Derivatives of 1h-3-aryl-pyrrolidin-2,4-dione, the source and intermediate products for their production and the means to combat the damaging plants by insects and mites

 

(57) Abstract:

Describes derivatives of 1H-3-aryl-pyrrolidin-2,4-dione of the formula I, where a and b together with the carbon atom to which they are connected, means interrupted by one heteroatom 5-or 6-membered spirits, which contains nitrogen, oxygen or sulfur as heteroatom and may be substituted at the nitrogen atom, R1or COR1; X and Y denote alkyl or halogen; Z signifies alkyl; n is 0 or 1; G denotes the group-C(O)R1, -SO2R3, Or E where E denotes ammonium ion, L and M denote O or S; R1means alkyl, alkenyl, alkoxyalkyl, cycloalkyl, substituted phenyl or heteroaryl, R2means alkyl, phenyl or benzyl; R3, R4and R5mean alkyl or alkylthio; R6and R7mean alkyl or together with the nitrogen atom to which they are bound denote a cycle which may be interrupted by oxygen, which can be an active ingredient to combat damaging plants by insects and mites. Also proposed esters of N-acylaminoacyl formula II representing the initial products to obtain the compounds of formula I and derivatives aminonitriles formula III, which represent intermediate products for po, 8 table.

< / BR>
< / BR>

The invention relates to new derivatives of pyrrolidinone possessing biological activity, in particular derivatives of 1H-3-aryl-pyrrolidin-2,4-dione.

Known derivatives of 1H-3-acyl-pyrrolidine-2,4-dione, which can be used as a means of pest control (see application EP n 0 456 063, MKI: C 07 D A 01 N, 1991).

The objective of the invention is the development of new derivatives of 1H-3-aryl-pyrrolidin-2,4-dione, which when applied as a tool for pest control, are the best biological activity, in particular herbicide and acaricidal activity, compared with the known pyrrolidone.

The problem is solved proposed derivatives of 1H-3-aryl-pyrrolidin-2,4-dione of the formula (I)

< / BR>
in which A and B denote, together with the carbon atom to which they relate, which is interrupted by at least one heteroatom 5 - to 6-membered spirits, which contains nitrogen, oxygen or sulfur as heteroatom and may be substituted at the nitrogen atom of the group R1or COR1,

X represents alkyl or halogen,

Y represents alkyl or halogen,

Z signifies alkyl,

n represents the number 0 or 1,

G means in the
R1means alkyl, alkenyl, alkoxyalkyl, cycloalkyl, substituted phenyl or heteroaryl,

R2means alkyl, phenyl or benzyl,

R3, R4and R5independently of one another denote alkyl, alkylthio,

R6and R7mean alkyl or together with the nitrogen atom to which they are bound denote a cycle which may be interrupted by oxygen.

The first group preferred pyrrolidinone formula (I) include compounds in which

A, B and the carbon atom to which they are bound, denote a 5 - to 6-membered spirits, which contains a group

< / BR>
oxygen or sulfur,

X represents alkyl with 1 to 6 carbon atoms or halogen,

Y represents alkyl with 1 to 6 carbon atoms or halogen,

Z denotes alkyl with 1 to 6 carbon atoms,

G denotes hydrogen or a group

< / BR>
in which E stands for ammonium ion, and

L and M each means oxygen or sulfur,

R1means alkyl with 1 to 20 carbon atoms, alkenyl with 2 to 10 carbon atoms, alkoxyalkyl with 1 - 8 carbon atoms in the alkyl and parts of the CNS, cycloalkyl with 3 to 8 atoms in the ring, phenyl, substituted by halogen, unsubstituted or substituted by halogen heteroaryl,

R2means alkyl with 1 to 20 atoms in the alkyl with 1 to 8 carbon atoms, alkylthio with 1 to 8 carbon atoms,

R6and R7denote alkyl with 1 to 10 carbon atoms or together with the nitrogen atom to which they are bound denote a 3 - to 7-membered ring which may be interrupted by oxygen,

R9means R1or COR1and R1can't take those specified in paragraph 3 for R1values

n represents the number 0 or 1.

