Heterocyclic nitrogen-containing or oxygen-containing insecticidal compounds formed from dialdehydes, and production and use thereof

FIELD: chemistry.

SUBSTANCE: invention relates to novel heterocyclic nitrogen- and oxygen-containing compounds having insecticidal activity. In formulae (A) (B) (C) (D) R₁ is a 5- or 6-member heterocyclic ring containing a nitrogen, oxygen and/ or sulphur atom, a halogen-substituted 5- or 6-member heterocyclic ring containing a nitrogen, oxygen and/or sulphur atom, a substituted or unsubstituted phenyl, where the substitutes are one or more groups selected from a group consisting of halogen atoms, C_1-4 halogen alkyl or C_1-4 chloroalkoxyl; R₅, R₆, R₇, R₈ and R₉ are H, saturated or unsaturated C_1-4 alkyl, halogen atom, saturated or unsaturated C_1-4 alkoxyl, saturated C_1-4 halogenalkoxyl, C_1-4 alkylcarbonyl, C_1-8 alkyl ester, C_1-4 alkylsulphonyl, phenyl, benzyl or trifluoromethane sulphonyl ether group; Y is nitro, cyano, trifluoromethyl, trifluoroacetyl or trifluoromethylsuphonyl. Values of radicals R, R₂-R₄ are given in the claim.

EFFECT: invention also relates to an agrochemical composition containing said compounds, use of the agrochemical composition in pest control and a method of producing said compounds.

12 cl, 7 tbl, 36 ex

The technical field

This invention relates to new derivatives of neonicotinoid, to a method for their production and to their applications.

Prior art

Submitted by Imidacloprid, neonicotinoid insecticide was the triggering factor in the opening of pesticides to the property of high insecticidal activity, a wide insecticidal spectrum, low toxicity to mammals and aquatic animals, a good system properties suitable field stability and favourable for the environment. After Imidacloprid was developed series neonicotinoid insecticides, such as thiacloprid, clothianidin, thiamethoxam, acetamiprid, nitenpyram and dinotefuran (EP 247477, 296453, 685477, 235725, 235725, 315826, 192060, 244777, 0386565, 580553, 1031566, JP 62292765, 8259568, 8291171 and 7242633).

However, the application and development of these compounds is limited due to resistance caused by too frequent use of Imidacloprid, and cross-resistance among neonicotinoids insecticides caused structural similarity. However, neonicotinoid insecticides, mainly exhibit high activity against pests Homoptera and Coleoptera, and narrow insecticidal spectrum limits their wide application in pest control.

Thus, in this technical field, it is imperative to develop a connection with effektivnye activities from high-level nitromethylene compounds, to solve the problem of sustainability, to enhance insecticidal spectrum and apply them in insecticidal compositions.

Brief description of the invention

In this invention the proposed new and effective insecticides, which allow to solve the problem of resistance to neonicotinoid insecticides to enhance insecticidal spectrum and to solve the problems existing in this field of technology.

One aim of the invention is the development of derivatives for effective pest control, and receipt of them.

Another aim of the invention is to develop a growing and protection of collected plants and prevent their infestation by insects.

In accordance with the first aspect of the invention proposed compound of formula (A), (B), (C) or (D), its optical isomer, CIS-TRANS-isomer or its agrokhimichesky acceptable salt

where R₁represents 5 - or 6-membered heterocycle containing nitrogen atom, oxygen and/or sulfur, substituted with halogen 5 - or 6-membered heterocycle containing nitrogen atom, oxygen and/or sulfur, substituted or unsubstituted phenyl, where the substituents are one or more than one group selected from the group consisting of halogen atoms, C_1-4halogenoalkane the C _1-4haloalkoxy;

R₂represents H, C_1-8saturated or unsaturated alkyl, substituted with halogen, C_1-8saturated or unsaturated alkyl, -CH₂CH₂OCH₂CH₃, -CH₂CH₂OCH₃C_1-8saturated or unsaturated alkoxyl, phenyl, benzyl, C_1-4alkylsulphonyl or_1-4alkylsulfonyl;

R₃and R₄independently selected from H, C_1-6of alkyl, allyl, benzyl, C_1-4alkoxy-C_1-4of alkyl, C_1-4alkoxycarbonyl, phenoxycarbonyl,_2-6alkynylaryl, C_2-3alkenylboronic,_3-6cycloalkylcarbonyl, unsubstituted bentilee group or benzoline group, substituted by one or more than one group selected from the group consisting of halogen atoms, C_1-4of alkyl, C_1-4halogenoalkane,_1-4alkoxyl or C_1-4alkylcarboxylic, furancarboxylic or N,N-dimethylcarbamyl; or R₃and R₄together form-CH₂-CH₂-, -CH₂-CH₂-CH₂- or-CH₂-XR-CH₂-where X represents N, O, S, or another heteroatom; R represents a Deputy on X and is selected from H, C_1-6of alkyl, allyl, benzyl, phenyl, C_1-4alkoxy-C_1-4of alkyl, C_1-4alkoxycarbonyl, phenoxycarbonyl, C_2-6alkynylaryl,_2-3alkenylboronic,_3-61-4halogenoalkane, C_1-8saturated or unsaturated alkyl or alkoxyl or_1-4alkylcarboxylic, furancarboxylic or N,N-dimethylcarbamyl.

R₅, R₆, R₇, R₈and R₉represents H, saturated or unsaturated With_1-4alkyl, halogen atom, saturated or unsaturated C_1-8alkoxy, saturated or unsaturated With_1-4halogenoalkanes, C_1-4alkylsulphonyl, C_1-8alkyl ester With_1-4alkylsulfonyl, phenyl or benzyl;

Y represents nitro, cyano, trifluoromethyl, TRIFLUOROACETYL or trifloromethyl.

In one preferred embodiment R₁selected from pyridyl, thiazolyl, pyrimidinyl, tetrahydrofuryl, oxazolyl or their halogenated groups.

In one preferred embodiment R₁is halogenerator, halogenoacetyl, halogenopyrimidines, halogenerator or halogenoacetyl. Preferred halogenated groups are chlorides.

In another embodiment R₁represents,or.

In another embodiment R₂pre is is a N, saturated or unsaturated With_1-4alkyl, saturated or unsaturated With_1-4halogenoalkane,_1-4alkylsulphonyl, unsubstituted benzyl or benzyl substituted by one or more than one group selected from the group consisting of a halogen atom, a C_1-4halogenoalkane or_1-4haloalkoxy.

In one embodiment R₂represents N or C_1-3alkyl. More preferably R₂represents H or methyl.

In another embodiment R₃and R₄represent H, C_1-6alkyl, or R₃and R₄together form-CH₂-CH₂- or-CH₂-CH₂-CH₂-.

In one embodiment R₃and R₄represent a hydrogen atom or a C_1-3alkyl, preferably H, methyl or ethyl. Alternative R₃and R₄together form-CH₂-CH₂- or-CH₂-CH₂-CH₂-.

In another embodiment R₅, R₆, R₇, R₈and R₉represents H, saturated or unsaturated With_1-2alkyl, halogen atom, saturated or unsaturated With_1-4alkoxy, saturated or unsaturated C_1-2halogenoalkanes,_1-4alkylamino group (RCOO -),_1-2alkylsulfonyl or triftormetilfosfinov group.

In one embodiment R₅, R₆, R₇, R₈and R₉pose is a N, methyl, chlorine atom, bromine atom, methoxy or atoxyl and preferably represent H, methyl and methoxy.

In another embodiment Y represents a nitro-group or cyano.

In one embodiment Y represents a nitro-group.

In accordance with the second aspect of the invention proposed agrochemical composition containing:

(a) 0.001 to 99.99 wt.% the aforementioned compound, its optical isomer, CIS-TRANS-isomer, it agrokhimichesky acceptable salts or combinations thereof; and

(b) agrokhimichesky acceptable carrier or excipient.

In one embodiment, the concentration of component (a) is from 0.01 to 99.9 wt.%, and preferably 0.05 to 90 wt.%.

In one embodiment of the agrochemical composition is used for the destruction or control of insects selected from the group consisting of Coleoptera, Lepidoptera, Hemiptera, Orthoptera, Isoptera and dipteran insects.

In one embodiment, the pests have mouthparts piercing-sucking type or biting type.

In another embodiment pests include this aphid, brown rice Cicada, whiteflies, cinadco, thrips, well cotton, caterpillar, followed by cabbage, cabbage moth, well litura or caterpillar grass plants.

In another embodiment of the agrochemical composition further comprises other active compounds, selected from the group consisting of the of insecticide, cobalt, a bactericidal agent, acaricide, nematicide, fungicides and growth regulators.

In accordance with a third aspect of the invention the application of the agrochemical composition for destruction or combating agricultural pests, hygiene pests and pests harmful to health of animals; or agrochemical composition is used as an insecticidal composition for the destruction or control agricultural pests, hygiene pests and pests that are harmful to animal health.

In accordance with the fourth aspect of the invention, a method for destroying or controlling crop pests, sanitary pests and pests that are harmful to animal health, including the application of the above agrochemical or insecticidal composition on plants, their surrounding soil or the environment, which is under attack or be attacked by insects.

In accordance with the fifth aspect of the invention it is proposed to use the connection, its optical isomer or CIS-TRANS isomer, it agrokhimichesky acceptable salts or combinations thereof upon receipt of insecticidal compositions.

In accordance with the sixth aspect of the invention, a method for obtaining compounds, its optical isomer or CIS-TRANS isomer, it agrohimicheskih salts, includes the following stages:

In the presence of catalytic acid and 0-60°With the interaction of the compounds of formula (a) with compound (b), (C) or (d), resulting in a compound (A), (B), (C) or (D), where R₂represents H,

where R₁, R₃, R₄, R₅, R₆, R₇, R₈, R₉and Y are as defined above, and n is 0 or 1.

In one embodiment the reaction temperature of 15-45°C., and preferably 20-30°C.

In another embodiment the solvent is selected from acetonitrile or ethanol, and preferably acetonitrile.

In another embodiment of the catalytic acid selected from concentrated hydrochloric acid, concentrated sulfuric acid or benzoic acid, preferably concentrated hydrochloric acid.

In one embodiment the method includes:

in the presence of catalytic acid, the following reaction is carried out at 20-30°C in acetonitrile for 2-24 hours, resulting in a compound (A), where R₂is a N:

in the presence of catalytic acid, the following reaction is carried out at 20-30°C in acetonitrile for 2-24 hours, resulting in brasaetsa connection (In):

in the presence of catalytic acid, the following reaction is carried out at 10-50°C. in acetonitrile for 2-24 hours, resulting in a connection (S):

in the presence of catalytic acid, the following reaction is carried out at 10-50°C. in acetonitrile for 2-24 hours, resulting in a compound (D):

Detailed description of the invention

After a long and deep research of the inventors synthesized a new class neonicotinoid derivatives, which are obtained by the interaction nitromethylene connection with the dialdehyde based on nitromethylene group modern nitromethylene neonicotinoids insecticides. These new derivatives are significantly high activity and enhanced insecticidal spectrum. The inventors have completed the present invention based on the above.

The definition of the substituents

The term "C_1-6alkyl" refers to pravarasena or branched alkyl with 1-6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, emop-butyl, mpem-butyl or some similar group.

The term "C_1-6alkoxyl" refers to pravarasena or branched alkoxy with 1-6 carbon atoms is kind, such as methoxyl, ethoxyl, propoxy, isopropoxy, butoxy, isobutoxy, second-butoxyl, tert-butoxy or some similar group.

The term "halogen" refers to fluorine atom, chlorine, bromine or iodine. The term "halogenated" refers to one or more than one substitution of the same or different atom of halogen as mentioned above, such cancriformis, pentafluoroethyl or similar group.

The term "5 - or 6-membered heterocyclic alkyl" refers to 5 - or 6-membered ring cyclic alkyl containing one or more than one heteroatom selected from a nitrogen atom, oxygen or sulfur, such as pyridyl, ciazil, pyrimidinyl, tetrahydrofuryl, oxazolyl etc.

Obtaining the compounds according to the invention

Compounds according to the invention can be synthesized as described above. The compound (a) can be obtained in accordance with the technical references in the art, such as WO 2006056108 A1, WO 2007101369 A1 and PCT/CN 2008/071115.

