Substituted pyrazole derivatives, intermediates for their production, herbicide composition and method of weed control

 

(57) Abstract:

Describes the new substituted pyrazole derivatives of General formula I, where the values of R1, R2, R3, R4, R5and R6specified in paragraph 1 of the claims. The new compounds possess herbicide activity. Describes herbicide composition based on compounds of the formula I, the method of combating weeds, as well as an intermediate for preparing compounds of formula I. 5 s and 3 C.p. f-crystals, 4 PL.

The present invention relates to new substituted derivatives of pyrazole, methods for their preparation, to intermediate compounds and to the use of these derivatives as herbicides.

It is known that 1-phenylpyrazoles have a weed-killing activity (EP 154115).

Herbicide-active 1-phenylpyrazoles known from EP-A-167028, as well as in the journal of Heterocyclic chemistry, including 26, 1989, pages 893-898 already described pyrazolylborate General formula I, namely, 1-(1,5-dimethyl-3-pyrazolyl)-3,5-dimethylpyrazol, substituted herbicide-active pyrazolylborate different substituent R6described in EP-A-0542388.

However, due to insufficiently high herbicide activity or selectivity of these compounds tour.

The present invention is the creation of new compounds with improved biological properties compared with known compounds.

Found that the substituted pyrazole derivatives of General formula I

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where R1represents a C1-C4-alkyl;

R2represents a C1-C4-alkyl, C1-C4-alkylthio; C1-C4-alkoxy, each of which is optionally substituted by one or more halogen atoms;

R1and R2taken together form the group -(CH2)m;

R3represents a hydrogen or halogen:

R4represents hydrogen or C1-C4-alkyl;

R5represents hydrogen, nitro, cyano or the group-COOCR7, -C(= x)NR8R9or-C(=x)R10;

R6represents hydrogen, halogen, cyano, C1-C4-alkyl (optionally substituted by one or more halogen atoms or hydroxy groups), phenyl (optionally substituted by one or more substituents, such as halogen, nitro, cyano, C1-C4-alkyl, C1-C4-alkoxy or halogeno-C1-C4-alkyl), Pirro is-alkylamino or C3-C8-alkoxygroup, each of which is interrupted by one or more oxygen atoms; or6represents a group:

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R7, R8and R9may be the same or different, and represent hydrogen or C1-C4-alkyl; or

R8and R9taken together with the nitrogen atom to which they are bound, form a 5 - or 6-membered saturated carbocyclic ring;

R10represents hydrogen or C1-C4-alkyl, optionally substituted by one or more halogen atoms;

R11represents hydrogen, C1-C4-alkyl, C2-C6alkenyl, C3-C6-quinil, or phenyl, each of which is optionally substituted by one or more halogen atoms), C3-C2-cycloalkyl, cyanomethyl, or group, R21CO-;

R12represents a C1-C6-alkyl, C2-C6alkenyl, C3-C6-quinil, or phenyl, each of which is optionally substituted by one or more halogen atoms), C3-C8-cycloalkyl, cyanomethyl, C1-C4-alkoxy-C1-C6-alkyl, CI-C3-C6-UB>-alkyl, benzyl (optionally substituted by one or more substituents, such as halogen, nitro, cyano, C1-C4-alkyl, C1-C4-alkoxy, or halogeno-C1-C4-alkyl), or R12represents a group-C(= x)R21, -(CH2)a-(O)d-R28, - (CH2)a-O-(CH2)b-R28or -(CH2)a-X-R34, R11and R12taken together with the nitrogen atom to which they are bound, form a 3-, 5 - or 6-membered saturated carbocyclic or aromatic ring in which a carbon atom is optionally replaced by oxygen atom;

R13represents hydrogen, C1-C4-alkyl, C2-C6alkenyl or C3-C6-quinil; or R13and R14taken together form the group -(CH2)p;

R14and R15may be the same or different and represents a C1-C4-alkyl, C2-C6alkenyl, C3-C6-quinil, or phenyl, each of which is optionally substituted by one or more halogen atoms), hydrogen, C3-C6-cycloalkyl or group-XR18or-NR19R20;

R16represents hydrogen, C1-C3-alkyl, C1-C4-alkoxycarbonyl-C1-C4-alkyl, CI-C1-C4-alkoxycarbonyl-C1-C4-alkyl, benzyl, C1-C4-alkoxy-C1-C4-quinil; or the group -(CH2)a-R33, -(CH2)a-X-R30, -(CH2)a-X-(CH2)b-R30or -(CH2)a-X-(CH2)b-X-(CH2)c-R30;

R17represents hydrogen, C1-C4-alkyl, C2-C6alkenyl, C3-C6-quinil, cyano-C1-C3-alkyl, C1-C4-alkylsulphonyl-C1-C3-alkyl or phenyl;

R18represents a C1-C4-alkyl, optionally substituted by one or more halogen atoms;

R19and R20may be the same or different and represent hydrogen or C1-C4-alkyl;

R21represents a C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, phenyl, (substituted by one or more atoms, nitro-, cyano-, C1-C4-alkyl, C1-C4- alkoxy, or halogeno-C1-C4-alkyl groups), or the group-NR31R32or -(CH2)<;

R23represents chloromethyl, tianmei, C3-C6-cycloalkyl (optionally interrupted by one or more oxygen atoms), or C1-C4-alkoxycarbonyl-C1-C4-alkyl;

R24represents a hydroxy-group or a group of the formula-NR25R26;

A represents-NR25R26or-S(O)n-R27;

R25and R26may be the same or different and represent hydrogen or C1-C4-alkyl;

R27represents a C1-C4-alkyl, C1-C4-alkoxycarbonyl-C1-C4-alkyl or carboxy;

R28represents hydrogen, hydroxy, halogen, C1-C4-alkyl (optionally substituted by one or more C1-C4-alkoxygroup), C3-C6-cycloalkyl (optionally interrupted by one or more oxygen atoms and optionally substituted by dimetilan), furyl, thienyl or - C(= O)R29;

R29and R30may be the same or different and represents a C1-C4-alkyl or C1-C4-alkoxy;

R31and R32may be the same or different and represents a C129;

R34represents a C1-C4-alkyl;

a, b and C is 1, 2 or 3;

d is 0 or 1;

m is 3 or 4;

n is 0, 1 or 2;

p is 2 or 3; and

x is oxygen or sulfur;

has the best weed-killing properties than the previously mentioned known compounds of related structure.

Especially active are the pyrazole derivatives of General formula I, as defined above, in which:

R1is stands;

R2is methylthio or deformedarse (and especially deformedarse); or

R1and R2taken together form the group -(CH2)4;

R3is hydrogen, chlorine or popgruppi;

R4is hydrogen;

R5is hydrogen, nitro, cyano or-C(=X)R10.

In a particularly preferred group of the above compounds, R6is hydrogen, halogen, cyano, C1-C4- alkyl, C1-C4-alkylthio or-NR11R12while it is preferable, if R11and R12are hydrogen, C1-C4-alkyl or C1-C4-alkoxycarbonyl.

