Connection dehalogenation containing them insecticide/acaricidal agents, and intermediates for their production

 

(57) Abstract:

Describes new compounds of General formula (I), where Z is oxygen, X is chlorine or bromine, Y is oxygen, R2and R3each independently - halogen, or C1-C3-alkyl, R1- Q1or Q2formula where R5and R6is hydrogen or lower alkyl, R7- hydrogen, oxygen, S(O)qwhere q=0, or NR9where R9is hydrogen, C(G1G2where G1and G2oxygen, P=0-6, integer, And - heterocyclic ring group, possibly substituted (R8)rselected from pyridine , furan, thiophene, imidazole, pyrazole, triazole, isoxazol, benzothiazole, benzoxazole, N-(1,2-dihydro-2-oxo)pyridine, quinoline, N-phthalimido, benzimidazole, 1,4-benzodioxane, 1,3-dioxolane, R8- halogen, C1-C4-alkyl, C1-C3-halogenated, C1-C4-alkoxy, formyl, phenyl, possibly substituted with halogen, r=0-4, integer. The compounds exhibit insecticide/acaricidal activity and can be part of insecticide/acaricidal agents. Also describes intermediates for their production. The technical result is an increase in the activity of the above agents. 6 C. and 18 h.p. f-crystals, 14 ill. 47 table.

From the slide, for example, in JP-A 48-86835/1973 and JP-A 49-1526/1974, it is well known that some species propenoic compounds can be used as active ingredients of insecticides.

From the point of view of their insecticide/acaricide activity is impossible in all cases to argue that these compounds are effective enough to combat harmful insects, carifornai and Parasitiformes ticks.

The authors of the present invention conducted intensive research in order to find a compound having excellent insecticide/acaricidal activity. Eventually detected, and that a separate connection dehalogenate have sufficient insecticide/acaricidal activity for combating harmful insects, carifornai and Parasitiformes ticks, thereby fulfilling the present invention.

In other words, the present invention provides compounds of dehalogenation (later used as the present compound), General formula

< / BR>
in which Z represents oxygen, sulfur or NR4(in which R4represents hydrogen or C1-C3-alkyl); Y is oxygen, sulfur or NH; X & rsquo; s not 3-alkyl; t represents an integer from 0 to 2; and R1is Q1, Q2, Q3, Q4, Q5, Q6or Q7the General formula

< / BR>
< / BR>
in which A represents optionally substituted heterocyclic ring group, provided that when A represents an optionally substituted heterocyclic ring group containing two oxygen atom, and a condensed benzene ring, A represents an optionally substituted 1,3 - benzodioxole-2-yl or optionally substituted 1,4 - benzodioxan-2-yl; B is oxygen, S(O)q, NR9C(=G1G2or G1C(=G2); q represents an integer from 0 to 2; R9represents hydrogen, acetyl or C1-C3-alkyl; G1and G2independently represent oxygen or sulfur; R5, R6, R7, R11and R12independently represent hydrogen, C1-C3-alkyl or trifluoromethyl; R13and R14independently represent hydrogen, C1-C3-alkyl, trifluoromethyl or halogen; and p represents an integer from 0 to 6; and s represents an integer from 1 to 6.

In addition, the present invention provides insecticide/acaricidal agent containing as predlagajutsja the following compounds, which as intermediates suitable for receiving some of the following connections:

the connection of phenol, which is 3,5-dichloro-4-(2-(2-(4-chlorophenyl)-1,3-dioxolan-4-yl) ethoxy) phenol;

compounds of General formula

< / BR>
in which R5, R6and R7independently represent hydrogen, C1-C3-alkyl or trifluoromethyl; R15represents halogen, C1-C3-alkyl, C1-C3-halogenated, C1-C3-alkoxy or C1-C3-halogenoalkane; R2, R3and R10independently represent halogen, C1-C3-alkyl or C1-C3-halogenated; t represents an integer from 0 to 3; u represents an integer from 1 to 4; w represents integers from 1 to 4; and B1represents oxygen, S(O)qor NR9in which R9represents hydrogen, acetyl or C1-C3-alkyl, and q represents an integer from 0 to 2;

compounds of General formula [I] in which R5, R6and R7all represent hydrogen; and R2and R3independently represent halogen or C1-C3-alkyl; and

2-(3-methanesulfonylaminoethyl) -5-triptorelin.

Variables in vicepresidentes group, presents R2, R3, R4, R5, R6, R7, R9, R10, R11, R12, R13or R14are methyl, ethyl, n-propyl and isopropyl.

Examples of the halogen atom represented by R13or R14are fluorine, chlorine, bromine and iodine.

Examples of heterocyclic rings optionally substituted heterocyclic ring group represented by A are isoxazol, isothiazol, thiazole, 1,3,4-thiadiazole, pyrrole, pyridine, pyridazine, pyrimidine, pyrazin, 1,2,4-triazine, 1,3,5-triazine, indole, benzofuran, tianeptine, indazole, benzimidazole, benzotriazole, benzisoxazol, benzoxazole, benzothiazole, quinoline, isoquinoline, hensol, piperidine, piperazine, tetrahydrofuran, tetrahydropyran, pyrazoline, phthalimide, dioxane, dioxolane and benzodioxole.

