Carboxanilide, atropatena composition and method of dealing with arthropode

 

(57) Abstract:

The invention relates to androidiani carboxanilides, compositions based on them and the way to deal with arteriotomy and can be used in agriculture. The inventive carboxanilide f-ly I listed in the description, where Q is the connection f-crystals, Q-1, X Is O, Y is selected from the group consisting of H, C1-C6-alkyl, C2-C6alkenyl, C2-C6-quinil, C2- C6-alkylsulphonyl,

C2-C6-alkoxycarbonyl, or C1-C3-alkyl, substituted Deputy, selected from the group consisting of SR32C1-C3-alkoxy, CO2R32and phenyl; G is phenyl, substituted by one or two substituents R1chosen from the group consisting of H, halogen, C1-C6-alkyl, C1-C6-haloalkyl, NO2CN, OR17, SR17. 3 C. and 10 C.p. f-crystals, 12 tab.

The invention relates to new carboxanilides with anthropocene action songs based on them and the way to deal with Arthropoda (arthropods).

The literature describes various compounds exhibiting insecticidal activity.

In particular, in WO 88/07994 and EP 33678 described insecticides on osmoglasnik the present invention provides carboxanilide General formula I

< / BR>
where

Q -

< / BR>
where A and E is a hydrogen atom,

or A and E together represent a group-CH2-, -CH2CH2- or-N(R7)CH2-,

Z' is chosen from the group O, or NR31,

Z is a carbon atom,

G -

< / BR>
where A' is a hydrogen atom, X is an oxygen atom, Y is chosen from the group comprising a hydrogen atom, a C1-C6alkyl, C2-C6alkenyl, C2-C6quinil, C2-C6alkylsulphonyl, C2-C6alkoxycarbonyl, or Y C1-C3alkyl, substituted Deputy chosen from the group comprising SR32C1-C3alkoxy, CO2R32or phenyl,

R1and R2independently from each other selected from the groups that include hydrogen atom, a C1-C6alkyl, a halogen atom, a C1-C6haloalkyl, NO2CN, OR17and SR17group

R3choose from the groups that include hydrogen atom, a C1-C6alkyl, CO2R17and unsubstituted phenyl, or phenyl substituted (R16)p,

R4and R5independently from each other selected from the groups that include hydrogen atom and C1-C4alkyl, or R4and R5together mean oxoprop,

R7R16halogen atom,

R17choose from the groups that include hydrogen atom, a C1-C6alkyl and C1-C6haloalkyl,

R31choose from the groups that include hydrogen atom, a C1-C3alkyl, C2-C4alkylsulphonyl and C2-C4alkoxycarbonyl,

R32C1-C3alkyl,

m is 1 or 2,

n 1

p 1.

Most preferred are compounds where a and E together form the group-CH2-, -CH2-CH2-, -N(R7)CH2-, and R7-H or methyl, and compounds where Z is O or NR31.

Preferred compounds in which Y is C1-C6alkyl, in particular Y is methyl.

In particular, from the group of compounds the most interesting from the point of view of use are the following connections:

methyl-7-chloro-2,3-dihydro-2[[4-(triptoreline)phenylamino] carbonyl]indeno[1,2-e][1,3,4]oxadiazine-4a(5H)-carboxylate;

methyl-7-chloro-2,5-dihydro-2-[N-methyl-N-[4-(triptoreline)phenyl] aminocarbonyl]indeno[1,2-e][1,3,4] oxadiazine-4a(3H)-carboxylate;

methyl-7-chloro-2,5-dihydro-2[[N-methyl-N-[4-(trifluoromethyl)phenyl] amino]carbonyl]indeno[1,2-e][1,3,4]-oxadiazine-4a(3H)-carboxylate;

7-fluoro-4-(4-florfenicol-N-[4-(triptoreline)phenyl] indeno[1,2-e] [1,3,4]-oxadiazol-2(3H)-carboxamide.

Compounds of General formula I include all geometric and stereoisomers, salts of these compounds, are suitable for use in agriculture, to fight Arthropoda and to control them.

The object of this invention is also Atropatena composition comprising an active component and a carrier containing as an active ingredient the compounds of formula I in an amount up to 99 wt.

The next object of the invention is a method of dealing with arthropode by contacting Arthropoda or their habitats with arthropode-effective amount of compounds of formula I. Arthropode-effective amount of compound I is 0.001 to 8 kg/ha.

The compounds of formula I receive as described in the diagrams below with the substituents specified above, unless otherwise indicated.

The compounds of formula I where X is oxygen, can be obtained by the reaction of compounds of formula V with isothioscyanates formula VI.

The reaction of compound V with compound VI is carried out in conventional organic solvent such as ethyl acetate, methylene chloride, chloroform, benzene or toluene. These compounds do not restrict the choice of possible rastvoriteli the metal hydride. Diagram 1 illustrates this transformation.

Alternatively (scheme 2) compounds of the formula I in which A and E together form a 1 - or 2-atom bridge, as described previously, can be obtained by the reaction of semicarbazones formula VII with compounds of formula VIII. The reaction is carried out at a molar excess of compound VIII (from 1.1 to 40 equivalents) with 1 equivalent of a compound of formula VII in the presence of less than one molar equivalent of an acid catalyst (from 0 to 0.9 equivalent).

Typical acid catalysts include alkyl - or arylsulfonate (such as methyl, camphor - or para-toluensulfonate) and mineral acids (such as hydrochloric acid or sulfuric acid).

Commonly used polar organic solvents, such as acetonitrile, dimethylformamide, tetrahydrofuran, methanol or ethanol.

The reaction temperature may vary from 0oC to the boiling point of the particular solvent used in the reaction, and the reaction usually completes in less than 24 h Scheme 2 illustrates this transformation (Scheme 1 and 2 are at the end of text).

Alternatively, the compounds of formula I, in which is dinani formula VII with compounds of formula IX (see scheme 3). The reaction involves reacting a molar excess of the compound of formula IX (1.1 equivalent to 5.0 equivalents) with one equivalent of a compound of formula VII in the presence of a base such as tertiary amine (e.g. triethylamine, pyridine or DBU), alkali metal, alkali metal hydride or alkali metal alkoxide or hydroxide (e.g. sodium methoxide, tert. -piperonyl potassium, sodium hydroxide or potassium hydroxide). Usually for the reaction, you can use polar organic solvents, such as methanol, ethanol, propanol, dimethylformamide, tetrahydrofuran, dichloromethane or acetonitrile. The reaction temperature may vary from 0oC to the boiling point of the particular solvent used and the reaction usually completes in less than 24 hours

Alternatively (scheme 3) when Z1this NR31; R4and R5represent H and L1and L2form together a group NMe2jthe reaction may be conducted in the absence of a base in an aprotic solvent such as tetrahydrofuran, dioxane, etc., Using equimolar quantities of VII and IX, and the reaction is usually completed within 72 hours

< / BR>
where L1L2where Z1this NR31provided that R4and R5don't mean together O.

The compounds of formula V, in which A and E together imply 1 - or 2-atom bridge, as described previously, can be obtained by the reaction of compounds of formula X or a compound of formula VIII or a compound of formula IX using methods similar to those demonstrated in obtaining compounds of formula I in schemes 2 and 3. Obtaining compounds of formula V shown by figure 4 (see end of text).