The term "halogen" means fluorine, chlorine is whether a straight chain.

The present invention also relates to intermediate compounds of General formula Ik:

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where R1, R2and R6have the meanings given in General formula 1;

and to intermediate compounds of General formula I:

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where R1, R2, R3and R6have the meanings defined in General formula I.

Compounds of the present invention of General formula I and intermediate compounds in which R6= NH2can be obtained in a manner that:

A) a compound of General formula II:

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where R1, R2and R3have the meanings defined in General formula I, is subjected to reaction with a compound of General formula III:

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where R4and R5have the meanings defined in General formula I, a Y represents a C1-C6-alkoxy, hydroxy or halogen, or, if is hydrogen, then:

C) the compound of General formula II:

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where R1, R2and R3have the meanings defined in General formula I, is subjected to reaction with 2-halogenoarylation formula IIIa:

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or 2,3-dehalogenation formula III:

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where Hal is halogen; or R3is halogen,

C) the compound of General fo the formula I, first is subjected to reaction with a halogenation agent, resulting in the receive connection of the formula Ib:

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where R1, R2, R5, R11and R12have the meanings defined in General formula I; a Hal is halogen, and then, after processing the receive target connection;

or, if R16is-OR16then:

E) a compound of General formula Id:

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where R1, R2, R3, R4and R5have the meanings defined in General formula I, is first subjected to diazotization with obtaining compounds of formula Ie:

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where R1, R2, R3, R4and R5have the meanings defined in General formula I, and then heated, resulting in a receive connection formula If;

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where R1, R2, R3, R4and R5have the meanings defined in General formula I, which, in turn, is subjected to reaction with a compound of General formula IV: QR16(IV) where R16has the meanings given in General formula I, Q is a leaving group: or, if R5is the nitro-group, and R6is SR17then:

F) the compound of General formula Ig:

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where R1, R2, R3and R4matter, theSR17(V)

where R17has the meanings given in General formula I; or, if R5is the nitrogroup, a R6is-S(O)nR17where n is 1 or 2, then:

G ) the compound of General formula Ih:

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where R1, R2, R3, R4and R17have the meanings defined in General formula I, is subjected to stepwise oxidation using m-chloroperbenzoic acid or, if R5is cyano, then:

H) a compound of General formula IIa:

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where R1and R2have the meanings defined in General formula I, is subjected to reaction with a compound of General formula Illc:

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where Y is C1-C6-alkoxy, hydroxy or halogen; or R16is halogen, then:

K) the compound of General formula II:

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where R1, R2and R3have the meanings defined in General formula I, is subjected to reaction with a compound of General formula IIIc

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where Y is C1-C6-alkoxy, dimethylamino or halogen, resulting in a receive connection formula Il

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where R1, R2and R3have the meanings defined in General formula I, which is then subjected to diazotization known ways formulas lk:

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where R1, R2and R6have the meanings defined in General formula I, process of halogenation agent; or

M) the compound of General formula Im:

< / BR>
where R1, R2and R3have the meanings defined in General formula I, and R6represents a C1-C4-alkyl (optionally substituted by one or more halogen atoms), or WITH2-C8-alkyl (which is interrupted by one or more oxygen atoms), turn in a known manner in the nitrile of General formula I; or, if R6is a group-NR11R12then

N) the compound of General formula In:

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where R1, R2and R3have the meanings defined in General formula I, is subjected to reaction with an amine in the presence of a solvent; or, if R6is a group-NR11R12where R11is hydrogen, a R12is C1-C6-alkyl, then:

O) the compound of General formula Il;

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where R1, R2and R3have the meanings defined in General formula I, is subjected to reaction with a complex trialkylamine ortho-ester, followed by reduction; or

R) compound of General formula Io:



where, R1, the Ohm, subjected to reaction with a base and an alkylating agent, or with an acid chloride; or, if R6is-NR11R12where R11and R12represents a C1-C6-alkyl,

Q) the compound of General formula Il:

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where R1, R2and R3have the meanings defined in General formula I, is subjected to the interaction with about 2 moles of base and 2 moles of the appropriate alkylating agent; or

R ) compound of General formula Il:

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where R1, R2and R3have the meanings defined in General formula I, is subjected to interaction with the bottom, or in the absence of the base, and c the corresponding acid chloride; or

S) compound of General formula Ip:

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where R1, R2, R3and R21have the meanings defined in General formula I, is subjected to reaction in the base and with appropriate alkylating agent; or

T), the compound of General formula In:

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where R1, R2and R3have the meanings defined in General formula I, and R5is the piano - or nitro-group, is subjected to reaction with a nucleophile oxygen, nitrogen, sulphur or carbon; or, if R6is replaced by stands, U ) connection obsei the formula I, subjected to reaction with a Lewis acid; or

V) a compound of General formula Ir:

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where R1, R2, R3, R4and R5have the meanings defined in General formula I, process halogenides agent; or

W) compound of General formula Is:

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where R1, R2, R3, R4and R5have the meanings given in General formula 1, is subjected to reaction with oxygen, nitrogen, sulfur or carbon nucleophile; or, if R6is mercaptopropyl:

X) a compound of General formula It:

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where R1, R2, R3and R4have the meanings defined in General formula I, is treated with bisulfite sodium; or

Y), the compound of General formula Iu:

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where R1, R2, R3and R4have the meanings defined in General formula I, is treated with an appropriate alkylating agent; or

Z), the compound of General formula Iv:

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where R1, R2, R3and R4have the meanings defined in General formula I, a Rxis C1-C4-alkyl, are subjected to stepwise oxidation.

Compounds of the present invention having the General formula I, in which R5is nitrogroup the I of the present invention, having the General formula I, in which R6is a group-NR11R12can also be obtained by known methods described in DE 3707686, DE 3543034, EP 224831, DE 3543035, JP 57167972, DE 2747531.

Compounds of the present invention having the General formula I, in which R14is group-OR18or-NR19R20can be obtained from undeclared compounds of General formula I, in which R6is an amino group, known methods described in Chem.Soc.Rev. 4, 231-50 (1975) and J. March, Advanced Organic Chemistry, 1985, p.370.

Compounds of the present invention having the General formula 1 in which R5is cyano - or nitro-group, and R6-C1-C4the alkyl can be obtained by known methods (J. Heterocyclic Chem. 24, 1669 (1987), ibid., 24, 739 (1987)).

The reaction of compounds of formulas II, IIa or III is usually carried out in a suitable solvent, at a temperature of from -30 to 150oC, and preferably at room temperature.

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

Deleted groups in the variant of method E is chlorine or popgruppi.

The reaction x2">

In a variant of the method L), the reaction is carried out in a suitable solvent, preferably acetonitrile or dichloromethane, at a temperature of from -10oC to 80oC.

Variant of method (M) is usually carried out according to the procedure described in Tetrahedron Letters, 1977, p. 1813.