Examples of the substituents in the optionally substituted heterocyclic ring group represented by A are the substituents of General formula: (R8)r(in which R8represents halogen, nitro, cyano, C1-C4-alkyl, C1-C3-halogenated, C1-C4-alkoxy, C1-C3-halogenoalkane, C1-C3-alkylthio, C1-C3-allogenicity, C2- halogenmethyl, C2-C4-halogenoalkanes, C2-C4-quinil, C2-C4-halogenoalkanes, amino, dimethylamino, acetamido, acetyl, halogenoacetyl, formyl, carboxyl, methoxycarbonyl, C3-C6-cycloalkyl, (C1-C2-alkyl)aminocarbonyl or [di(C1-C2-alkyl) amino] carbonyl, or R8represents phenyl, benzyl, phenoxy, benzyloxy or pyridyloxy, each of which is optionally substituted by halogen, C1-C4-alkyl, C1-C3-halogenated, C1-C4-alkoxy or C1-C3-halogenoalkane, r is a whole number from 0 to 7.

Examples of the halogen atom represented by R8or present in R8are fluorine, chlorine, bromine and iodine.

Examples of C1-C4is an alkyl group represented by R8or present in R8are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl.

Examples of C1-C3-halogenoalkanes group represented by R8or present in R8are trifluoromethyl, deformity, bromodifluoromethyl, 2,2,2-triptorelin, 2-foretel, 2-chloroethyl, 2-bromacil, 1-foretel, 1-chloroethyl, 1-bromacil, 2,2,3,3,3-pentafour is a system of groups, presents R8or present in R8are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and tert-butoxy.

Examples of C1-C3-halogenlampe represented by R8or present in R8are triptoreline, deformedarse, brotherlocks, 2-floratone, 2,2,2-triptoreline, 2-chloroethoxy, 2-bromoethoxy, 2-chloro-1,1,2-triptoreline, 2-bromo-1,1,2-triptoreline, 1,1,2,2-tetrafluoroethoxy, 1,2,2,3,3,3-hexaferrite, 3 forproperty, 3 chloropropoxy, 3 bromopropane, 2,2,3,3,3-pentafluoropropane, 3,3,3-cryptochromes and 1,1,2,2,2-pentaverate.

Examples of C1-C3-ancilliary represented by R8are methylthio, ethylthio, n-propylthio, isopropylthio.

Examples of C1-C3-halogenation represented by R8are triptoreline, deformality, bromodifluoromethyl, 2,2,2-triptoreline, 2-chloro, 1,1,2-triptoreline, 2-bromo-1,1,2-triptoreline, 1,1,2,2-tetrafluorethylene, 2-chloroethylthio, 2-foretelling, 2-brometalia, 3 forproperty, 3 chlorpropyl, (3 bromopropylate, 2,2,3,3,3-pentafluoropropyl and 3,3,3-cryptosporidia.

Examples of C1-C2-alkylsulfonyl, predstavnennoy, presents R8are methylsulphonyl and ethylsulfonyl.

Examples of C1-C2-halogenatedsolvents represented by R8are triptoreline, 2,2,2-triptorelin and performcalculation.

Examples of C1-C2-halogenated.sulphonated represented by R8are trifloromethyl, 2,2,2-cryptonemiales and performcalculation.

Examples of C2-C4-alkenylphenol group represented by R8are vinyl, Isopropenyl, 1-propenyl, 2-ethyl-1-propenyl, 1-methyl-1-propenyl, allyl, 2-methylpropanol and 2-butenyl.

Examples of C2-C4-halogenoalkanes group represented by R8are 2,2-dichloroethenyl, 2,2-dibromoethenyl, 3,3-dichlorethyl, 3,3-dibromoethyl, 2,3-dichlorethyl, 2,3-dibromoethyl, 2-chloro-2-propenyl, 3-chloro-2-propenyl, 2-bromo-2-propenyl and 3-chloro-2-butenyl.

Examples of C2-C4-alkenylphenol group represented by R8are ethinyl, 1-PROPYNYL, 2-PROPYNYL and 1-methyl-2-PROPYNYL.

Examples of C2-C4-halogenosilanes group represented by R8are chloramines, bromamines, iodating, 3-chloro-2-PROPYNYL, 3-bromo-2-PROPYNYL, 3-iodovanillin group, presents R8are cryptomailer and trichloracetic.

Examples of C3-C6-cycloalkyl group represented by R8are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

Examples of C5-C6-cycloalkenyl are 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl and 3-cyclohexenyl.

Examples (C1-C2-alkyl)aminocarbonyl group represented by R8are methylaminoethanol and utilization.carbons.

Examples [di(C1-C2-alkyl)amino]carbonyl group represented by R8are dimethylaminoethyl, N-methyl-N-ethylaminomethyl and diethylaminoethyl.

The following are preferred examples of this connection:

connection dehalogenation, in which A represents A 5 - or 6-membered heterocyclic ring group containing at least one oxygen, sulfur or nitrogen, and optionally substituted (R8)r(in which R8represents halogen, nitro, cyano, C1-C4-alkyl, C1-C3-halogenated, C1-C4-alkoxy, C1-C3-halogenoalkane, C1-C3-alkisti-C2-halogenallylacetic, C2-C4alkenyl, C2-C4-halogenoalkanes, C2-C4-quinil, C2-C4-halogenoalkanes, amino, dimethylamino, acetamido, acetyl, halogenoacetyl, formyl, carboxyl, methoxycarbonyl, C3-C6-cycloalkyl, (C1-C2-alkyl)aminocarbonyl or [di(C1-C2-alkyl) amino] carbonyl, or R8provides a phenyl, benzyl, phenoxy, benzyloxy or pyridyloxy, each of which is optionally substituted by halogen, C1-C4-alkyl, C1-C3-halogenated, C1-C4-alkoxy or C1-C3-halogenoalkane; r is a whole number from 0 to 7);

connection dehalogenation, in which A represents A 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-thienyl, 3-thienyl, 2-furanyl, 3 - furanyl, 5-(1,3-thiazolyl), N-(1,2-dihydro-2-oxo)-pyridine, 1,3 - DIOXOLANYL, 1,4-benzodioxane, 2-Persil, 2-benzothiazolyl, 2 - benzoxazolyl, 2-benzimidazolyl, 2-honokalani, N-benzimidazolyl, 2-chinolin, 3-chinolin or N-phthalimido, each of which is optionally substituted by (R8)r(in which R8and each r is as defined above);

