Pyrrolopyridine or agricultural-acceptable salt, herbicide composition and method of suppressing unwanted vegetation

 

(57) Abstract:

Pyrrolopyridine General formula 1, where one of Y, Z, and J denotes N or N - O, and the remainder of Y, Z and J denote the C-R; R is hydrogen, halogen, cyano or-OR5, R1- C1-C6alkyl, R2- C1-C6halogenated, R3Is n; X is nitrogen or C - R4, R4Is h or halogen, or agricultural-acceptable salts, are useful as herbicides. 3 s and 5 C.p. f-crystals, 3 tables.

The present invention relates, firstly, to new pyrrolopyridine, which unexpectedly are useful herbicide activity. Secondly, the present invention relates to herbicide compositions containing these pyrrolopyridine and a suitable carrier, and to a method for suppression of unwanted vegetation, which consists in coating the surface which must be controlled, herbicide effective amount of a derivative pyrrolopyridine.

Background of the invention

The need for the development of effective herbicides requires no special explanation. Control of weeds and undesirable vegetation is of great economic importance as a competitive weed growth reduces production the structure of the harvest and its quality. Weeds on UN-cropped crop fields can be sources of fire hazard, can cause unwanted movement of sand or snow and/or to cause annoyance to the people damaged by allergies. Thus, the suppression of unwanted weed growth is very important.

Thus, the aim of the present invention is an effective new herbicide compounds, as well as new herbicide composition and a new method of weed control.

Brief description of the invention

One aspect of the present invention is a compound of formula (1):

< / BR>
in which at least one of Y, Z and I denotes N or N-O, and the remainder of Y, Z or I mean C-R

where

R denotes a hydrogen atom, halogen atom, cyano group; (C1-C6)alkyl; (C1-C6)halogenated; (C1-C6)alkoxy(C1-C6)alkyl; formyl group; (C1-C6)alkylcarboxylic group; (C1-C6)alkylcarboxylic group, carboxyl group and its salts, esters and amides; amino group; a substituted amino group in which a Deputy (deputies) are selected from (C1-C6)alkyl, (C1-C6)alkoxy groups, hydroxyl groups, formyl groups, (C1-C6)alkylcarboxylic group, (C1-C6)alkoxycarbonyl group, (C1-C6)alkoxycarbonyl(C1-Crappy, (C1-C6)halogenated.sulphonated group, aminocarbonyl groups, di-(C1-C6)alkylaminocarbonyl group, amino group and di-(C1-C6)alkylamino group; sulfonamide-group in which the nitrogen atom contains as a substituent a hydrogen atom and/or (C1-C6)alkyl; QR5, where Q denotes-O - or-S(O)m-, and R5 is chosen from a hydrogen atom, (C1-C6)alkyl, (C1-C6)halogenoalkane, cyano(C1-C6)alkyl, (C1-C6)alkoxycarbonyl(C1-C6)alkyl, (C2-C4)alkenyl, (C3-C6)quinil, hydroxycarbonyl(C1-C6)alkyl and aminocarbonyl(C1-C6)alkyl, and the nitrogen atom optionally may contain as substituent (C1-C6)alkyl, (C1-C6)alkoxy group, (C1-C6)alkylsulfonyl group, (C1-C6)halogenoacetyl group, amino group or a di-(C1-C6)alkylamino group.

R1 denotes a hydrogen atom, nitro group, halogen atom, cyano group, a group (C1-C6)alkyl-S(O)mor (C1-C6)alkoxy group;

R2 denotes a halogen atom, (C1-C6)halogenated; cyano group or a group (C1-C6)-S(O)m-;

R3 denotes a hydrogen atom or a halogen atom;

X represents N or C-R4;

where R4 denotes a hydrogen atom, (C1-C6)halogenated, halogen atom, cyano group, nitro group, a group (C1-C6)alkyl-S(O)mor (C1-C6)alkoxy group;

m is 0, 1, 2, and

its salts, applicable for different composition, comprising: (A) the above compound of formula (1); and (B) a carrier for the specified connection.

Another aspect of the present invention is a method of suppressing unwanted vegetation, which consists in applying to controlled surface herbicide effective amount of the compounds of formula (1).

Detailed description of preferred embodiments of the invention

New herbicide compounds of the present invention are the compounds of formula (1):

< / BR>
in which at least one of Y, Z or I denotes N or N-O, and the remainder of Y, Z or I mean C-R, where

R denotes a hydrogen atom; halogen atom; cyano group; (C1-C6)alkyl; (C1-C6)halogenated; (C1-C6)alkoxy(C1-C6)alkyl; formyl group; (C1-C6)alkylcarboxylic group; (C1-C6)alkylcarboxylic; carboxyl group and its salts, esters and amides; amino; substituted an amino group, in which the Deputy (deputies) are selected from (C1-C6)alkyl, (C1-C6)alkoxy group, a hydroxyl group, formyl group, (C1-C6)alkylcarboxylic group, (C1-C6)alkoxycarbonyl group, (C1-C6)alkoxycarbonyl(C1-C6)alkylaminocarbonyl group, hydroxycarbonyl(C1-C6)alkylaminocarbonyl group, (C1-C6) - Rev. decarbonising group, amino group and di-(C1-C6)alkylamino group; sulfamidihappo, in which the nitrogen atom contains as a substituent a hydrogen atom and/or (C1-C6)alkyl; QR5, where Q denotes-O - or-S(O)m-, and R5 is chosen from a hydrogen atom, (C1-C6)alkyl, (C1-C6)halogenoalkane, cyano(C1-C6)alkyl, (C1-C6)alkoxycarbonyl(C1-C6)alkyl, (C2-C4)alkenyl, (C3-C6)quinil, hydroxycarbonyl(C1-C6)alkyl and aminocarbonyl(C1-C6) alkyl, and the nitrogen atom optionally may contain as substituent (C1-C6)alkyl, (C1-C6)alkoxy group, (C1-C6)alkylsulfonyl group, (C1-C6)halogenated.sulphonated group, amino group and di-(C1-C6)alkylamino-group;

