicity on wheat (Triticum aestivum), soybean (Glycine max) and rice (Oryza sativa) with herbicide activity, assessed mainly by the index 0.

INDUSTRIAL APPLICABILITY

Substituted pyrazol compounds of the present invention are new substances synthesized from pyrazol-derived and terrestrial derived halogenosilanes. They have excellent herbicide activity.

Herbicide compositions containing substituted pyrazol compounds as the active ingredients have a high gerbic is the initial action and a broad spectrum herbicide, can be used in relatively low doses and safe for crops. Therefore, herbicides containing these compounds as active ingredients are useful in agriculture, horticulture and many other fields.

1. Substituted pyrazole derivative represented by the formula (I)

in which n is 0 or 1; independently

group a represents a hydrogen atom, a branched or unbranched alkyl group with 1-4 carbon atoms, branched or unbranched halogenating group with 1-4 carbon atoms, cycloalkyl group with 3-6 carbon atoms or phenyl group, optionally having a substituting group;

moreover, these substituting groups are the same or different from each other and are selected from branched or unbranched alkyl groups with 1-4 carbon atoms, branched or unbranched halogenating groups with 1-4 carbon atoms, branched or unbranched alkoxygroup with 1-4 carbon atoms, a hydroxyl group, a branched or unbranched halogenlamp with 1-4 carbon atoms, branched or unbranched alkylcarboxylic with 1-4 carbon atoms, branched or unbranched dialkylaminoalkyl with 1 to 4 atoms of carbon is a, branched or unbranched dialkylaminoalkyl with 1-4 carbon atoms, branched or unbranched alkylthio with 1-4 carbon atoms, branched or unbranched halogenation with 1-4 carbon atoms, branched or unbranched alkylsulfonyl groups with 1-4 carbon atoms, halogen atoms, cyanopropyl, phenyl group, phenoxy and benzyloxy;

these replacement group replaces the hydrogen atom in 0-3 arbitrary positions of the phenyl group;

group D represents a hydrogen atom, a branched or unbranched alkyl group with 1-4 carbon atoms, branched or unbranched halogenating group with 1-4 carbon atoms, alkylamino group with 2-4 carbon atoms, branched or unbranched alkoxy group with 1-4 carbon atoms, a halogen atom, a branched or unbranched alkoxycarbonyl group with 1-4 carbon atoms, branched or unbranched alkylsulfonyl group with 1-4 carbon atoms or phenyl group;

group E represents a hydrogen atom, halogen atom or phenyl group;

group R1and R2both represent a hydrogen atom;

the group R3represents a hydrogen atom, a branched or unbranched alkyl group is from 1 to 4 carbon atoms, branched or unbranched halogenating group with 1-4 carbon atoms, alkenylphenol group with 2-4 carbon atoms, alkylamino group with 2-4 carbon atoms or benzyl group;

group R4and R5are the same or different and each represents a hydrogen atom, a branched or unbranched alkyl group with 1-4 carbon atoms, branched or unbranched halogenating group with 1-4 carbon atoms, cycloalkyl group with 3-8 carbon atoms which may be substituted by branched or unbranched alkyl group with 1-4 carbon atoms, alkenylphenol group with 2-4 carbon atoms, alkylamino group with 2-4 carbon atoms, cyanomethyl group substituted by an amino group N(R11R12), where the group R11and R12are the same or different and each denotes a hydrogen atom, a branched or unbranched alkyl group with 1 to 4-carbon atoms, branched or unbranched alkoxycarbonyl group with 1 to 4-carbon atoms or phenyl group;

or R4and R5each is a benzyl group;

or R4and R5each is a αor β-fenetylline group, not necessarily with substitute groups on the benzene ring, these replacing the groups are branched or non-branched alkoxycarbonyl with 1-4 carbon atoms, where these replacement group replaces the hydrogen atom 0-2 in arbitrary positions of the benzene ring;

or groups of R4and R5together form a five-membered or six-membered aliphatic ring, in which the indicated ring may be substituted by branched or unbranched alkyl groups with 1-4 carbon atoms and the specified ring may contain one or two heteroatoms, including nitrogen, oxygen and sulphur.

2. Substituted derivatives of pyrazole with herbicide activity, according to claim 1, having the formula (1)in which R4represents a hydrogen atom and R5represents a substituted an amino group - N(R11,R12), and having the following formula (4):

where n is 0 or 1;

Rather it represents a phenyl;

E, R1and R2represent hydrogen;

D and R3independently represent a branched or unbranched alkyl group with 1-4 carbon atoms and

group R11and R12are the same or different and each denotes a hydrogen atom, a branched or unbranched alkyl group with 1-4 carbon atoms, branched or unbranched alkoxycarbonyl group with 1-4 carbon atoms.