connection dehalogenation, in which R2and R3independently represent halogen nezavisimo represent chlorine, bromine, methyl, ethyl or isopropyl, and t is 0;

connection dehalogenation, in which R2and R3both represent chlorine, and t is 0;

connection dehalogenation, in which R2is chlorine, R3is methyl, and t is 0;

connection dehalogenation, in which R2is ethyl, R3is methyl, and t is 0;

connection dehalogenation, in which R2and R3both represent bromine, and t is 0;

connection dehalogenation, in which R2and R3both represent ethyl, a t is 0;

connection dehalogenation, in which R2and R3independently represent halogen or C1-C3-alkyl, t. represents 1 or 2, and R10represents halogen or C1-C3-alkyl;

connection dehalogenation, in which R2and R3independently represent halogen or C1-C3-alkyl, t is 1 or 2, and R10represents halogen;

connection dehalogenation, in which Y and Z both represent oxygen;

connection dehalogenation, in which R1is Q1, p is 1-6, and A represents 2-pyridyl, 3-PI is imido, each of which is optionally substituted (R8)r(in which R8and r are each as defined above);

connection dehalogenation, in which R1is Q1, p is 1-6, R5, R6and R7all represent hydrogen, and A represents A 1,3-DIOXOLANYL, optionally substituted (R8)r(in which R8and r are each as defined above);

connection dehalogenation, in which R1is Q1, p is 1-4, R5, R6and R7all represent halogen, and A represents A 1,3-DIOXOLANYL, optionally substituted (R8)r(in which R8and r are each as defined above);

connection dehalogenation, in which R1is Q1, p represents 0, and A is 2-pyridyl, 4-pyridyl, 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, 5-(1,3-thiazolyl), 1,3-dioxolane or 1,4-benzodioxolyl, each of which is optionally substituted (R8)r(in which R8and r are each as defined above);

connection dehalogenation, in which R4is Q2;

connection dehalogenation, in which R1is Q2and A represents 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-thienyl, 2-furanyl, 3-furnishingsand or 3-chinolin, each of which is optionally substituted (R8)r(in which R8and r are each as defined above);

connection dehalogenation, in which R1is Q2, p is 1-4, and a is 2-pyridyl, optionally substituted (R8)r(in which R8and r are each as defined above);

connection dehalogenation, in which R1is Q2, p is 1-4, R5, R6and R7all represent hydrogen, and A is 2-pyridyl, optionally substituted (R8)r(in which R8and r are each as defined above);

connection dehalogenation, in which R1is Q2, p is 1-4, R5, R6and R7all represent hydrogen, A is 2-pyridyl, optionally substituted (R8)r(in which R8represents halogen or C1-C3-halogenated, a r defined above);

connection dehalogenation, in which R1is Q2p represents 2 or 3, R5, R6and R7all represent hydrogen, A is 2-pyridyl, optionally substituted (R8)r(in which R8represents halogen or C1-C3-halogenated, a r determi is 3, R5, R6and R7all represent hydrogen, A is 2-pyridyl, optionally substituted (R8)r(in which R8represents halogen or trifluoromethyl, a r defined above); and

connection dehalogenation, in which R1is Q2p represents 2 or 3, R5, R6and R7all represent hydrogen, B represents oxygen, A is 2-pyridyl, optionally substituted (R8)r(in which R8represents halogen or trifluoromethyl, a r defined above).

Below is particularly preferred examples of the present compounds, where the numbers in brackets correspond to the numbers of the compounds used next:

(36) 3,5-Dichloro-4-(3-(5-trifluoromethyl-2-pyridyloxy)propyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene;

(37) 3-Ethyl-5-methyl-4-(3-(5-trifluoromethyl-2-pyridyloxy)propyloxy)- 1-(3,3-dichloro-2-propenyloxy)benzene; and

(49) 3,5-Dichloro-4-(3-(5-trifluoromethyl-2-pyridylamino)-propyloxy)- 1-(3,3-dichloro-2-propenyloxy)benzene.

These compounds can be obtained using the following methods of obtaining A-H.

(Method of obtaining (A)

In this method, the compound of General formula;

< / BR>
in which R1, R2, R3, R102,

in which X is defined above, and L represents a halogen (e.g. chlorine, bromine, iodine), mesilate(methylsulfonylamino) or tosyloxy(tolilsulfonil).

This reaction is preferably carried out in an inert solvent in the presence of an appropriate base.

Examples of solvents that can be used are ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethers such as 1,2-dimethoxyethane, tetrahydrofuran, dioxane and disciline (for example, C1-C4) ethers (e.g. diethyl ether, diisopropyl ether); N,N-dimethylformamide, dimethylsulfoxide, sulfolan, acetonitrile, nitromethane; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane and chlorobenzene; hydrocarbons such as toluene, benzene; and water. If necessary, you can use a mixture of these solvents.

Examples of bases that can be used are hydroxides of alkali metals or alkaline earth metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; carbonates of alkali metals or alkaline earth metals such as lithium carbonate, potassium carbonate, sodium carbonate and calscale hydride and calcium hydride; the alcoholate of alkali metals (for example, C1-C4), such as sodium methylalcohol, sodium ethylalcohol and potassium, trebuchet; and organic bases such as triethylamine and pyridine. If necessary, the reaction system was added catalysts, such as ammonium salts (e.g., triethylmethylammonium), in a ratio of 0.01 to 1 mol per mol of the compounds of General formula [III].