The compounds of formula VII in which X is O, can be obtained by the reaction of compounds of formula X with an isocyanate of formula VI, as shown in reaction scheme 5 (see diagram at the end of the text). The reaction is carried out at equimolar quantities X And VI in the presence of 1 molar equivalent of water in a polar organic solvent such as tetrahydrofuran or dimethylformamide. The reaction usually completes in less than 24 hours

Alternatively, the compounds of formula VII where X is O, can be obtained by the reaction of compounds of formula XI with semicarbazide formula XII. The flow conditions for this reaction include the possible presence of an acid catalyst, such as chlorotoluene from 0 to 150oC, as a rule, it is preferable to conduct the reaction at the boiling temperature of the solvent used in the reaction.

Suitable solvents include methanol, ethanol, isopropanol, tetrahydrofuran and dioxane, but they do not exhaust the whole range of possible solvents. Scheme 6 illustrates this transformation (see end of text).

The compounds of formula X can be obtained by the reaction of compounds of formula XI with an excess (1.1 to 10.0 equivalents) of hydrazine, managerseminare, hydrazinoacetate, hydrazinecarboxamide, etc., the Reaction is carried out in an alcohol solvent such as methanol, ethanol, n-propanol, isopropanol, n-butanol, etc., or acetic acid, and the temperature that are due to the boiling point of the particular solvent used. The reaction is usually completed within 24 h Scheme 7 illustrates this transformation (see end of text).

The compounds of formula XI in which X3is O, can be obtained by hydroxylation of ketones of formula XIII using methods well known to specialists in this field. (for example, J. Am. Chem. Soc. 1974, 96, 5944; Tetrahedron Lett. 1988, 29, 2835; J. Org. Chem. 1986, 51, 2402). Scheme 8 illustrates this transformation (see end of text).

nye ways. Such methods are well known in the art (March, Advanced Org. Chem. 3 rd edition, 1985, p. 1164). The compounds of formula XI in which X3this is oxygen, R3is aryl and E is H, are benzoinum, the receipt of which is well known to specialists.

a-Aminoketone formula XI in which X3this NR31can be obtained from ketones of formula XIII using procedures well known in the art (J. Chem. Soc. 1959, 1479; Synthesis, 1972, 191).

The compounds of formula XI in which X3this other31Clcan be obtained by the coupling of compounds of formula XIII compounds of the type Ha using procedures described in Synthesis, 1991, 327. Conditions for this reaction are as follows: use of equimolar amounts of derivatives of the formulae XIII and XIII a, the reaction is carried out in the presence of a base as catalyst, for example, such grounds as DABCO, DBU (dibutylamine), sodium hydroxide, etc., Suitable solvents for the implementation of the reaction are toluene, dioxane and water, but is not limited to the list of possible solvents. Scheme 9 illustrates this transformation (see end of text).

Source ketones of formula XIII are known or can be polnia formula XIII include indanone, tetralone.

Professionals in this field must be known that the conversion of compounds of formula XIII in the compounds of formula XI may require the introduction of protective groups, in order to avoid undesirable side reactions of functional groups, which can be sensitive to the reaction conditions.

The semicarbazides of the formula XII in which X is oxygen and G as above, can be obtained using procedures well known in the field of chemistry.

In addition, the compounds of formula I in which Q has the above meaning, And it is H, Z is CH, E is H, and R3is H, alkyl or aryl, can be obtained according to scheme 10. Typically, this reaction interaction of equimolar amounts of such heterocyclic compounds, as XXVI, arylisocyanate formula VI in a conventional organic solvent such as ether or tetrahydrofuran.

Alkylation of dianion such compounds as the compounds of formula XXVII is another useful way of introducing the set R3groups. This method is presented in figure 11 (see end of text). R3group that is usually obtained in this way are supplied alkylating reagents R3

The compounds of formula I in which Q has the above meanings and R4and R5together with the carbon atom to which they are attached, form a carbonyl group (for example, as a compound XXVIII) can be obtained by the reaction of amide, such as V, in which R4and R5together mean O arylisocyanates. This method is illustrated by figure 12 (see end of text). This reaction can be performed using a variety of traditional organic solvents such as ether, tetrahydrofuran or ethyl acetate, and preferably at the boiling temperature of the solvent.

Alternatively, the compounds of formula I can be obtained by the reaction of compounds of formula XXXII with aniline formula XVII, as presented in figure 13 (see end of text).

The reaction conditions include the interaction of compound XXXII with 1 to 5 molar equivalents of compound XVII in a suitable solvent in the presence of 0 to 10 molar equivalents of such bases as pyridine, potassium carbonate or triethylamine. A suitable solvent is THF, DMF and acetonitrile.

The compounds of formula XXXIII is oxadiazine and thiadiazine, the receipt of which is known from literature data (see, for example, Synthesis, 1988, 208; Synthesis, 1990, 491).

The following examples illustrate the invention.

Example 1

Stage A: 3-chloro--(4-chlorophenyl)benzoylpropionate acid

To a solution of 6.8 g (to 0.17 mol) of 60% sodium hydride in 150 ml of dimethylformamide in a nitrogen atmosphere are added dropwise 30.0 g (rate £ 0.162 mol) of methyl-4-chlorophenylacetic so that hydrogen gas was moderate, and the reaction temperature was kept not exceeding 50oC. After the cessation of evolution of hydrogen was added to the solution 33,2 g (rate £ 0.162 mol) 3-chlorobenzylamino in 30 ml of dimethylformamide; the addition was carried out very carefully, so that the reaction temperature did not exceed 60oC. the Reaction mixture is maintained under stirring at 50 to 60oC during the night, Posada ether and the combined organic extracts are then washed with water. The ether extracts are dried over anhydrous magnesium sulfate, filtered, and concentrated, as a result got to 48.0 g of brown oil.

The crude product was combined with 300 ml of methanol, 40 ml of water and 20 ml of 50% aqueous sodium hydroxide solution and heated under reflux overnight. After this time the reaction mixture was concentrated and the crude residue is divided between water and ether. Aqueous extracts were acidified by adding concentrated hydrochloric acid, and was Proektirovanie several times with ether. The ether extracts are dried over anhydrous magnesium sulfate, filtered, and concentrated, as a result got to 48.8 g of oily product solid yellow color.

1H-NMR (CDCl3d: 3,0 (dd. 1 H), 3,3 (m, 1H), 3,84 (t, 1H), 6,77 (d, 1H), 6,9 7,4 (m, 6H).

Stage B: 5-chloro-2-(4-chlorophenyl)-2,3-dihydro-1H-inden-1-he

The crude product from stage A was combined with 50 ml of thionyl chloride and then heated under reflux for 2 hours thionyl chloride was distilled under reduced pressure and then the mixture was concentrated several times from carbon tetrachloride. The residue was combined with 200 ml of dichloroethane, cooled under nitrogen atmosphere to 0oC and then added 24.5 g alwoodley acid, was Proektirovanie three times with ether, and skipped through the chromatographic column Packed with silica gel (10% ethyl acetate/hexane), got to 18.6 g of oily product solid yellow color.

1H-NMR (CDCl3d: 3,20 (dd. 1H), 3,68 (dd. 1H), 3,90 (dd. 1H), 6,9 7,6 (m, 6H), of 7.75 (d, 1H).