Variant of the method) is usually carried out with known methods (J. March, Advanced Organic Chemistry 1985, p. 798-800, and the works cited in the present description).

In variants of the method P), Q), R) and S), suitable bases are, for example, hydroxides of alkali metals and alkaline earth metals, sodium methylate, hydrides of alkali metals, carbonates of alkali and alkaline earth metals, tertiary aliphatic and aromatic amines, such as triethylamine and pyridine, as well as heterocyclic bases.

Way T option) carried out mainly in accordance with the methods described in J. Heterocyclic Chem. 25, 555 (1988).

Obtaining compounds can be carried out with or without using a solvent. If necessary, there may be used solvents or diluents that are inert towards the reagents. Examples of such solvents or diluents are aliphati for example, such as hexane, cyclohexane, petroleum ether, naphtha, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane and chlorobenzene; ethers, such as diethyl ether, methyl ether, methyl t-butylether, diisopropyl ether, disutility ether, dioxane and tetrahydrofuran; ketones, such as acetone, methyl ethyl ketone, methylisobutylketone and methyl isobutyl ketone; NITRILES, such as acetonitrile and propionitrile; alcohols, such as methanol, ethanol, isopropanol, butanol, tert-butanol, tert-amyl alcohol and ethylene glycol; esters such as ethyl acetate and amylacetate; amides, such as dimethylformamide and dimethylacetamide; sulfoxidov, such as dimethyl sulfoxide; sulfones, such as sulfolane; bases, such as pyridine and triethylamine; carboxylic acids, such as acetic acid; and mineral acids such as sulfuric acid and hydrochloric acid.

Compounds of the present invention can be processed in accordance with standard procedures. For example, the treatment can be carried out by crystallization or column chromatographically or liquids, any substances that are very well soluble in halogenated hydrocarbons such as methylene chloride or chloroform; ethers such as diethyl ether or tetrahydrofuran; alcohols such as methanol or ethanol; ketones such as acetone or butanone; Amidah such as dimethylformamide; and sulfoxidov such as dimethylsulfoxide.

Intermediate compounds of General formula II:

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where R1, R2and R3have the meanings defined in General formula I, can be obtained by a known method (see, for example, JP 62158 260) from compounds of General formula VI:

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where R1, R2and R3have the meanings defined in General formula I.

Compounds of General formula II, where R1and R2taken together form the group -(CH2)m-, and R3is hydrogen, can be obtained by treating compounds of General formula IIIc;

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the hydrazine with the addition of the base. The compound of General formula IIIc can be obtained by reaction of compounds of General formula IIId

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with 1,1-dehalogenation. Compounds of General formula VI, where R1and R2have the meanings defined in General formula I, and R3is halogen, megaterium agent.

As starting materials for preparing compounds of General formula VI are compounds of General formula VII:

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where R1defined in General formula I, which can be obtained, for example, by the way, where if R2is C1-C4-alkyl, optionally substituted with halogen,

a) compound of General formula VIII, VIIIa, or IX:

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where R2is C1-C4-alkyl, optionally substituted with halogen, is subjected to reaction with a compound of General formula X:

R1-NHNH2< / BR>
where R1defined in General formula I, optionally in the presence of a solvent; or, if R2is C1-C4-alkylthiophene, optionally substituted by one or more halogen atoms, then:

b) the compound of General formula XI:

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where R35is cyano or a group-COOR36in which R36represents a C1-C4-alkyl, are subjected to reaction with a compound of General formula I, optionally in the presence of a solvent, e.g. in water, and receive the connection of General formula XII:

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where R1defined in General formula I, a R36have the above values, which then podvergaja, optionally substituted by one or more halogen atoms, and Q is a leaving group, and the resulting compound of General formula XIV:

(XIV)

subjected to saponification and decarboxylation in accordance with known methods (see, for example, Zeitschrift fur Chemie 420, (1968)); or

c) the compound of General formula XV:

< / BR>
where R35is cyano or a group-COOR36in which R36represents a C1-C4-alkyl, a R37is C1-C4-alkyl, optionally substituted by one or more halogen atoms, is subjected to reaction with a compound of General formula X, optionally in the presence of a solvent, for example, water, resulting in the receive connection of General formula XIV; or, if R2is C1-C4-alkoxygroup, optionally substituted by one or more atoms of halogen,

d) the compound of General formula XVI:

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where R1defined in General formula I, is subjected to reaction with a compound of General formula XIII in the presence of a base; or

h) a compound of General formula XVII:

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where R1defined in General formula I and Z is C1-C4-alkyl, are subjected to reaction in the presence of snowm, optionally substituted by one or more halogen atoms, and Q is removed by the group, and the resulting reaction compound of General formula XVIII:

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where R1defined in General formula I, R37is C1-C4-alkyl, optionally substituted by one or more halogen atoms, and Z is C1-C4-alkyl, are subjected to reaction with ammonia, resulting in the receive connection of General formula XIX:

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where R1defined in General formula I, and R37is C1-C4-alkyl, optionally substituted by one or more halogen atoms, which is subjected to reaction with sodium hydroxide and halogen; or, if in the General formula I, R3is halogen, then :

f) the compound of General formula XVIII or XIX:

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< / BR>
where R1defined in General formula I, R37is C1-C4-alkyl, optionally substituted by one or more halogen, and Z is C1-C4-alkyl, are subjected to reaction with a halogenation agent, resulting in a receive connection General formula XVIIIa and XIX:

< / BR>
< / BR>
where R1, R37and Z have the meanings defined in General formula XVIII and XIX: either
is C1-C4-alkyl, optionally substituted by one or more halogen atoms, and Hal is halogen, is subjected to reaction with sodium hydroxide and bromine, resulting in the receive connection of General formula XX:

< / BR>
where R1, R37and Hal have the meanings given in the formula XIXa; or, if R1and R2taken together form a three - or tetramethylene group

h) a compound of General formula XXI:

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where n is 2 or 3, is subjected to reaction with hydrazine, resulting in a gain of 3(5)-amino-5(3)-hydroxyalkylated General formula XXII

< / BR>
where n is 2 or 3, which is then subjected to reaction with hexane-2,5-dione, the anhydride of phthalic acid or anhydride tetrahydrophthalic acid in accordance with known methods described in the literature (Bull. Chem. Soc. JP., 44, 2856-2858 (1971) or EP 305826) and I get the connection of General formula XXIII:

< / BR>
where n is 2 or 3, and Q is aminosidine group, such as Q1, Q2or Q3:

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which is subjected to cyclization in the method Mitsunobu (Synthesis I, (1981)) and get a connection General formula XXIV:

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where n is 2 or 3, and then, if Q is Q1this connection of the , the specified connection is treated with hydrazine in accordance with known procedures described in the literature (Org. Synthesis, Coll. Vol. 3, 148 (1955)).

Starting materials of General formula XXI can be obtained by known methods (Chem. Ber., 109(1), 253-260, 1976).