The temperature of this reaction was usually set within the range from -20oC to 150oC or the boiling point of the solvent used in this reaction, preferably -5oC-100oC or the boiling point of the solvent used in this reaction.

The molar ratio of initial substances and bases used in this reaction, can be determined freely, but a beneficial effect on this reaction has been observed when equimolar ratio or a ratio close to him.

After completion of the reaction, the resulting reaction mixture was subjected to further conventional operations, such as extraction with an organic solvent and concentration, and allocate the appropriate connection of the present invention. Further, if necessary ejecta is SS="ptx2">

(Method of obtaining B of the present compounds in which Y is oxygen).

In this method, the compound of General formula [III] interacts with the combination of alcohol of General formula

HO - CH2CH = CX2< / BR>
in which X is defined above.

If necessary, this reaction is preferably carried out in an inert solvent, in the presence of an appropriate dehydrating agent.

Examples of dehydrating agents which can be used are dicyclohexylcarbodiimide and disciline (for example, C1-C4) azodicarboxylate (for example, diethylazodicarboxylate, diisopropylsalicylic)-trialkyl (for example, C1-C20) phosphine or triarylphosphine (for example, triphenylphosphine, though, tributylphosphine).

Examples of solvents that can be used are hydrocarbons, such as benzene, xylene and toluene; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane; and halogenated hydrocarbons such as carbon tetrachloride, dichloromethane, chlorobenzene and dichlorobenzene.

The temperature of this reaction was usually set in the range from -20oC to 200oC or the TV and dehydrating agents, used in this reaction, can be determined freely, but a beneficial effect on this reaction has been observed when equimolar ratio or a ratio close to him.

After completion of the reaction, the resulting reaction mixture was subjected to further conventional operations, such as extraction solvent and concentration, and allocate the appropriate connection of the present invention. Further highlighting the purification was carried out by conventional techniques such as chromatography, distillation or recrystallization.

(Method of obtaining C compounds in which Y is oxygen).

In this way the connection of the aldehyde of General formula

< / BR>
in which R1, R2, R3, R10, t and Z are each as defined above, interacts with the tetrachloride or cetarehhloristam carbon.

This reaction is preferably carried out in an inert solvent in the presence of an appropriate trialkylphosphine or triarylphosphine and, if necessary, in the presence of metallic zinc.

Examples of solvents that can be used are hydrocarbons, such as benzene, xylene and toluene; ethers, such as dietro the carbon tetrachloride), such as dichloromethane, 1,2-dichloroethane and chlorobenzene.

The temperature of this reaction was usually set in the range from -30oC to 150oC or the boiling point of the solvent used in this reaction.

Examples of trialkyl (e.g., C1-C20) phosphine or triarylphosphine are triphenylphosphine and though. Metallic zinc, which is optionally used, preferably presented in the form of zinc dust.

The molar ratio of the starting compounds and reagents used in this reaction, can be determined freely, but the preferred ratio is one in which carbon tetrabromide or tetrachloride, trialkylphosphine or triarylphosphine and zinc is represented by 2 moles, 2 or 4 moles (2 mol when using zinc), and 2 moles, respectively, per mol of compound of the aldehyde of General formula [VI], or close to that ratio, a positive effect on the reaction.

After completion of the reaction, the resulting reaction mixture was subjected to further conventional operations, such as extraction with an organic solvent and concentration, and allocate the appropriate connection of the present invention. Next wide.

(Method D produce compounds in which Y and Z both represent oxygen).

In this method, the compound of General formula

< / BR>
in which R2, R3, R10, t and X are each as defined above, interacts with the compound of General formula

R1-L

in which R1and L are each as defined above.

This reaction is preferably carried out in an inert solvent in the presence of an appropriate base.

Examples of solvents that can be used are ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethers such as 1,2-dimethoxyethane, tetrahydrofuran, dioxane and disciline (for example, C1-C4) ethers (e.g. diethyl ether, diisopropyl ether); N,N-dimethylformamide, dimethylsulfoxide, hexamethylphosphoramide, sulfolan, acetonitrile, nitromethane; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane and chlorobenzene; hydrocarbons such as toluene, benzene and xylene; and water. If necessary, you can use a mixture of these solvents.

Examples of bases that can be used are hydroxides of alkali metals or alkaline earth metals, such as Rosemaling metals, such as lithium carbonate, potassium carbonate, sodium carbonate and calcium carbonate; hydrides of alkali metals or alkaline earth metals such as lithium hydride, sodium hydride, potassium hydride and calcium hydride; alkali metal alcoholate (for example, C1-C4), such as sodium methylalcohol, sodium ethylalcohol and potassium, trebuchet; organic bases such as triethylamine and pyridine. If necessary, the reaction system it is possible to add catalysts, such as ammonium salts (e.g., triethylmethylammonium), in a ratio of from 0.01 to 1 mole per mole of the compounds of General formula [VII].

The temperature of this reaction was usually set in the range from -20oC to 150oC or the boiling point of the solvent used in this reaction, preferably -5oC - 100oC or the boiling point of the solvent used in this reaction.

The molar ratio of initial substances and dehydrating agent used in this reaction can be defined freely, but a beneficial effect on this reaction has been observed when equimolar ratio or a ratio close to him.

After completion of this reaction obtained reaction is the generation, and allocated the appropriate connection of the present invention. Further highlighting the purification was carried out by conventional techniques such as chromatography, distillation or recrystallization.

(Method E produce compounds in which Y and Z both represent oxygen).

In this method, the compound of General formula [VII] interacts with the combination of alcohol of General formula

R1- OH,

in which R1defined above.

This reaction is preferably carried out in an inert solvent, optionally in the presence of an appropriate dehydrating agent.