Stage C: 5-chloro-2-(4-chlorophenyl)-2,3-dihydro-2-hydroxy-1H-inden-1-he

A solution containing 2.4 g (0,009 mol) of the product obtained at stage B, and 20 ml of toluene was added with stirring to a mixture of 1.8 g (0,010 mol) of triethylphosphite, 0.1 g (of 0.0004 mol) of benzyltriethylammonium, 100 ml of toluene and 50 ml of 50% aqueous sodium hydroxide solution. A steady stream of air was passed into the vigorously stirred reaction mixture at room temperature for one hour. The resulting mixture was divided between 100 ml of diethyl ether and 200 ml of water, and the aqueous layer was Proektirovanie two portions of 100 ml of diethyl ether. The combined organic layers were washed with two portions of 100 ml of water, twice with saturated aqueous solution of sodium bisulfite, dried over anhydrous magnesium sulfate and concentrated. The crude product was programatorului on silica gel using a mixture of 2 1 hexane ethyl acetate in the results(each. C. 2H), 7,25 (abq, 4H), 7,44 (d, 1H), 7,53 (ush. C. 1H), 7,78 (d, 1 H).

Stage D: 2-[5-chloro-2-(4-chlorophenyl)-2,3-dihydro-2-hydroxy-1H-inden-1-ilidene]-N-[4-(trifluoromethyl)phenyl]hydrazinecarboxamide

A solution containing 1.0 g (of 0.003 mol) of the product obtained in stage C of 0.66 ml (0.014 mol) of hydrazine monohydrate and 17 ml of ethanol was heated under reflux for 3 hours the resulting solution was divided between water and dichloromethane and the aqueous layer was Proektirovanie dichloromethane. The combined organic layers washed twice with water, dried over anhydrous sulfate and concentrated. The residue was programatorului on silica gel using a mixture of 1 1 hexane ethyl acetate resulted 0,53 g solid yellow color.

A solution of 0.5 g of product obtained above, of 0.24 ml (0,0016 mol) a, , -Cryptor-pair-toluenesulfonate, 25 ml of tetrahydrofuran and 1 ml of water was stirred at room temperature for one hour and then concentrated. The residue is suspended in acetonitrile and concentrated. He got to 0.60 g of a solid white product with a melting point of 225oC (decomp.).

1H-NMR (d6-DMSO) d: 3,3 (d, 1H partially mixed with the peak of the H2O) 3,55 (d, 1H), and 7.3 to 7.5 (m, 7H), to 7.64 (d, 2H), 7,82 (d, 2H), oxadiazon-3H-carboxamid

A mixture of 0.30 g (0,0006 mol) of the product obtained in stage D, 0.36 g (0.012 mol) of para-formaldehyde, 50 mg of the monohydrate of para-toluenesulfonic acid and 30 ml of acetonitrile was heated under reflux for one hour. The resulting mixture was separated between dichloromethane and saturated aqueous sodium bicarbonate and the aqueous layer was Proektirovanie twice with dichloromethane. The combined organic layers were dried over anhydrous magnesium sulfate and concentrated, and the obtained oil, which was programatorului on silica gel, using a mixture of 4 1 hexane in ethyl acetate. He got to 0.23 g of oil, which solidified upon standing, melting point 213 214oC.

1H-NMR (CDCl3d: 3,39 (d, 1H), to 3.58 (d, 1H), 4,54 (d, 1H), 5,78 (d, 1H), 7.29 trend 7,42 (m, 6H), to 7.61 (q, 4H), 7,72 (d, 1H), 8,58 (ush. C. 1H).

Example 2

Stage A: Methyl 5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-inden-2-carboxylate

Sodium hydride (24 g of 60% solution in oil, 0.6 mol) was washed with hexane to remove the oil. Received the washed sodium hydride suspended in 200 ml of DMF and then treated with a solution containing 50 g (0.3 mol) of 5-chloro-1-indanone and 150 ml of DMF; the treatment was carried out so that the temperature did not rise above 35oC. Then polucen obavljale within 15 minutes. The resulting mixture was stirred at room temperature for 1.5 hours and then left overnight. The reaction mixture is carefully poured into a mixture of 100 ml of concentrated hydrochloric acid and about 1000 ml of ice. Then added 500 ml of ether, and the aqueous layer was twice Proektirovanie ether. The combined organic layers were washed with three portions of water, dried over anhydrous magnesium sulfate and concentrated, the result was a 64.6 grams of a brown oil.

A solution of 5.0 g (0,0022 mol) obtained above product and 70 ml of methylene chloride was treated with 10 g (about to 0.032 mol) 50 60% metallocarboranes acid (Aldrich) at room temperature. After one hour the reaction mixture was cooled to 0oC and the reaction stopped by the careful addition of a saturated aqueous solution of sodium carbonate. The mixture is washed twice with a saturated aqueous solution of sodium carbonate, once with a saturated solution of sodium bisulfite, dried over anhydrous magnesium sulfate and concentrated, and the obtained 4.0 g of solid product yellow.

IR spectrum (CCl4solution) 3560, 1770, 1745 cm-1.

1H-NMR (CDCl3, 200 MHz) d 7,73 (d, 1 H), 7,50 (ush. C. 1 H), 7,42 (d, 1 H), 4.04 the (c, 1 H, exchanges with D2O in), 3.75 (s, IMT]hydrazono]-1 H-inden-2-carboxylate

A solution of 1 g (0,004 mol) of the product of stage a and 10 ml of methanol was added at 0oC to a solution containing 0,61 ml (0.012 mol) of hydrazine monohydrate, to 0.72 ml (0.012 mol) of glacial acetic acid and 20 ml of methanol. The resulting mixture was heated under reflux for 2 hours, then cooled to room temperature and divided between 200 ml of methylene chloride and 200 ml of water. The aqueous layer was Proektirovanie with methylene chloride and the combined organic layers washed twice with water, dried over anhydrous potassium carbonate and concentrated, the result was obtained 0.6 g of the solid product is yellow.

A solution of 0.5 g (0.002 mol) of the product obtained above and 20 ml of tetrahydrofuran was treated with a solution of 0.4 g (0.002 mol) of 4-(triptoreline)phenylisocyanate and 5 ml THF. Added two drops of water and the resulting solution was stirred at room temperature for 30 minutes. Then the reaction mixture was concentrated and received from 0.90 g of slightly contaminated product, which was used in the next stage without further purification. The sample for analysis was obtained by recrystallization from a mixture of THF-hexane, melting point 233 235oC.

1H-NMR (200 MHz, d6-DMSO) d 9,43 (s, 1 H), 9,40 (s, 1 H), of 7.93 (d, 1H), 7,78 (d, 2 h), 7,methoxy)phenyl] amino] carbonyl]indeno[1,2-e][1,3,4]oxadiazine-4 a-(3h)-carboxylate

A mixture of 0.85 g (0.002 mol) of the product from stage B, 0.9 g of para-formaldehyde, 0.05 g of monohydrate para-toluenesulfonic acid and 50 ml of acetonitrile was heated under reflux for one hour. The resulting mixture was cooled to room temperature and divided between dichloromethane and saturated aqueous sodium bicarbonate. The aqueous layer was Proektirovanie dichloromethane and the combined organic layers were washed with saturated aqueous sodium bicarbonate solution, dried over anhydrous magnesium sulfate and concentrated. The residue was purified using flash chromatography on silica gel, using a mixture of 4 1 hexane ethyl acetate, the result was obtained 0.50 g of the solid product is a pale yellow color, melting point 99 101oC. This product is rubbed in hot hexane, and the obtained white solid product with a melting point 126,5 128oC.