3. The method of obtaining substituted derivatives of pyrazole f is rmula (1), which involves the reaction of pyrazole derivative of the formula (5) with ether derivative halogenatom formulas (6) to obtain the ether derivative of pyrazole of the formula (7)

and hydrolysis of the ether group of an ester derivative of pyrazole of the formula (7) in the presence of a base, getting a carboxylic acid derivative of the formula (8), and the reaction of the carboxylic acid derivative with an amine R4-NH-R5in the presence of a condensing agent

where in formulas (5)-(8) n is 0 or 1, the group Z represents a halogen atom, a group R13represents a methyl or ethyl group, and each group A, D, E, R1, R2, R3, R4and R5means independently the same replacement group for formula (1).

4. Herbicide composition comprising a compound selected from substituted derivatives of pyrazole according to claim 1 as an active ingredient.

5. Herbicide composition comprising a compound selected from substituted derivatives of pyrazole according to claim 2 as an active ingredient.

6. Substituted pyrazole derivative with herbicide activity and represented by the following formula (I):

where n is 0 or 1; independently

group And to depict the place of a hydrogen atom, branched or unbranched alkyl group with 1-4 carbon atoms, branched or unbranched halogenating group with 1-4 carbon atoms, cycloalkyl group with 3-6 carbon atoms or a phenyl group substituted by 0-3 substitute groups (0 substituting groups means unsubstituted phenyl group);

these substituting groups are the same or different from each other and are selected from alkyl groups with 1-4 carbon atoms, halogenating groups with 1-4 carbon atoms, alkoxygroup with 1-4 carbon atoms, halogenlamp with 1-4 carbon atoms, alkylcarboxylic with 1-4 carbon atoms, dialkylaminoalkyl with 1-4 carbon atoms, alkylthio with 1-4 carbon atoms, halogenation with 1-4 carbon atoms, halogen atoms, hydroxyl group, cyanopropyl, phenyl group, fenoxaprop and benzyloxy;

group D represents a hydrogen atom, a halogen atom, a branched or unbranched alkyl group with 1-4 carbon atoms, branched or unbranched halogenating group with 1 to 4 carbon atoms, alkylamino group with 2-4 carbon atoms, branched or unbranched alkoxygroup with 1-4 carbon atoms, alkoxycarbonyl group with 1-4 carbon atoms, or phenyl group;

the group made the focus of a hydrogen atom, halogen atom or phenyl group;

the group R1and R2both represents a hydrogen atom;

the group R3represents a hydrogen atom, a branched or unbranched alkyl group with 1-4 carbon atoms, alkylamino group with 2-4 carbon atoms, formeterol group or benzyl group;

group R4and R5together form a five-membered or six-membered aliphatic ring which may contain 1 or 2 heteroatoms including nitrogen, oxygen and sulfur, and which may be substituted by an alkyl group with 1-4 carbon atoms, or independently

the group R4represents a hydrogen atom or a branched or unbranched alkyl group with 1-4 carbon atoms, and

the group R5represents a hydrogen atom, a branched or unbranched alkyl group with 1-4 carbon atoms, branched or unbranched halogenating group with 1-4 carbon atoms, branched or unbranched cyanoaniline group with 1-4 carbon atoms, cycloalkyl group with 3-6 carbon atoms that may be substituted by branched or unbranched alkyl group with 1-4 carbon atoms, alkenylphenol group with 2-4 carbon atoms, alkenylphenol group with 2-4 carbon atoms, phenyl group, benzyl group or α or β-fenetylline group optionally having a (branched or unbranched) alkoxygroup with 1-4 carbon atoms in a benzene ring.

7. Herbicide composition comprising a compound selected from substituted derivatives of pyrazole according to claim 6 as an active ingredient.



 

Same patents:

FIELD: organic chemistry, biochemistry, medicine.