Examples of dehydrating agents which can be used are dicyclohexylcarbodiimide and disciline (for example, C1-C4) azodicarboxylate (for example, diethylazodicarboxylate, diisopropylsalicylic)-trialkyl (for example, C1-C20) phosphine or triarylphosphine (for example, triphenylphosphine, though, tributylphosphine).

Examples of solvents that can be used are hydrocarbons, such as benzene, xylene and toluene; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane; and halogenerator this reaction was usually set in the range from -20oC to 200oC or the boiling point of the solvent used in this reaction.

The molar ratio of initial substances and dehydrating agent used in this reaction, can be determined freely, but a beneficial effect on this reaction has been observed when equimolar ratio or a ratio close to him.

After completion of the reaction, the resulting reaction mixture was subjected to further conventional operations, such as extraction with an organic solvent and concentration, and allocate the appropriate connection of the present invention. Further highlighting the purification was carried out by conventional techniques such as chromatography, distillation and recrystallization.

(Method F producing compounds in which Y and Z both represent oxygen, R1is Q2or Q3and B represents the B1(where B1represents oxygen, sulfur or NR9[in which R9defined above])).

In this method, the compound of General formula

< / BR>
which1, R2, R3, R5, R6, R7, R10, p, t and X are each as defined above, interacts with the compound of General formula

< / BR>
in which nerton solvent in the presence of an appropriate base.

Examples of these solvents that can be used are ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethers such as 1,2-dimethoxyethane, tetrahydrofuran, dioxane and disciline (for example, C1-C4) ethers (e.g. diethyl ether, diisopropyl ether); N, N-dimethylformamide, dimethylsulfoxide, hexamethylphosphoramide, sulfolan, acetonitrile, nitromethane; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane and chlorobenzene; hydrocarbons such as toluene, benzene and xylene; and water. If necessary, used a mixture of these solvents.

Examples of bases that can be used are hydroxides of alkali metals or alkaline earth metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; carbonates of alkali metals or alkaline earth metals such as lithium carbonate, potassium carbonate, sodium carbonate and calcium carbonate; hydrides of alkali metals or alkaline earth metals such as lithium hydride, sodium hydride, potassium hydride and calcium hydride; alkali metal alcoholate (for example, C1-C4), such as sodium methylalcohol, sodium ethylalcohol the treatment can be added catalysts in the form of ammonium salts (for example, triethylmethylammonium) in a ratio of from 0.01 to 1 mole per mole of the compounds of General formula [X].

The temperature of this reaction was usually set in the range from -20oC to 150oC or the boiling point of the solvent used in this reaction, preferably -5oC - 100oC or the boiling point of the solvent used in this reaction.

The molar ratio of initial substances and dehydrating agent used in this reaction, can be determined freely, but a beneficial effect on the reaction observed at equimolar ratio or a ratio close to him.

After the specified reaction, the resulting reaction mixture was subjected to further conventional operations, such as extraction with an organic solvent and concentration, and allocate the appropriate connection of the present invention. Further highlighting the purification was carried out by conventional techniques such as chromatography, distillation or recrystallization.

(Method G producing compounds in which Y, Z and all represent oxygen, a R1is Q2, Q3, Q6or Q7).

In this way the combination of alcohol Oleny above, interacts with the connection Q21, Q31, Q61or Q71the General formula

< / BR>
in which R11, R12, R13, R14A and s are each as defined above.

This reaction is preferably carried out in an inert solvent, optionally in the presence of an appropriate dehydrating agent.

Examples of dehydrating agents which can be used are dicyclohexylcarbodiimide, and disciline (for example, C1-C20) azodicarboxylate (for example, diethyl - azodicarboxylate, diisopropylsalicylic)-trialkyl (for example, C1-C20) phosphine or triarylphosphine (for example, triphenylphosphine, though, tributylphosphine).

Examples of solvents that can be used are hydrocarbons, such as benzene, xylene and toluene; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane; and halogenated hydrocarbons such as carbon tetrachloride, dichloromethane, chlorobenzene and dichlorobenzene.

The temperature of this reaction is typically installed within a - 20oC to 200oC or the boiling point of the solvent used in this reaction.

Mole is received freely, but a beneficial effect on this reaction has been observed when equimolar ratio or a ratio close to him.

After completion of the reaction, the resulting reaction mixture was subjected to further conventional operations, such as extraction with an organic solvent and concentration, and allocate the appropriate connection of the present invention. Further highlighting the purification was carried out by conventional techniques such as chromatography, distillation and recrystallization.

(Method H produce compounds in which Y and Z both represent oxygen, a R1is Q2, Q3, Q6or Q7).

In this method, the compound of General formula

< / BR>
in which R2, R3, R5, R6, R7, R10, X, L, p and t are each as defined above, communicates with the connection Q22, Q32, Q62or Q7the General formula

< / BR>
in which R11, R12, R13, R14A , B and s are each as defined above.

This reaction is preferably carried out in an inert solvent in the presence of an appropriate base.

Examples of solvents that can be used are ketones such as AOC is alkyl (e.g., C1-C4) ethers (e.g. diethyl ether, diisopropyl ether); N,N-dimethylformamide, dimethylsulfoxide, hexamethylphosphoramide, sulfolan, acetonitrile, nitromethane; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane and chlorobenzene; hydrocarbons such as toluene, benzene and xylene; and water. If necessary, you can use a mixture of these solvents.

Examples of bases that can be used are hydroxides of alkali metals or alkaline earth metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; carbonates of alkali metals or alkaline earth metals such as lithium carbonate, potassium carbonate, sodium carbonate and calcium carbonate; hydrides of alkali metals or alkaline earth metals such as lithium hydride, sodium hydride, potassium hydride and calcium hydride; alkali metal alcoholate (for example, C1-C4), such as sodium methylalcohol, sodium ethylalcohol and potassium, trebuchet; organic bases such as triethylamine and pyridine. If necessary, to the reaction system it is possible to add catalysts, such as ammonium salts (e.g., triethylmethylammonium), usually set in the range from -20oC to 150oC boiling point of the solvent used in this reaction, preferably -5oC - 100oC or the boiling point of the solvent used in this reaction.