1H-NMR (200 MHz, CDCl3d of 8.37 (ush. C. 1 H), 7,66 is 7.50 (m, 3 H), 7,35 (d, 1 H), 7,32 (s, 1 H), 7,18 (d, 2 H), of 5.92 (d, 1 H), of 5.05 (d, 1 H), of 3.73 (s, 3 H), 3,52 (d, 1 H), 3.27 to (d, 1 H).

Stage D: Methyl-7-chloro-2,5-dihydro-2-[[N-methyl-N-4- (trifloromethyl)amino] carbonyl] indeno[1,2-e] [1,3,4]oxadiazine-4 a (3 H)-carboxylate

A solution containing 1.0 g (0.002 mol) of the product from stage C and 10.5 ml of DMF, was treated with 0.2 g ETANA. The resulting mixture was stirred at room temperature for 2 hours and then poured into a cooled ice 1 N. HCl and Proektirovanie with three portions of ether. The combined organic layers were washed with water, dried over anhydrous magnesium sulfate and concentrated, and the obtained crude solid yellow product, which was washed with methanol, resulted 0,70 g of the yellow solid product, melting point 130 131oC.

1H-NMR (200 MHz, CDCl3d 7,20 (EV. C. 1 H), 7,16 (EV. C. 5 H), at 6.84 (d, 1 H), of 5.29 (abq. 2 H). 3,67 (c. 3 H), 3,38 (overlapping d, 1 H, and c, 3 H), 3,13 (d, 1 H).

EXAMPLE 3

Stage A: Hydrochloride of methyl 2-amino-5-chloro-2,3-dihydro-1-oxo-1 H-inden-2-carboxylate

Ice solution containing 11.4 g (100,8 mmol) of hydroxylamine-O-sulfonic acids in 102 ml of water and 20 ml of 2n sodium hydroxide solution in one portion was added at 0oC to 10 g (102 mmol) of cyclohexanone in 180 ml of toluene and 50 ml of 2 n sodium hydroxide solution. The mixture was stirred for 10 minutes. The organic layer was separated and dried over anhydrous magnesium sulfate. Then to portions of a solution with a volume of 155 ml) was added 7 g (31,3 mmol) of methyl 5-chloro-2,3-dihydro-1-oxo-2-1 H-inden-2-carboxylate, and then added 0.1 g (0,89 is l 1 n hydrochloric acid. The acidic layer was evaporated under reduced pressure, the obtained 4,37 g of the solid product with a melting point of 145 - 148oC (decomp.).

1H-NMR (free base) (200 MHz, CDCl3d 7,73 (d, 1 H), of 7.48 (s, 1 H), 7,41 (d, 1 H), of 3.69 (s, 3 H), 3,68 (1/2 of ABq, 1 H), 3,05 (1/2 of ABq, 1 H).

Stage B: Methyl 2-amino-5-chloro-2,3-dihydro-1-[[[[4- (triptoreline)phenyl]amino]carbonyl]-hydrazono]-1 H-inden-2-carboxylate

A mixture of 2 g (7,24 mmol) of the product of stage A and 1.83 g (7,78 mmol) of 4-(4-triptoreline)-phenylsemicarbazide in 18 ml of ethanol is boiled for 2 hours. Gave the mixture to cool and again stirred at room temperature overnight. The mixture was poured into 200 ml of saturated sodium bicarbonate and then Proektirovanie with three portions of 100 ml of ethyl acetate. The combined extracts were dried and evaporated and the resulting product was washed with ether, resulted in 1.0 g of the solid product is almost white in color, a small portion of which was subjected to further purification by chromatography was carried out on silica gel (ethyl acetate ethanol / 5 1), resulted in a product with a melting point 156,5 158oC (decomp.).

1H-NMR (200 MHz, CDCl3d to 8.4 (s, 1 H), to 8.20 (s, 1 H), 7,83 (d, 1 H), 7,56 (d, 2 H), 7,42 to 2.18 (m, 4 H), to 3.73 of 3.65 (m, 4 H), 3,05 (1/2 of ABq, 1 H).

One hundred is t

The strain of 0.12 g (6,48 mmol) salt Eschenmosers in 3 ml of tetrahydrofuran was added to 0.3 g (to 6.57 mmol) of the product from stage 2 ml of tetrahydrofuran at room temperature. The mixture was stirred at room temperature for 65 hours. The mixture is then poured into 100 ml saturated aqueous sodium bicarbonate solution and was Proektirovanie with three portions of 50 ml of ethyl acetate. The combined extracts dried and evaporated. Was programatorului on silica gel (suirable a mixture of ethyl acetate/hexane 1 1), the result obtained white solid product with a melting point 135 140oC (decomp.).

X (mineral oil): 3372, 3298, 1751, 1658, 1631, 1603, 1535, 1315, 1266, 1199, 1109, 1009, 967, 919, 889, 826 cm-1.

1H-NMR (200 MHz, CDCl3d 8,43 (s, 1 H), of 7.64 7,14 (m, 7 H), 5,38 (1/2 of ABq, 1 H), 4,39 (1/2 of ABq, 1 H), 3,71 (s, 3 H), 3,53 (1/2 of ABq, 1 H), is 3.08 (1/2 of ABq, 1 H), 3,40 (ush. C. 1 H).

According to the General procedures described herein or modifications of these procedures can be obtained the compounds shown in tables 1 to 11.

The composition and use

Compounds of the present invention typically can be used in a mixture with suitable for agricultural purposes, the carrier comprising a liquid or solid diluent or an organic solvent. Useful rnih powders, granules, baits, lozenges, solutions, pills, suspensions, emulsions, irrigated powders, emulsifiable concentrates, dry flowable (granular) formulations, etc., Many of them can be applied directly. Compositions for spraying can be sprayed in a suitable medium and the spray volume can be from about one to several hundred liters per hectare. Highly concentrated compositions are used first as intermediates for the preparation of further structure. Generally speaking, these compositions contain from less than about 1% to 99% by weight of active ingredient(s) and (a) at least one surfactant in an amount of about from 0.1% to 20% and b) from about 5% to 99% solid or liquid diluent. More specifically, they may contain effective amounts of these ingredients in the following approximate proportions(% mass. (see table. 12).

Low or high concentration of active ingredient is determined by the purpose of their use and the physical properties of compounds. Sometimes it is desirable to achieve a high ratio of surface-active substance (surfactant-surfactant) to the active ingredient, and to reach this aim by incorporating the latest in the composition or by mixing it in the edition, Dorland Books, Caldwell, New Jersey. For irrigated powders are more appropriate thinners, high absorption capacity, and Farrukh Dustov require a more dense thinners. Typical liquid diluents described in Maraden, "Solvents Guide", 2nd edition, Interscience, New York, 1950. For suspension concentrates preferred solubility within 0.1% preferably concentrated solutions were stable from the point of view of phase separation at 0oC. McCutcheon''s "Detergents and Emulsifiers Annual", Allured Publ. Corp. Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publ. Co. Inc. New York, 1964, include a list surfactants and recommended use. All formulations can contain minimal amounts of additives intended to reduce foam, caking, corrosion, microbiological growth, and so on, it is Preferable that the ingredients have permission to use from the U.S. Bureau for the protection of the environment.