In one embodiment the compound of formula (A) can be synthesized according to the following method, where R₂represents N;

In one embodiment the compound of formula (I) can be synthesized according to the following method:

In one embodiment the compound of formula (C) can sintezirovat is, according to the following method:

In one embodiment the compound of formula (D) can be synthesized according to the following method:

In one embodiment the compound of formula (A) can be synthesized according to the following method:

(1) a Solution of 2-chloro-5-(chloromethyl)pyridine in acetonitrile is added dropwise to a solution of 5-10 mol of diamine. The reaction is carried out at 0-50°C. for 5-10 hours. After the mixture is distilled under reduced pressure to remove diamine, dissolved in ethyl acetate and evaporated to obtain N-((6-chloropyridin-3-yl)methyl)diamine.

(2) a Mixture of N-((6-chloropyridin-3-yl)methyl)diamine and 1,1-dimethyldi-2-nitroethene dissolved in ethanol and refluxed for 4-8 hours with obtaining nitromethylene connection.

(3) In the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, heteroalicyclic etc., nitromethylene compound interacts with octaldehyde (glyoxal) to obtain the compounds of formula (A).

In another embodiment the compound of formula (I) can be synthesized according to the following method:

(1) To aqueous solution of ethylamine add the appropriate amount of acetonitrile. Then 2-chloro-5-(chloromethyl)pyridine in acetonitrile is added dropwise in an ice b is not. The reaction monitoring is carried out using TLC (thin layer chromatography). After the mixture was added a large amount of water, extracted with DHM (dichloromethane), dried, filtered and evaporated to obtain N-((6-chloropyridin-3-yl)methyl)ethanamine in the form of oil.

(2) a Mixture of N-((6-chloropyridin-3-yl)methyl)ethanamine and 1,1-dimethyldi-2-nitroethene dissolved in ethanol and refluxed for 4-8 hours. After the mixture was concentrated and purified column chromatography to obtain N-((6-chloropyridin-3-yl)methyl)-N-ethyl-1-(methylthio)-2-nitroenamine.

(3) a Mixture of an alcohol solution of methylamine and N-((6-chloropyridin-3-yl)methyl)-N-ethyl-1-(methylthio)-2-nitroenamine dissolved in ethanol and subjected to interaction within 4-8 hours in an ice bath. After the mixture was concentrated and purified column chromatography to obtain N-((6-chloropyridin-3-yl)methyl)-N-ethyl-N'-methyl-2-nitroethene-1,1-diamine.

(4) In the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, heteroalicyclic etc., N-((6-chloropyridin-3-yl)methyl)-N-ethyl-N'-methyl-2-nitroethene-1,1-diamine interacts with malonic aldehyde with obtaining the compounds of formula (In).

In another embodiment the compound of formula (C) can be synthesized according to the following method:

(1) a Solution of 2-chloro-5-(chloromethyl)pyridine in which aconitine added dropwise to a solution of 5-10 mol of diamine. The reaction is carried out at 0-50°C. for 5-10 hours. After the mixture is distilled under reduced pressure to remove diamine, dissolved in ethyl acetate and evaporated to obtain N-((6-chloropyridin-3-yl)methyl)diamine.

(2) a Mixture of N-((6-chloropyridin-3-yl)methyl)diamine and 1,1-dimethyldi-2-nitroethene dissolved in ethanol and refluxed for 4-8 hours with obtaining nitromethylene connection.

(3) In the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, heteroalicyclic etc., nitromethylene connection communicates with succinic aldehyde with obtaining the compounds of formula (C).

In another embodiment the compound of formula (D) can be synthesized according to the following method:

(1) a Solution of 2-chloro-5-(chloromethyl)pyridine in acetonitrile is added dropwise to a solution of 5-10 mol of diamine. The reaction is carried out at 0-50°C. for 5-10 hours. After the mixture is distilled under reduced pressure to remove diamine, dissolved in ethyl acetate and evaporated to obtain N-((6-chloropyridin-3-yl)methyl)diamine.

(2) a Mixture of N-((6-chloropyridin-3-yl)methyl)diamine and 1,1-dimethyldi-2-nitroethene dissolved in ethanol and refluxed for 4-8 hours with obtaining nitromethylene connection.

(3) In the presence of an acid catalyst such as hydrochloric sour is a, sulfuric acid, heteroalicyclic etc., nitromethylene compound interacts with glutaraldehyde to obtain the compounds of formula (D).

Insecticidal activity of the active compounds according to the invention

The terms "active ingredient according to the invention" or "active compound according to the invention are a compound according to the invention, its optical isomer or CIS-TRANS isomer, or its agrokhimichesky acceptable salt. "Active compound according to the invention show significantly increased activity and enhanced insecticidal spectrum.

The term "agrokhimichesky acceptable salt" means a salt anion is known or acceptable in the formation insecticide acceptable salt. Preferably the salt is soluble in water. Salts formed by the compounds of the formula (A), (B), (C) and (D)include salts formed with inorganic acid (for example, hydrochlorate, phosphate, sulfate and nitrate), and salts formed with organic acids (such as acetate and benzoate).

The active compound according to this invention may be applied to the struggle and destruction of the normal insect pests of agricultural crops and plants, insect pests of grain, insects, harmful to health, and insects that are harmful to animal health. In this invention, the term "insecticide" the present is the focus of any connection which prevents or fights with any of the above insects. Approximate insects include, but are not limited to;

Coleoptera: Sitophilus zeamai, Tribolium castaneum, Henosepilachna vigintioctomaculata, Henosepilachna spars, Agriotes fuscicollis, Anomala cupripes, Popillia quadriguttata, Monolepta hieroglyphica, Monochamus alternatus, Echinocnemus squameus, Basiprionota bisignata, Anoplophora chinensis, Apripona gennari, Scolytus schevy, Agriotes fuscicollis.

Lepidoptera: Lymantria dispar, Malacosoma neustria testacea, Diaphania perspectalis, Clania variegate, Cnidocampa flauescens, Dendrolimus punctatus, Orgyia gonostigma, Paranthrene tabaniformis, Spodoptera litura, Chilo suppressalis, Ostrinia nubilalis, Ephestia cautella, Adoxophyes orana, Laspyresia splendana, Agrotis fucosa, Galleria mellonella, Plutella xylostella, Phyllocnistis citrella, or Mythimna separate.

Homoptera: Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzus persicae, Aphis gossydii, Lipaphis erysimi pseudobrassicae, Stephanitis nashi, or Bemisia tabaci.

Orthoptera: Blattella germanica, Periplaneta americana, Gryllotalpa africana, or Locusta migratoria.

Isoptera: Solenopsis invicta, Coptotermes formosanus.

Diptera: Musca domestica, Aedes aegypti, Delia platura, Culex sp., Anopheles sinensis.

Insects that are harmful to human health: Boophilus microplus, Haemaphysalis longicornis, Hyalomma anatolicum, Hypoderma spp., Fasciola hepatica, Moniezia Blanchard, Ostertagia spp., Trypanosoma enansi, Babesia bigemina, etc.

Compounds according to the invention have specific effects on nasekomykh pests of agricultural crops and plants that have piercing-sucking or biting mouthparts, such as aphids, Cicada, brown rice Cicada, thrips, whiteflies, etc.

Insecticidal composition comprising a compound according to the invention

Active the compounds according to the invention can usually be included in the insecticidal composition. The active compounds according to the invention can be included in conventional preparations such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active compounds, microcapsules in polymers, covering complex for seeds, products used with the combustion chamber (such as flue-cylinder, smoke box and flue plate) and preparations of cold spray and warm aerosol ULV.

These drugs can be obtained in a known manner, for example by mixing the active compounds with extenders, that is liquid or in the form of liquefied gas, solid diluents or carriers, optionally with the use of surface-active agents, that is emulsifying agents and/or dispersing agents and/or foaming agents. In the case of using water as a filler of organic solvents can also be used as auxiliary solvents.

Usually properly use liquid solvents as a diluent or carrier, for example, aromatic hydrocarbons such as xylene, toluene and alkylnaphthalenes; chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylene and methylene chloride; aliphatic hydrocarbons is childbirth, such as cyclohexane or paraffins, for example petroleum fractions; alcohols, such as ethanol or glycol and also their ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; or uncommon polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water. Under liquefied gaseous diluents or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.

The solid carrier includes crushed natural minerals such as kaolins, clays, only, quartz, attapulgite, montmorillonite or diatomaceous earth; of ground synthetic minerals such as highly disperse silicic acid, alumina and silicate. Solid media used for particles, is a crushed and fractionated natural rocks such as calcite, marble, pumice, thick and dolomite, and also synthetic granules of inorganic or organic large powder and granules of organic material such as sawdust, coconut shell, corn cobs and stalks of tobacco, and the like.

As amongyou is their and/or foaming agents can be used non-ionic and anionic emulsifiers, such as esters of polyoxyethylene and fatty acids, ethers of polyoxyethylene and fatty alcohols, for example, alkyldiphenylamine ethers, alkyl sulphonates, alkyl sulphates, arylsulfonate, as well as the products of hydrolysis of albumin. Dispersing agents include, for example, lignin, spent sulfite liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers (such as Arabian gum, polyvinyl alcohol and polyvinyl acetate) in the form of powders, granules or emulsions can be used in the preparations. It is possible to use colorants such as inorganic pigments, e.g. iron oxide, cobalt oxide and Prussian blue, and organic dyes, such as dyes, which are diazocompounds, or coloring matter, representing phthalocyanines metals and micronutrients, such as iron salts, manganese, boron, copper, cobalt, aluminum and zinc.

The active compound according to the invention can be presented in the form of a mixture with other active compounds in the commercial preparation or in the form of application, obtained from the commercial product. Other compounds can be an insecticide, a bactericide agent, acaricide, nematocide, fungicide, growth regulator and tomopterna. The insecticides include, for example, phosphates, carbamates, pyrethroids, chlorinated hydrocarbons, benzoylacetone, nereistoxin and the substance produced by microorganisms, such as ivermectin.

In addition, the active compound according to the invention can be presented in the form of a mixture with synergists in the commercial preparation or in the form of application, obtained from the commercial product. The synergist is used to enhance the action of the active connection, if the connection is active, do not have to use a synergist.

Generally, the preparations contain 0.001 to 99.99 wt.%, preferably from 0.01 to 99.9 wt.% and more preferably 0.05 to 90 wt.% the active compounds according to the invention. The concentration of the active compounds in the form of an application received from a commercial product, can vary over a wide range. The concentration of the active compound in the preparation for use is, for example, 0,0000001-100% (wt./about.) and preferably of 0.0001-1%.

Examples

Further, the invention is illustrated below by examples. It should be clear that these examples are intended only to illustrate the invention and do not limit the scope of the invention. With regard to experimental methods in the examples below, they are in normal conditions or in accordance with the manufacturer's instructions, unless otherwise specified Percentage and the share calculated by weight. The term "K.T." represents room temperature.

Example 1

Synthesis of 4-(1-((6-chloropyridin-3-yl)methyl)-4,5-dihydro-1H-imidazol-2-yl)-1-(1-((6-chloropyridin-3-yl)methyl)imidazolidin-2-ilidene)-1,4-dinitroso-3-EN-2-ol (compound 13)

In accordance with the method described in WO 2006056108 A1 and WO 2007101369 A1, 2-chloro-5-((2-(nitromethylene)imidazolidine-1-yl)methyl)pyridine was obtained from 2-chloro-5-(chloromethyl)pyridine (0.03 mol) at exit 56%. Rf=0,46 (petroleum ether: EtOAc=1:1); TPL=156,9°C To 161.8°C.; LC-MS (m/s): 220 (25), 126 (100), 90 (9).

Synthesis of 4-(1-((6-chloropyridin-3-yl)methyl)-4,5-dihydro-1H-imidazol-2-yl)-1-(1-((6-chloropyridin-3-yl)methyl)imidazolidin-2-ilidene)-1,4-dinitroso-3-EN-2-ol

In a 50 ml round bottom flask was added 1.27 g (0,005 mol) of 2-chloro-5-((2-(nitromethylene)imidazolidine-1-yl)methyl)pyridine, 30 ml of acetonitrile and 3 ml of 30% aqueous solution of Hexaldehyde. After stirring for 0.5 hours was added to the catalyst - concentrated HCl. Then the reaction mixture was stirred and monitored by TLC until completion. After that, the mixture was filtered to obtain a white powder, which was led with the receipt of 1.05 g of pure final product as a white powdery solid. Output: approximately 76%.