R1 denotes a hydrogen atom, a nitro-group, halogen atom, cyano group, a group (C1-C6)alkyl-S(O)mor (C1-C6)alkoxy group;

R2 denotes a halogen atom, (C1-C6)halogenated, cyano group, or a group (C1-C6)-S(O)m-

R3 denotes a hydrogen atom or halogen atom,

X represents N or C-R4;

where R4 denotes a hydrogen atom, (C1-C6)halogenated, halogen atom, cyano group, nitro group, a group (C1-C6)alkyl-S(O)mor (C1-C6)alkoxy group;

m is 0, 1, 2; and

its salts, suitable for use in agriculture.

Preferred:

R denotes a halogen atom, cyano group; (SPU, in which Deputy (deputies) are selected from (C1-C6)alkyl, (C1-C6)alkoxy groups, hydroxyl groups, formyl groups, (C1-C6)alkylcarboxylic group, (C1-C6)alkoxycarbonyl group, (C1-C6)alkoxycarbonyl(C1-C6)alkylaminocarbonyl group, hydroxycarbonyl(C1-C6)alkylaminocarbonyl group, (C1-C6)alkylsulfonyl group, (C1-C6)halogenated.sulphonated group, aminocarbonyl groups, amino groups, di-(C1-C6)alkylamino group; sulfonamide-group in which the nitrogen atom contains as a substituent a hydrogen atom and/or (C1-C6)alkyl; QR5, where Q denotes-O - or-S(O)m-, and R5 are selected from (C1-C6)alkyl, (C1-C6)halogenoalkane, cyano(C1-C6)alkyl, (C1-C6)alkoxycarbonyl(C1-C6)alkyl, (C2-C4)alkenyl, (C3-C6)quinil, hydroxycarbonyl(C1-C6)Aquila and aminocarbonyl(C1-C6)alkyl, and the nitrogen atom optionally may contain as substituent (C1-C6)alkyl, (C1-C6)alkoxy group, (C1-C6)alkylsulfonyl group, (C1-C6)halogenated.sulphonated group, amino group or a di-(C1-C6)alkylamino-group;

R1 denotes a halogen atom, a hydrogen atom, a nitro-group, (C1-C6)halogenated or a group (C1-C6)alkyl-S(O)m- where n is 1 or 2;

R2 denotes a hydrogen atom, halogen atom, (C1-C6)halogenated or a group (C1-C6)-S(O)m- where n is 1 ilicis.

Even more preferably;

R denotes a halogen atom; cyano group, substituted amino group in which a Deputy (deputies) are selected from (C1-C6)alkyl, (C1-C6)alkoxy groups, hydroxyl groups, formyl groups, (C1-C6)alkylcarboxylic group, (C1-C6)alkoxycarbonyl group, (C1-C6)alkoxycarbonyl(C1-C6)alkylaminocarbonyl group, hydroxycarbonyl(C1-C6)alkylaminocarbonyl group, (C1-C6)alkylsulfonyl group, (C1-C6)halogenated.sulphonated group, aminocarbonyl groups, di-(C1-C6)alkylaminocarbonyl group, amino group and di-(C1-C6)alkylamino group; QR5, where Q denotes-O - or-S-, and R5 are selected from (C1-C6)alkyl, cyano(C1-C6)alkyl, (C1-C6)alkoxycarbonyl(C1-C6)alkyl, (C3-C6)quinil, hydroxycarbonyl(C1-C6)alkyl and aminocarbonyl(C1-C6)alkyl, when the nitrogen atom optionally may contain as substituent (C1-C6)alkyl, (C1-C6)alkoxy group, (C1-C6)alkylsulfonyl group, (C1-C6)halogenated.sulphonated group, amino group and di-(C1-C6)alkylamino-group;

R1 denotes a chlorine atom or a fluorine atom;

R2 represents trifluoromethyl;

R3 denotes a hydrogen atom; and

X represents N or C-H, C-Cl or C-F.

The most preferred compounds are:

4-chloro-1-(2-chloro-4-tripto the chloro-4-triptoreline)-4-methoxyphenol[3,2-c]pyridine;

4-chloro-1-(3'-chloro-5'-triptorelin-2'-yl)-pyrrolo[3,2-c] pyridine;

4-chloro-1-(3'-chloro-5-triptorelin-2'-yl)-pyrrolo[3,2-c] pyridine 5-oxide;

4-chloro-1-(2',6'-dichloro-4'-triptoreline)-pyrrolo[3,2-c]pyridine;

4-methoxy-1-(2',6'-dichloro-4'-triptoreline)-pyrrolo[3,2-c] pyridine;

1-(2'-chloro-4'-triptoreline)-4-cyanoprop[3,2-c]pyridine; and

1-(2',6'-dichloro-4'-triptoreline)-4-cyanoprop[3,2-c] pyridine.