Intermediate compounds of General formula Ik can be obtained by reaction of compounds of General formula IIb

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where R1and R2have the meanings defined in General formula IIb, which is carried out in the manner described above.

Intermediate compounds of General formula Im, where R6is C1-C4-alkyl, optionally substituted by one or more halogen atoms; or C2-C8-alkyl, which is interrupted by one or more oxygen atoms, can be obtained in a known manner, namely, by conversion of compounds of General formula Iq:

< / BR>
where R1, R2and R3have the meanings defined in General formula I, R6is C1-C4-alkyl, optionally substituted by one or more halogen atoms, or C2-C8-alkyl, which is interrupted by one or more oxygen atoms, and R7is C1-C4-alkyl, amide.

ptx2">

The intermediate compounds can be carried out in the presence of a solvent. If there is a necessity of carrying out the reaction in the presence of a solvent for this purpose can be used one of the solvents mentioned above.

The above starting materials are either known compounds or they can be obtained by known methods.

Compounds of the present invention have good weed-killing activity against broadleaf weeds and grasses. In addition, the compounds of the present invention have a selective effect against various crops, such as rapeseed, sugar beet, soybean crops, cotton, rice, barley, wheat and other cereals. Individual active compounds are particularly effective herbicides selective action in respect of such crops as sugar beet, cotton, soybean, maize and cereals. However, compounds of the present invention can be used for combating weeds in order to protect monocultures, such as forest plantations, ornamental plants, fruit trees, vineyards, citrus trees, nut crops, bananas, coffee tree is, the example compounds of the present invention can be used against the following species of plants:

Dicotyledonous weeds: Siparis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Brassica, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Lamium, Veronica, Abutilon, Datura, Viola, Galeopsis, Papaver, Centauera and Chrysanthemum.

Monocotyledonous weeds species: Avena, Alopecurus, Echinochloa, Setaria, Panicum, Digitaria, Poa, Eleusine, rachiaria, Lolium, Bromus, Cyperus, Agropyron, Sagittaria, Monocharia, Fimbristylis, Eleocharis, Ischaemum and Apera.

The dose used compounds varies depending on whether the processing of pre-emergence or post-harvest and generally ranges from 0.001 to 5 kg/ha.

Compounds of the present invention can also be used as defoliants, desicants and herbicides non-selective actions.

Compounds of the present invention can be used both separately and in combination with another compound of the present invention or with other active agents. Depending on the purpose of the processing can be added, but not necessarily, and other plant protection products or pesticides. In case you need to expand the range of protective actions can also be added other Weed Abstracts, Vol. 40, No. 1, 1991, under the heading "Lists of common names and abbreviations employed for currently used herbicides and plant growth regulators in Weed Abstracts".

Improving the efficiency and speed of action of the active ingredient can be achieved, for example, by the addition of appropriate adjuvants, such as organic solvents, wetting agents and oils. These additives can reduce the dose of the active compounds.

The above active ingredients or mixtures thereof can be produced, for example, in the form of powders, Farrukh Dustov, granular products, solutions, emulsions or suspensions, with the addition of liquid and/or solid carriers and/or diluents, and optionally, a binder, a wetting, emulsifying and/or dispersing additives.

Suitable liquid carriers are, for example, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulfoxide, dimethylformamide and other petroleum fractions, as well as vegetable oils.

Suitable solid carriers are crushed minerals, such as bentonite, silica gel, talc, kaolin, attapulgite, limestone, silicic acid and plant products, such as flour.

In to Yenakieve ethers, naphthalenesulfonic acids and their salts, phenolsulfonic acids and their salts, condensates of formaldehyde, sulfates of fatty alcohols, and substituted benzosulfimide acids and their salts.

The percentage of active ingredients in various preparations can vary within wide limits. For example, the composition can contain from about 10 to 90 wt.% the active ingredient and from about 90 to 10 wt.% liquid or solid carriers, and optionally up to 20 wt.% surface-active substances.

These agents can be applied in the traditional way, for example, in the form of a mixture for spraying in the amount of approximately from 100 to 1000 l/ha where as media use water. These agents can be introduced by low-volume or ultra-low volume spraying or in the form of so-called micro granules.

The manufacture of the above products can be carried out by known methods, for example, by milling or mixing. Individual components can be, but not necessarily, mixed immediately before use using commonly used method is the so-called mixing in the tank.

Using the following phrases is the

35 wt.% mineral-filler

8 wt.% the calcium lignosulfonate

2 wt.% sodium salt of N-methyl-N-reitoria

25 wt.% silicic acid

B) Paste

45 wt.% the active ingredient

5 wt.% aluminosilicate sodium

15 wt.% atrological with 8 M of ethylene oxide

2 wt.% spun oil

10 wt.% polyethylene glycol

23 wt.% water

C) emulsifiable Concentrate

20 wt.% the active ingredient

75 wt.% isophorone

5 wt. % mixture of sodium salt of N-methyl-N-reitoria and calcium lignosulfonate.

The following examples illustrate the formation of compounds of the present invention.

Example 1.2

N-[1-(3-Chloro-4,5,6,7-tetrahydropyrazolo[1,5-a] pyridine-2-yl)-4-nitro-5 - pyrazolyl]propionamide

8.72 g (29.7 mm) of N-[1-(3-Chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-2-yl)-5 - pyrazolyl]propionamide suspended in 33 ml of acetic acid. To the resulting suspension at a temperature of 0-5oC add 3.31 g (32.5 mm) of acetic anhydride, cooling while the ice. Then to the solution drop by drop add 1.93 g (31 mm) fuming nitric acid. After stirring for 6 hours at room temperature the mixture is concentrated. The resulting residue is dissolved in dichloromethane, neitralizuyushchego magnesium sulfate and concentrated. The resulting residue is purified by chromatography on silica gel, using as eluent a mixture of hexane/ethyl acetate (1:1).

Output: 6.03 g = 60%].

So pl.: 46-49oC.

Example 2.0

N-[1-(4-Chloro-5-deformedarse-1-methyl-3-pyrazolyl)-4-nitro-5-pyrazolyl] - 2,2,2-trifurcated

0.79 g (2.1 mm) of N-[1-(5-deformedarse-1-methyl-3-pyrazolyl)-4-nitro-5-pyrazolyl] - 2,2,2-trifurcated suspended in 35 ml of dichloromethane and treated with 0.17 ml of sulfurylchloride. The resulting mixture is stirred for one hour at room temperature, and then concentrated.

Yield: 0.77 g = 89.5%].

So pl.: 136-139oC.