SUBSTANCE: invention relates to a new biologically active compound of 4-oxoquinoline that is useful as an anti-HIV agent and to its pharmaceutically acceptable salt. Invention describes an anti-HIV agent comprising compound of 4-oxoquinoline represented by the following formula [I] or its pharmaceutically acceptable salt as an active component wherein ring Cy represents phenyl group, naphthyl group or pyridyl group and each this group is substituted optionally with 1-5 substituted chosen from the following group A wherein A represents the group consisting of cyano-group, phenyl group, nitro-group, halogen atom, (C1-C4)-alkyl group, halogen-(C1-C4)-alkyl group, halogen-(C1-C4)-alkoxy-group, -ORa1, -SRa1, -NRa1Ra2, -CONRa1Ra2, -SO2NRa1Ra2, -NRa1CORa3, -SO2Ra3, -NRa1SO2Ra3 and -COORa1 wherein Ra1 and Ra2 are similar or different and each represents hydrogen atom, (C1-C4)-alkyl group or benzyl group, and Ra3 represents (C1-C4)-alkyl group; R1 represent a substitute chosen from the following group B, or (C1-C10)-alkyl group optionally substituted with 1-3 substitutes chosen from halogen atom and the following group B wherein the group B represents the group consisting of phenyl group optionally substituted with phenyl group or 1-5 halogen atoms; (C3-C6)-cycloalkyl group, imidazolyl group, benzothiophenyl group, thiazolyl group optionally substituted with 1-3 (C1-C6)-alkyl groups, morpholinyl group, pyridyl group, -ORa4, -SRa4, -NRa4Ra5, -CONRa4Ra5, -SO2NRa4Ra5, -CORa6, -NRa4CORa6, -SO2Ra6, -NRa4SO2Ra6, -COORa4 and -NRa5COORa6 wherein Ra4 and Ra5 are similar or different and each represents hydrogen atom, (C1-C4)-alkyl group or phenyl group; Ra6 represents (C1-C4)-alkyl group; R2 represents hydrogen atom or (C1-C4)-alkyl group; R31 represents hydrogen atom, cyano-group, hydroxy-group, halogen atom or (C1-C4)-alkoxy-group; X represents -C-R32, and Y represents -C-R33 or nitrogen atom wherein R32 and R33 are similar or different and each represents hydrogen atom, cyano-group, halogen atom, pyrrolidinyl group, (C1-C10)-alkyl group optionally substituted with 1-3 halogen atoms, -ORa7, -SRa7, -NRa7Ra8, -NRa7CORa9, -COORa10 or -N=CH-NRa10Ra11 wherein Ra7 and Ra8 are similar or different and each represents hydrogen atom, phenyl group or (C1-C10)-alkyl group optionally substituted with (C3-C6)-cycloalkyl group or hydroxy-group; Ra9 represents (C1-C4)-alkyl group and Ra10 and Ra11 are similar or different and each represents hydrogen atom or (C1-C4)-alkyl group. Also, invention describes compound of the formula (III) given in the invention description, integrase inhibitor, antiviral agent, ant-HIV composition, anti-HIV agent, using compound of 4-oxoqionoline, method for inhibition of integrase activity, method for prophylaxis or treatment of viral infectious disease, pharmaceutical composition used for inhibition of integrase activity, antiviral composition and commercial package (variants). Invention provides the development of a pharmaceutical agent possessing inhibitory effect on activity of integrase.

EFFECT: valuable medicinal properties of compound, agent and composition.

40 cl, 7 tbl, 250 ex

FIELD: organic chemistry, medicine, biochemistry, pharmacy.

SUBSTANCE: invention describes derivatives of substituted triazoldiamine of the formula (I): wherein R1 represents (C1-C4)-alkyl, phenyl possibly substituted with halogen atom, amino-group substituted with -SO2-(C1-C4)-alkyl, imidazolyl, 1,2,4-triazolyl, imidazolidinone, dioxidoisothiazolidinyl, (C1-C4)-alkylpiperazinyl, residue -SO2- substituted with amino-group, (C1-C4)-alkylamino-group, (C1-C4)-dialkylamino-group, pyridinylamino-group, piperidinyl, hydroxyl or (C1-C4)-dialkylamino-(C1-C3)-alkylamino-group; R2 represents hydrogen atom (H); or R1 represents H and R2 means phenyl possibly substituted with halogen atom or -SO2-NH2; X represents -C(O)-, -C(S)- or -SO2-;R3 represents phenyl optionally substituted with 1-3 substitutes comprising halogen atom and nitro-group or 1-2 substitutes comprising (C1-C4)-alkoxy-group, hydroxy-(C1-C4)-alkyl, amino-group or (C1-C4)-alkyl possibly substituted with 1-3 halogen atoms by terminal carbon atom; (C3-C7)-cycloalkyl possibly substituted with 1-2 groups of (C1-C4)-alkyl; thienyl possibly substituted with halogen atom, (C1-C4)-alkyl that is substituted possibly with -CO2-(C1-C4)-alkyl, (C2-C4)-alkenyl that is substituted possibly with -CO2-(C1-C4)-alkyl, (C1-C4)-alkoxy-group, pyrrolyl, pyridinyl or amino-group substituted with -C(O)-C1-C4)-alkyl; (C1-C4)-alkyl substituted with thienyl or phenyl substituted with halogen atom; (C2-C8)-alkynyl substituted with phenyl; amino-group substituted with halogen-substituted phenyl; furyl, isoxazolyl, pyridinyl, dehydrobenzothienyl, thiazolyl or thiadiazolyl wherein thiazolyl and thiadiazolyl are substituted possibly with (C1-C4)-alkyl; to their pharmaceutically acceptable salts, a pharmaceutical composition based on thereof and a method for its preparing. New compounds possess selective inhibitory effect on activity of cyclin-dependent kinases and can be used in treatment of tumor diseases.