It should be understood that the above formula include the tautomeric formula of the above structures, as well as physically separable modification of connections that can occur, e.g. due to different arrangement of molecules in the crystal lattice or because of the inability of the molecule to rotate freely relative to another part of the molecule, or due to geometrical isomerism, or due to the formation of intramolecular or intermolecular hydrogen bonds, etc.

Compounds having the above formulas, it can exist in enantiomeric formulas. The invention encompasses both individual enantiomers and their mixtures in any ratio.

The expression "its salts, amides and esters", as used above in connection with kaleem or lithium), alkaline earth metals (in particular, calcium and magnesium), ammonium ion or substituted ammonium ions, in which one, two, three or four hydrogen atoms replaced by not necessarily containing substituents (C1-C6)hydrocarbon fragments. These terms primarily include substituted carboxamido-group in which the substituents are selected from (C1-C6)alkyl, (C1-C6)alkylsulfonyl group and (C1 - C6)halogenated.sulphonated group.

In the present description assumes that the term "alkyl" and all groups containing alkyl fragments, include groups with straight and branched chain and cyclic groups.

Examples are methyl, ethyl, n-propyl, ISO-propyl, cyclo-propyl, n-butyl and tert-butyl.

Further, in the above definitions, the term "halogen" includes fluorine atoms, chlorine, bromine and iodine. In POLYHALOGENATED groups, halogen atoms may be identical or different. The term "halogenated", etc. refers to substituents containing one or more halogen atoms.

It has been found that compounds of the present invention are active ingredients with herbicide actions when using as before the advent of rasteniy and herbs.

Therefore, the present invention relates to a method of controlling undesirable vegetation, which consists in applying to the surface, where said control both before and after occurrence of the specified vegetation, herbicide-effective amount of the compounds described in the present description, together with an inert diluent or carrier suitable for use with herbicides.

The terms "herbicide" and "herbicide" is used in this description to refer to inhibitory control or modify the growth of unwanted vegetation. Inhibitory control or modification of growth include all deviations from natural development, such as, for example, total annihilation, stunted growth, leaf removal, dehydration, regulation, cultivation, stimulation, burning leaves and stop development. The term "herbicide-effective amount" is used to denote any quantity that reaches the specified control or modification when applied as undesirable plants, and on the surface of the soil where these plants grow. The term "plant" includes sprouted seeds, plantlets and is for use in agriculture", it is quite obvious to a person skilled in the art and include inorganic and organic salts halogenation acid, acetic acid, sulfonic acids, phosphonic acid, acidic, inorganic and organic salts.

In General, compounds of the present invention can be obtained by the interaction of pyrrolopyridine formula:

< / BR>
where I, Y, and Z described above, with a substituted derivatives of pyridine or benzene of the formula:

< / BR>
where Hal denotes a halogen atom; and X, R1, R2 and R3 above; in the presence of a suitable base (such as a hydride or hydroxide of the metal, etc) in a suitable solvent (such as dimethylsulfoxide, N, N-dimethylformamide, etc.,).

Source pyrrolopyridine can be obtained by the techniques given in the literature, for example, in R. E. Willete, Advances in Heterocyclic Chmistry, Vol. 9, 27 (1968) or I. Mahadevan and M. Rasmussen, J. Heterocyclic. Chem., Vol. 29, 359 (1992).

The original halogen-containing pyridine or benzenes or issued by the industry, or can be obtained by well-known specialists of ways.

Otherwise, the derivatives of pyrrolopyridine of the present invention can be obtained by cyclization of the preferred 1-acylpyrrole according to the method, an the Tetrahedron, Vol. 32, 773 (1976).

The compositions of the present invention include the above-mentioned compound of formula (1) and a suitable carrier; these carriers are well known to specialists in this field of technology.

Compounds of the present invention are useful as Gabrielov and can be applied using various methods known to experts in the field of technology, and with different concentrations. The compounds are useful for controlling the growth of unwanted plants by making connections in the place of growing plants where it is necessary to control both before and after germination. In practice the connection is applied in the form of compositions containing various excipients and carriers that are known or used in industry to facilitate dispersion. The choice of the composition and method of application for each connection can have an impact on its activity, so you need to make the right choice. Thus, the compounds of the present invention in compositions can be prepared in the form of granules, wettable powders, emulsifiable concentrates, powders or Farrukh Dustov, solids, solutions, suspensions or Amul is to contain at least about 0.5 to about 95% or more of the active ingredient. The optimal number for each connection depends on the nature of the seeds or plants that you want to monitor. Consumption rates usually vary approximately from 0.01 (11.2 g/ha) to about 10 (11.2 kg/ha) pounds per acre, primarily approximately from 0.02 (22,5 g/ha) to about 4 (4,49 kg/ha) pounds per acre.