Example 2.1

N- [1- (4-Chloro-5-deformedarse-1-methyl-3-pyrazolyl)-4-nitro-5-pyrazolyl] ndimethylacetamide

1.3 g (5.0 mm) of 5-Amino-1-(4-chloro-5-deformedarse-1-methyl-3-pyrazolyl) pyrazole was dissolved in 20 ml of acetic acid and treated with 0.55 g (5.4 mm) of acetic anhydride. After 2 hours stirring at room temperature, the reaction solution is cooled to 0oC, and then add 0.4 g (6.4.mm) concentrated nitric acid. After 8 hours of stirring at room temperature, the reaction mixture is poured into ice water and extracted with ethyl acetate. Body column of silica gel, using as eluent a mixture of hexane and ethyl acetate (1:1).

Yield: 1.4 g = 81.5%].

So pl.: 132oC.

Example 4.1

1- (3-Chloro-2, 4, 5, 6,7-tetrahydropyrazolo[1,5-a]pyridine-2-yl)- 5-diethylamino-4-pyrazolecarboxylate

10.45 g (0.35 M) of 80% sodium hydride is added to 100 ml of tetrahydrofuran and the resulting mixture was cooled to 0oC. To this mixture in a nitrogen atmosphere by drop add the suspension 43.6 g (0.17 M) of 5-amino-1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-a] pyridine-2-yl) -4-pyrazolecarboxylate in 500 ml of tetrahydrofuran. The resulting mixture was stirred for 1.5 hours and then at a temperature of 15oC drop by drop add 31.4 ml (0.38 M) iodoethane in 20 ml of tetrahydrofuran. After stirring for 3 hours at a temperature of 15oC the mixture is cooled. To this mixture drop by drop add water, and then extracted with ethyl acetate. The organic phase is separated, dried, and then concentrated. The obtained residue is recrystallized from ethyl acetate.

Output: 47.3 g = 89.4 per cent from].

So pl.: 68-70oC.

Example 4.2

1-(3-Chloro-4,5,6,7-tetrahydropyrazolo[1,5-a] pyridine-2-yl)-5-(ethylmethylamino)-4-pyrazolecarboxylate

23.3 g (88.7 mm) 5-Amino-1-(3-chloro - 4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-2-yl is E. 5 hours in a water bath at a temperature of 150oC. thereafter, water was removed and the reaction solution was concentrated. The resulting residue is suspended in 250 ml of ethanol, after which the portions treated with 4.2 g (106.4 mm) sodium borohydride, cooling, while the resulting mixture was heated under reflux until then, until the evolution of gas ceases. After that, the mixture was concentrated and the resulting residue is carefully added to a mixture of ice and water. Thus obtained mixture is extracted three times with methylene chloride, after which the extracts are dried up. The organic phase is concentrated. After this, at a temperature of 0oC to the mixture 2,61 g (87.1 mm) of 80% sodium hydride in 150 ml of tetrahydrofuran, and then drop by drop add 24.1 g (87.1 mm) pre-obtained 1-(3-chloro-4,5,6,7-tetrahydropyrazolo [1,5-a] pyridine-2-yl)-5-methylamino-4-pyrazolecarboxylate in 500 ml of tetrahydrofuran. After stirring for one hour at room temperature to the mixture 7.82 ml (95.8 mm) iodata and heated at a temperature of 70oC for 3 hours. After adding one drop of water the mixture is extracted three times with ethyl acetate. The organic phase is separated, dried and concentrated and the resulting residue is recrystallized from ethyl acetate.

You the and-1-methyl-3-pyrazolyl) -4-pyrazolecarboxylate

5.68 g (19.7 mm) 5-Amino-1-(4-chloro-5-deformedarse-1-methyl-3-pyrazolyl)-4 - pyrazolecarboxylate dissolved in 66.3 ml of 47% pomodorini acid and the resulting mixture is cooled to -6oC. then, to the mixture drop by drop in nitrogen atmosphere add 2.36 g (34.2 mm) of sodium nitrite in 5.9 ml of water. Then this mixture is stirred for 15 minutes at the same temperature, then warmed to room temperature. After adding 200 ml of water the mixture is extracted 4 times with methylene chloride. The organic phase is washed with saturated aqueous sodium bicarbonate, dried with magnesium sulfate and concentrate.

Output: 6.94 g = 99.5%].

So pl.: 78oC.

Obtaining raw materials

1. 5-Amino-1- (4-chloro-5-deformedarse-1-methyl-3-pyrazolyl)-4-pyrazolecarboxylate

5.0 g (19.7 mm) 5-Amino-1- (5-deformedarse-1-methyl-3 - pyrazolyl)-4-pyrazolecarboxylate dissolved in 180 ml of acetonitrile and add one drop of 2.65 g (19.7 mm) sulfurylchloride. The resulting mixture is stirred for one hour at room temperature and concentrate.

Output: 5.68 g = 99.5%].

So pl.: 140-142oC.

2. 5-Amino-1-(5-deformedarse-1-methyl-3-pyrazolyl)-4-pyrazolecarboxylate

22.5 g (0.13 M) 5-Diformate the and. The resulting mixture was heated under reflux for one hour and then cooled. The resulting residue is subjected to vacuum filtration, and then washed with a small amount of ethanol.

Output: 19.28 g = 60%].

So pl.: 141-143oC.

3. 5-Deformedarse-3-hydrazino-1-methylpyrazole

39.8 g (0.25 m) of 3-Amino-5-deformedarse-1-methylpyrazole dissolved in 225 ml of water and 450 ml of concentrated hydrochloric acid, To the mixture drop by drop and the temperature is -10oC add 18.55 g (0.27 M.) of sodium nitrite in 80 ml of water. After stirring for one hour at a temperature of -10oC to the mixture drop by drop and at the same temperature, add 137.6 g of tin chloride (II), dissolved in 180 ml of concentrated hydrochloric acid. After stirring for another hour at a temperature of -10oC to the reaction mixture drop by drop and at room temperature add 805 ml of 32% aqueous sodium hydroxide. Then this mixture is 8 times mix by shaking with ethyl acetate, then the combined organic phases are washed with saturated aqueous sodium chloride, dry with magnesium sulfate and concentrate.

Output: 42.24 g = 97.2%].

4. Z-Amino-6-deformedarse-1-metalpar the same temperature to the mixture drop by drop add 57.3 g (0.36 M) of bromine so, to ensure that the temperature did not rise above 0oC. thereafter, to the mixture in portions at 0oC add 57.1 g (0.3 M) 3-carbarnoyl-5-deformedarse-1-methylpyrazole. The reaction mixture is stirred for one hour at 80oC and then saturated with sodium chloride. The resulting reaction residue is subjected to vacuum filtration, then the filtrate is 6 times mix by shaking with ethyl acetate. The organic phase is dried with magnesium sulfate and concentrate. Previously removed is dissolved in 500 ml of water and the resulting solution was heated to boiling for one hour. Then, this reaction solution is saturated with sodium chloride and 6 times shaken out with ethyl acetate. The organic phase is dried with magnesium sulfate and concentrate.

Output: 34.2 g = 70.5%].

So pl.: 57oC.