EFFECT: improved preparing method, valuable medicinal and biochemical properties of compounds and composition.

16 cl, 3 tbl, 26 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing heterocyclic compounds describing by the general formula (I): . Invention describes a method for preparing compounds of the formula (I) wherein R1 represents hydrogen atom or alkyl group; A represents ethylene group that can be substituted with alkyl or trimethylene group that can be substituted with alkyl; D represents nitro- or cyano-group; X represents oxygen or sulfur atom, or the group of the formula: or wherein R3 represents hydrogen atom or alkyl group; Z represents 2-chloropyrid-5-yl. Method involves interaction of compound of the formula (II): wherein A, D and X abovementioned values with a base in the presence of diluting agent followed by interaction of the reaction mixture with a mixture consisting of 2-chloro-5-chloromethylpyridine/2-chloro-5-methylpyridine with corresponding hydrochlorides.

EFFECT: simplified technology, enhanced yield of end product.

4 ex

FIELD: organic chemistry, chemical technology, medicine.

SUBSTANCE: invention relates to water-soluble azole compounds that can be used in biology and medicine. Invention describes a water-soluble azole compound of the formula (I):

or its pharmaceutically acceptable salt wherein each R and R1 means independently hydrogen atom or (C1-C6)-alkyl; A means group of the formula:

wherein R3 represents phenyl group with one or more halide atoms as substitutes; R4 represents hydrogen atom or -CH3; R5 represents hydrogen atom or in common with R4 it can represent =CH2; R6 represents 5- or 6-membered nitrogen-containing cycle that can comprise if necessary as substituted one or more groups taken among halogen atom, =O group, phenyl substituted with one or more groups taken among -CN, -(C6H4)-OCH2-CF2-CHF2 and -CH=CH-(C6H4)-OCH2-CF2-CHF2 or phenyl substituted with one or more groups taken among halogen atom and methylpyrazolyl group. Also, invention describes a method for preparing a water-soluble azole compound. Invention provides preparing new compounds that can be useful in medicine.

EFFECT: improved preparing method, valuable medicinal properties of compounds.

4 ex

FIELD: organic chemistry, medicine, pharmacy.

SUBSTANCE: invention relates to a prophylactic or therapeutic agent used against hyperlipidemia and comprising as an active component the heterocyclic compound of the formula [1]:

or its pharmaceutically acceptable salt wherein R1 represents aryl optionally substituted with similar or different one-three groups taken among alkyl, halogenalkyl, trihalogen alkyl, alkoxy-group and halogen atom; Het represents bivalent aromatic heterocyclic group of the formula [5]:

wherein X represents oxygen, sulfur atom or NR6 wherein R6 represents hydrogen atom or alkyl; R2 represents hydrogen atom, alkyl or trihalogenalkyl; D represents alkylene and alkenylene; E represents group of the formulae [3] or [4] wherein Y represents oxygen or sulfur atom; R3 and R4 are similar or different and each represents hydrogen atom or alkyl; p = 1; Z represents carboxy-group, alkoxycarbonyl, cyano-group or 1H-5-tetrazolyl. Also, invention relates to new compounds belonging to group of above enumerated heterocyclic compounds of the formula [1] that show effect reducing blood triglycerides level, low density lipoprotein cholesterol, glucose and insulin or effect enhancing high density lipoprotein cholesterol and effect reducing the atherogenic effect. Therefore, these compounds can be used in prophylaxis or treatment of hyperlipidemia, arteriosclerosis, heart ischemic disease, brain infarction, rheocclusion after percutaneous intraluminal coronary angioplasty, diabetes mellitus and obesity.

EFFECT: valuable medicinal properties of compounds and pharmaceutical composition.

29 cl, 1 tbl, 170 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing compound of the formula: . Method involves interaction of compound of the formula: with compound of the formula: wherein Q means chlorine or bromine atom in the presence of solvent or diluting agent, an interphase catalyst and a base wherein solvent or diluting agent represent carbonic acid esters, an interphase catalyst represents ammonium quaternary salt, and a base represents carbonate. Method provides inhibition of process in formation of undesirable isomers.

EFFECT: improved preparing method.

1 cl, 1 ex

FIELD: organic chemistry, medicine, pharmacy.