TPL=164,6-165,3°C;¹H NMR (400 MHz, DMSO-d₆): δ 9,01 (s, 1H), to 8.41 (d, J=2.0 Hz, 1H), scored 8.38 (d, J=2.0 Hz, 1H), 7,80-7,86 (m, 2H), 7,51-rate of 7.54 (m, 2H), 6,50 (d, J=7.2 Hz, 1H), of 5.34 (d, J=15.2 Hz, 1H), 5,18 (d, J=15.2 Hz, 1H), 4,84 (dd, J₁=2.4 Hz, J₂=7.2 Hz, 1H), 4,77 (d, J=16,8 Hz, 1H), 4,67 (d, J=16,8 Hz, 1H), 3,98 (d, J=2.4 Hz, 1H), 3,86-3,95 (m, 2H), 3,61-of 3.80 (m, 5H), 3,40-3,47 (m, 1H) million^-1;¹³With NMR (100 MHz, DMSO-d₆): δ 162,7, 158,7, 148,3, 148,2, 148,0, 147,7, 138,1, 137,7, 130,9, 130,2, 123,1, 123,0, 102,5, 101,4, 81,4, 53,8, 52,6, 49,4, 48,8, 46,4, 41,2, 41,0 million^-1; MVR (mass spectrometry high resolution) (ES+) calculated for C₂₂H₂₃N₈O₅³⁵Cl₂(M+N)⁺549,1168; found 549,1178. calculated for C₂₂H₂₃N₈O₅³⁵Cl³⁷Cl (M+H)⁺551,1139; found 551,1152. calculated for C₂₂H₂₃N₈O₅³⁷Cl₂(M+N)⁺553,1109; found 553,1108.

Example 2

Synthesis of 2-chloro-5-((4-(1-((6-chloropyridin-3-yl)methyl)imidazolidin-2-ilidene)-2-methoxy-1,4-dinitroso-3-enyl)-4,5-dihydroimidazole-1-yl)methyl) pyridine (compound 14)

In a 50 ml round bottom flask was added 0,549 g (0.001 mol) of the compound 13, 10 ml of methanol, 50 ml of dichloromethane and a catalytic amount of concentrated HCl. The reaction mixture is boiled under reflux and monitored by TLC. After the mixture is evaporated to remove solvent and purified column chromatography to obtain the final product as a yellow powder (yield 62%).

TPL=USD 151.6-153,1°C;¹H NMR (400 MHz, DMSO-d₆): δ 9,03 (s, 1H), scored 8.38 (d, J=2.0 Hz, 1H), at 8.36 (d, J=2.0 Hz, 1H), ,81-7,85 (m, 2H), 7,49-7,51 (m, 2H), 6,50 (d, J=7.2 Hz, 1H), 5,35 (d, J=15.2 Hz, 1H), 5,19 (d, J=15.2 Hz, 1H), 4,80 (d, J₁=7.2 Hz, 1H), 4,77 (d, J=16,8 Hz, 1H), 4,69 (d, J=16,8 Hz, 1H), 3,68 (s, 3H), 3,88-3,95 (m, 2H), 3,61-of 3.85 (m, 5H), 3,38-to 3.41 (m, 1H) million^-1;¹³C NMR (100 MHz, DMSO-d₆): δ 162,6, 158,7, 148,9, 148,3, 148,1, 147,6, 138,1, 137,8, 130,9, 129,9, 122,8, 123,1, 102,2, 101,6, 81,6, 58,7, 53,8, 52,6, 49,6, 48,9, 46,4, 41,3, 41,0 million^-1; MCBP (ES+) calculated for C₂₃H₂₅N₈O₅³⁵Cl₂(M+N)⁺563,1325; found 563,1311. calculated for C₂₃H₂₅N₈O₅³⁵Cl³⁷Cl (M+H)⁺565,1295.

Example 3

Synthesis of N¹N⁷bis((6-chloropyridin-3-yl)methyl)-N¹N⁷-diethyl-N¹N⁷-dimethyl-2,6-dinitrate-2,5-Vendimia (Compound 37)

(1): Synthesis of N-((6-chloropyridin-3-yl)methyl)ethanamine

65-70% solution of ethylamine (70 g, 1 mol), acetonitrile, 50 ml, was added into the three-neck round bottom flask equipped with addition funnel with pressure compensation and a thermometer. The solution was stirred in an ice bath for 15 min with controlled temperature of about 0°C. Then was added 2-chloro-5-(chloromethyl)pyridine (16,10 g, 0.10 mol) in 25 ml of acetonitrile using a dropping funnel with pressure compensation for 3.5 h with a speed of 3 drops/min After added water, and the reaction mixture was extracted with DHM. The organic phase was collected with obtaining, thus, 14 g of N-((6-chloropyridin-3-the l)methyl)ethanamine in the form of oil at the exit of 70%. LC-MS: m/z (%)=170 ([M]+, 20), 155 (80), 126 (100), 114 (10), 90 (12).

(2): Synthesis of N-((6-chloropyridin-3-yl)methyl)-N-ethyl-1-(methylthio)-2-nitroenamine

In a 100 ml three-neck round bottom flask was added N-((6-chloropyridin-3-yl)methyl)ethanamine (17.0 g, 0.1 mol), (2-nitroethene-1,1-diyl)bis(methylsulfanyl) (15.0 g, 0.09 mol), dry ethanol (50 ml). The mixture is boiled under reflux. After completion, the reaction mixture was cooled to K.T. and concentrated under reduced pressure to get crude product in the form of oil, which was purified column chromatography to obtain 5.3 g of N-((6-chloropyridin-3-yl)methyl)-M-ethyl-1-(methylthio)-2-nitroenamine when the output of 18.5%.

LC-MS: m/z (%)=242 ([M]+-46, 53), 227 (15), 213 (100), 169 (45), 155 (28), 141 (29), 126 (91), 90 (12).

(3): Synthesis of N-((6-chloropyridin-3-yl)methyl)-N-ethyl-N'-methyl-2-nitroethene-1,1-diamine

In a 100 ml round bottom flask was added N-((6-chloropyridin-3-yl)methyl)-N-ethyl-1-(methylthio)-2-nitroethene (5 g, of 0.017 mol), alcoholic solution of methylamine (1.8 g, is 0.017 mol), dry ethanol (30 ml). The mixture was stirred in the bath with ice to reduce the temperature to 0°C and continuously stirred to complete the reaction. The reaction mixture is evaporated under reduced pressure to remove solvent and then concentrated to obtain a syrup, which was dissolved in a certain amount DHM and was purified column chromatography, ISOE is isua DHM/Meon=25:1 as the eluent and silica gel as a filler. Received 0.9 g of N-((6-chloropyridin-3-yl)methyl)-N-ethyl-N-methyl-2-nitroethene-1,1-diamine when the output of 19.1%. Rf=0,23 (DHM/acetone=5:1,); TPL=78-80°C (lit. [67] 79-81°C); LC-MS: m/z (%)=236 ([M]+-34, 32), 207 (49), 169 (52), 126 (49), 110 (20), 90 (16), 67 (100). 16,65.

(4): Synthesis of N¹N⁷bis((6-chloropyridin-3-yl)methyl)-N¹N⁷-diethyl-N^1'N^7'-dimethyl-2,6-dinitrate-2,5-thienamycin (compound 37)

In a 50 ml round bottom flask was added 1.35 g (0,005 mol) of N-((6-chloropyridin-3-yl)methyl)-N-ethyl-N-methyl-2-nitroethene-1,1-diamine, 30 ml of dry acetonitrile, 0,72 g (0.01 mol) of malonic aldehyde and a catalytic amount of concentrated HCl. The reaction mixture was stirred at K.T. and monitored by TLC. After the mixture is evaporated to remove solvent and purified column chromatography to obtain the final product in the form of a pale yellow powder with a yield of 56%.

TPL=117,3-118,7°C;¹H NMR (400 MHz, DMSO-d₆): δ at 8.36 (d, J=2.4 Hz, 2H), 7,88 (dd, J₁=2.4 Hz, J₂=8,4 Hz, 2H), 7,51 (d, J=8,4 Hz, 2H), equal to 4.97 (t, J=2,8 Hz, 2H), a 4.86 (d, J=15.2 Hz, 2H), 4,49 (d, J=15.2 Hz, 2H), 3.95 to 3,99 (m, 4H), 3,66-of 3.78 (m, 6H), 3,12-is 3.21 (m, 2H), 1,91-of 1.93 (m, 6H) million^-1;¹³With NMR (100 MHz, DMSO-d₆): δ 156,3, 148,5, 148,1, 137,3, 131,9, 122,5, 104,8, 49,2, 48,9, 48,0, 48,5, 28,1, 20,2 million¹; MVR (EI+) calculated for C₂₅H₃₀N₈O₄³⁵Cl₂(M⁺) 576,1767; found 576,1751.

Example 4

Synthesis of 2-chloro-5-((5-(1((6-chloropyridin-3-yl)methyl)-4,5-dihydro-1H-imidazol-2-yl)-1,5-dinitrophenol-1,4-dienyl)-4,5-dihydroimidazole-1-yl)methyl)pyridine (compound 39)

In a 50 ml round bottom flask was added 1.27 g (0,005 mol) of 2-chloro-5-((2-(nitromethylene)imidazolidine-1-yl)methyl)pyridine, 30 ml of dry acetonitrile, determined as 0.720 g (0.01 mol) of malonic aldehyde and a catalytic amount of HCl. The reaction mixture was stirred at K.T. and monitored by TLC. After the mixture is evaporated to remove solvent and purified column chromatography to obtain the final product in the form of a pale yellow powder with a yield of 52%.

TPL=136,5-137,8°C;¹H NMR (400 MHz, DMSO-d₆): δ 8.34 per (d, J=2.4 Hz, 2H), 7,82 (dd, J₁=2.4 Hz, J₂=8,4 Hz, 2H), 7,47 (d, J=8,4 Hz, 2H), 4,96 (t, J=2,8 Hz, 2H), to 4.81 (d, J=15,8 Hz, 2H), of 4.44 (d, J=15,8 Hz, 2H), 3,92-of 3.97 (m, 4H), 3,65-and 3.72 (m, 2H), 3.49 points of 3.56 (m, 2H), 1,92-of 1.93 (m, 2H) million^-1;¹³With NMR (100 MHz, DMSO-d₆): δ 155,3, 147,9, 147,8, 138,0, 130,9, 122,7, 104,8, 50,2, 48,9, 48,5, 48,5, 28,1 million^-1; MVR (ES+) calculated for C₂₃H₂₃N₈O₄³⁵Cl₂(M+N)⁺545,1219; found 545,1201. Calculated for C₂₃H₂₃N₈O₄³⁵Cl³⁷Cl (M+H)⁺547,1190; found 547,1178. Calculated for C₂₃H₂₃N₈O₄³⁷Cl₂(M+N)⁺549,1160; found 549,1181.

Example 5

Synthesis of 1-((2-chlorothiazole-5-yl)methyl)-5-(1-((2-chlorothiazole-5-yl)methyl)-4,5-dihydro-1H-imidazol-2-yl)-1,5-dinitrophenol-1,4-dienyl)-4,5-dihydro-1H-imidazole (compound 41)

Following the method described in Examples is e 1, 0.03 mol of 2-chloro-5-(chloromethyl)thiazole was used instead of 2-chloro-5-(chloromethyl)pyridine as starting substances and obtained 1-((2-chlorothiazole-5-yl)methyl)-2-(nitromethylene)imidazolidine at exit 56%. LC-MS (m/s) 226 (24), 132 (100), 77 (9).

Synthesis of 1-((2-chlorothiazole-5-yl)methyl)-5-(1-((2-chlorothiazole-5-yl)methyl)-4,5-dihydro-1H-imidazol-2-yl)-1,5-dinitrophenol-1,4-dienyl)-4,5-dihydro-1H-imidazole

In a 50 ml round bottom flask was added to 1.30 g (0,005 mol) 1-((2-chlorothiazole-5-yl)methyl)-2-(nitromethylene)imidazolidine, 30 ml of dry acetonitrile, determined as 0.720 g (0.01 mol) of malonic aldehyde and a catalytic amount of concentrated HCl. The reaction mixture was stirred at K.T. and monitored no TCX. After the mixture is evaporated to remove solvent and purified column chromatography to obtain the final product in the form of a pale yellow powder in a yield of 44%.

TPL=138,6-139,9°C;¹H NMR (400 MHz, DMSO-d₆): δ 7,63 (s, 1H), to 4.98 (t, J=2,8 Hz, 2H), around 4.85 (d, J=15,8 Hz, 2H), 4,43 (d, J=15,8 Hz, 2H), 3.96 points-to 3.99 (m, 4H), 3,67-3,71 (m, 2H), 3,51 of 3.56 (m, 2H), 1,95-of 1.97 (m, 2H) million^-1;¹³With NMR (100 MHz, DMSO-d₆): δ 157,6, 149,3, 138,3, 105,8, 50,6, 48,9, 48,4, 48,1, 29,1 million^-1; MCBP (ES+) calculated for C₁₉H₁₉N₈O₄S₂³⁵Cl₂(M+N)⁺557,0348; found 557,0363 calculated for C₁₉H₁₉N₈O₄S₂³⁵Cl³⁷Cl (M+N)⁺559,0318; detecting the network 559,0620.