The molar ratio of initial substances and dehydrating agent used in this reaction are determined freely, but a beneficial effect on this reaction has been observed when equimolar ratio or a ratio close to him.

After completion of the reaction, the resulting reaction mixture was then subjected to the usual operations, such as extraction with an organic solvent and concentration, and allocate the appropriate connection of the present invention. Further highlighting the purification was carried out by conventional techniques such as chromatography, distillation and recrystallization.

If the connection according to the invention has an asymmetric carbon atom, it indicates the inclusion of its optically active isomer ((+)-form and (-)-form) having biological activity, and their mixtures in any proportion in the scope of the invention. If the specified connection shows the geometric isomerism, it indicates the inclusion of its geometric isomers (CIS-Fonte according to the invention (in which R4shown in Tables 1-46), which however do not limit the scope of the present invention. Examples, diagrams, tables, and the continuation of the description, see the graphics part. T T T

1. Connection dehalogenation General formula

< / BR>
where Z is oxygen;

X is chlorine or bromine;

Y is oxygen;

R2and R3each independently - halogen, or C1-C3-alkyl;

R1- Q1or Q2formulas

< / BR>
< / BR>
where R5and R6is hydrogen or lower alkyl,

R7is hydrogen,

B is oxygen, S(O)qwhere q = O, or NR9where R9is hydrogen, C(=G1G2where G1and G2oxygen;

p = 0 to 6, an integer;

A - heterocyclic ring group, possibly substituted (R8)rselected from pyridine , furan, thiophene, imidazole, pyrazole, triazole, isoxazol, benzothiazole, benzoxazole, N-(1,2-dihydro-2-oxo)pyridine, quinoline, N-phthalimido, benzimidazole, 1,4-benzodioxane, 1,3-dioxolane, R8-halogen, C1-C4-alkyl, C1-C3-halogenated, C1-C4-alkoxy, formyl, phenyl, possibly substituted with halogen, r = 0 - 4, an integer.

2. Connection dehalogenation under item 1, in which A is 2-pyridyl, 3-pyridyl, 4-feast of the sludge, 2-benzothiazolyl, 2-benzoxazolyl, 1-pyrazolyl, 3-chinolin, N-phthalimido, imidazolyl, each of which is optionally substituted (R8)rwhere R8- halogen, C1-C4-alkyl, C1-C3-halogenated, C1-C4-alkoxy, formyl, phenyl which may be substituted with halogen, r = 0 - 4, an integer.

3. Connection dehalogenation under item 1, in which R2and R3- chlorine, bromine, methyl, ethyl or isopropyl.

4. Connection dehalogenation under item 1, in which R2and R3both chlorine.

5. Connection dehalogenation under item 1, in which R2is chlorine, R3is methyl.

6. Connection dehalogenation under item 1, in which R2is ethyl, R3is methyl.

7. Connection dehalogenation under item 1, in which R2and R3both bromine.

8. Connection dehalogenation under item 1, in which R2and R3both ethyl.

9. Connection dehalogenation under item 1, in which R1- Q1.

10. Connection dehalogenation under item 1, in which R1- Q1p = 1 - 6, and A is 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, 2-thiazolyl, N-(1,2-dihydro-2-oxo-pyridyl), 1,3-DIOXOLANYL or N-phthalimido, each of which SUB>-alkyl, C1-C4-alkoxy, formyl or phenyl, optionally substituted with halogen, r = 0 - 4.

11. Connection dehalogenation under item 1, in which R1- Q1p = 1 - 6, R5- R7is hydrogen, A - 1,3-DIOXOLANYL, optionally substituted (R8)rin which R8- halogen, C1-C4-alkyl, C1-C3-halogenated, C1-C4-alkoxy, formyl or phenyl, optionally substituted with halogen, r = 0 - 4, an integer.

12. Connection dehalogenation under item 1, in which R1- Q1p = 1 - 4, R5- R7all hydrogen, and A is 1,3-DIOXOLANYL, optionally substituted (R8)rin which R8- halogen, C1-C4-alkyl, C1-C3-halogenated, C1-C4-alkoxy, formyl or phenyl, optionally substituted with halogen, r = 0 - 4, an integer.

13. Connection dehalogenation under item 1, in which R1- Q1p = 0, A is 2-pyridyl, 4-pyridyl, 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, 1,3-DIOXOLANYL, 2-thiazolyl, 1,4-benzodioxane, each of which is optionally substituted (R8)rwhere R8- halogen, C1-C4-alkyl, C1-C3-halogenated, C1-C4-alkoxy, formyl or phenyl, optional C

15. Connection dehalogenation under item 1, in which R1- Q2p = 1 - 4, and A is 2-pyridyl, optionally substituted (R8)rin which R8- halogen, C1-C4-alkyl, C1-C3-halogenated, C1-C4-alkoxy, formyl or phenyl, which is optionally substituted with halogen, r = 0 - 4, an integer.

16. Connection dehalogenate on p. 14, in which p = 1 - 4, R5- R7all hydrogen, and A is 2-pyridyl, optionally substituted (R8)rin which R8- halogen, C1-C4-alkyl, C1-C3-halogenated, C1-C4-alkoxy, formyl or phenyl, which is optionally substituted with halogen, r = 0 - 4, an integer.