SUBSTANCE: invention relates to new derivatives of indol-3-yl of the formula (I):

wherein each A and B represents independently of one another oxygen atom (O), NH, CONH, NHCO or a direct bond; X means (C1-C2)-alkylene or a direct bond; R1 means hydrogen atom (H); R2 means hydrogen atom (H); R3 means NHR6, -NR6-C(=NR6)-NHR6, -C(=NR6)-NHR6, -NR6-C(=NR9)-NHR6, -C(=NR9)-NHR6 or Het1; each R4 and R5 represents independently of one another hydrogen atom (H); R7 means -(CH2)o-Ar, Het, OR6; R6 means hydrogen atom (H); R7 means (C1-C10)-alkyl, (C3-C10)-cycloalkyl; R8 means Hal, NO2 (nitro-group), CN (cyano-group), Z, -(CH2)o-Ar, COOR1, OR1, CF3, OCF3, NHR1; R9 means CN or NO2; Z means (C1-C6)-alkyl; Ar means aryl that can represent unsubstituted, monosubstituted, or polysubstituted R8; Hal means F, Cl, Br, J; Het means saturated, partially or completely saturated monocyclic or bicyclic heterocyclic radical comprising from 5 to 10 ring members wherein 1 or 2 nitrogen atom (N) and/or 1 or two sulfur atom (S) present, and heterocyclic radical can be monosubstituted with phenyl; Het1 means saturated, partially or completely unsaturated monocyclic or bicyclic heterocyclic radical comprising from 5 to 10 ring members and from 1 to 4 nitrogen atoms (N) that can be unsubstituted or monosubstituted NHX, or oxo-group; n = 0, 1 or 2; m = 0, 1, 2, 3, 4, 5 or 6; o means 0, 1 or 2; and their physiologically acceptable salts and solvates. Compounds of the formula (I) elicit intergin-inhibitory effect that allows their using as components of pharmaceutical composition. Also, invention describes intermediate compounds.

EFFECT: valuable medicinal properties of compounds.

11 cl, 4 sch, 1 tbl, 34 ex

FIELD: organic chemistry, biochemistry.

SUBSTANCE: invention relates to epothilones with modified thiazole substituent, methods for production thereof and pharmaceutical composition capable of cell growth inhibiting containing the same. Claimed compounds have general formula I , wherein P-Q represents double carbon bond or epoxy; R represents H, C1-C6-alkyl; G represents ; R1 represents and ; G1 and G2 represent hydrogen; G3 represents O, S, and NZ1; G4 represents H, optionally substituted C1-C6-alkyl, OZ2, Z2C=O and Z4SO2; G5 represents halogen, N3, CN, NC, heteroaryl containing nitrogen or oxygen, and heterocycle; G6 represents H, C1-C6-alkyl, or OZ5, wherein Z5 represents H, C1-C6-alkyl; G9 represents oxygen; Z1 represents H, optionally substituted C1-C6-alkyl, optionally substituted acyl; Z2 represents optionally substituted C1-C6-alkyl or aryl; Z4 represents optionally substituted aryl.

EFFECT: new epothilones capable of cell growth inhibiting.

19 cl, 39 ex

New drug substances // 2237657
The invention relates to organic chemistry and can find application in medicine

New drugs // 2237057
The invention relates to organic chemistry and can find application in medicine

FIELD: organic chemistry, medicine, biochemistry, pharmacy.

SUBSTANCE: invention describes derivatives of substituted triazoldiamine of the formula (I): wherein R1 represents (C1-C4)-alkyl, phenyl possibly substituted with halogen atom, amino-group substituted with -SO2-(C1-C4)-alkyl, imidazolyl, 1,2,4-triazolyl, imidazolidinone, dioxidoisothiazolidinyl, (C1-C4)-alkylpiperazinyl, residue -SO2- substituted with amino-group, (C1-C4)-alkylamino-group, (C1-C4)-dialkylamino-group, pyridinylamino-group, piperidinyl, hydroxyl or (C1-C4)-dialkylamino-(C1-C3)-alkylamino-group; R2 represents hydrogen atom (H); or R1 represents H and R2 means phenyl possibly substituted with halogen atom or -SO2-NH2; X represents -C(O)-, -C(S)- or -SO2-;R3 represents phenyl optionally substituted with 1-3 substitutes comprising halogen atom and nitro-group or 1-2 substitutes comprising (C1-C4)-alkoxy-group, hydroxy-(C1-C4)-alkyl, amino-group or (C1-C4)-alkyl possibly substituted with 1-3 halogen atoms by terminal carbon atom; (C3-C7)-cycloalkyl possibly substituted with 1-2 groups of (C1-C4)-alkyl; thienyl possibly substituted with halogen atom, (C1-C4)-alkyl that is substituted possibly with -CO2-(C1-C4)-alkyl, (C2-C4)-alkenyl that is substituted possibly with -CO2-(C1-C4)-alkyl, (C1-C4)-alkoxy-group, pyrrolyl, pyridinyl or amino-group substituted with -C(O)-C1-C4)-alkyl; (C1-C4)-alkyl substituted with thienyl or phenyl substituted with halogen atom; (C2-C8)-alkynyl substituted with phenyl; amino-group substituted with halogen-substituted phenyl; furyl, isoxazolyl, pyridinyl, dehydrobenzothienyl, thiazolyl or thiadiazolyl wherein thiazolyl and thiadiazolyl are substituted possibly with (C1-C4)-alkyl; to their pharmaceutically acceptable salts, a pharmaceutical composition based on thereof and a method for its preparing. New compounds possess selective inhibitory effect on activity of cyclin-dependent kinases and can be used in treatment of tumor diseases.