Example 6

Synthesis of 1-((6-chloropyridin-3-yl)methyl)-5-(1-((6-chloropyridin-3-yl)methyl)-1,4,5,6-tetrahydropyrimidin-2-yl)-1,5-dinitrophenol-1,4-dienyl)-1,4,5,6-tetrahydropyrimidine (compound 43)

In accordance with the method described in WO 2006056108 A1 and WO 2007101369 A1, 1-((6-chloropyridin-3-yl)methyl)-2-(nitromethylene)-hexahydropirimidine series were obtained from 2,42 g (0.015 mmol) of 2-chloro-5-(chloromethyl)pyridine at exit 56%; R_f=0,19 (EtOH: DHM=1:1); TPL=175,7°C-182,6°C.; LC-MS (m/s): 225 (100), 196 (9), 154 (10), 139 (11), 126 (31), 113 (10), 90 (31).

Synthesis of 1-((6-chloropyridin-3-yl)methyl)-5-(1-((6-chloropyridin-3-yl)methyl)-1,4,5,6-tetrahydropyrimidin-2-yl)-1,5-dinitrophenol-1,4-dienyl)-1,4,5,6-tetrahydropyrimidine

In a 50 ml round bottom flask was added 1,34 g (0,005 mol) 1-((6-chloropyridin-3-yl)methyl)-2-(nitromethylene)-hexahydropirimidine series, 30 ml of dry acetonitrile and determined as 0.720 g (0.01 mol) of malonic aldehyde and a catalytic amount of concentrated HCl. The reaction mixture was stirred at K.T. and monitored by TLC. After the mixture is evaporated to remove solvent and purified column chromatography to obtain the final product in the form of a pale yellow powder with a yield of 55%.

TPL=133,7-134,9°C;¹H NMR (400 MHz, DMSO-d₆): δ 8,32 (d, J=2.4 Hz, 2H), 7,81 (dd, J₁=2.4 Hz, J₂=8,4 Hz, 2H), 7,49 (d, J=8,4 Hz, 2H), is 4.93 (t, J=2,8 Hz, 2H), 4,78 (d, J=15,8 Hz, 2H), and 4.40 (d, J=15,8 Hz, 2H), 3,91-of 3.96 (m, 4H), 3,63-3,71 (m, 2H), 3,49-of 3.53 (m, 2H, 2,32-is 2.37 (m, 2H), 1,92-of 1.93 (m, 2H) million^-1;¹³With NMR (100 MHz, DMSO-d₆): δ 155,6, 148,3, 147,9, 138,0, 130,7, 122,7, 105,1, 50,2, 48,8, 48,5, 48,1, 36,2, 28,0 million^-1; MVR (ES+) calculated for C₂₅H₂₇N₈O₄³⁵Cl₂(M+H)⁺572,1454; found 572,1468; calculated for C₂₅H₂₇N₈O₄³⁵Cl³⁷Cl (M+H)⁺574,1425; found 574,1416.

Example 7

Synthesis of N-((6-chloropyridin-3-yl)methyl)-N-ethyl-2-methyl-4-nitro-8-oxa-2-Aza-bicyclo[3.2.1]Oct-3-EN-3-amine (compound 46)

In a 50 ml round bottom flask was added 1.35 g (0,005 mol) of N-((6-chloropyridin-3-yl)methyl)-N-ethyl-N'-methyl-2-nitroethene-1,1-diamine, 30 ml of dry acetonitrile, 0,860 g (0.01 mol) of succinic aldehyde and a catalytic amount of concentrated HCl. The reaction mixture was stirred at K.T. and monitored by TLC. After the mixture is evaporated to remove solvent and purified column chromatography to obtain the final product in the form of a pale yellow powder with a yield of 40%.

TPL=125,3-125,7°C;¹H NMR (400 MHz, DMSO-d₆): δ 8,72 (s, 1H), 8,27 (d, J=2.4 Hz, 1H), of 7.75 (dd, J₁=2.4 Hz, J₂=8,4 Hz, 1H), 7,58 (d, J=8,4 Hz, 1H), 5.25-in, and 5.30 (s, 2H), to 4.41-4,50 (m, 2H), 2,96-3,26 (m, 2H), 2,86 (s, 3H), 2,36-to 2.41 (m, 2H), 1,81-1,5 (m, 4H), 1,16-of 1.26 (m, 3H) million^-1;¹³With NMR (100 MHz, DMSO-d₆): δ 158,5, 154,4, 151,6, 150,8, 148,1, 139,3, 137,1, 107,8, 89,5, 65,8, 49,8, 46,9, 40,6, 21,9, 20,3 million^-1; MVR (EI+) calculated for C₁₅H 21N₄O₃³⁵Cl (M⁺) 339,1224; found 339,1257. calculated for C₁₅H₂₁N₄O₃³⁷Cl (M⁺) 341,1194; found 341,1213.

Example 8

Synthesis of 1-((6-chloropyridin-3-yl)methyl)-9-nitro-2,3,5,6,7,8-hexahydro-1H-5,8-epoxidase[1,2-a]azepine (compound 52)

In a 50 ml round bottom flask was added 1.27 g (0,005 mol) of 2-chloro-5-((2-(nitromethylene)imidazolidine-1-yl)methyl)pyridine, 30 ml of dry acetonitrile, 0,860 g (0.01 mol) of succinic aldehyde and a catalytic amount of concentrated HCl. The reaction mixture was stirred at K.T. and monitored by TLC. After the mixture is evaporated to remove solvent and purified column chromatography to obtain the final product in the form of a pale yellow powder with a yield of 71%.

TPL=of 149.0-150,0°C;¹H NMR (400 MHz, DMSO-d₆): δ 8,35 (d, J=2.4 Hz, 1H), 7,81 (dd, J₁=2.4 Hz, J₂=8,4 Hz, 1H), 7,51 (d, J=8,4 Hz, 1H), are 5.36 of 5.39 (s, 2H), 5,00 (d, J=15.6 Hz, 1H), and 4.68 (d, J=15.6 Hz, 1H), 3,57-to 3.73 (m, 4H), 1,94-2,04 (m, 4H) ppm;¹³C NMR (100 MHz, DMSO-d₆): δ 155,6, 149,7, 149,6, 139,7, 132,6, 124,5, 109,6, 87,0, 75,1, 51,2, 50,3, 46,6, 31,9, 31,7 million^-1; MVR (ES+) calculated for C₁₄H₁₆N₄O₃³⁵Cl (M+N)⁺323,0911; found 323,0912; calculated for C₁₄H₁₆N₄O₃³⁷Cl (M+N)⁺325.0811; found 325,0895; calculated for C₁₄H₁₅N₄O₃^{35 ClNa (M+Na)+345,0730; found 345,0722; calculated for C₁₄H₁₅N₄O₃37ClNa (M+Na)+347,0701; found 347,0692.}

Example 9

Synthesis of 1-((2-chlorothiazole-5-yl)methyl)-9-nitro-2,3,5,6,7,8-hexahydro-1H-5,8-epoxidase[1,2-a]azepine (compound 53)

In a 50 ml round bottom flask was added to 1.30 g (0,005 mol) 1-((2-chlorothiazole-5-yl)methyl)-2-(nitromethylene)imidazolidine, 30 ml of dry acetonitrile, 0,860 g (0.01 mol) of succinic aldehyde and a catalytic amount of concentrated HCl. The reaction mixture was stirred at RT and monitored by TLC. After the mixture is evaporated to remove solvent and purified column chromatography to obtain the final product in the form of a pale yellow powder with a yield of 63%.

TPL=151,7-152,1°C;¹H NMR (400 MHz, DMSO-d₆): δ 7.65 (s, 1H), 5.33-5.37 (s, 2H), 5.01 (d, J=15.6 Hz, 1H), 4.69 (d, J=15.6 Hz, 1H), 3.52-3.70 (m, 4H), 1.90-2.01 (m, 4H) million^-1;¹³With NMR (100 MHz, DMSO-d₆): δ 155.2, 149.6, 139.1, 124.5, 110.6, 87.1, 75.6, 51.3, 50.6, 46.9, 31.9, 31.2 million^-1; MVR (ES+) calculated for C₁₂H₁₅N₄O₃S³⁵Cl (M+H)⁺329,0475; found 329,0412; calculated for C₁₂H₁₅N₄O₃S³⁷Cl (M+N)⁺331,0446; found 331,0423.

Example 10

Synthesis of 1-((6-chloropyridin-3-yl)methyl)-10-nitro-1,2,3,4,6,7,8,9-octahydro-6,9-epoxidized[1,2-a]azepine (compound 61)

In a 50 ml round bottom flask was added 1,34 g (0,005 mol) of (E)-1-((6-chloropyridin-3-yl)methyl)-2-(nitromethylene)-hexahydropirimidine series, 30 ml of dry acetonitrile and 0,860 g (0.01 mol) of succinic aldehyde and a catalytic amount of concentrated HCl. The reaction mixture was stirred at K.T. and monitored by TLC. After the mixture is evaporated to remove solvent and purified column chromatography to obtain the final product in the form of a pale yellow powder with a yield of 38%.

TPL=143,2 is 144.9°C;¹H NMR (400 MHz, DMSO-d₆): δ with 8.33 (d, J=2.4 Hz, 1H), 7,80 (dd, J₁=2.4 Hz, J₂=8,4 Hz, 1H), 7,49 (d, J=8,4 Hz, 1H), 5,32 to 5.35 (s, 2H), 5,00 (d, J=15.6 Hz, 1H), 4,66 (d, J=15.6 Hz, 1H), 3,51-3,68 (m, 4H), 2,33-to 2.41 (m, 2H), 1,89 is 2.00 (m, 4H) million^-1;¹³With NMR (100 MHz, DMSO-d₆): δ 155,5, 149,6, 149,3, 139,7, 132,6, 124,1, 109,3, 86,6, 75,1, 51,2, 50,7, 46,6, 32,1, 31,7, 26,9 million^-1; MVR (ES+) calculated for C₁₅H₁₉N₄O₃³⁵Cl (M+H)⁺337,1067; found 337,1015; calculated for C₁₅H₁₉N₄O₃³⁷Cl (M+H)⁺339,1038; found 339,0995.

Example 11

Synthesis of 1-((6-chloropyridin-3-yl)methyl)-2,3,5,6,7,8-hexahydro-1H-5,8-epoxidase[1,2-a]azepin-9-carbonitrile (compound 64)

In a 50 ml round bottom flask was added 1,17 g (0,005 mol) of 2-(1-((6-chloropyridin-3-yl)methyl)imidazolidin-2-ilidene)acetonitrile, 30 ml of dry acetonitrile and 0,860 g (0.01 mol) of succinic and is of elegida and a catalytic amount of concentrated HCl. The reaction mixture was stirred at K.T. and monitored by TLC. After the mixture is evaporated to remove solvent and purified column chromatography to obtain the final product in the form of a pale yellow powder with a yield of 66%.

TPL=125,1-to 126.8°C;¹H NMR (400 MHz, DMSO-d₆): δ 8.34 per (d, J=2.4 Hz, 1H), 7,82 (dd, J₁=2.4 Hz, J₂=8,4 Hz, 1H), 7,55 (d, J=8,4 Hz, 1H), 5,33 (s, 1H), 5.25 in (s, 1H), 5,00 (d, J=15.6 Hz, 1H), 4,78 (d, J=15.6 Hz, 1H), 3,56-of 3.78 (m, 4H), 1.91 a is 2.00 (m, 4H) million^-1;¹³With NMR (100 MHz, DMSO-d₆): δ 153,6, 149,0, 148,6, 139,7, 132,3, 121,5, 99,6, 87,3, 75,7, 51,3, 50,2, 46,6, 31,5, 29,7 million^-1; MVR (ES+) calculated for C₁₅H₁₆N₄O³⁵Cl (M+N)⁺303,1013; found 303,0992; calculated for C₁₅H₁₆N₄O³⁷Cl (M+H)⁺305,0983; found 305,0957.