Methods of preparing such compositions are well known. The solutions are obtained by simple mixing of the ingredients. Finely powdered solid composition is prepared by mixing and, as a rule, grinding in a hammer mill or crusher that uses the energy of the jet. From the s by spraying the active material on a pre-fabricated pellets carriers or by agglomeration techniques (see J. E. Browning "Agglomeration", Chemical Engineering, December 4, 1967, pages 147 et seq, Perry's Chemical Engineer''s Handbook", 4th Ed. McGraw Hill, New York 1963, pp. 8 59 and below).

AN EXAMPLE OF A

Emulsifiable concentrate

7-chloro-4 a-(4-chlorophenyl)-4 a, 5-dihydro-N-[4-(trifluoromethyl)phenyl]indeno[1,2-e][1,3,4]-oxadiazol - 2(3 H)carboxamid 20%

The mixture of oil-soluble sulfonates and esters of polyoxyethylene 10

Isophorone 70%

The ingredients are combined together and stirred at accurate heating to accelerate dissolution. Before packaging the composition is filtered through a sieve with small holes in order to be sure of the absence of any extraneous insoluble materials in the product.

EXAMPLE B

Wettable powder

7-chloro-4 a-(4-chlorophenyl)-4 a, 5-dihydro-N-[4-(trifluoromethyl)phenyl]indeno[1,2-e][1,3,4]-oxadiazol - 2(3 H)-carboxamide 30%

Alkylnaphthalene sodium 2

Ligninsulfonate sodium 2%

Synthetic amorphous silica 3%

Kaolinite 63

The active ingredient is mixed with inert materials in the mixer. After grinding in a hammer mill again mix the material and sift through a sieve with a mesh size of 50 mesh.

EXAMPLE C

Douste

Wettable powder of example B 10%

Pyrophyllite. The product is suitable for use in the form of dust (dust).

EXAMPLE D

Granules

7-chloro-4 a-(4-chlorophenyl)-4 a,5-dihydro-N-[4-(trifluoromethyl)phenyl]indeno [1,2-e] [1,3,4]-oxadiazol-2(3 H)-carboxamide 10%

Granules attapulgite (low-volatile material of 0.71/0.30 mm; U. S. S. sieve N 25 50) 90%

The active ingredient is dissolved in a volatile solvent, for example acetone, and sprayed on the compressed and preheated granules attapulgite in a double-cone mixer. Then when heated to remove the acetone. Allow to cool pellets and then packaged.

EXAMPLE E

Granules

Irrigated (wettable powder of example 15%

Gypsum 69%

Potassium sulfate 16%

The ingredients are mixed in a rotary mixer and sprayed with water to complete the granulation. After most of the material reaches the desired size from 0.1 to 0.42 mm (U. S. S. sieve N 18 40), the granules are removed from the mixer, dried and sieved. Granules exceeding the desired size, grind for additional material required size. These granules contain 4.5% of the active ingredient.

EXAMPLE F

Solution

7-chloro-4 a-(4-chlorophenyl)-4 a,5-dihydro-N-[4- (trifluoromethyl)phenyl]indeno[1,2-e][1,3,4]-oxadiazol-RA, suitable for direct, low volume application (the volume of the small size).

EXAMPLE G

Water suspension

7-chloro-4 a-(4-chlorophenyl)-4 a, 5-dihydro-N-[4-(trifluoromethyl)phenyl]indeno[1,2-e] [1,3,4]-oxadiazol-2(3 H)-carboxamide 40%

The polyacrylic acid thickener 0.3% of

Ether dodecylphenol and polyethylene glycol 0,5%

Phosphate sodium 1,0%

Sodium dihydrophosphate 0,5%

Polyvinyl alcohol 1,0

Water 56,7%

The ingredients are mixed and pulverized in a mill to obtain a particle size which basically amounts to 5 microns.

EXAMPLE H

Oil suspension

7-chloro-4 a-(4-chlorophenyl)-4 a, 5-dihydro-N-[4-(trifluoromethyl)phenyl]indeno[1,2-e][1,3,4]-oxadiazol -2(3 H)-carboxanilide 35

The mixture polioksidony esters and oil soluble petroleum sulphonic acids

6%

The solvent xylene range 59%

The ingredients are combined and milled together in a mill to obtain a particle size which generally does not exceed 5 microns. The product can be used directly dissolved in the oil or emulsified in water.

EXAMPLE 1

Pellets groundbait

7-chloro-4 a-(4-chlorophenyl)-4 a, 5-dihydro-N-[4-(trifluoromethyl)phenyl]indeno[1,2-e][1,3,4]-oxadiazol - 2R> Crushed cobs of corn 88,0%

The mixture of active ingredient and a surfactant are dissolved in a suitable solvent, such as acetone and sprayed on the crushed cobs of corn. The granules are then dried and packaged.

The compounds of formula 1 can also be mixed with one or more representatives from other insecticides, fungicides, nematicides, bactericides, acaricides or other biologically-active compounds, forming a multi-component pesticide with a wide spectrum of action as an effective means of crop protection. Examples of other protective equipment used in agriculture, which can be included in the compositions with the compounds of the present invention:

Insecticides

3-hydroxy-N-methylcrotonate dimethyl-phosphate (monocrotophos), ether methylcarbamyl acid and 2,3-dihydro-2,2-dimethyl-7-benzofuran (carbofuran),

O, O-dimethyl O-[2,4,5-trichloro - d -(chloromethyl)benzyl]-phosphoric acid (tetrachlorvinphos),

diethyl ether 2-mercaptoethanol acid, S-ester dimethylthiophenol acid (Malathion),

O,O-dimethyl-O-para-nitrophenyloctyl ether phosphothioate (methyl-paratacamite (methomyl),

N'-(4-chloro-ortho-toluene)-N,N-dimethylforamide (Chlordimeform),

O,O-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidinetrione (diazinon),

octachlorinated (toxaphene),

O-ethyl-O-para-nitrophenyl-phenylphosphonate (EPN),

(S)- a-cyano-meta-phenoxybenzyl(1 R, 3 R)-3-(2,2-dibromovinyl)-2,2 - dimethylcyclopropanecarboxylate (deltamethrin),

methyl-N,N'-dimethyl-N - [(methylcarbamoyl)oxy]-1-toxemia (oxamyl),

cyano(3-phenoxyphenyl) methyl-4-chloro - a -(1-methylethyl)benzoylacetate (fenvalerate),

(3-phenoxyphenyl)methyl-2,2-dimethylcyclopropanecarboxylate (permethrin),

a-cyano-3-phenoxybenzyl-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane - carboxylate (cypermethrin),

O-ethyl-S-(ortho-chlorophenyl)ethylphosphonate (profenofos),

O-ethyl-O-[4-(methylthio)-phenyl]-S-n-propyl ether phosphorylation acid (sulprofos).