EFFECT: improved preparing method, valuable medicinal and biochemical properties of compounds and composition.

16 cl, 3 tbl, 26 ex

FIELD: organic chemistry, medicine, pharmacy.

SUBSTANCE: invention proposes derivative of 3,4-dihydroisoquinoline of the formula (I) or its nontoxic salt and a pharmaceutical agent comprising its as an active component (wherein all symbols have the same values as given in description). Compound of the formula (I) possesses agonistic effect on CB2-receptors and, therefore, it can be used for prophylaxis and/or treatment of different diseases, for example, asthma, nasal allergy, atopic dermatitis, autoimmune diseases, rheumatic arthritis, immune dysfunction, postoperative pain and carcinomatous pain.

EFFECT: valuable medicinal properties of derivatives.

14 cl, 33 tbl, 561 ex

FIELD: organic chemistry, medicine.

SUBSTANCE: invention relates to new derivatives of sulfonylpyrrolidine of the formula (I): wherein R1 means aryl optionally substituted with halogen atom; R2 means aryl optionally substituted with halogen atom or (lower)-alkyl; R3 means -OR', cyano-group, halogen atom, N-hydroxyamidino-group, -C(O)-OR, -C(O)NR'R'', -N(R')-C(O)-R4, -N(R')-S(O)2-R, -N(R')-C(S)-NR'R, or 5- or 6-membered heteroaryl group comprising from 1 to 4 heteroatoms one of that represents oxygen atom and others represent nitrogen atom, or all heteroatoms represent nitrogen atom only and optionally substituted with (lower)-alkyl or (C3-C7)-cycloalkyl; R4 means (C3-C7)-cycloalkyl, phenyl or (lower)-alkyl that are optionally substituted with halogen atom; R means (lower)-alkyl; R' means hydrogen atom (H), (lower)-alkyl or (C3-C7)-cycloalkyl-(lower)-alkyl being independently of one another if above one R' presents; R'' means H, (lower)-alkyl; n means a whole number from 0 to 5, and to their pharmaceutically acceptable salts under condition that 1-[4-(methylphenyl)sulfonyl]-5-phenylpyrrolidinemethanol is excluded. Compounds of the formula (I) possess affinity to metabotropic glutamate receptors of group I that allows their using as a medicinal agent in treatment, prophylaxis of acute and/or chronic neurological disturbances and states that result to development of glutamate insufficiency taken among the following disorders: damage of spinal cord, head trauma, hypoxia caused by pregnancy, hypoglycemia, Alzheimer's disease, Huntington chorea, amyotrophic lateral sclerosis, disturbance in cognitive ability, memory disturbance and chronic and acute pain, schizophrenia, idiopathic parkinsonism and parkinsonism caused by medicinal agents, convulsions, anxiety (fear) and depressions.

EFFECT: valuable medicinal properties of compounds.

21 cl, 6 sch, 1 tbl, 153 ex

Muscarinic agonists // 2269523

FIELD: organic chemistry, medicine.

SUBSTANCE: invention relates to compounds of the general formula (I): wherein Z1 represents -CR1 or nitrogen atom (N); Z2 represents -CR2; Z3 represents -CR3 or N; Z4 represents -CR4; W1 represents oxygen (O), sulfur (S) atom or -NR5; one of W2 and W3 represents N or -CR6 and another among W2 and W3 represents CG; W1 represents NG; W2 represents -CR5 or N; W3 represents -CR6 or N; or W1 and W3 represent N and W2 represents NG; G represents compound of the formula (II): wherein Y represents oxygen atom (O), -C(O)- or absent; p = 1, 2, 3, 4 or 5; Z is absent; each t = 2. Also, invention describes a method for enhancing activity of the muscarinic cholinergic receptor and a method for treatment of morbid states when modification of cholinergic and, especially, muscarinic receptors m1, m4 or both m1 and m4 offers the favorable effect.

EFFECT: valuable medicinal properties of agonists.

14 cl, 2 tbl, 101 ex

FIELD: organic chemistry, chemical technology, biochemistry, medicine, pharmacy.