Example 12

Synthesis of 1-((6-chloropyridin-3-yl)methyl)-10-nitro-1,2,3,5,6,7,8,9-octahydro-5,9-epoxidase[1,2-a]azocine (compound 77)

In a 50 ml round bottom flask was added 1.27 g (0,005 mol) of 2-chloro-5-((2-(nitromethylene)imidazolidine-1-yl)methyl)pyridine, 30 ml of acetonitrile, 3 ml of 25% aqueous glutaraldehyde (0,0075 mole of glutaraldehyde) and a catalytic amount of concentrated HCl. The reaction mixture was stirred at RT and monitored by TLC. After the mixture is evaporated to remove solvent and purified column chromatography to obtain of course what about the product as a pale yellow powder with a yield of 86%.

TPL=174,7-175,4°C;¹H NMR (400 MHz, DMSO-d₆): δ scored 8.38 (dd, J₁=0.6 Hz, J₂=2.4 Hz, 1H), to 7.84 (dd, J₁=2.4 Hz, J₂=8,4 Hz, 1H), 7,52 (dd, J₁=0.6 Hz, J₂=8,4 Hz, 1H), 5,12 (s, 1H), 5,04-of 5.05 (m, 1H), equal to 4.97 (d, J=15.6 Hz, 1H), 4,71 (d, J=15.6 Hz, 1H), 3,62-3,74 (m, 4H), 1,66-of 1.81 (m, 4H), 1,51-of 1.55 (m, 1H), 1.32 to the 1.44 (m, 1H) million^-1;¹³With NMR (100 MHz, DMSO-d₆): δ 156,6, 149,7, 149,6, 139,7, 132,9, 124,5, 105,8, 81,7, 68,9, 51,7, 50,0, 46,3, 28,8, 27,2, 14,8 million^-1; MVR (EI+) calculated for C₁₅H₁₇N₄O₃³⁵Cl (M⁺) 336,0989; found 336,0988; calculated for C₁₅H₁₇N₄O₃³⁷Cl (M⁺) 338,0960; found 338,0968.

Example 13

Synthesis of 10-nitro-1-((tetrahydrofuran-3-yl)methyl)-1,2,3,5,6,7,8,9-octahydro-5,9-epoxidase[1,2-a]azocine (compound 80)

Following the method described in Example 1, 0.2 mol of 3-(chloromethyl)tetrahydrofuran (THF) was used instead of 2-chloro-5-(chloromethyl)pyridine as starting substances. Received 2-(nitromethylene)-1-((tetrahydrofuran-3-yl)methyl)imidazolidin at exit 51%. LC-MS (m/s) 177 (29), 99 (100), 56 (9).

Synthesis of 10-nitro-1-((tetrahydrofuran-3-yl)methyl)-1,2,3,5,6,7,8,9-octahydro-5,9-epoxidase[1,2-a]azocine

In a 50 ml round bottom flask was added 1,065 g (0,005 mol) of 2-(nitromethylene)-1-((tetrahydrofuran-3-yl)methyl)imidazolidine, 30 ml of acetonitrile, 3 ml of 25% aqueous glutaraldehyde (0,0075 mole of glutaraldehyde) and a catalytic amount to zentrierung HCl. The reaction mixture was stirred at K.T. and monitored by TLC. After the mixture is evaporated to remove solvent and purified column chromatography to obtain the final product in the form of a pale yellow powder with a yield of 36%.

TPL=115,3-116,9°C;¹H NMR (400 MHz, DMSO-d₆): δ 5,11 (s, 1H), 5,00-to 5.03 (m, 1H), 4,18 (d, J=3.2 Hz, 2H), 4,05-of 4.25 (m, 2H), 3,85-of 3.96 (m, 4H), of 2.25 (m, 1H), 1,66-of 1.81 (m, 4H), 1,63 -1,64 (m, 2H), 1,57-to 1.59 (m, 2H), 1,51-of 1.55 (m, 1H), 1.32 to the 1.44 (m, 1H) million^-1;¹³With NMR (100 MHz, DMSO-d₆): 6 81,7, 80,6, 78,5, 68,9, 50,0, 49,7, 46,9, 44,6, 36,8, 33,9, 28,8, 27,2, 17,8, 14,8 million^-1; MVR (EI+) calculated for C₁₄H₂₁N₃O₄(M⁺) 295,1532; found 295,1598.

Example 14

Test for insecticidal activity of the compounds according to the invention

(1) the Test for activity against alfalfa aphid (Aphis craccivoral)

Aphids, which belong to Homoptera and have piercing-sucking mouthparts, are common insects for agricultural plants. Aphis craccivoral tested by immersion.

Test method: accurately weighed various samples independently added to N,N-dimethylformamide to obtain 10 g/l stock solution. The mixture was diluted with 0.2 ml/l aqueous solution of Triton X-100 to a concentration of 500 ppm stable After sucking on seedlings of beans adults of aphids without wings together with the bean sprouts were immersed into the breeding of 500 ppm, was removed after 5 with the Kund, and excessive breeding was aspirated blotting paper, and adults of aphids without wings incubated in a clean vessel at a constant temperature of 23°C. Each concentration was repeated 3 times, and the control group contained 0.2 ml/l aqueous solution of Triton X-100. The number of dead aphids were counted after 24 hours to calculate the mortality rate according to the following formula:

mortality (%) = (number of control live aphids - the number of processed live aphids)/control number of living aphids × 100%.

The results are shown below in tables 1-4.

(2) Test for activity against brown rice cicadas {Nilaparvata lugens)

Brown rice cicadas, which belong to Homoptera and have piercing-sucking mouthparts, are common insects for agricultural plants. Nilaparvata lugens tested by spraying.

Test method; test the connection, just prepared in acetone solution to a final concentration of 500, 250, 100, 50, 25, 12,5, 6,25, 3,13, 1,57 and 0.79 ppm Aqueous solution of acetone was used as control. Each process was repeated 3 vessels (3 times). 2 ml of the solution is uniformly sprayed on each Cup using a handheld mini-sprayer. 10 Nilaparvata lugens were introduced in each bath for 6 hours before spraying. Conducted three series of experiments. The death toll Nilaparvata lugens were counted after 24 hours to calculate SMARTNET is using the above formula. The results are presented below in tables 1-4.

(3) Test for activity against caterpillars, affecting crop plants (Pseudaletia separate Walker)

Larvae that infect crop plants, was tested by feeding submerged leaves. Test the connection, just prepared in acetone solution to a final concentration of 500, 250, 100, 50, 25, 12,5, 6,25, 3,13, 1,57 and 0.79 ppm Aqueous solution of acetone was used as control. Fresh corn leaves were immersed into the solution for 3 seconds and dried at room temperature and used for feeding the test insects. Each process was repeated 3 times, and each experiment was tested 10 caterpillars. The number of dead larvae were counted after 24 hours to calculate mortality using the above formula. The results are presented below in tables 1-4.

(4) Test for activity against Diamondback moth (Plutella xylostella)

Diamondback moth was tested by feeding submerged leaves. Fresh cabbage leaves were immersed in the above solution for 3 seconds and dried at room temperature and used for feeding the test insects. Each process was repeated 3 times, and each experiment was tested 10 cabbage moths. The death toll cabbage moths were counted after 24 hours to calculate mortality using seumanutafa formula. The results are presented below in tables 1-4.

Table 1
Insecticidal activity of the compounds of formula (A)
Conn. No.	R1	R2	R3	R4	Y	Insecticidal activity
Aphid alfalfa	Brown rice Cicada	Caterpillar cereal	The cabbage moth
Mortality (100%) 500 ppm	Mortality (100%) 500 ppm	Mortality (100%) 500 ppm	Mortality (100%) 500 ppm
1		H	C2H5	CH3	NO2	80	91	100	100
2		CH3	C2H5	CH3	NO2	100	100	100	100
3		C2H5	C2H5	CH3	NO2	100	100	100	100
4		With3H7	C2H5	CH3	NO2	100	100	100	100
5		i-C3H7	With2H5	CH3	NO2	100	100	100	100
6		benzil	C2H5	CH3	NO2	100	100	100	100
7		H	N	CH3	NO2	24	35	35	21
8		CH3	N	CH3	NO2	45	44	67	56
9		C2H5	N	CH3	NO2	89	87	100	100
10		With3H7	N	CH3	NO2	45	36	87	90
11		i-C3H7	N	CH3	NO2	76	90	95	100
12		benzil	N	CH3	NO2	67	92	97	100
13		N	R3and R4together form-CH2-CH2	NO2	NO2	85	100	100
14		CH3	R3and R4together form-CH2-CH2	NO2	100	100	100	100
15		C2H5	R3and R4together form-CH2-CH2	NO2	100	100	100	100
16		With3H7	R3and R4together form-CH2-CH2	NO2	100	100	100	100
17		i-C3H7	R3and R4together form-CH2-CH2	NO2	100	100	100	100
18		benzil	R3and R4together form-CH2-CH2	NO2	100	100	100	100
19		N	R 3and R4together form-CH2-CH2	CN	90	100	100	100
20		N	R3and R4together form-CH2-CH2	CN	98	100	100	100
21		N	R3and R4together form-CH2-	CN	100	100	100	100
			CH2-
22		H	CN	73	100	92	100
23		H	R3and R4together form-CH2-CH2	CN	56	87	87	100
24		H	R3and R4together form-CH2-CH2	CN	65	83	90	100
25		H	R3and R4together form-CH2-CH2	NO2	89	87	100	100
26		H	R3and R4together form-CH2-CH2	NO2	100	100	100	100
27		H	R3and R4together form-CH2-CH2	NO2	100	100	100	100
28		H	R3and R4together form-CH2-CH2	NO2	100	100	100	100
29		H	R3and R4together form-CH2-CH2	NO2	100	100	100	100
30		H	R3and R4together form-CH2-CH2-CH2-	NO2	100	100	100	100
31		H	R3and R4together form-CH2-CH2-CH2-	NO2	46	77	77	83
32		H	R3and R4together form-CH2-CH2-CH2-	NO2	65	61	87	92
33		H	R3and R4together form-CH2-CH2-CH2-	NO2	32	50	58	52
34		H	R3and R4together form-CH2-CH2-CH2-	NO2	76	88	90	86
35		H	R3and R4together form-CH2-CH2-CH2-	NO2	76	90	68	77
36		H	R3and R4together form-CH2-CH2-CH2-	NO2	87	97	100	100

Table 2
Insecticidal activity of the compounds of formula (In)
Conn. No.	R1	R3	R4	Y	Insecticidal activity
Aphid alfalfa	Aphid alfalfa	Aphid alfalfa	Aphid alfalfa
Mortality (100%) 500 ppm	Mortality (100%) 500 ppm	Mortality (100%) 500 ppm	Mortality (100%) 500 ppm
37		C2H5	CH3	NO2	100	100	100	100
38		H	CH3	NO2	100	100	100	100
39		R3and R4together form-CH2-CH2	NO2	NO2	100	100	100
40		R3and R4together form-CH2-CH2	CN	56	87	87	100
41		R3and R4together form-CH2-CH2	NO2	100	100	100	100
42		R3and R4together form-CH2-CH2	NO2	100	100	100	100
43		R3and R4together form-CH2-CH2-CH2-	NO2	78	87	100	96

Table 4
Insecticidal activity of the compounds of formula (D)
Conn. No.	R1	R3	R4	R7 , R8, R9	Y	Insecticidal activity
Aphid alfalfa	Aphid alfalfa	Aphid alfalfa	Aphid alfalfa
Mortality (100%) 500 ppm	Mortality (100%) 500 ppm	Mortality (100%) 500 ppm	Mortality (100%) 500 ppm
75		C2H5	CH3	H	NO2	100	100	100	100
76		H	CH3	H	NO2	100	100	100	100
77		R3and R4together form-CH2-CH2	H	NO2	100	100	100	100
78		R3and R4together form-CH2-CH2	H	CN	56	87	87	100
79		R3and R4together form-CH2-CH2	H	NO2	100	100	100	100
80		R3and R4together form-CH2-CH2	H	NO2	100	100	100	100
81		R3and R4together form-CH2-CH2-CH2-	H	NO2	78	87	100	96

Example 15

Getting insecticidal compositions containing the active compound according to the invention

a) Oil suspension

Prepared from the following ingredients: 25 wt.% any compounds selected from compounds 1-73; 5 wt.% polyoxyethylenesorbitan of hexalate and 70 wt.% higher aliphatic hydrocarbon oils. All components was ground in a sand mill until such time as solid granules was reduced to less than about 5 micrometers. The resulting viscous slurry can be used directly or used after emulsification in water.

b) suspension in Water

Was prepared following components: 25 wt.% any compounds selected from compounds 1-73; 3 wt.% hydrate of attapulgite; 10 wt.% calcium lignosulfonate; 0.5 wt.% sodium dihydrophosphate and 61.5 wt.% water. All components were crushed in a ball mill until such time as solid granules was reduced to the size of the RA less than about 10 micrometers. The aqueous suspension can be used directly.