5. 3-Carbarnoyl-5-deformedarse-1-methylpyrazole

80.6 g (0.39 M) 3-Methoxycarbonyl-5-deformedarse-1-methylpyrazole and 300 ml of 33% aqueous ammonia solution is stirred for one hour at reflux. After the reaction the solution is cooled. The resulting residue is subjected to vacuum filtration, and then washed with water and diisopropyl ether.

Output: 58.9 g = 78.8% of theorem is) 5-Hydroxy-3-methoxycarbonyl-1-methylpyrazole and 299.2 g (2.17 M) of carbonate of Qadi dissolved in 1500 ml of dimethylformamide and heated to 70oC. At the same temperature in the mixture for 2 hours enter Chlorodifluoromethane. The resulting mixture is stirred for one and a half hours at a temperature of 80oC. After adding water, the reaction mixture was extracted 6 times with ethyl acetate. The combined organic phases are washed with saturated aqueous sodium chloride and dried with magnesium sulfate. The resulting reaction solution was concentrated.

Yield: 80.6 g = 90.3%].

7. 5-Hydroxy-3-methoxycarbonyl-1-methylpyrazole

102.3 g (0.72 M) of Diethylazodicarboxylate add to 1000 ml of ether and the resulting mixture is cooled to -5oC in a bath of ice/methanol. To this mixture drop by drop add 33 g (0.72 M) methylhydrazine in 100 ml of ether so that the internal temperature did not rise above 0oC. then the mixture is stirred one hour at 0oC, resulting in a precipitate formed. The residue is subjected to vacuum filtration, and then washed with ether and dried in vacuum at 40 ° oC. Intermediate compound is placed in an oil bath heated to 120oC. the resulting reaction product is recrystallized from methanol.

Yield: 67.6 g = 60.1%].

So pl.: 197oC.

is alprazola, dissolved in 30 ml of methylene chloride, treated with 1.35 g (10 mm) sulfurylchloride and the resulting mixture was stirred at room temperature for 10 minutes. After concentration, the obtained residue is recrystallized from diisopropyl ether/ethyl acetate.

Yield: 1.8 g = 74.8%].

So pl.: 51oC.

Example 4.4

1-(4-Chloro-5-deformedarse-1-methyl-3-pyrazolyl)- 5-methyl-4-pyrazolecarboxylate

0.57 g (2.25 mm) 1-(5-Deformedarse-1-methyl-3-pyrazolyl) -5-methyl-4-pyrazolecarboxylate dissolved in 30 ml of methylene chloride at room temperature is treated with 0.30 g (2.25 M) sulfurylchloride. The resulting mixture is stirred for one hour and then concentrated.

Yield: 0.65 g = 99.8%].

So pl.: 69-70oC.

Obtaining raw materials

1. 1-(5-Deformedarse-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarboxylate

A mixture of 0.79 g (2.91 mm) 1-(5-deformedarse-1 - methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarboxylate, 0.46 g (5.85 mm) of pyridine and 20 ml of 1,4-dioxane is cooled to 5oC, and then drop by drop add 0.74 g (3.51 mm) anhydride triperoxonane acid. The resulting mixture is stirred for 3 hours at room temperature, and then add 100 ml of water 2">

Yield: 0.74 g = 99.8%].

So pl.: 106-107oC.

2. 1-(5-Deformedarse-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarboxylate

0.98 g (3.38 mm) 1-(5-Deformedarse-1-methyl-3-pyrazolyl)- 5-methyl-4-pyrazolecarboxylate dissolved in 20 ml of tetrahydrofuran, and with stirring 50 ml of an aqueous solution of ammonia (33%). After stirring for 3 hours at room temperature the resulting mixture was concentrated to half volume and acidified with diluted hydrochloric acid. The resulting precipitate is filtered under vacuum, washed with a small amount of water and dried.

Yield: 0.27 g = 73%].

So pl.: 116-118oC.

3. 1-(5-Deformedarse-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarboxylate

0.2 g (3.8 mm) of 1-(5-Deformedarse-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolylborate acid are suspended in 30 ml of 1,2-dichloroethane. To the resulting suspension drop by drop and at room temperature is added 1.19 g (10.0 mm) of thionyl chloride. After that, the mixture is heated under reflux for one hour, and then concentrated.

Yield: 0.98 g = 100%].

4. 1-(5-Deformedarse-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolylborate acid

A mixture of 1.25 g (4.16 mm) Athericidae sodium stirred for one hour at a temperature of 80oC. the resulting reaction solution was concentrated to half volume and acidified with 37% hydrochloric acid. The resulting precipitate is filtered under vacuum, washed with water, and then drain.

Yield: 1.05 g = 93%].

So pl.: 205-207oC.

5. Ethyl 1-(5-deformedarse-1-methyl-3-pyrazolyl)-5-methyl-4 - pyrazolecarboxylate

3.0 g (16.8 mm) 5-Deformedarse-3-hydrazino-1-methylpyrazole add 25 ml of ethanol and the mixture drop by drop process 2.96 g (16.0 mm) ethyldimethylamine dissolved in 25 ml of ethanol. The mixture is then heated under reflux for 2 hours. After cooling, the precipitate is filtered off under vacuum.

Output: 2.52 g = 53%].

So pl.: 110oC.

Getting used starting materials are described below.

1.1,1,7-Trichloro-1-heptane-3-one

To 78.53 g (0.589 mm) of aluminum chloride in 150 ml of methylene chloride, at room temperature, drop by drop add 100 g (0.62 M) 5-chlorovaleronitrile. After stirring for one hour to the mixture drop by drop add 45 ml (0.558 M) 1,1-dichlorethylene in 25 ml of methylene chloride. Then to the mixture drop by drop and under ice cooling, add 100 ml of water. The solid material is subjected to vacuum filtrat the STATCOM is subjected to distillation on a rotary evaporator.

Output: 112.76 g = 93.8%].

So Kip.: 125oC/0.4 mbar.

2. 2 Hydrazino-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine

261.9 ml (5.4 M) of hydrazine hydrate drop and at a temperature of -2oC (bath of dry ice/acetone) are added to 116.6 g (0.54 M) 1,1,7-trichloro-1-heptane-3-one in 2000 ml of 2-propanol. After 12 hours stirring at room temperature add 60.6 g (1.08 mm) of potassium hydroxide and the resulting mixture heated under reflux for 5 hours. Then the reaction mixture is evaporated to dryness and the resulting residue is treated with 100 ml water and 100 ml of saline solution. After extraction (9 times) with ethyl acetate the organic phase is washed with saline, dried with sodium sulfate and concentrated.

Output: 29.29 g = 35.6%].

The resulting product is a yellow oily substance.

3. 5-Amino-4-cyano-1-(1-methyl-5-methylmercapto-3-pyrazolyl)-pyrazole

A mixture of 2.0 g (13.1 mm) 3-hydrazino-1-methyl-5-methylmercaptopurine and 1.8 g (14.4 mm) ethoxymethylenemalononitrile in 25 ml of ethanol is stirred for 30 minutes at room temperature and heated to boiling for 3 hours. The reaction mixture was concentrated and the obtained residue chromatographic/SUP>C.