Can wetted powders formed of finely ground particles, which are easily dispersed in water and other liquid media. The particles contain an active ingredient that is enclosed in a solid matrix. As a typical solid matrices using fallerovo earth, kaolin clay, silicates, and other easily wettable organic and inorganic solids. Can wetted powders usually contain from about 5% to about 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.

Capable of forming the emulsion concentrates are homogeneous liquid compositions which can dispergirujutsja in water and other liquids and can be entirely of the active compound with a liquid or solid emulsifying agent, or may also contain the definition solvents. When using these concentrates are dispersed in water or other liquid and is usually applied on the treated surface by spraying. The concentration of active ingredient in the concentrate may range from approximately 0.5% to approximately 95%.

Granular formulations receive products grinding, and in the form of relatively large particles, and is usually applied without dilution on the surface, where it is necessary to suppress the growth of plants. Typical carriers for granular compositions are sand, mullerova earth, attapulgite clay, bentonite clay, montmorillonite clay, vermiculite, perlite and other organic or inorganic substances that can absorb the active compounds or which can be applied active compounds. Granular compositions usually contain from about 5% to 25% of the active ingredient, and may include surface-active substances, such as heavy aromatic fraction of crude oil, kerosene and other oils or vegetable oils, and / or binders, such as dextrins, animal glue or synthetic resins.

Dusty are movable mixture of the active ingredient with finely Ismail substances, which act as dispersants and carriers.

Microcapsules are usually droplets or granules of active substance enclosed in an inert porous membrane that allows the prisoner to the substance to stand out with a controlled speed. Encased in capsules liquid is usually from 50 to 95% by weight of the capsule and may include in addition to the active compounds and even solvent. Enclosed in capsules, pellets are usually porous granules having a porous membrane covering the openings of the pores and preserving liquid active substance within the pores of the granules. The diameter of the granules is usually from 1 millimeter to 1 centimeter, mostly from 1 to 2 millimeters. Pellets produced by extrusion, aglomeracji or curing, spray or use natural products. Examples of such compounds are vermiculite, calcined clay, kaolin, attapulgite clay, sawdust and granular carbon black. Materials shell or membrane include natural and synthetic resins, cellulose derivatives, styrene-butadiene copolymers, polyacrylonitrile, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and xanthate starch.

The other is storytale, in which he is completely dissolved to the desired concentration, such as acetone, alkilirovanie naphthalenes, xylene and other organic solvents. You can also use sprays containing composition under pressure, with which the active ingredients are finely dispersed in the evaporation of the low boiling solvent carrier, such as freon.

Many of these compounds include wetting, dispersing or emulsifying agents. Examples are alkyl - and arylsulfonate and sulfates and their salts; polyhydric alcohols; polyethoxysiloxane alcohols, esters and fatty amines. The contents of these agents, when used, is usually from 0.1% to 15% by weight of the composition.

Each of the above compositions can be obtained in the form of packages containing the herbicide together with other ingredients included in the composition (diluents, emulsifiers, surfactants, etc.,). The composition can also be prepared according to the method of mixing and the capacity in which the ingredients are obtained separately and then mixed on site vegetation growth.

Compounds of the present invention are also useful in combination sleuth approximately 5% to approximately 95% of the amount of the active ingredient in the composition. These combinations are often more effective for controlling weeds and often allow you to achieve results unattainable with separate compositions of the individual Gabrielov.

Examples of other Gabrielov, defoliants, moist collectors and inhibitors of plant growth, which can be mixed compounds of the present invention, are:

A. benzo-2,1,3-thiadiazin-4-one-2,2-dioxides such as bentazon;

B. Germanova herbicides, in particular, phenoxyalkanoic acid, as MSRA, MSRA-thioethyl, dichlorprop, 2,4,5-t, MSRV, 2,4-D, 2,4-DB, mecoprop, triclopyr, peroxides, clopyralid and their derivatives (in particular, salts, esters and amides);

C. derivatives of 1,3-dimethylpyrazole, such as paradoxien, pyrazolate, benzefoam;

D. dinitrophenol and their derivatives (in particular, acetates, such as DNOC, dinoterb, dinoseb and its ester, acetate of dinoseb;

E. dinitroaniline herbicides, such as dinitramine, trifluralin, ethalfluralin, pendimethalin; and oryzalin;

P. herbicides based arelatively, such as Diuron, fluometuron, metoxuron, neburon, Isoproturon, chlorotoluron, chloroxuron, linuron, monolinuron, chlorbromuron, demuren and methabenzthiazuron;

I. herbicides on the basis of uracil, such as lenacil, bromacil and terbacil;

J. herbicides based on triazine, such as atrazine, Simazine, isoprotein, cyanazine, prometryn, deltamethrin, simetryn and terbutryn;

K. herbicides on the basis of phosphorothioate, such as piperophos, bensulide and butamifos;

L. herbicides based thiolcarbamate, such as cycloate, vernolate, molinet, thiobencarb, butyl (*), ARTS (*), triallate, diallate, tilespace, thiocarbonyl, peridot and timepart;

M. herbicides based on 1,2,4-triazine-5-it, such as metamitron, metribuzin;

N. herbicides on the basis of benzoic acid, such as 2,3,6-TBA, dicamba and chloramben;

O. anilide herbicides, such as pretilachlor, butachlor corresponding alachlor, corresponding derived propachlor, propanil, metazachlor, metolachlor, acetochlor and dimethachlor;