C) Preparation of bait

Prepared from the following ingredients: 0.1 to 10 wt.% any compounds selected from compounds 1-73; 80 wt.% wheat flour and 19.9-10 wt.% the molasses. All the ingredients are sufficiently mixed, and if necessary formed. Food bait can be swallowed, or it can be distributed in a domestic or industrial areas, such as kitchen, hospital, store, and outdoors in the area affected by insects that are harmful to the health of the population.

All documents cited in this application are included in the invention by reference, as if each was incorporated individually. In addition, it should be clear that in light of the above provisions, the invention is a specialist in the art can make various changes or modifications of the invention, and these equivalents will, however, be within the scope of the invention defined below by the claims.

Additional example 1:

Stage 1. Synthesis of N-benzyl-1,2-academia

Benzylchloride (1.26 g, 10 mmol) was dissolved in anhydrous ethanol (40 ml), the mixture was stirred in an ice bath was added anhydrous amandemen (50 mmol). The solution became yellow. After adding a mixture of peremeci the Ali at room temperature for 24 hours and monitored by TLC. After completion the mixture was filtered, and the filtrate was evaporated to remove ethanol. To the residue was added water and was extracted with the mixture using CH₂Cl₂(30 ml × 10). The organic phases were combined, dried over Na₂SO₄and concentrated to obtain the final product as a yellow oil (0,627, Output: 41,8%).

Stage 2. Synthesis of ((2-(nitromethylene)imidazolin-1-yl)methyl)benzene

N-benzyl-1,2-amandemen (10 mmol) was dissolved in anhydrous ethanol (10 ml) was added (2-nitroethylene-1,1-diyl)bis(methylsulfanyl) (1,61 g, 10 mmol). The mixture was boiled under reflux and monitored by TLC. After the mixture was cooled to room temperature and filtered. The filter cake was washed with ethyl acetate three times and dried to obtain the target product (1,012, Yield: 46%).

Stage 3. Synthesis of 1-benzyl-9-nitro-2,3,5,6,7,8-hexahydro-1H-5,8-epoxidase[1,2-a]azepine

The target compound was obtained by the method according to Example 8 except that 2-chloro-5-((2-(nitromethylene)imidazolidine-1-yl)methyl)pyridine was replaced by ((2-(nitromethylene)imidazolidine-1-yl)methyl)benzene. The yield was 30%.

MP. of 124.7-125,6°C,

¹H NMR (400 MHz, DMSO-d6) δ 8,54 (d, J=2.2 Hz, 1 H), 8,51 (dd, J=4,8, 1.7 Hz, 1H), 7,74 (dt, J=7,8, 2.0 Hz, 2H), 7,39 (dd, J=7,8, a 4.7 Hz, 1H), 5,39 (d, J=4.5 Hz, 2H), to 5.03 (d,J=to 15.4 Hz, 1H), amounts to 4.76 (d, aJ=to 15.4 Hz, 1H),3,76-3,59 (m, 4H), 2,07-of 1.92 (m,4H).¹³With NMR (100 MHz, DMSO) δ 155,60; 149,44; 149,15; 135,95; 135,95; 132,81; 124,00; 109,66; 87,00; 75,19; 51,75; 50,23; 46,67; 31,84; 31,65. (ES+) calculated for C₁₄H₁₆N₄O₃(M+N)⁺, 288,1270; found 288,1301.

Additional example 2:

1. Synthesis of N-((pyridin-3-yl)methyl)-1,2-academia

Specified in the title compound was obtained according to Stage 1 of Additional example 1, except that benzylchloride substituted 3-chloromethyl-pyridine hydrochloride. The output was 41.8%.

2. 3-((2-(trifluoromethyl)Sulfuryl-vinyl)imidazolidin-1-yl)methyl)pyridine

The connection specified in the header, obtained according to Stage 2 Extra example 1, except that used other source materials, as indicated in the reaction scheme. The yield was 48%.

3. Synthesis of 1-(pyridin-3-yl)methyl)-9-(trifluoromethyl)Sulfuryl-2,3,5,6,7,8-hexahydro-1H-5,8-epoxidase[1,2-a]azepine

The connection specified in the header, obtained according to Stage 3 Additional example 1, except that used other source materials, as indicated in the reaction scheme. The yield was 36%.

¹H NMR (400 MHz, DMSO-d6) δ charged 8.52 (d, J=2.2 Hz, 1 H), to 8.45 (dd, J=4,8, 1.7 Hz, 1H), 7,86 (dt, J=7,8, 2.0 Hz, 1H), 7,38 (dd, J=7,8, a 4.7 Hz, 1H), 4,88 (d, J=4.5 Hz, 2H), 4,43 (d, J=to 15.4 Hz, 1H), 4.26 deaths (d, J=to 15.4 Hz, 1H), was 2.76 at 2.59 (m, 4H, 2,05-of 1.73 (m, 4H).¹³With NMR (100 MHz, DMSO) δ 157,80; 154,70; 148,55; 147,35; 135,51; 135,60; 123,06; 107,90; 88,71; 66,51; 58,30; 53,76; 51,49; 35,51; 27,52.

Additional example 3:

1. Synthesis of N-((2-chloro-pyridin-5-yl)methyl)-1,2-academia

The connection specified in the header, obtained according to Stage 1 of Additional example 1, except that used other source materials, as indicated in the reaction scheme. The output amounted to 47.2%.

2. Synthesis of 2-chloro-5-((2-(trifluoromethyl-vinyl)imidazolidin-1-yl)methyl)pyridine

The connection specified in the header, obtained according to Stage 2 Extra example 1, except that used other source materials, as indicated in the reaction scheme. The yield was 57%.

3. Synthesis of 1-(2-chloro-pyridin-5-yl)methyl)-9-trifluoromethyl-2,3,5,6,7,8-hexahydro-1H-5,8-epoxidase[1,2-a]azepine

The connection specified in the header, obtained according to Stage 3 Additional example 1, except that used other source materials, as indicated in the reaction scheme. The yield was 61%.

¹H NMR (400 MHz, DMSO-d6) δ charged 8.52 (d, J=2.2 Hz, 1 H), 7,86 (dt, J=7,8, 2.0 Hz, 1H), 7,38 (dd, J=7,8, a 4.7 Hz, 1H), 4,82 (d, J=4.5 Hz, 2H), 4,34 (d, J=to 15.4 Hz, 1 H), 4.26 deaths (d,J=to 15.4 Hz, 1H), 2,67 at 2.59 (m, 4H), 2,15-of 1.73 (m, 4H).

¹³With NMR (100 MHz, DMSO) δ 155,00; 148,50; 147,53; 135,51; 135,60; 123,06; 113,73; 108,29; 86,01; 58,57 58,31; 53,96; 52,24; 35,45; 28,62.

Additional example 4:

1. Synthesis of N-((5-chlorothiazole-2-yl)methyl)-1,2-academia

The connection specified in the header, obtained according to Stage 1 of Additional example 1, except that used other source materials, as indicated in the reaction scheme. The output amounted to 39.1%.

2. Synthesis of 5-chloro-2-((2-(triptoreline-vinyl)imidazolidin-1-yl)methyl)thiazole

The connection specified in the header, obtained according to Stage 2 Extra example 1, except that used other source materials, as indicated in the reaction scheme. The yield was 44%.

3. Synthesis of 1-(5-chlorothiazole-2-yl)methyl)-9-three formatosi-2,3,5,6,7,8-escogido-1H-5,8-Apostolides[1,2-a]azepine

The connection specified in the header, obtained according to Stage 3 Additional example 1, except that used other source materials, as indicated in the reaction scheme. The yield was 48%.

¹H NMR (400 MHz, DMSO-d6) δ 7,49 (s, 1H), 4,88 (d, J=4.5 Hz, 2H), 4,43 (d, J=to 15.4 Hz, 1H), 4.26 deaths (d, J=to 15.4 Hz, 1H), 2,67 at 2.59 (m, 4H), 2,15-of 1.73 (m, 4H).

¹³With NMR (100 MHz, DMSO) δ 168,60; 138,53; 121,30; 123,05; 115,70; 108,29; 106,04; 79,11; 58,35; 53,96; 52,24; 35,45; 25,26.

Additional example 5:

Insecticidal activity of the compounds obtained according to Additional examples, what am 1-4 were tested in the same way, as in Example 14.

The test results showed that the mortality of the aphid alfalfa, brown rice cicadas, caterpillars, affecting crop plants, and cabbage moth was 90~100% at 500 million^-1.

			Insecticidal activity
Connection	R1	Y	aphid alfalfa	Brown rice Cicada	Caterpillar cereal	Diamondback moth
Mortality (100%) 500 million-1	Mortality (100%) 500 million-1	Mortality (100%) 500 million-1	Mortality (100%) 500 million-1
Additional example 1		-NO2	95	100	90	90
Additional example 2			100	100	100	100
Additional example 3			100	100	100	100
Additional example 3			100	100	100	100

Additional example 6: Synthesis of compound I-1

Compound 13 (0.01 mol) was subjected to a reaction with benzyl bromide (0.01 mol) in the presence of triethanolamine (TEA) (0.01 mol) in MeCN (30 ml) at room temperature. Monitored the reaction by TLC. After the mixture was evaporated to remove solvent, and the resulting mixture was purified column chromatography to obtain the final compounds. Yield: 85%.

TPL=168,1-168,9°C;

¹H NMR (400 MHz; DMSO-d₆): δ 8,42 (d; J=2.0 Hz; 1H); 8,39 (d; J=2.0 Hz; 1H); 7,81-7,86 (m; 2H); to 7.64 (d, J=8.0 Hz; 2H); 7,49-7,53 (m; 2H);7,47 (t; J=8.0 Hz; 1H); 7,41 (d; J=8.0 Hz; 2H); 6,51(d; J=7.2 Hz; 1H); from 6.22 (s; 2H); 5,34 (d; J=15.2 Hz; 1H); 5,18 (d; J=15.2 Hz; 1H); 4,84 (dd; J1=2.4 Hz; J2=7.2 Hz; 1H); 4.75 V (d; J=16,8 Hz; 1H); 4.63 to (d; J=16,8 Hz; 1H); 3.96 points (d; J=2,4 Hz; 1H); 3,84-3,92 (m; 2H); 3,63-3,81 (m; 5H); 3,35 is-3.45 (m; 1H) ppm;¹³C NMR (100 MHz; DMSO-d₆): δ 154,9; 151,3; 150,0; 149,3; 137,1; 136,0; 128,3; 128,2; 125,2; 104,3; 84,6; 71,1; 54,6; 52,6; 44,5 ppm;

Mass spectrometry high resolution (ES+) calculated for C₂₉H₂₉³⁵Cl₂N₈O₅(M+H)⁺639,1560; found 639,1566. Calculated for C₂₉H₂₉³⁷Cl₂N₈O₅(M+H)⁺643,1560; found 643,1560.

Additional example 7: Synthesis of compound I-2

Compound I-2 was obtained according to example 5, except that used other source materials, as shown in the reaction scheme. Yield: 83%.

TPL=169, 5mm of 171.2°C;

¹H NMR (400 MHz, DMSO-d₆): δ to 8.41 (d, J=2.0 Hz; 1H); to 8.34 (d, J=2.0 Hz; 1H); 7,80-a 7.85 (m; 2H); 7,63 (d; J=8.0 Hz; 2H); 7,47-7,52 (m; 2H); 7,40 (d; J=8.0 Hz; 2H); 6,50 (d; J=7.2 Hz; 1H); 6,21 (s; 2H); 5,62 (s; 2H); 5,34 (d; J=15.2 Hz; 1H); 5,15 (d; J=15.2 Hz; 1H); 4.80 to (dd; J1=2.4 Hz; J2=7.2 Hz; 1H); to 4.81 (d; J=16,8 Hz; 1H); 4,62 (d; J=16,8 Hz; 1H); to 3.92 (d, J=2,4 Hz; 1H); 3,82-3,92 (m; 2H); 3,62-3,81 (m; 5H); 3,32-3,39 (m; 1H) ppm;¹³C NMR (100 MHz; DMSO-d₆): δ 154,9; 151,4; 151,3; 150,0; 149,3; 136,0; 135,4; 130,4; 129,7; 128,7; 125,2; 104,3; 84,5; 71,1; 54,6; 52,8; 47,1; 44,5 ppm;

Mass spectrometry high resolution (ES+)calculated for C₃₀H₃₀N₈O₅³⁵Cl₃(M+H)⁺687,1326; obnarujeno 687,1320. Calculated for C₃₀H₃₀N₈O₅³⁷Cl₃(M+H)⁺689,1326; found 689,1320.