4. 3 Hydrazino-1-methyl-5-methylmercaptopurine

1.1 g (15.8 mm) of sodium nitrite in 4 ml of water one drop at a time and at a temperature of 0oC is added to 1.9 g (13.1 mm) 3-amino-1-methyl-5-methylmercaptopurine in 28 ml of concentrated hydrochloric acid and the resulting mixture stirred for 2 hours at 0oC. To this mixture at a temperature of -30oC drop added 7.4 g (32.8 mm) SnCl22H2O in 5.5 ml of concentrated hydrochloric acid. The resulting mixture is stirred for 3 hours at the same temperature. Then the reaction mixture was alkalinized by addition of 32% sodium hydroxide and extracted with methylene chloride. The organic phase is dried with sodium sulfate and concentrated. Thereby obtaining 2.0 g of the product, which is used without further purification.

5. 3-Amino-1-methyl-5-methylmercaptopurine

5.55 g (33.0 mm) 3-Amino-4-cyano-1-methyl-5-methylmercaptopurine heated to boiling for 24 hours with 50 ml of 32% sodium hydroxide. The resulting reaction mixture is cooled, slightly acidified aqueous solution of sodium phosphate, heated for 8 hours at a temperature of 50oC, and then extracted with ethyl acetate. The organic phase is dried with sodium sulfate and conc is Xan/ethyl acetate, 1:1).

Yield: 19 g = 39.8%].

So pl.: 164-168oC.

6. 3-Amino-4-cyano-1-methyl-5-methylmercaptopurine

9.63 g (56.6 mm) [Bis(methylmercapto)methylene]malononitrile suspended in 50 ml of water and treated with 3.7 ml (67.9 mm) methylhydrazine. The resulting mixture is heated to boiling for one hour, after which the reaction solution is cooled and the precipitate is subjected to vacuum filtration, and then recrystallized from ethanol.

Yield: 6.5 g = 68.0%].

So pl.: 120-121oC.

7. 5-Amino-1-( 4,5,6,7-tetrahydropyrazolo[1,5-a] pyridine-2-yl)- 4-pyrazolylborate acid and 2-hydrazino-4,5,6,7-tetrahydropyrazolo [1,5-a]pyridine

The following compounds receive in accordance with known methods.

a) 2-Amino-4,5,6,7-tetrahydropyrazolo[1,5-a] pyridine

A solution of 8.19 g (146 mm) of potassium hydroxide in 122 ml of water and 122 ml of ethanol is added to 19.19 g (292 mm) of hydroxylamine hydrochloride in 200 ml of ethanol. The resulting mixture is stirred for 15 minutes and then add 12.5 g (58 mm) of 2-(2,5-dimethyl-1-pyrrolyl)-4,5,6,7-tetrahydropyrazolo[1,5-a] -pyridine. After that, the mixture is heated under reflux for 30 hours. After distillation of ethanol, the mixture is treated with atilon. The organic phase is washed with saturated aqueous sodium chloride, and then dried with sodium sulfate and concentrated. The crude product was then purified using chromatography on silica gel (eluent: ethyl acetate/methanol).

Output: 6.12 g = 77%].

1H-NMR (CDCl3, 300 MHz): 1.75-1.85 (m, 2H), 1.95-2.05 (m, 2H), 2,68 (t, 2H, J = 7.51), 3.5 (Shir.S., 2H), 3.92 (t, 2H, J = 7.5 Hz), 5.33 (s, 1H).

b) 2-(2,5-Dimethyl-1-pyrrolyl)-4,5,6,7-tetrahydropyrazolo-[1,5-a] pyridine

To 19.7 g (84 mm) 3(5)-(4-hydroxybutyl)-5(3)-(2,5-dimethyl-1-pyrrolyl)of pyrazole and 22.1 g (84 mm) of triphenylphosphine in 300 ml of tetrahydrofuran (THF) drop by drop and under cooling with ice, add 16 g (92 mm) of diethylazodicarboxylate. The resulting mixture is stirred for 4 hours at room temperature, and then concentrated. The resulting residue is purified by chromatography on silica gel (eluent: hexane/ethyl acetate).

Output: 14.27 g = 97%].

nD20: 1.5630.

c) 3 (5)-(4-Hydroxybutyl)-5(3)-(2,5-dimethyl-1-pyrrolyl)-pyrazole

A mixture of 18 g (116 mm) 3(5)-amino-5(3)-(hydroxybutyl)-pyrazole, 14.6 g (128 mm) 2.5-hexanedione and 3.2 ml of acetic acid in 100 ml of toluene is heated under reflux for 8 hours, thereby removing water. The precipitate podet.sq.: 147-148oC.

(d) 3 (5)- Amino-5(3)-(hydroxybutyl)pyrazole

4.8 ml of hydrazine Monohydrate at room temperature and added to a solution of 12.3 g (0.1 M) tetrahydro-2H-Piran-2-iridencleisis in 100 ml of toluene. The resulting mixture was heated under reflux for five hours. The resulting dark yellow oily substance separated, and then the reaction mixture was concentrated. The residue is purified by chromatography on silica gel (eluent: ethyl acetate/ methanol).

Yield: 11 g = 71%].

The following compounds (see table) are obtained by methods similar to the methods described in the previous Examples.

1. Substituted pyrazole derivatives of General formula I

< / BR>
where R1represents a C1-C4-alkyl;

R2represents a C1-C4-alkylthio, C1-C4-alkoxy, each of which is optionally substituted by one or more halogen atoms;

R1and R2taken together form the group -(CH2)m;

R3represents hydrogen or halogen;

R4represents hydrogen or C1-C4-alkyl;

R5represents hydrogen, nitro, cyano one or more halogen atoms or hydroxy groups, phenyl, optionally substituted with substituents like nitro, pyrrolyl; or

R6represents a C2-C8-alkyl, C3-C8-alkenylphenol, C3-C8-alkylamino or C3-C8-alkoxygroup, each of which is interrupted by one or more oxygen atoms; or-NR11R12or

R6represents a group

< / BR>
R11represents hydrogen, C1-C4-alkyl, C2-C6alkenyl, C3-C6-quinil, or group, R21CO-;

R12represents a C1-C6-alkyl, C2-C6alkenyl, C3-C6-quinil or phenyl, optionally substituted by a halogen atom, a C3-C8-cycloalkyl, cyanomethyl, C1-C4-alkoxy-C1-C6-alkyl, CI-C1-C4-alkylamino-C1-C4-alkyl, benzyl, group-C(= O)R21, -(CH2)a-(O)d-R28, -(CH2)2-O(CH2)b-R28or -(CH2)a-S'-R34,

R11and R12taken together with the nitrogen atom to which they are bound, form pyrrolidinyl, piperidinyl, morpholinyl or aziridinyl group;

R13represents hydrogen;