P. herbicides based developementally, such as dichlobenil, bromoxynil and ioxynil;

Q. herbicides based halogenoalkanes acids, such as dalapon, TCA and its salts;

R. herbicides based on diphenyl ether, such as lactofen, fluoroglycofen or its salts or esters, nitrogen, bifenox, acifluorfen or its salts or esters, oxyfluorfen and fomesafen; x is an ester, such as methyl ether, fluazifop and its esters, haloxyfop and its esters, hisamoto and its esters and fenoxaprop and its esters, such as ethyl ether;

T. herbicides based cyclohexandione, such as aloxide and its salts, sethoxydim, cycloxydim, tralkoxydim, clethodim;

U. herbicides on the basis of sulfonylureas, such as chlorsulfuron, sulfometuron, metsulfuron and its esters; beskulture and its esters, such as methyl ether, DPX-M6313, chlorimuron and its esters, such as ethyl ether, primisulfuron and its esters, such as methyl ether, DPX-LS300 and pyrazosulfuron;

V. imidazolinone herbicides, such as imazighen, imazamethabenz, imazapyr and his isopropylammonium salt, imazethapyr;

W. herbicides based aryanised, such as femprep and its esters, bandolero-ethyl, diflufenican;

X. herbicides based on amino acids, such as glyphosate and glufosinate and their salts and esters, sulfosate and milanapos;

Y. herbicides on the basis of organic arsenic compounds, such as MSMA;

Z. herbicide proprovide amides, such as napropamide, propyzamide, carbetamide, tabulam, bromobutyl, isoxaben, nitroanilide, diphenamid and naptalam;

AA. various herbicides, including ethofumesate, qi is the ratio 3:1) flurochloridone, jinjarak and mefenacet;

BB. an example of a useful contact herbicides can serve BIPYRIDILIUM herbicides, in which the active principle is paraquat and in which the active principle is an Diquat.

(*) These connections are mainly used in combination with such a connection, increasing the safety of the use of herbicide as 2,2-dichloro-N,N-di-2-propenyl-ndimethylacetamide (dichlormid).

These compositions can be applied to the testing surface by conventional means. Dusty and liquid compositions, for example, can be applied using boom sprayers with nozzles and using hand sprayers and sprayer Farrukh Dustov. The composition can also be applied from airplanes as Farrukh Dustov or aerosols. The purpose of the modification of growth or for control of germinating seeds or emerging seedlings, dusty and liquid compositions can be incorporated into the soil to a depth of at least one-half inch (12.7 mm) from the soil surface or only be applied to the soil surface by spraying or sprinkling. The composition can also contribute by adding them to the water used for irrigation. It promotes the penetration of the compositions into the soil with the irrigation is s, you can make under the soil using conventional methods such as treatment of disc blades, harrowing or mixing.

Below are examples of typical compositions.

5% dust:

5 parts of active compound, 95 parts of talcum;

2% dust:

2 parts of active compound, 1 part of finely powdered silicic acid, 97 parts of talcum.

These dusty is produced by mixing the components and then crushed to the desired particle size.

the 5% granules:

5 parts of active compound, 0.25 parts of epichlorohydrin, 0.25 parts of cetyl-polyglycolic ether, 3.5 parts of polyethylene glycol, 91 part of kaolin (particle size 0.3 to 0.8 mm).

The granules are obtained by mixing the active compounds with epichlorohydrin and dissolving the mixture in 6 parts of acetone. Then add the polyethylene glycol and cetyl ether polyglycol.

The resulting solution is sprayed on kaolin, and the acetone evaporated in vacuo.

Wettable powders

70%:

70 parts of active compound, 5 parts dibutylphthalate sodium; 3 parts of the condensation naphtalenesulfonic acid/phenolsulfonic acid/formaldehyde (3:2:1) 10 parts of kaolin; 12 parts of champagne m is fonate sodium, 54 parts of silicic acid;

25%:

25 parts of active compound, 4.5 parts ligninsulfonate calcium, 1.9 parts of champagne chalk/hydroxyethyl cellulose (1:1); 1.5 parts dibutyldithiocarbamate sodium; 19.5 parts of silicic acid, 19.5 parts of champagne chalk, 28.1 parts of kaolin;

25%:

25 parts of active compound, 2.5 parts of isooctylphenol-polyethylene-ethanol, 1.7 parts of champagne chalk/hydroxyethyl cellulose (1:1), and 8.3 parts of sodium aluminosilicate, 16.5 parts of kieselguhr, 46 parts of kaolin;

10%:

10 parts of active compound, 3 parts of a mixture of sodium salts of sulfates of saturated fatty alcohols, 5 parts of the condensation products naphtalenesulfonic acid formaldehyde, 82 parts of kaolin.

These can wetted powders receive thorough mixing the active compounds with additives in suitable mixers and grinding the mixture in a mill or on rolls.

Can emulgirovanija concentrates:

25%:

25 parts of active compound, 2.5 parts epoxidizing vegetable oil, 10 parts of a mixture of ether alkylarylsulfonate and fatty alcohol with polyglycols, 5 parts of dimethylformamide, 57.5 parts of xylene.