Additional example 8: Synthesis of compound I-3

Compound I-3 was obtained according to example 5 except that used other source materials, as shown in the reaction scheme. Yield: 73%.

TPL=202,2-203,1°C;

¹H NMR (400 MHz; DMSO-d₆): δ 8,43 (d; J=2.0 Hz; 1H); of 8.37 (d, J=2.0 Hz; 1H); 7,82-a 7.85 (m; 2H); the 7.65 (d, J=8.0 Hz; 2H); 7,44-7,50 (m; 2H); of 7.48 (t, J=8.0 Hz; 1H); 7,40 (d; J=8.0 Hz; 2H); is 6.61 (d, J=7,2 Hz; 1H); 5,35 (d; J=15,2 Hz; 1H); 5,18 (d; J=15.2 Hz; 1H); 4,82 (dd; J1=2.4 Hz; J2=7.2 Hz; 1H); 4.72 in (d; J=16,8 Hz; 1H); with 4.64 (d; J=16,8 Hz; 1H); 3,93 (d; J=2,4 Hz; 1H); 3,84-3,92 (m; 2H); 3,67-3,81 (m; 5H); of 3.25 to 3.35 (m; 1H) ppm;¹³C NMR (100 MHz; DMSO-d₆): δ 151,4; 150,0; 149,3; 146,9; 136,0; 133,0; 130,0; 129,1; 128,7; 125,2; 102,7; 97,3; 54,6; 52,7; 44,5 ppm;

Mass spectrometry high resolution (ES+)calculated for C₂₈H₂₇N₈O₇³⁵Cl₂S (M+N)⁺689,1022; found 689,1008. Calculated for C₂₈H₂₇N₈O₇³⁷Cl₂S (M+H)⁺691,1022; found 691,1008.

Additional example 9: Synthesis of compound I-4

Compound I-4 was obtained according to Example 8, except that used other source materials, as shown in the reaction scheme. Yield: 62%.

TPL=128,2-129,8°C;

¹H NMR (400 MHz; DMSO-d₆): δ 8,35 (d; J=2,4 Hz; 1H); 781 (dd; L=2,4 Hz; J2=8,4 Hz; 1H); 7,51 (d; J=8,4 Hz; 1H); 7,47 (d; J=8.0 Hz; 1H); to 7.32 (t, J=8.0 Hz; 2H); 7,28 (d; J=8.0 Hz; 2H); are 5.36 (s; 2H); 5,18 (s; 2H); 5,00 (d; J=15.6 Hz; 1H); and 4.68 (d, J=15.6 Hz; 1H); 1,94-2,04 (m; 4H) ppm; 13C NMR (100 MHz; DMSO-d₆): δ 155,6:149,7; 149,6; 139,7; 132,6; 124,5; 109,6; 87,0; 75,1; 51,2; 50,3; 46,6; 31,9; 31,7 ppm;¹³With NMR (100 MHz; DMSO-d₆): δ 152,2; 150,0; 149,3; 144,7; 129,8; 125,2; 118,7; 84,4; 74,6; 56,9; 55,78; 31,6; 29,4; 14,2 ppm;

Mass spectrometry high resolution (ES+)calculated for C₁₉H₂₀N₄O₃³⁵Cl (M+H)+ 387,1146; found 387,1139. Calculated for C₁₉H₂₀N₄O₃³⁷Cl (M+H)⁺389,1146; found 389,1139.

Additional example 10: Synthesis of compound I-5

Compound I-5 was obtained according to Example 8, except that used other source materials, as shown in the reaction scheme. Yield: 68%.

TPL=130,2-130, 8mm°C;

¹H NMR (400 MHz; DMSO-d₆): δ 8,35 (d; J=2,4 Hz; 1H); 7,81 (dd; J1=2.4 Hz; J2=8,4 Hz; 1H);7,51 (d; J=8,4 Hz; 1H); are 5.36 (s; 2H); 5,18 (s; 2H); 5,00 (d; J=15.6 Hz; 1H); and 4.68 (d, J=15.6 Hz; 1H); 3,35 (s; ZN); 2,85 (s; 2H);1,94-2,04 (m; 4H) ppm;¹³C NMR (100 MHz; DMSO-d₆): δ 156,1; 149,2; 135,4; 132,3; 124,7; 88,4; 81,4; 74,6; 56,6; 48,8; 30,8; 27,9 ppm;

Mass spectrometry high resolution (ES+)calculated for C₁₄H₁₈N₄O₄³⁵Cl (M+H)⁺341,0938; found 341,0933. Calculated for C₁₄H₁₈N₄O₄³⁷Cl (M+H)⁺343,0938; found 343,0933.

Additional example 11: Synthesis of connection is through the I-6

Compound I-6 was obtained according to Example 8, except that used other source materials, as shown in the reaction scheme. Yield: 71%.

TPL=144,2-145,8°C;

¹H NMR (400 MHz; DMSO-d₆): δ 8,32 (d; J=2,4 Hz; 1H); to 7.84 (dd; L=2,4 Hz; J2=8,4 Hz; 1H); EUR 7.57 (d, J=8,4 Hz; 1H); from 5.29 (s; 2H); 5,15(s; 2H); 5,10 (d; J=15.6 Hz; 1H); 4,78 (d; J=15.6 Hz; 1H); 3,37 (s; 3H); 1,94-2,00 (m; 4H) ppm;¹³C NMR (100 MHz; DMSO-d₆): δ 162,4; 156,5; 149,2; 135,4; 124,7; 88,1; 74,6; 53,5; 48,8; 31,3; 27,9 ppm;

Mass spectrometry high resolution (ES+)calculated for C₁₄H₁₆N₄O₅³⁵Cl (M+N)⁺355,0731; found 355,0723. Calculated for C₁₄H₁₆N₄O₅³⁷Cl (M+N)⁺357,0731; found 357,0723.

Additional example 12: Synthesis of compound I-7

Compound I-7 was obtained according to Example 8, except that used other source materials, as shown in the reaction scheme. Yield: 72%.

TPL=158,2-159,8°C;

¹H NMR (400 MHz; DMSO-d₆): δ 8,32 (d; J=2,4 Hz; 1H); 7,80 (dd; J1=2.4 Hz; J2=8,4 Hz; 1H); 7,54 (d; J=8,4 Hz; 1H); 7,42 (d; J=8.0 Hz; 1H); 7,22 (d; J=8.0 Hz; 2H); 5,34 (s; 2H); 5,11 (s; 2H); 5,02 (d; J=15.6 Hz; 1H); 4,67 (d; J=the 15.6 Hz; 1H); 1,92 is 2.01 (m; 4H) ppm;¹³C NMR (100 MHz; DMSO-d₆): δ 155,6; 149,7; 149,6; 139,7; 132,6; 124,5; 109,6; 87,0; 75,1; 51,2; 50,3; 46,6; 31,9; 31,7 ppm;¹³With NMR (100 MHz; DMSO-d₆): δ 170,3; 151,0; 150,2; 148,6; 143,5; 135,8; 134,9; 129,8; 129,0; 127,7; 124,8; 84,4; 74,6; 47,9; 31,6; 30,8; 29,4 ppm;

Wt is spectrometry high resolution (ES+), calculated for C₂₀H₁₉N₄O₄Br³⁵Cl (M+H)⁺493,0200; found 493,0191. Calculated for C₂₀H₁₉N₄O₄Br³⁷Cl (M+H)⁺495,0200; found 495,0191.

Additional example 13: Synthesis of compound I-8

Compound I-8 was obtained according to Example 8, except that used other source materials, as shown in the reaction scheme.

Yield: 66%.

TPL=138,2-139,7°C;

¹H NMR (400 MHz; DMSO-d₆): δ 8,32 (d; J=2,4 Hz; 1H); 7,81 (dd; J1=2.4 Hz; J2=8,4 Hz; 1H); at 7.55 (d, J=8,4 Hz; 1H); 5,70 (s; 2H); 5,57 (s; 2H); 5,32 (s; 2H); 5,04 (d; J=15.6 Hz; 1H); br4.61 (d; J=15.6 Hz; 1H); 1,92-2,04 (m; 4H) ppm; 13C NMR (100 MHz; DMSO-d₆): δ 155,6; 149,7; 149,6; 139,7; 132,6; 124,5; 109,6; 87,0; 75,1; 51,2; 50,3; 46,6; 31,9; 31,7 ppm; 13C NMR (100 MHz; DMSO-d₆): δ 155,8; 150,0; 149,3; 136,0; 130,4; 125,2; 77,3; 70,9; 63,3; 53,9; 24,7 ppm;

Mass spectrometry high resolution (ES+)calculated for C₁₄H₁₆N₄O₄³⁵Cl (M+H)⁺339,0784; found 3390789. Calculated for C₁₄H₁₆N₄O₄³⁷Cl (M+H)⁺, 341,0784; found 341,0789.

Additional example 14: Synthesis of compound I-9

Compound I-9 was obtained according to Example 8, except that used other source materials, as shown in the reaction scheme. Yield: 63%,

TPL=168,2-169,4°C;

¹H NMR (400 MHz; DMSO-d₆): δ 8,31 (d; J=2,4 Hz; 1H); to 7.84 (dd; J1=2 Hz; J2=8,4 Hz; 1H); 7,52 (d, J=8,4 Hz; 1H); 5,71 (s; 2H); 5,57 (s; 2H); 5,31 (s; 2H); of 5.05 (d, J=15.6 Hz; 1H); br4.61 (d; J=15.6 Hz; 1H); 1.93 and-2,07 (m; 4H) ppm; 13C NMR (100 MHz; DMSO-d₆): δ 155,6; 149,7; 149,6; 139,7; 132,6; 124,5; 109,6; 87,0; 75,1; 51,2; 50,3; 46,6; 31,9; 31,7 ppm;¹³With NMR (100 MHz; DMSO-d₆): δ 178,2; 150,0; 149,3; 136,0; 130,4; 125,2; 89,2; 73,9; 57,5; 53,9; 51,5; 30,9; 27,9 ppm;

Mass spectrometry high resolution (ES+)calculated for C₁₄H₁₆N₄O₃S³⁵Cl (M+N)⁺355,0553; found 355,0559. Calculated for C₁₄H₁₆N₄O₃S³⁷Cl (M+H)⁺357,0553; found 357,0559.

Additional example 15: Synthesis of compound I-10

Compound I-10 was obtained according to Example 8, except that used other source materials, as shown in the reaction scheme. Yield: 68%.

TPL=155, 2mm-156,7°C;

¹H NMR (400 MHz; DMSO-d₆): δ 8,32 (d; J=2,4 Hz; 1H); of 7.82 (dd; J1=2.4 Hz; J2=8,4 Hz; 1H); 7,54 (d; J=8,4 Hz; 1H); 5,72 (s; 2H); 5,57 (s; 2H); 5,35 (s; 2H); 5,02 (d; J=15.6 Hz; 1H); with 4.64 (d, J=15.6 Hz; 1H); 1,94-2,07 (m; 4H); 1,15 (s; 3H) ppm;¹³C NMR (100 MHz; DMSO-d₆): 6 162,1; 150,0; 149,3; 136,0; 130,4; 125,2; 89,5; 73,9; 67,2; 56,4; 42,9; 30,9; 27,9 ppm;

Mass spectrometry high resolution (ES+)calculated for C₁₅H₁₉N₆O₃³⁵Cl (M+N)⁺352,1098; found 352,1092. Calculated for C₁₅H₁₉N₅O₃³⁷Cl (M+N)⁺354,1092; found 354,1098.

Additional example 16: Synthesis of compound I-11

Compound I-11 was obtained according to Example 8, except that used other source materials, as shown in the reaction scheme. Yield: 71%.