Further specifies a number of insecticides under their usual names: triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, Arafat, azinphosmethyl, chlorpyrifos, fonofos, isofenphos, mitigation, monocrotophos, phosmet, phosphamidon, fozalon, pirimicarb, Fort, terbufos, trichlorfon, Methoxychlor, bifenthrin, lifenet, cyfluthrin, fluvalinate, flucythrinate, tralomethrin, metaldehyde and rotenone, which is a carbamate (carbendazim),

tetramethylpyrazine (thiuram),

acetate n-dodecylguanidine (Dodin),

ethylenebisdithiocarbamate manganese (MANEB),

1,4-dichloro-2,5-dimethoxybenzene (chloroneb),

methyl-1-(butylcarbamoyl)-2-benzimidazolecarbamate (benomyl),

1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolane-2-ylmethyl] -1 H-1,2,4 - triazole (propiconazole),

2-cyano-N-ethylcarbamate-2-methoxybenzamide (having cymoxanil), 1-(4-chlorphenoxy)-3,3-dimethyl-1-(1 H-1,2,4-triazole-1-yl)-2-butanone (triadimefon),

N-(trichloromethylthio)tetrahydrophthalate (Captan),

N-(trichloromethylthio)phthalimide (folpet),

1- [[[bis(4-forfinal)methyl]silyl]methyl]-1 H-1,2,4-triazole.

The nematicides

S-methyl-1-(dimethylcarbamoyl)-N-(methylcarbamoyl)- Titrimeter,

S-methyl-1-carbarnoyl-N-(methylcarbamoyl)-Titrimeter,

O-ethyl-O'-[4-(methylthio)-meta-toluene] W N-isopropylacetanilide (fenamiphos).

Bactericides

trehosnovnoy copper sulfate, streptomycin sulfate

The acaricides

ether 2-Deut. -butyl-4,6-dinitrophenol and 3-methylcrotonate acid (binapacryl),

6-methyl-1,3-dithiolo[4,5 - b)cinoxacin-2-he (oxythioquinox),

ethyl-4,4'-dichlorobenzil (Chlorobenzilate),

1,1-bis(ortho-chlorophenyl)-2,2,2-trichloroethanol (dicofol),

bicarpheni)-N-cyclohexyl-4-methyl-2-oxothiazolidine-3 - carboxamide (vexations),

amitraz, propargite, fanbot-tin-oxide.

Biological controls are sewn

Bacillus thuringiensis,

Avermectin.

The usefulness

Compounds of the present invention are characterized by favorable metabolic properties and/or residual effect on the soil, and also have activity against a wide range of arthropod inhabiting deciduous cover and soil, which are pests of growing and stored crops, forestry, greenhouses, ornamental plants, seedlings, food and fiber (spinning) of crops, livestock, household, human and animal health. Professionals in this field, it should be clear that not all connections have the same effective against all pests. For example, some of the compounds in which Y is alkyl, have increased field activity. Compounds of the present invention are active against these pests that cause economically significant damage to agricultural crops, forestry, greenhouse agriculture, ornamental plants, fiber (spinning) cultures and stocks of products for various purposes, domashnego and other Spodoptera spp.

butterfly-Brunico, tobacco Budennogo worm, cereal grains worm, and other Heliothis spp. borer corn, butterflies-the liquidation, shovels, stem and stem grinders and other pyralid, larvae of the geometrid moths of cabbage and saii, and other larvae, moth Apple, black caterpillars winter moths, moth vine, spotted caterpillar podgryzayuschie shoots scoops, other caterpillars and other fireflies, moths, cabbage, green clover moth caterpillars velvet bean boxed pink worm, the caterpillar of the moth and coniferous wood worm (: Packed spruce); larvae feeding on foliage and adults of the order of Coleoptera, including the Colorado potato beetle, Mexican bean beetle, earth Blasco, Japanese beetle and other beetles, abyudaya leaves, cotton weevil, rice water weevil, and other harmful weevils and insects living on earth, such as the larvae damage the roots of cereals and other Diabrotica spp. Japanese beetle-garden chafer, European beetle beetle and other pests of the root system of the order of Coleoptera, and beetles-the Nutcracker (wireworms); adult and larvae of the order Hemiptera and Homoptera, including clipica meadow and other plant-sucking bugs (miridae), star and other e weevils (fulgoroidae), Psalidi, aleyrodidae (aleurodidae), (aphids), aphidiidae (aphidae), Lepidoptera (scale) (coccidae and diaspididae). bugs-lace (tingidae), stink bugs (pentatomidae), bugs turtles and other grain beetles (lyggedidae), cicadas (cicadidae), cicadas are pennisi (cercopids), bugs-robowiki (coreidae), red chlopicki and cotton krasnolipe (pyrrhocoridae);

adults and larvae of detachment acari (mites), including European red mite, Clasica arachnoid hairy, spotted spider Clasica, the tick, causing rust plants, mite McDaniela and herbivorous mites; adult and immature Orthoptera order. locusts;

adults and immature individuals detachment Diptera. including fodder leaves, fruit flies (terphitidae) and soil legless larvae (especially flies); adult and immature individuals detachment Thysanoptera, including tobacco trip and other herbivorous thrips.

Compounds of the present invention are also active against such pests that cause economic damage and cause harm to livestock, home to the property and health of humans and animals, as:

harmful insects of the order Hymenoptera, including carpenter ants, bees, hornets and wasps;

harmful insects squad Dyptera, including house flies, house flies, W is the blood-sucking mosquitoes, sand flies, flies, and other Nematocera;

harmful insects of the Orthoptera order, including cockroaches Prussians and crickets;

harmful insects of the suborder Isoptera including the Eastern subterranean termite and other termites;

harmful insects squad Mallophaga and Anoplura. including head lice, body lice, chicken head louse and other blood-sucking and biting lice are parasites that attack man and animals;

harmful insects squad Siphonoptera. including cat fleas, dog fleas and other fleas.

For the following specific types and examples of control. These include butterfly-scoop/scoop-marching worm (Spodoptera fruigiperda), the weevil cotton (Anthonomus grandis), tobacco botany worm (Heliothis virescens), aphids, black Bob (Aphis fabae); star hopping insects that eat the leaves of cycatki (Macrostelles fascitrons): blaska 11-point Howard, larvae, feeding on roots of maize (Diabrotica undecimpunctata).

Compounds of the present invention have a protective effect not only against listed pests. Compounds of the present invention can also be used as a means of killing rodents (rodenticides).

Methods of application

Control the s is achieved by processing one or more of the compounds of formula I of the present invention. The habitat of the pests, including the loci of crops and agronomic loci of infection on the area that should be protected, treated an effective amount of these compounds, or they are applied directly to the pests, the number of which should be regulated. Because of the diversity of the habitat and behavior of these Arthropoda you can use many different methods of application. A preferred method of spraying using a device that distributes the connection in the habitat of pests on the plants, animals, the subject, or indoors, in soil, on the part of the plant that is infected or needs protection. Alternatively, the granular compositions of the present invention containing these toxic compounds can be applied to or incorporated into the soil. Can be used and other methods of application, including direct and residual spray, air spray, feeding, large pills (balls, aerosols, foggers) and many others.

Connections can be included in food (bait) that is consumed Arthropoda, or can be used in devices such as traps, etc., forcing Arthropoda the unity of the present invention can be applied in pure form, but most often, the applying is carried out in the form of compositions comprising one or more compounds of the present invention with suitable fillers, diluents and surfactants and possibly with food, depending on the proposed goal. The preferred method of application is to spray water dispersion or solution of the compounds in light petroleum products/refined vegetable oils. Combination with raspryskivanii oil solutions, oil concentrates and synergists, for example, piperonylbutoxide, often increases the effectiveness of the compounds of formula I.