The number of tracks on this is Jan or plants. The rate of application of active ingredients varies from about 0.01 to (11.2 g/ha) to about 25 (28,1 kg/ha) pounds per acre, mainly about from 0.10 (112 g/ha) to about 10 (11.2 kg/ha) pounds per acre, while the actual number depends on the total cost and the desired results. For professionals it should be apparent that compositions exhibiting less herbicide activity, are required to exercise the same degree of control of large dosages, the more active compounds.

The following examples are provided to further illustrate the present invention and in no way limit the scope of the claims of the present invention.

Example 1.

Obtain 1-(3'-chloro-5'-triptorelin-2-yl) pyrrolo [2,3-C] pyridine (Compound No. 1).

Stage 1.

Dimethylacetal N, N-dimethylformamide (10 ml) and pyrrolidine (3 ml) are added to a solution of 3-nitro-4-methylpyridine (0.5 g, 36 mmol) in N, N-dimethylformamide (50 ml) and the resulting mixture is heated to a temperature of 120oC for 2 hours. Cooled to room temperature, and poured into a mixture of diethyl ether and water. The ether layer is separated, dried over magnesium sulfate, filtered and the filtrate parivuode.

Stage 2.

A mixture of nitroenamine obtained in stage 1 (3.8 g), hydronaut under pressure 40 psi (275,8 kPa), using as catalyst palladium on coal (0.4 g) in ethanol (125 ml) for 1.5 hour. The catalyst was removed by filtration, the filtrate evaporated, and the residue is purified column chromatography on silica gel (20% methanol in ethyl acetate) to give 1H-pyrrolo [2,3-C] pyridine (6-azaindole) in the form of a solid pale yellow color.

Stage 3.

1H-Pyrrolo [2,3-C] pyridine (1.0 g, 8 mmol) are added to a suspension of sodium hydride (80% dispersion in oil, 0.5 g, 17 mmol) and the mixture is left to mix overnight at room temperature. Added 2,3-dichloro-5-trifluoromethyl-pyridine (1.7 g, 8 mmol) and the mixture is left overnight to mix at room temperature. The mixture is separated in a mixture of diethyl ether and water. The ether layer is separated, dried over magnesium sulfate, filtered and the filtrate is evaporated, obtaining 1-(3-chloro-5-triptorelin-2-yl) pyrrolo [2,3-C] pyridine (1.4 g) as a solid yellow color with so pl. 88 - 90oC.

Example 2.

Getting 4-chloro-1-(2'-chloro-4'-triptoreline) pyrrolo [2,3-C] pyridine (Compound No. 3).

Stage 1.

The solution p is rija (80% dispersion in oil, 6.3 g, of 0.21 mol) in N, N-dimethylformamide (100 ml), maintaining the reaction temperature at 5 - 10oC using baths with ice. At the end of the addition stirring is continued for 30 minutes, and then add 3-chloro-4-fermentatively (and 39.7 g of 0.20 mol). The mixture is stirred for 3 hours, and then heated for 18 hours to a temperature of 50oC. Cool to room temperature and separated in a mixture of diethyl ether and water, the ether layer was separated and sequentially washed with water and saturated salt solution, dried over magnesium sulfate, filtered and the filtrate evaporated. Triturated with hexane and get 1-(2'-chloro-4'-triptoreline) pyrrol-2-carboxaldehyde in the form of a solid pale yellow color (30,6 g) so pl. 119 - 120oC.

Stage 2.

A mixture of aldehyde obtained previously in stage 1 (of 29.5 g of 0.11 mol), and karboksimetilirovannogo (45,0 g of 0.13 mol) is boiled in toluene under reflux for 15 hours. Cool the mixture to room temperature, and most of the solvent is distilled off in vacuum. Add hexane (400 ml), and precipitated precipitate was separated by filtration. The filtrate is evaporated, and get the oil red-brown color, which without further purification in the use of slack to a solution of ester, obtained above in stage 2, ISO-propyl alcohol (300 ml) and refluxed for 3 hours. A large part of the solvent is distilled off in vacuo and added to the water. Washed with diethyl ether, the aqueous phase is acidified to pH = 1. The precipitate is isolated and dried, obtaining 3-(1-[2'-chloro-4'-triptoreline] pyrrol-2-yl) acrylic acid (27.4 g) as a colourless solid substances, etc., 209 - 211oC.

Stage 4.

Ethylchloride (7,16 g, 5.3 ml, 66 mol) is added dropwise to a mixture of triethylamine (of 6.68 g of 9.2 ml, 66 mmol) and the acid obtained previously (19,0 g, 60 mmol), in acetone, maintaining the temperature of the mixture below 10oC using baths with ice, and then the mixture is stirred for 1 hour. To the cooled mixture is added dropwise a solution of sodium azide (4,29 g, 66 mmol) in water (40 ml) and stirred for 1 hour. Poured into water and extracted with dichloromethane. The organic extract is dried over magnesium sulfate, filtered, and the filtrate is used in the next stage.

Stage 5.