17. Connection dehalogenate on p. 14, in which p = 1 - 4, R5- R7everything is hydrogen, A is 2-pyridyl, optionally substituted (R8)rin which R8- halogen or C1-C3-halogenated, r = 0 - 4, an integer.

18. Connection dehalogenate on p. 14, in which p = 2 or 3, R5- R7everything is hydrogen, A is 2-pyridyl, optionally substituted (R8)rin which R8- halogen or C1-C3-halogenated, r = 0 - 4, an integer.

19. Connection dehalogenate on p. 14, in which p =8
- halogen or trifluoromethyl, r = 0 - 4, an integer.

20. Connection dehalogenate on p. 14, in which p = 2 or 3, R5- R7everything is hydrogen, B is oxygen, A is 2-pyridyl, optionally substituted (R8)rin which R8- halogen or trifluoromethyl, r = 0 - 4, an integer.

21. Insecticidal agent comprising the compound of dehalogenation under item 1, as an active ingredient.

22. Acaricidal agent, comprising as an active agent a compound of the formula (I) under item 1, in which Z is oxygen, Y is oxygen, X is chlorine, R2and R3independently - halogen, C1-C3-alkyl, R1- Q1, Q2, where A is optionally substituted (R8)rheterocyclic ring group selected from pyridine, benzoxazole, furan, thiophene, in which R8represents halogen, C1-C4-alkyl, r = 0, 1, 2, B - O, S(O)q, q = O, where R5- R7is hydrogen, p = 0 to 6, an integer.

23. Connection dehalogenation under item 1, which is:

3,5-dichloro-4-(2-(2-(4-chlorophenyl)-1,3-dioxolane-4-yl)ethoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,

3,5-dichloro-4-(3-(5-trifluoromethyl-2-pyridyloxy)-propyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,

3,5-dichloro-4-(4-(5-crypto is lexi)propyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,

3,5-dichloro-4-(4-(3-trifluoromethyl-2-pyridyloxy)butoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,

3-chloro-5-methyl-4-(3-(5-trifluoromethyl-2-pyridyloxy)propyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,

3-chloro-5-methyl-4-(4-(5-trifluoromethyl-2-pyridyloxy)butoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,

3,5-diethyl-4-(3-(5-trifluoromethyl-2-pyridyloxy)propyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,

3,5-diethyl-4-(4-(5-trifluoromethyl-2-pyridyloxy)butoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,

3-ethyl-5-methyl-4-(3-(5-trifluoromethyl-2-pyridyloxy)propyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,

3-ethyl-5-methyl-4-(4-(5-trifluoromethyl-2-pyridyloxy)butoxy)-1-(3,3-dichloro-2-propenyloxy)benzene.

24. Connection pyridine of General formula II

< / BR>
where R5- R7independently is hydrogen;

R15- CF3;

R2and R3each chlorine;

u = 1,

w = 2,

B1the oxygen.

25. Connection on p. 24, which represents a 3,5-dichloro-4-(3-(5-trifluoromethyl-2-pyridyloxy)propyloxy)phenol.

26. 2-(3-Methanesulfonylaminoethyl)-5-triptorelin.

Priority points:

14.10.94 on PP.15 - 20, 22;

17.04.95 on PP.11 - 13, 23 - 26;

12.10.95 on PP.1 - 10, 14 and 21.

 

Same patents:

Iodinated esters // 2088579

The invention relates to 1-alkyl, 1-alkenyl, and 1-alkynylaryl-2-amino-1,3-propandiol formula 1:

< / BR>
where R is

< / BR>
< / BR>
R5represents a group of the formula:

CH3(CH2)mCC-, CH3(CH2)mCH CH-,

CH3(CH2)mCH2-CH2-,< / BR>
,< / BR>
m is from 3 to 15 and n is from 0 to 12

The invention relates to the field of organic chemistry, namely the chemistry of azo compounds which are used as acid-base indicators

The invention relates to 1-alkyl, 1-alkenyl or 1-alkynylaryl-2-amino-1,3-propandiol formula I

RCH (OR1)CHN(R2R3)P4whereOSO

R5-CH3(CH2)mCC,

CH3(CH2)mCH=CH-, CH3(CH2)mCH2-CH2-,-CH2(CH2)nCC-,

-CH2(CH2)nCH= CH or-CH2(CH2)nCH2-CH2-, where m = 3-15; n = 0-12;

R1is hydrogen orR6where R6is hydrogen, alkyl, alkoxy, or OCH2-;

R2is hydrogen or alkyl;

R3is hydrogen, alkyl orOR7where R7is hydrogen or alkyl, or CH2OR8where R8is hydrogen orR6where R6is defined above,

R1and R8taken together with the oxygen atom to which they are attached, form a group of the formula

where R9and R10independently are hydrogen or alkyl

,-unsaturated ketones aromatic or heteroaromatic number" target="_blank">

The invention relates to synthetic organic chemistry, and in particular to methods of obtaining,unsaturated carbonyl compounds, aromatic and heterocyclic series, many of which are biologically active, and are widely used as intermediates for the synthesis of diverse heterocyclic and other hard-to-reach connections

The invention relates to synthetic organic chemistry, namely to a process for the preparation of esters of carboxylic acids of General formula:

< / BR>
where R is alkyl, aryl, substituted aryl, furyl, substituted furyl

R' is alkyl WITH1-C4

The invention relates to new compounds selected from the group consisting of derivatives of 2-arylpropionate and derivatives tiefer, which are represented by the General formula I

Ar-H2-J-CH2-B where Ar describes panelgroup; or panelgroup, substituted lower accelgroup, alkoxygroup, alkylthiol,5-C6-cycloalkylcarbonyl, phenyl, halogen, lower alkenyl, halo-lower alkenylacyl, halo-lower alkyl, Alonissos alkoxy, lower alkoxyalkyl, lower alkanolammonium, lower alkyloxy, lower alkoxyalkyl-, lower acyl, lower alkoxycarbonyl, nitrile, nitro, phenoxy, Alonissos alkoxycarbonyl, methylendioxyphenyl or unsubstituted naphthyl or naphthyl substituted by lower alkyl,