The frequency of treatment with compounds of the formula I, is necessary for effective control and/or regulation depends on such factors as type of arthropod, the number of which must be controlled, life-time/life cycle of harmful arthropod, its size, habitat, time of year, objedive crop or animal, feeding behavior, mating, environmental humidity, temperature, etc. As a rule, the dose comprising from 0.01 to 2 kg per hectare of active ingredient, it is often sufficient to ensure effective large-scale control (requirements.about and not less than 0.001 kg/hectare or not more than 8 kg/ha. When processing non-agricultural crops effectively used doses may vary from about 1.0 to 50 mg/m2but at least they are 0.1 mg/m2and about the maximum, as may be necessary to 150 mg/m2.

Data for biological studies

Connection 1 83 shown in Tests A-E, was used at a concentration of component 1000 parts per million ('clock N. m). Connection 84 - 250, marked with a single asterisk (or two asterisks) were used in the respective tests in concentration, component 250 o'clock N. m or 0.5 o'clock N. M. In other respects, the test conditions for compounds 1 83 and 84 250 were in all experiments, identical.

Test A

Butterfly-scoop (scoop-marching worm)

For testing use plastic cups with a volume of 230 ml (8 oz); they are filled with a layer of approximately 0.5 cm depth, consisting of a diet based on wheat. Ten larvae of the noctuid Spodoptera fruigiperda located in the third growth phase, is placed in each Cup. The contents of the cups are sprayed with a solution of the test compounds (solvent-acetone/ distilled water 75/25), the control experience three cups sprayed with just solvent.

Oprah is ity to apply the dose, component of 0.55 kg/ha/a 0.5 lb (1000 parts per million of active ingredient per acre), at a pressure of 30 pounds per inch2(207 kPa). After this Cup is closed and incubated at 27oC and 50% relative humidity for 72 hours, then count. For the following compounds was achieved mortality is higher or equal to 80% 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 15, 19, 20, 21 23, 25 29, 31, 34, 35, 36, 37, 39, 40, 43 49, 51 55, 56, 58, 61 63, 65, 70, 74, 78, 79, 80, 87, 88, 89, 90, 91, 92*, 93, 94*, 95, 96, 98*, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108*, 109*, 113*, 114*, 117, 119, 120, 122, 123, 124, 125, 126, 128*, 129, 132*, 133, 140, 141, 142, 143*, 144*, 145*, 148*, 149*. 150*, 152*, 153*, 154*, 155*, 157*, 158*, 159*, 160*, 161*, 162*, 163*, 164*, 167*, 168*, 171*, 172*, 173*, 174*, 177, 178, 180, 187, 188, 189, 191, 192, 193, 194, 195**, 196, 197, 198, 199, 200, 201, 202, 203**, 204, 205, 206, 207, 208, 209, 210, 211, 212, 213, 214, 215**, 216, 217**, 218, 219, 220, 221, 222, 223, 224, 225, 226, 227, 228, 229, 230, 231, 232, 233, 235, 237, 238, 239, 240, 241, 242, 243, 244, 245, 246.

Test B

Butterfly-Soto (kidney worm butterflies)

Test method test A was repeated with the larvae of a butterfly-moth (Heliothis virescens). in the third phase of development, except for the fact that mortality was determined after 48 hours. For the following compounds was achieved mortality is higher or equal to 80% 2 5, 6 10, 11, 12, 15 23, 25 29, 32 35, 37, 39, 40 49, 51, 52 56, 61 63, 65, 70, 71, 74, 79, 84, 85, 87, 88, 89, 90, 91, 92*, 93, 94*, 95, 98*, 99, 100, 101, 102, 103, 108*, 169*, 171*, 172*, 174*, 178, 180, 187, 188, 189, 191, 192, 193, 194, 195**, 196, 197, 198, 199, 200, 201, 202, 203, 204, 205, 206, 208, 209, 210, 211, 212, 214, 215**, 216, 217**, 218, 219, 220, 221**, 222, 223, 224, 225, 226, 227, 228, 229, 230, 231, 232, 235**, 237, 238, 240, 241, 242, 243, 244, 245, 246.

Test C

Blaska 11-point Howard (Diabrotica undecimpunctata howardi)

For testing use plastic cups with a volume of 230 ml (8 oz), which contains 1 the germ of corn. A set of three of these cups sprayed, as described above, the individual solutions of the test compounds. After drying the applied solution into each Cup was placed on five larvae flea 11-point, in the third stage of development. In each Cup was placed moistened dental swab to prevent drying and then the Cup was closed. After this Cup kept at 27oC and 50% relative humidity for 48 hours, and then assessed. For the following compounds was achieved mortality is higher or equal to 80% 1 3, 6, 7 12, 15 20, 21 23, 25 28, 32, 35, 36, 37, 39, 41, 42, 43, 44, 46 49, 51, 52 56, 59, 61 63, 65, 70, 71, 74 80, 84, 85, 87, 89, 91, 92*, 93, 94*, 95, 96, 98*, 99, 100, 101, 102, 103, 104, 105, 107, 108*, 109*, 117, 119, 120, 122, 123, 124, 125, 129, 132*, 133, 134, 135, 138, 140, 141, 142, 143*, 144*, 145*, 148*, 149*, 150*, 151*, 152*, 153*, 154*, 155*, 156*, 157*, 158*, 159*, 160*, 161*, 162*, 163*, 164*, 165*, 167*, 172*, 177, 178, 189, 191, 192, 193, 195, 198, 200**, 203, 204, 205, 206, 208, 209, 210, 211, 212, 21�cal was prepared a series of 12 unsieved cups 350 ml, each Cup contained the seeds of oat (Avena sativa) in the layer of sterilized soil with a thickness of 1 inch (1,54 cm). Each Cup was sprayed as described in test A, the individual solution the following compounds. After the oats obsah after spraying, from 10 to 15 adult star cycatki (Macrosteles fascitrons) were aspirated into each closed Cup. Cup stood at the 27oC and 50% humidity for 48 hours, after which calculated the dead insects. For the following compounds was achieved mortality is higher or equal to 80% 2 13, 15 19, 21 22, 25 28, 35 37, 39 41, 48 49, 51 56, 63, 65, 70, 71, 74, 76, 77-79, 87, 91, 92*, 93, 94*, 98*, 99, 101, 102, 104, 105, 106, 107, 108*, 123, 124, 125, 126, 133, 142, 145*, 148*, 150*, 152*, 153*, 154*, 157*, 160*, 161*, 162*, 165*, 166*, 167*, 171*, 177, 178, 180, 187, 188, 189, 193, 194, 195, 200, 203, 209, 210, 211, 215, 216, 218, 219, 226, 231, 232, 233, 235, 239, 240, 241, 242, 244, 246.

Test E

The weevil cotton

Five adult weevil cotton (Anthonomies grandis grandis) was placed in each series of 9-unsieved cups (260 ml). The test procedure was then repeated for A test on three cups per treatment. Mortality was determined 48 hours after treatment. For the following compounds was achieved mortality is higher or equal to 80% 1 13, 15, 16, 18 23, 25, 26 - 28, 32, 33, 35, 37, 39, 41 49, 51 56, 61 63, 65, 70, 71, 74, 75-80, 84, 85, 87, 91, 92*67*, 169*, 171*, 172*, 177, 178, 180, 191, 193, 195, 198, 200, 203, 204, 205, 206, 208, 209, 211, 213, 215, 216, 226, 227, 228, 230, 235, 237, 238, 240, 242.