The solution utilised obtained above in Stage 4, in dichloromethane is added dropwise to a mixture of tributylamine (11.1 g, and 14.3 ml, 60 mmol) and diphenyl ether (190 ml) at a temperature of 195 - 205oC; speed select add to dir>oC. Upon completion of addition the mixture is cooled to room temperature, add hexane (800 ml), and leave the mixture was mixed overnight. The precipitate was separated, washed with hexane and get 1-(2'-chloro-4'-triptoreline)-4,5-dihydro-4-oxopyrrolo [2,3-C] pyridine (10,9 g). A small part then purified by dissolving in chloroform, followed by precipitation with toluene, and get oxopyrrolo [2,3-C] pyridine as a colourless solid with so pl. 233 - 235oC.

Stage 6.

Oxopyrrolo [2,3-C] pyridine (8.0 g, 26 mmol) obtained previously, and phosphorus oxychloride (80 ml) is refluxed for 3 h and then cooled to room temperature. A large part of the solvent is distilled off in vacuum and the residue is poured into ice water. Add solid sodium carbonate until then, until the pH of the mixture reaches 7, and extracted with diethyl ether. The organic extract is dried over magnesium sulfate, filtered, and the filtrate evaporated. The residue is dissolved in boiling hexane, again filtered and evaporated, receiving 4-chloro-1-(2'-chloro-4'-triptoreline) pyrrolo [2,3-C] pyridine (5.5 g) as a solid pale yellow color with so pl. 133 - 135oC.

Example 3.

Getting 4-chloro-1-(2'-chloro-4'-trifluoromethyl what C] pyridine (1.10 g, 33 mmol) and meta-chlormadinone acid (approximately 80 - 85% and 1.15 g) leave at night mixed in chloroform (20 ml) at room temperature. Adds extra meta-chlormadinone acid (1,15 g) and stirred for 2 hours. The mixture is diluted with dichloromethane and washed with saturated aqueous sodium carbonate. The organic solution is dried over magnesium sulfate, filtered, and the filtrate evaporated in vacuum. The residue is triturated with hexane and receive 4-chloro-1-(2'-chloro-4'-triptoreline) pyrrolo [2,3-C] pyridine 5-oxide (0,69 g) as a solid brown color with so pl. 119 - 123oC (decomposition).

Example 4.

Obtain 1-(2'-chloro-4'-triptoreline)-4-methoxy-pyrrolo [2,3-C] pyridine (Compound No. 7).

Potassium hydroxide (0.7 g, 12 mmol) and methanol (2 ml) is stirred in dimethyl sulfoxide (20 ml) at room temperature for 30 minutes. Add 4-chloro-1-(2-chloro-4-triptoreline) pyrrolo [2,3-C] pyridine (2.0 g, 6 mmol) and stirred for 18 hours. The mixture was poured into water and the precipitate are filtered. Further cleaning is performed column chromatography on silica gel and get 1-(2'-chloro-4'-triptoreline)-4-methoxyphenol [2,3-C] pyridine (0.35 in the s 1-(2-chloro-4-triptoreline)-4-cyanoprop [2,3-C] pyridine (Compound No. 13).

A solution of 1-(2-chloro-4-triptoreline) pyrrolo [2,3-c] pyridine 5-oxide (3.5 g, 12 mmol) in triethylamine (50 ml) is cooled in a bath with ice and added dropwise to trimethylsilylacetamide (10,7 ml, 80 mmol). Bath ice is removed, and the mixture is stirred for another 5 hours. The precipitate was separated and dried, obtaining 1-(2-chloro-4-triptoreline)-4-cyanoprop [2,3-C] pyridine (1.8 g) as colorless solids with so pl. 160 - 161oC.

Example 6.

Obtain 1-(3-chloro-5-triptorelin-2-yl)-4,6-dichlorprop [2,3-C] pyridine (compound No. 16).

N-Oxide of 4-chloro-1-(3-chloro-5-triptorelin-2-yl) pyrrolo [2,3-C] pyridine (compound 4, 1.2 g, 3.5 mmol) is boiled with phosphorus oxychloride (280 ml) under reflux for 18 hours. The mixture is cooled to room temperature and poured into ice water. Neutralized by adding solid sodium carbonate, and the resulting mixture extracted with dichloromethane. The organic extracts are combined, dried over magnesium sulfate, filtered, and the filtrate evaporated in vacuum. The residue is purified column chromatography on silica gel and get 1-(3-chloro-5-triptorelin-2-yl)-4,6-dichlorprop [2,3-C] pyridine (0.24 g) as a colourless oil.

Example 7.

Methodologies analogichnaya upon detection of herbicide activity.

The compounds presented in the table above, is subjected to different tests on herbicide activity with different consumption rates. The results of some of these tests are presented below. The results obtained were screened for herbicide activity depend on several factors, which include: the amount of sunlight, soil type, soil pH, temperature, and humidity, depth of planting, the stage of plant development, application rates of the herbicide, as well as many other factors. All tests are conducted so that the amount of change was minimal. To the conditions of screening remained constant, and the test results are reliable, apply known from the field of machinery and equipment known methods.

Gabrichidze tests before emergence.