R is methyl or telgraph, Y is oxygen atom or sulfur,

In the group of the formula

where Z is an oxygen atom or sulfur or a carbonyl or methylene group,

R1a hydrogen atom or Gal who

The invention relates to thiazole derivative, method for their production and their use as fungicides

The invention relates to methods of producing derivatives of thiazolidinone formula II:

in which R1represents a C2-C6alkenyl,2-C6quinil or group (CH2)n-Sin which n is an integer in the range 0-3, including extreme values of the interval;

R2represents hydrogen, C1-C6alkyl, C1-C6alkoxy,

WITH2-C6alkenyl,2-C6quinil,1-C4-alkyl-O-

-CC1-Calkyl or -CH-Swhere n is an integer in the range 0-3, including both extreme values;

R3represents hydrogen or C1-C6alkyl;

R4and R5represents hydrogen or together form a bond;

R6and R7each represents hydrogen and the another group-OH or SCH3;

X represents a group ofwhere m is 0,1 or 2, and

Q represents NR8where R8represents hydrogen, C1-C6alkyl, C2-C6alkenyl,3-C8cycloalkyl, SO2CH3or -(CH2)n-Y; where n is an integer in the range 0-3, including both extreme values, and

Y represents cyano, OR9, -R10< / BR>
-NR11TO12S-(C1WITH4) alkyl or a group

O-C1-C4alkyl where R9represents hydrogen, C1-C4alkyl or the group --C1-C4-alkyl

R10represents a C1-C4alkyl, C1-C4alkoxy, or-NH2< / BR>
R11and R12independently of one another represent hydrogen, C2-C6alkenyl,2-C6quinil,1-C6alkyl, (CH2)qOH, -(CH2)q-N(C1-C4alkyl)2,

-(CH2)q-S(C1-C4alkyl) or

-(CH2)11and R12together form morpholino, piperidinyl, piperazinilnom or N-methyl-piperazinilnom ring, or its pharmaceutically acceptable salts, characterized in that exercise: the reaction of the compound of the formula

HO-R3with the compound of the formula

in which R1, R2, R3and X have the above values, Q represents N-R8(where R8has the specified values), and R6and R7together form a group S, with the aim of obtaining the compounds of formula

in which R1, R2, R3, R6, R7, X and Q have the above meanings;

(a) with subsequent optional recovery of the compounds of formula II in which R6and R7together form a group S in order to obtain the compound of formula II in which R6and R7represents hydrogen;

(C) recovering the compounds of formula II in which R4and R5together form a connection with the purpose of obtaining compounds of formula II in which R4and R5before the form a bond, and R6and R7together form a group=S to obtain the compounds of formula II in which R4, R5, R6and R7represent hydrogen;

(d) alkylation of compounds of formula II in which R3represents hydrogen with formation of compounds of formula II in which R8represents a C1-C6alkyl, C2-C6alkenyl,3-C6cycloalkyl or -(CH2)n-Y (where n is an integer in the range 0-3, including extreme values, and Y represents cyano, OR9,-SH, -S(C1-C4alkyl)-NR11R12or

O-C1-C4alkyl, where R9,R11and R12have the listed meanings: (e) atilirovanie the compounds of formula II in which R8represents a hydrogen in order to obtain the compounds of formula II in which R8represents -(CH2)n-Y, where n is an integer in the range 0-3, including both extreme values of the interval, and Y represents -R10where R10has the specified values;

(f) oxidation of compounds of formula II, Kotor is Lew obtain the compounds of formula II, in which X represents a group -m is 1;

(K) the recovery of the compounds of formula II in which R3represents a group -(CH2)n-Y where n has values in the range 0-3, including extreme values of the interval, Y is a OR9where R9represents a group --C1-C4alkyl order to obtain the compounds of formula II in which R8represents a group -(CH2)n-Y where n is 0-3, including both extreme values, and Y is a OR9where R9represents hydrogen;

(l) the reaction of compounds of formula II in which R8represents a group -(CH2)n-Y, where n is 0-3, including both extreme values of the interval, Y is-OR9where R9represents hydrogen, tosylchloramide, with the aim of obtaining the compounds of formula II in which R8represents -(CH2)n-Y, where n is 0-3, including both extreme values of the interval, and Y is a OR9where R9is tosyl;

(m) the reaction of compounds of formula is I, and Y is-OR9where R9toil, with an amine of the formula HNR11R12(where R11and R12have the specified values), with the aim of obtaining the compounds of formula II in which R8represents a group -(CH2)n-Y, where n is 0-3, including both extreme values, and Y represents NR11, R12;

(n) heating the compounds of formula II in which R8represents -(CH2)n-Y, and Y represents NR11R12(R11, R12not hydrogen) in a mixture of ethanol/water in the presence of the catalyst in order to obtain the compounds of formula II in which R8represents -(CH2)n-Y, Y represents NR11R12where R11, R12one hydrogen and the other is not a hydrogen

The invention relates to a new process for the preparation of 2-substituted 5-chloroimidazo-4-carbaldehyde General formula I

< / BR>
where

R denotes hydrogen, alkyl group, alkenylphenol group, cycloalkyl group, benzyl group, phenyl group or aryl group

The invention relates to methods of producing 2-substituted 5-chloroimidazo-4-carbaldehyde General formula 1

< / BR>
These connections form a valuable intermediate products for the manufacture of medicines that lower blood pressure, and compounds with herbicide action
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