SUBSTANCE: invention relates to new derivatives of propene carboxylic acid amidooximes of the formula (I):

wherein R means phenyl that is substituted optionally with 1-3 substitutes wherein substitute means (C1-C2)-alkyl or (C1-C2)-alkoxy-group; R' means hydrogen atom (H); R4 and R5 mean independently of one another H, (C1-C5)-alkyl, phenyl that is substituted optionally with 1-3 substitutes wherein substitute means (C1-C2)-alkyl or (C1-C2)-alkoxy-group; or R4 and R5 in common with adjacent nitrogen atom form 5- or 6-membered saturated or unsaturated heterocyclic group that can comprise additional nitrogen atom or oxygen atom as a heteroatom and it can be condensed with benzene ring, and heterocyclic group and/or benzene ring can comprise one or two substitutes wherein substitute means (C1-C2)-alkyl or (C1-C2)-alkoxy-group; R1 and R2 mean H; R3 means H, OH; or R1 in common with R2 forms carbonyl group wherein carbon atom is joined with oxygen atom adjacent with R1 and with nitrogen atom adjacent with R2; R3 means H, OH; or R2 means H; and R1 in common with R3 form a valence bond between oxygen atom adjacent with R1 and carbon atom adjacent with R3; and its geometric isomers and/or optical isomers, and/or its pharmaceutically acceptable acid-additive salts. Compounds of the formula (I) inhibit activity of poly(adenisone diphosphate ribose) polymerase and can be used in pharmaceutical composition in treatment of states based on inhibition of this enzyme activity, and in treatment of states associated with oxygen insufficiency of heart and brain. Also, invention describes methods for preparing compounds of the formula (I).

EFFECT: improved preparing method, valuable medicinal properties of compounds and compositions.

9 cl, 1 tbl, 41 ex

FIELD: organic chemistry, medicine, pharmacy.

SUBSTANCE: invention relates to a prophylactic or therapeutic agent used against hyperlipidemia and comprising as an active component the heterocyclic compound of the formula [1]:

or its pharmaceutically acceptable salt wherein R1 represents aryl optionally substituted with similar or different one-three groups taken among alkyl, halogenalkyl, trihalogen alkyl, alkoxy-group and halogen atom; Het represents bivalent aromatic heterocyclic group of the formula [5]:

wherein X represents oxygen, sulfur atom or NR6 wherein R6 represents hydrogen atom or alkyl; R2 represents hydrogen atom, alkyl or trihalogenalkyl; D represents alkylene and alkenylene; E represents group of the formulae [3] or [4] wherein Y represents oxygen or sulfur atom; R3 and R4 are similar or different and each represents hydrogen atom or alkyl; p = 1; Z represents carboxy-group, alkoxycarbonyl, cyano-group or 1H-5-tetrazolyl. Also, invention relates to new compounds belonging to group of above enumerated heterocyclic compounds of the formula [1] that show effect reducing blood triglycerides level, low density lipoprotein cholesterol, glucose and insulin or effect enhancing high density lipoprotein cholesterol and effect reducing the atherogenic effect. Therefore, these compounds can be used in prophylaxis or treatment of hyperlipidemia, arteriosclerosis, heart ischemic disease, brain infarction, rheocclusion after percutaneous intraluminal coronary angioplasty, diabetes mellitus and obesity.

EFFECT: valuable medicinal properties of compounds and pharmaceutical composition.

29 cl, 1 tbl, 170 ex

FIELD: organic chemistry, medicine, pharmacy.

SUBSTANCE: invention describes derivative of aroylpiperazine of the formula (I):

wherein Y means lower alkylene; R1 means phenyl with 1 or 2 substitutes taken among group consisting of trihalogen-(lower)-alkyl, halogen atom, lower alkylamino-, di-(lower)-alkylamino- and nitro-group; R2 means phenyl or indolyl and each comprises 1 or 2 substitutes taken among group consisting of lower alkyl, trihalogen-(lower)-alkyl, lower alkylene dioxy-, hydroxy-group, hydroxy-(lower)-alkyl, lower alkoxy- lower alkylamino- and di-(lower)-alkylamino-group; R3 means hydrogen atom; R4 means morpholinyl-(lower)-alkyl comprising 1 or 2 substitutes taken among group consisting of ethyl, hydroxy-(lower)-alkyl, halogen-(lower)-alkyl and lower alkoxy-(lower)-alkyl, or morpholinyl-(lower)-alkynyl that can comprise 1 or 2 substitutes taken among group consisting of ethyl, propyl, isopropyl, isobutyl, spirocyclo-(lower)-alkyl, lower alkoxy-(lower)-alkyl, hydroxy-(lower)-alkyl, carboxy-(lower)-alkyl, di-(lower)-alkyl-carbamoyl, lower alkoxycarbonyl and halogen-(lower)-alkyl. Also, invention relates to a method for preparing, pharmaceutical composition based on these compounds and a method for treatment of tachykinine-mediated diseases, such as respiratory diseases, ophthalmic, cutaneous, inflammatory diseases, and as analgetic agents. Describes compounds are antagonists of tachykinine.