The day before the test in sandy loam soil containing only trace amounts of organic substances, sow seeds of several different weeds. Sprouts are planted in separate rows, one species in the garden, across the width of the block is made of aluminum (19,5 x 9,5 x 6 cm). Of herbaceous plants planted spickle green (Setaria viridis) ("SETVI), wild oat ("Avena fatua") ("AVEFA"), postnow also, as (Sinatis arvensis) ("SINAR"), cord Theophrastus (Abutilon theophrasti) ("ABUTH) and plants of the family Vukovich (Ipomoea spp. ) ("IPOSS"). Additionally sown syt yellow (Cyperus esculentus) ("CYPES"). Planting depth ranges from 1.0 to 1.5 cm, and the density of planting, depending on species ranges from 3 to 25, on the bed.

The solutions of the tested compounds get when 74,7 mg of the test compounds in a wide-mouthed flask with a capacity of 60 ml and dissolving it in 7.0 ml of acetone containing 1% vol/about Twen 20 (emulsifier based polyethoxyethanol of monolaurate sorbitol), and then add 7 ml of deionized water so that the final volume was 14 ml Contents Twen 20 in the final volume of the composition for spraying of 0.5% vol/vol. If you want to dissolve the compounds, the use of additional solvents in an amount of not more than 2 ml (15% of the spray volume).

The soil layer is subjected to moistening with linear sprinklers, nozzles which are located at a distance of 30.5 cm (12 inches) above the soil level. Sprinkler calibrated so that the volume of liquid was 748 l/ha (80 Gal/acre) with a consumption rate of 4.0 kg/ha 1.0 kg/ha (as shown in Table II at the end of the description). After processing de the regulation inside the greenhouse provides the supply to the plants natural and artificial (using a metal halogen lamps) lighting, to the light period was 14 hours a day. Day and night temperature is maintained at 29 and 21oC, respectively.

The degree of weekly control weeds assessed visually and recorded after 17 to 21 days after treatment, expressed as a percentage in comparison with the growth of the same samples of the same age in untreated control plot. Expressed as a percentage degree of suppression corresponds to the General damage to plants as a result of the impact of all factors, including inhibition of germination, stunted growth, abnormal development, chlorosis, and other types of lesions. The degree of control varies from 0 to 100 percent, where 0% means no effect on growth in comparison with the control samples, and 100% means complete plant death. The dash means that testing for this consumption rate was not conducted.

Herbicide trials after germination.

Prepare the soil and sow her the same species, using methods described previously for testing hebicides to germination. Plots are placed in the greenhouse in the same conditions as previously described for plots that were used for testing asualt for 10 12 days (or until it reaches an appropriate stage of development). Herbaceous plants are treated by spraying on stage appearance 3 - 4 leaves, and broad-leaved plants at the stage of appearance of 1 - 2 leaves. Syt yellow handle, when it will grow in length by 5 to 7, see

Plants watered by sprinkling from a distance of 30.5 cm (12 inches) from the leaves, using the same solution as obtained earlier for testing of herbicides prior to germination. The usage rate is 4.0 kg/ha 1.0 kg/ha (as shown in table III at the end of the description). After processing plants again returned to the greenhouse and watered daily so that water falling on leaves. The degree of control over weeds assessed visually and recorded after 17 to 21 days after treatment, expressed as a percentage in comparison with the growth of the same samples of the same age in untreated control plot. To evaluate the test results after germination, use the same scale degree of control (0 - 100%) when the qualification test prior to emergence.

The results show that the compounds are effective against grassy or broadleaf plants as to the emergence and achut N or N --> O, and the remainder of Y, Z and I mean C - R, where R denotes a hydrogen atom, halogen, cyano or the group-OR5where R5represents C1- C6-alkyl;

R1denotes halogen;

R2represents C1- C6-halogenated;

R3denotes a hydrogen atom;

X represents N or C - R4where R4denotes a hydrogen atom or halogen,

or agricultural-acceptable salt.

2. Connection on p. 1, where R1denotes chlorine or fluorine, R2represents trifluoromethyl, R3denotes hydrogen, X is N, C - H, C - Cl or C - F.

3. Connection on p. 1, where R denotes halogen, cyano or the group-OR5where R5represents C1- C6-alkyl, R1denotes halogen, R2represents C1- C6-halogenated, R3denotes hydrogen, R4denotes a hydrogen or halogen.

4. Connection on p. 1, representing

4-chloro-1-(2-chloro-4-triptoreline)-pyrrolo[3,2-C]pyridine,

4-chloro-1-(2-chloro-4-triptoreline)-pyrrolo[3,2-C]pyridine-5-oxide,

1-(2-chloro-4-triptoreline)4-methoxyphenol[3,2-C]pyridine,

4-chloro-1-(3'-chloro-5'-triptorelin-2'-yl)-pyrrolo[3,2-C]pyridine,

5. Herbicide composition comprising the active ingredient is derived pyrrolopyridine and a suitable carrier, characterized in that the quality of the derived pyrrolopyridine it contains a compound according to any one of paragraphs.1 - 4 or its salt, acceptable for use in agriculture, in the amount of 0.5 - 95%.

6. The method of suppressing undesired vegetation by applying to the surface on which you want the specified suppression, active ingredient, wherein the active ingredient is used as a compound according to any one of paragraphs.1 - 4 or its salt, acceptable for use in agriculture in herbicide effective amount.

7. The method according to p. 6, characterized in that the said compound is applied prior to emergence.

8. The method according to p. 6, characterized in that the said compound is applied after germination.

 

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