* tested at 250 parts per million

* * tested at 0.5 parts on million

1. Carboxanilide formula 1

< / BR>
in which Q -

< / BR>
A H;

E H or A and E can be combined together to form-CH2-, -CH2-CH2- or-N(R7)CH2-;

Z C;

Z1selected from the group comprising 0 or NR31;

< / BR>
A1H;

X O;

Y is chosen from the group comprising H, C1C6-alkyl, C2C6alkenyl, C2C6-quinil, C2- C6-alkylsulphonyl, C2C6-alkoxycarbonyl, or Y - C1C3-alkyl, substituted Deputy chosen from the group comprising SR32C1C3-alkoxy, CO2R32and phenyl;

R1and R2independently from each other selected from the group including H, halogen, C1C6-alkyl, C1- C6-haloalkyl, NO2CN, OR17and SR17;

R3selected from the group including H, C1C6-alkyl, CO2R17, phenyl or phenyl substituted (R16)p;

R4and R5an is may be combined together, obrazu;

R7choose from a group that includes H, C1- C6-alkyl and

C1C6haloalkyl;

R16halogen;

R17selected from the group including H, C1- C6-alkyl and

C1C6-haloalkyl;

R31selected from the group including H, C1- C3-alkyl, C2C4-alkylsulphonyl and C2C4-alkoxycarbonyl;

R32C1C3-alkyl;

m is 1 or 2;

n 1;

p 1.

2. Connection on p. 1, in which A and E together form a-CH2-, -CH2-CH2or N(R7)CH2-; R7selected from the group comprising H and methyl.

3. Connection on p. 2, in which Z10.

4. Connection on p. 2, in which Z1this NR31.

5. Connection on p. 3, in which Y is C1C6-alkyl.

6. Connection on p. 5, in which Y is CH3.

7. Connection on p. 3, represent methyl-7-chloro-2,3-dihyro-2[[ 4-(triptoreline)phenylamino] carbonyl] indeno[1,2-e] [1,3,4] oxadiazine-4(5H)-carboxylate.

8. Connection on p. 6, represent methyl-7-chloro-2,5-dihydro-2- [N-N[4-(triptoreline)phenyl] -aminocarb-chloro-2,5-dihydro-2 [[N-methyl - N -[4-(trifluoromethyl)phenyl]-amino]carbonyl]indeno[1,2-e] [1,3,4] -oxadiazine-4A(3H)-carboxylate.

10. Connection on p. 3, representing 7-fluoro-4A-4-forfinal)-4A, 5-dihydro-N-[4- (triptoreline)phenyl] indeno-[1,2-e] [1,3,4] -oxadiazol(3H)-carboxamide.

11. Connection on p. 3, representing 7-chloro-4A,5-dihydro-4A-methyl - N- [4-(triptoreline)phenyl]indeno-[1,2-e] [1,3,4] oxadiazine-2(3H)-carboxamide.

12. Atropatena composition comprising an active component and a carrier, wherein the active component includes a connection PP. 1 11 in an amount up to 99 wt.

13. The way to fight arthropode by contacting Arthropoda or their habitats with anthropocene effective amount of the active substance, characterized in that the active substance is used as a compound for PP. 1 11, anthropocene effective amount is 0.001 to 8 kg/ha

 

Same patents:

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

< / BR>
where X is oxygen or sulfur;

Y is carbon or nitrogen;

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

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

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

R5and R6independent from each other and denote hydrogen or methyl;

n is 0,1 or 2,

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

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

The invention relates to new derivatives of pianolasociety, pharmaceutical compositions containing these derivatives, their use for the treatment of hypertension or asthma in mammals, including humans, and method for producing the above compounds and compositions

The invention relates to methods of optical separation pornoencaricaturas compounds, which are important intermediate product in the synthesis of optically active derivative of pianolasociety, useful in the treatment of hypertension (hypertension) and asthma

The invention relates to a derivative of pyrazine, which has antagonistic activity relative to the glutamate receptor, represented by the formula:

< / BR>
in which Z represents C or N, provided that two Z are nitrogen atoms; R1is:

< / BR>
in whichisor, R6represents H or alkyl, and R7and R8are each H, alkyl, nitro or phenyl, or alternatively, R7and R8taken together, represent butadiene or 1,4-butylene; R2and R3are each H, F, cyano, acyl, nitro, alkyl, morpholino or one of the above definitions for R1; R4and R5are each H, hydroxyl, alkyl, cycloalkyl, heterocycle, phenyl, or Y-substituted alkyl; Y represents a hydroxyl, acyloxy, F - substituted methyl, cycloalkyl, tetrahydrofuranyl, carboxyl, alkoxycarbonyl or

The invention relates to new triazolo[4,3-a][1,4] benzodiazepine or a thieno[3,2-f][1,2,4]triazolo[4,3-a]benzodiazepines of General formula I

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where X is-CH=CH -, or S; R1- lower alkyl or trifluoromethyl; R2is chlorine or fluorine; R3is a radical of the formula R4-(CH2)n-CC - or R5-O-CH2-CC -, where n is an integer of 0,1 or 2; s is 0 or 1; R4is phenyl or mono-, di - or tricyclic 5-7-membered heterocyclic radical containing as heteroatoms O or S and/or 1-3 nitrogen atom, unsubstituted or substituted lower alkoxy, oxo, actigraphy or chlorine; R5is phenyl or pyridyl radical, provided that when n is 0, the radical R4must be attached through a carbon to carbon link, and that R5always attached through carbon to oxygen of communication, and in the presence of at least one asymmetric center, their enantiomers and racemates and pharmaceutically-acceptable salts accession acids exhibiting the properties of antagonists of platelet activating factor (PAF) and, respectively, with angioprotective, immunological, is omposition based on them

The invention relates to new substituted pyrazolylborate, and to their use as herbicide compositions

The invention relates to compounds of formula (I) listed in the description, where R1represents a hydrogen atom or unsubstituted or substituted alkyl group; and A represents the number of cyclic or acyclic nitrogen containing groups

The invention relates to the production of Riboflavin (vitamin B2)

The invention relates to a derivative of pyrazine, which has antagonistic activity relative to the glutamate receptor, represented by the formula:

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in which Z represents C or N, provided that two Z are nitrogen atoms; R1is:

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in whichisor, R6represents H or alkyl, and R7and R8are each H, alkyl, nitro or phenyl, or alternatively, R7and R8taken together, represent butadiene or 1,4-butylene; R2and R3are each H, F, cyano, acyl, nitro, alkyl, morpholino or one of the above definitions for R1; R4and R5are each H, hydroxyl, alkyl, cycloalkyl, heterocycle, phenyl, or Y-substituted alkyl; Y represents a hydroxyl, acyloxy, F - substituted methyl, cycloalkyl, tetrahydrofuranyl, carboxyl, alkoxycarbonyl or

The invention relates to new substituted pyrazolylborate, and to their use as herbicide compositions

The invention relates to lactam derivative, method of production thereof, to pharmaceutical compositions containing them and to their use in medicine

The invention relates to imidazo - annelirovaniya ISO - and heterocyclic compounds, method of their production and to the tools based on them
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