EFFECT: improved preparing method, valuable medicinal properties of compounds and pharmaceutical composition.

8 cl, 94 ex

FIELD: organic chemistry, medicine, pharmacy.

SUBSTANCE: invention describes derivatives of piperazine of the general formula (I): wherein Y represents lower alkylene; R1 represents phenyl substituted with one or two similar or different substitutes taken among a group including lower alkoxy-group, mono- (or di-, or tri-)-halogen-lower)-alkyl, nitro-, amino-, lower alkylamino-, di-(lower)-alkylamino-, lower alkylthio-group,alkylsulfonyl, lower alkylaminosulfonyl, di-(lower)-alkylaminosulfonyl, and pyrrolyl; R2 means phenyl substituted with hydroxy-group at position 3 and with lower alkyl and halogen atom additionally; R3 means hydrogen atom; R4 represents (2,6-dimethylmorpholino)-(lower)-alkyl, (2-methoxymethylmorpholino)-(lower)-alkyl, (3-methoxymethylmorpholino)-(lower)-alkyl. Also, invention relates to their pharmaceutically acceptable salts, to method for their preparing, pharmaceutical composition and a method for vomiting inhibition. Proposed compounds are antagonists of tachykinin and can be used for vomiting inhibition.

EFFECT: improved preparing method, valuable medicinal properties of compounds.

9 cl, 47 ex

FIELD: organic chemistry, medicine.

SUBSTANCE: invention describes N-substituted azaheterocyclic carboxylic acids and their esters of the formula (I):

wherein R1 and R2 represent independently hydrogen, halogen atom, NR6R7 or (C1-C6)-alkyl; Y represents >N-CH2 or >C=CH2- wherein only underlined atom is a component of the ring system; X represents -O-, -S-, -CH2CH2- wherein R6 and R7 represent independently (C1-C6)-alkyl; r = 1, 2 or 3; Z represents heterocycle taken among formulas (a), (b), (c), (d), (f), (k), (g) and (j) given in the invention claim. Also, invention relates to a method for their preparing and pharmaceutical composition based on compounds of the formula (I). Invention describes a method for inhibition of neurogenous pain, inflammation and blood glucose level increase to patient by administration to patient the effective dose of compound of the formula (I). Compounds of the formula (I) elicit ability to inhibit the neurogenous pain and blood glucose enhanced level.

EFFECT: improved preparing method, valuable medicinal properties of compounds.

13 cl, 1 tbl, 30 ex

The invention relates to organic chemistry and can find application in medicine

FIELD: organic chemistry, pharmacy.

SUBSTANCE: invention relates to new compounds of the general formula (I) in racemic form, enantiomer form or in any combinations of these forms possessing affinity to somatostatin receptors. In the general formula (I): R1 means phenyl; R2 means hydrogen atom (H) or -(CH2)p-Z3 or one of the following radicals: and Z3 means (C3-C8)-cycloalkyl, possibly substituted carbocyclic or heterocyclic aryl wherein carbocyclic aryl is chosen from phenyl, naphthyl and fluorenyl being it can be substituted, and heterocyclic aryl is chosen from indolyl, thienyl, thiazolyl, carbazolyl, or radicals of the formulae and and it can be substituted with one or some substitutes, or also radical of the formula: R4 means -(CH2)p-Z4 or wherein Z4 means amino-group, (C1-C12)-alkyl, (C3-C8)-cycloalkyl substituted with -CH2-NH-C(O)O-(C1-C6)-alkyl, radical (C1-C6)-alkylamino-, N,N-di-(C1-C12)-alkylamino-, amino-(C3-C6)-cycloalkyl, amino-(C1-C6)-alkyl-(C3-C6)-cycloalkyl-(C1-C6)-alkyl, (C1-C12)-alkoxy-, (C1-C12)-alkenyl, -NH-C(O)O-(C1-C6)-alkyl, possibly substituted carbocyclic or heterocyclic aryl; p = 0 or a whole number from 1 to 6 if it presents; q = a whole number from 1 to 5 if it presents; X means oxygen (O) or sulfur (S) atom n = 0 or 1. Also, invention relates to methods for preparing compounds of the general formula (I), intermediate compounds and a pharmaceutical composition. Proposed compounds can be used in treatment of pathological states or diseases, for example, acromegaly, hypophysis adenomas, Cushing's syndrome and others.

EFFECT: improved preparing method, valuable medicinal properties of compounds and composition.

11 cl, 2 tbl

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