R14represents a C1-C6-alkyl, C3-C6-quinil, C1-C4-alkoxycarbonyl-C1-C4-alkyl, CI-C1-C4-alkoxy-carbonyl-C1-C4-alkyl, benzyl, or the group -(CH2)a-R33, -(CH2)a-O-R30, -(CH2)a-O-(CH2)b-R30,

R17represents a C1-C4-alkyl, C3-C6-quinil, C1-C4-alkylsulphonyl-C1-C3-alkyl or phenyl;

R18represents a C1-C4-alkyl,

R19and R20may be the same or different and represent hydrogen or C1-C4-alkyl;

R21represents a C1-C4alkyl, optionally substituted by one or more halogen atoms, C1-C4-alkoxy-C1-C4-alkyl, phenyl, optionally substituted with halogen, a nitro-group or a group NR31R32;

R22represents a C1-C4-alkoxycarbonyl or carboxy;

R23represents a C3-C6-cycloalkyl, optionally interrupted by one or more oxygen atoms;

R24represents a hydroxy group or a group of the formula - NR may be the same or different and represent hydrogen or C1-C4-alkyl;

R27represents a C1-C4-alkyl, C1-C4-alkoxycarbonyl-C1-C4-alkyl or carboxy;

R28represents hydroxy, halogen, C1-C4is alkyl, substituted with two C1-C4-alkoxy groups, C3-C6-cycloalkyl, optionally interrupted by one or more oxygen atoms and optionally substituted by 1-2 stands, furyl, thienyl or - C(=O)R29;

R29and R30may be the same or different and represents a C1-C4-alkyl or C1-C4-alkoxy;

R31and R32may be the same or different and represents a C1-C4-alkyl or phenyl;

R33represents a C3-C6-cycloalkyl, interrupted by one or two oxygen atoms and optionally substituted by 1-2 stands, furyl, thienyl or group-C(=O)R29;

R34represents a C1-C4-alkyl;

and, b is 1, 2 or 3;

d is 0 or 1;

m is 3 or 4;

n is 0,1 or 2;

X represents oxygen or sulphur.

2. Replaced personalality or deformedarse, preferably, deformedarse or

R1and R2taken together form the group - (CH2)4;

R3represents a hydrogen, chlorine or bromine;

R4represents hydrogen;

R5represents hydrogen, nitro, cyano.

3. Substituted pyrazolinone derivatives under item 1 or p. 2, in which R6represents hydrogen, halogen, cyano, C1-C4-alkyl, C1-C4-alkylthio or - NR11R12.

4. Substituted pyrazolinone derivatives under item 3, in which R11and R12may be the same or different and represents a C1-C4-alkyl or C1-C4-alkoxycarbonyl.

5. Derivatives of pyrazole of the General formula Ik

< / BR>
in which R1, R2and R6have the meanings defined in General formula I, in paragraph 1, as intermediates for obtaining substituted derivatives of pyrazole on p. 1, where R3means halogen.

6. Derivatives of pyrazole of the General formula Im

< / BR>
in which R1, R2and R3have the meanings defined in General formula I, in paragraph 1, and R6- represents a C1-C4alkyl, optionally substituted by one the volumes of oxygen, as intermediate compounds for obtaining substituted derivatives of pyrazole under item 1, in which R1, R2, R3and R6have videopreteen values, and R5denotes cyan.

7. Herbicide composition comprising the active ingredient and agronomically acceptable carriers and diluents characterized in that as the active ingredient using an effective amount of a compound according to any one of paragraphs.1 to 4.

8. Method of weed control by the weeds or their habitat herbicide, wherein the treatment is carried out effective amount of a compound according to any one of paragraphs.1 to 4.

 

Same patents:

The invention relates to new chemical compounds with valuable properties, in particular to derive hinolan and naphthyridinone acid of General formula

< / BR>
in which

A is CH, CF, CCl, C-OCH3C-CH3N;

X1hydrogen, halogen, NH2CH3;

R1alkyl containing 1 to 3 carbon atoms, FCH2CH2- cyclopropyl, phenyl, which can be from one to three times substituted by halogen, or

A and R1together can mean the bridge structure C-O-CH2-CH(CH)3,

R2hydrogen, not substituted or substituted by a hydroxy-group, halogen or amino alkyl containing 1 to 3 carbon atoms, or 5-methyl-2-oxo-1,3-dioxol-4-yl-methyl;

B balance formulas

< / BR>
where

Y is O or CH2;

R3oxaalkyl containing 2 to 5 carbon atoms, CH2-CO-C6H5CH2CH2CO2R', R O2C-CH=-CO2R', -CH=CH-CO2R' or CH2CH2-CN, where R' denotes hydrogen or alkyl containing 1 to 3 carbon atoms;

R4hydrogen, alkyl containing 1 to 3 carbon atoms, окMG SRC="http://www.fips.ru/fullimg2/rupat3/19981/010.dwl/2105770-6t.gif" ALIGN="ABSMIDDLE">CH=CH-CO2-R' or CH2CH2-CN or 5-methyl-2-oxo-1,3-dioxol-4-yl-methyl, where R' denotes hydrogen or alkyl containing 1 to 3 carbon atom,

in the form of mixtures of isomers or individual isomers, pharmaceutically applicable hydrates and salts, for example acid additive salts and alkaline, alkaline earth, silver and guanidinium salts of the corresponding carboxylic acids

The invention relates to pharmaceutically active bicyclic heterocyclic amines (XXX) and can be used as pharmaceuticals for the treatment of diseases and injuries

The invention relates to compounds which inhibit the protease encoded by human immunodeficiency virus, or their pharmaceutically acceptable salts, and such compounds are used for the prevention of infection by HIV, treating infection by HIV and the treatment of acquired as a result immunodeficiency syndrome (AIDS)

The invention relates to new substituted dihydropyrimidines, methods for their preparation, pharmaceutical compositions containing them and their use as pharmaceuticals, in particular for the prevention or treatment of disorders characterized by excessive expansion of vessels, in particular migraine

The invention relates to tricyclic derivatives of pyrrole General formula (I), where R1-R4denote hydrogen, halogen, lower alkyl, phenyl, cycloalkyl or lower alkoxy, a R2indicates additional lower alkoxycarbonyl, acyloxy or mesilate; R5denotes lower alkyl; R6, R7represent hydrogen or lower alkyl; X represents-CH2CH(C6H5), -CH= C(C6H5)-, -YCH2-, -CH=CH - (CR11R12)n; R11and R12denote hydrogen, phenyl, lower alkyl; h denotes 1-3 and Y denotes O or S, and pharmaceutically acceptable acid additive salts

The invention relates to new nitrogen-containing heterocyclic compounds possessing biological activity, and more particularly to derivatives of 1,2,4-triazolo[1,5-a]pyrimidines, their pharmaceutically acceptable salts and stereoisomers, pharmaceutical compositions containing them, and method of inhibiting seizures
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