TPL=142,2-143,8°C;

¹H NMR (400 MHz; DMSO-d₆): δ 8,35 (d; J=2,4 Hz; 1H); of 7.82 (dd; J1=2.4 Hz; J2=8,4 Hz; 1H); 7,52 (d, J=8,4 Hz; 1H); 7,43 (d; J=8,4 Hz; 2H); to 7.32 (t, J=8,4 Hz; 1H); 7,29 (d; J=8,4 Hz; 2H); 5,72 (s; 2H); 5,54 (s; 2H); 5,32 (s; 2H); of 5.05 (d, J=15.6 Hz; 1H); to 4.62 (d, J=15.6 Hz; 1H); 1,95-2,07 (m; 4H) ppm;¹³With NMR (100 MHz; DMSO-d₆): δ 162,1; 150,0; 149,3; 146,9; 136,0; 130,4; 130,3; 125,2; 122,5; 117,7; 89,5; 73,9; 62,2; 60,5; 56,4; 30,9; 27,8 ppm;

Mass spectrometry high resolution (ES+)calculated for C₂₀H₂₁N₅O₃³⁵Cl (M+N)⁺414,1255; found 414,1263. Calculated for C₂₀H₂₁N₅O₃³⁷Cl (M+N)⁺416,1255; found 416,1263.

Additional example 17: Synthesis of compound I-12

Compound I-12 was obtained according to Example 8, except that used other source materials, as shown in the reaction scheme. Yield: 58%.

TPL=151,2-152,9°C;

¹H NMR (400 MHz; DMSO-d₆): δ 8,32 (d; J=2,4 Hz; 1H); to 7.84 (dd; J1=2.4 Hz; J2=8,4 Hz; 1H); 7,53 (d; J=8,4 Hz; 1H); 5,32 (s; 2H); to 5.03 (d, J=15.6 Hz; 1H); with 4.64 (d, J=15.6 Hz; 1H); 3,52-to 3.73 (m; 4H); 2,32 (s; 2H); 3,17 (s; 2H); 1,95-2,04 (m; 2H) ppm;¹³C NMR (100 MHz; DMSO-d₆): δ 155,6; 149,7; 149,6; 139,7; 132,6; 124,5; 109,6; 87,0; 75,1; 51,2; 50,3; 46,6; 31,9; 31,7 ppm; 13C NMR (100 MHz; DMSO-d₆): δ 171,7; 171,5; 150,0; 149,3; 136,0; 130,4; 125,2; 89,0; 71,6; 54,9; 52,2; 51,5; 50,6; 49,0 46,9 ppm;

Mass spectrometry high resolution (ES+)calculated for C₁₈H₁₉N₄O³⁵Cl (M+H)+ 439.0942; found 439,0933. Calculated for C₁₈H₁₉N₄O³⁵Cl (M+H)+, 441,0942; found 441,0933.

Additional example 18: Synthesis of compound I-13

Compound I-13 was obtained according to Example 8, except that used other source materials, as shown in the reaction scheme. Yield: 69%.

TPL=145, 2mm-146,8°C;

¹H NMR (400 MHz; DMSO-d₆): δ 8,33 (d; J=2,4 Hz; 1H); 7,81 (dd; J1=2.4 Hz; J2=8,4 Hz; 1H); 7,51 (d; J=8,4 Hz; 1H); 7,43 (t; J=8,4 Hz; 1H); 7,25-7,38 (m; 8H); 7,14 (t; J=8,4 Hz; 1H); 6,57 (s; 2H); 6,51 (s; 2H); 5,33 (s; 2H); of 5.05 (d; J=15.6 Hz; 1H); 4,67 (d; J=15.6 Hz; 1H); 3,54-to 3.73 (m; 2H); 2,32 (s; 2H); 3,21 (s; 2H); 1,98-2,04 (m; 2H) ppm; 13C NMR (100 MHz; DMSO-d₆): δ 150,0; 149,3; 136,0; 130,4; 129,1; 128,7; 127,0; 125,2; 90,5; 76,8; 58,2; 50,6; 48,1; 46,9; 34,9; 33,2 ppm;

Mass spectrometry high resolution (ES+)calculated for C₂₈H₂₈N₄O₃³⁵Cl (M+N)⁺503,1772; found 503,1763. Calculated for C₂₈H₂₈N₄O₃³⁷Cl (M+N)⁺, 505,1772; found 505,1763.

Additional example 19: Synthesis of compound I-14

Compound I-14 was obtained according to Example 8, except that used other source materials, as shown in the reaction scheme. Yield: 64%.

TPL=188,2-189,8°C;

1H NMR (400 MHz; DMSO-d₆): δ 8,35 (dd;J1=0.6 Hz; J2=2.4 Hz; 1H); of 7.82 (dd; J1=2.4 Hz; J2=8,4 Hz; 1H); 7,53 (dd; J1=0.6 Hz; J2=8,4 Hz; 1H); 5,12 (s; 1H); 5,04-of 5.06 (m; 1H); 4.92 in (d; J=15.6 Hz; 1H); 4.72 in (d; J=15.6 Hz; 1H); 3,64-3,74 (m; 4H); 3,55 (s; 3H); 1,71-of 1.84 (m; 3H); 1,51-of 1.56 (m; 1H); 1,31-1,40 (m; 1H) ppm; 13C NMR (100 MHz; DMSO-d₆): δ 157,6; 150,0; 149,3; 136,0; 130,4; 125,2; 75,6; 66,3; 54,9; 50,6; 47,7; 39,2; 32,5; 26,8 ppm;

Mass spectrometry high resolution (ES+)calculated for C₁₆H₂₀N₄O₅S³⁵Cl (M+H)+ 415,0765; found 415,0760. Calculated for C₁₆H₂₀N₄O₅S³⁷Cl (M+N)⁺, 417,0765; found 417,0760.

Additional example 20: Synthesis of compound I-15

Compound I-15 was obtained according to Example 8, except that used other source materials, as shown in the reaction scheme. Yield: 63%.

TPL=148,2-149,8°C;

¹H NMR (400 MHz; DMSO-d₆): δ 8,33 (dd; J1=0.6 Hz; J2=2.4 Hz; 1H); to 7.84 (dd; J1=2.4 Hz; J2=8,4 Hz; 1H); 7,63 (d; J=8,4 Hz; 1H); 7,41 (t; J=8,4 Hz; 2H); 7,52 (dd; J1=0.6 Hz; J2=8,4 Hz; 1H); 7,29 (d; J=8,4 Hz; 2H); 5,15 (s; 1H); 5,04-5,06 (m; 1H); to 4.98 (d, J=15.6 Hz; 1H); 4.72 in(d; J=15.6 Hz; 1H); 3,66-3,74 (m; 4H); 1,78-of 1.88 (m; 3H); of 1.52-1.55V (m; 1H); 1.32 to 1.41 for (m; 1H) ppm;¹³C NMR (100 MHz; DMSO-d₆): δ 155,9; 150,4; 149,2; 142,8; 140,2; 137,4; 136,1; 130,4; 125,6; 75,8; 66,5; 54,4; 50,8; 47,1; 32,8; 26,8 ppm;

Mass spectrometry high resolution (ES+)calculated for C₂₁H₂₂N₄O₃³⁵Cl (M+H)⁺413,1302; found 413,1311. Calculated C₂₁H₂₂N₄O₃³⁷Cl (M+H)⁺415,1295; found 415,1304.

Augment the capacity example 21:

Insecticidal activity of the compounds obtained according to Examples 5 to 20 was determined by the same method as in Example 14 of the present application.

The test showed that all compounds I-1 to I-15 have very good insecticidal activity.

1. The compound of formula (A), (B), (C) or (D), or agrokhimichesky acceptable salt,


where R₁represents 5 - or 6-membered heterocycle containing nitrogen atom, oxygen and/or sulfur, halogenosilanes 5 - or 6-membered heterocycle containing nitrogen atom, oxygen and/or sulfur, substituted or unsubstituted phenyl, where the substituents are one or more than one group selected from the group consisting of halogen atoms, C_1-4halogenoalkane or_1-4chlorococcal;
R₂represents H, C_1-8saturated or unsaturated alkyl, halogenosilanes C_1-8saturated or unsaturated alkyl, -CH₂CH₂OCH₂CH₃, -CH₂CH₂Och₃, phenyl, unsubstituted benzyl or benzyl substituted by one or more than one group selected from the group consisting of a halogen atom, a C_1-4ha is genealogie or _1-4chlorococcal,_1-4alkylsulphonyl or_1-4alkylsulfonyl;
R₃and R₄independently selected from H, C_1-6of alkyl, allyl, benzyl,_1-4alkoxy-C_1-4of alkyl, C_1-4alkoxycarbonyl, unsubstituted bentilee group or benzoline group, substituted by one or more than one group selected from the group consisting of halogen atoms, C_1-4of alkyl, C_1-4halogenoalkane,_1-4alkoxyl or C_1-4alkylsulphonyl; or R₃and R₄together form-CH₂-CH₂-, -CH₂-CH₂-CH₂- or-CH₂-XR-CH₂-where X is a heteroatom N, O and S; R is a Deputy on X and is selected from H, C_1-6of alkyl, allyl, benzyl, phenyl, C_1-4alkoxy-C_1-4of alkyl, C_1-4alkoxycarbonyl, unsubstituted bentilee group or benzoline group, substituted by one or more than one group selected from the group consisting of halogen atoms, C_1-4halogenoalkane, C_1-8saturated or unsaturated alkyl or alkoxyl or_1-4alkylcarboxylic,
R₅, R₆, R₇, R₈and R₉represents H, saturated or unsaturated C_1-4alkyl, halogen atom, saturated or unsaturated With_1-8alkoxy, saturated C_1-4halogenoalkanes,_1-4alkylsulphonyl, sub> 1-8alkilany ester, C_1-4alkylsulfonyl, phenyl, benzyl or trifloromethyl ester group;
Y represents nitro, cyano, trifluoromethyl, TRIFLUOROACETYL or trifloromethyl.

2. Connection or agrokhimichesky acceptable salt according to claim 1, where R₁selected from pyridyl, thiazolyl, tetrahydrofuryl, oxazolyl or their halogenated groups.

3. Connection or agrokhimichesky acceptable salt according to claim 1, where R₂represents H, saturated or unsaturated With_1-4alkyl, saturated or unsaturated With_1-4halogenoalkane,_1-4alkylsulphonyl, unsubstituted benzyl or benzyl substituted by one or more than one group selected from the group consisting of a halogen atom, a C_1-4halogenoalkane or_1-4chlorococcal.

4. Connection or agrokhimichesky acceptable salt according to claim 1, wherein R₃and R₄represent H, C_1-6alkyl group, or R₃and R₄together form-CH₂-CH₂- or-CH₂-CH₂-CH₂-.

5. Connection or agrokhimichesky acceptable salt according to claim 1, where R₅, R₆, R₇, R₈and R₉represent H, saturated With_1-2alkyl, halogen atom, saturated or unsaturated With_1-4alkoxyl saturated With_1-2halogenoalkanes,_1-2alkyls hanil or trifloromethyl ester group.

6. Connection or agrokhimichesky acceptable salt according to claim 1, where Y is a nitro-group or cyano.

7. Agrochemical composition having insecticidal activity, containing:
(a) 0.001 to 99.99 wt.% connection or agrokhimichesky acceptable salts according to any one of claims 1 to 6, or combinations thereof; and
(b) agrokhimichesky acceptable carrier or excipient.

8. The application of the agrochemical composition according to claim 7 for the destruction or control agricultural pests, hygiene pests and pests that are harmful to animal health.

9. The method of obtaining the compound or its agrokhimichesky acceptable salts according to any one of claims 1 to 6, comprising the following stages:
in the presence of catalytic acid and 0-60°With the interaction of the compounds of formula (a) with compound (b) by means of which one obtains the compound (A) or (B), where R₂represents H,

where R₁, R₃, R₄, R₅, R₆, R₇, R₈, R₉and Y are as defined in claim 1, and n is 0 or 1.

10. The method according to claim 9, including:
in the presence of catalytic acid carry out the following reaction at 20-30°C in acetonitrile for 2-24 h, through which they receive a connection (A), where R₂is a N:

in the presence of catalytic acid, conduct the following reaction at 20-30°C in acetonitrile for 2-24 h, whereby get connection ():
.

11. The method of obtaining the compound or its agrokhimichesky acceptable salts according to any one of claims 1 to 6, comprising the following stages:
in the presence of catalytic acid and 0-60°With the interaction of the compounds of formula (a) with compound (C) or (d), through which they receive a connection (C) or (D)

where R₁, R₃, R₄, R₅, R₆, R₇, R₈, R₉and Y are as defined in claim 1, and n is 0 or 1.

12. The method according to claim 11, including:
in the presence of catalytic acid carry out the following reaction at 10-50°C. in acetonitrile for 2-24 h, whereby get connection ():
;
in the presence of catalytic acid carry out the following reaction at 10-50°C. in acetonitrile for 2-24 h, through which they receive a connection (D):
.