The second group preferred pyrrolidinone formula (I) include compounds in which

A, B and the carbon atom to which they are bound, denote a 5 - to 6-membered spirits, which contains a group

< / BR>
oxygen or sulfur,

X represents alkyl with 1 to 4 carbon atoms or halogen,

Y represents alkyl with 1 to 4 carbon atoms or halogen,

Z denotes alkyl with 1 to 4 carbon atoms,

G denotes hydrogen or a group

< / BR>
in which E stands for ammonium ion, and

L and M each means oxygen or sulfur,

R1means alkyl with 1 to 16 carbon atoms, alkenyl with 2 to 8 carbon atoms, alkoxyalkyl with 1 to 6 carbon atoms in the alkyl and parts of the CNS, cycloalkyl from 3 to 7 atoms in the ring, substituted by halogen phenyl, unsubstituted or substituted with chlorine furanyl, thienyl, pyridyl.

R2performance of each other denote alkyl with 1 to 6 carbon atoms, or alkylthio with 1 to 6 carbon atoms,

R6and R7denote alkyl with 1 to 8 carbon atoms, or together with the nitrogen atom to which they are linked, form a 4 - to 7-membered ring which may be interrupted by oxygen,

R9means COR1'and R1'means alkyl with 1 to 6 carbon atoms,

n represents the number 0 or 1.

The third group preferred pyrrolidinone includes compounds that have

A, B and the carbon atom to which they are bound, denote a 5 - to 6-membered spirits, which contains a group

< / BR>
oxygen or sulfur,

X represents methyl or chlorine,

Y represents methyl or chlorine,

Z signifies methyl,

G denotes hydrogen or a group

< / BR>
in which E stands for ammonium ion, and

L and M each means oxygen or sulfur,

R1means alkyl with 1 to 14 carbon atoms, alkenyl with 2 to 6 carbon atoms, alkoxyalkyl with 1 to 4 carbon atoms in the alkyl part and 1 to 6 carbon atoms in the alkyl part is substituted by chlorine, phenyl, unsubstituted or substituted with chlorine thienyl, furanyl or pyridyl,

R2means alkyl with 1 to 14 carbon atoms, unsubstituted phenyl or benzyl,

R3, R4and R5independently from each other the keel 1 6 carbon atoms, or together with the nitrogen atom to which they are bound, denote a 5 - to 7-membered ring which may be interrupted by oxygen,

R9means COR1'and R1'means alkyl with 1 to 4 carbon atoms,

n represents the number 0 or 1.

Derivatives of 1H-3-aryl-pyrrolidin-2,4-dione of the above formula (I) can be obtained well-known specialists of ways, for example, by methods described in the following examples.

For example, pyrrolidinone formula (I), where G denotes a hydrogen atom, can be obtained by the intramolecular condensation of ester N-acylaminoacyl formula (II)

< / BR>
in which A, B, X, Y, Z and n have the above values

R8means alkyl,

in the presence of a diluent and base.

This method is hereinafter referred to as "method A".

When this compound of formula (II) can be obtained by alcoholysis of the compounds of the formula (III)

< / BR>
in which A, B, X, Y, Z and n have the above values,

using sulphuric acid.

The compounds of formula (II) and (III) are new and therefore are further objects of the invention.

The compounds of formula (III) can be obtained due to the fact that s is s with halogenide phenylacetic acid of the formula (V)

< / BR>
in which X, Y, Z and n have the above values.

Pyrrolidinone the above formula (I), where G stands for a group-COR1you can get due to the fact that the compounds (Ia)

< / BR>
in which A, B, X, Y, Z and n have the above values,

subjected to interaction

() halogenerator acid of formula (V)

< / BR>
in which R1has the above value and

Hal means halogen, in particular chlorine or bromine,

optionally, in the presence of a diluent and an acid binding tools

or

() with the anhydride of carboxylic acid (VI)

R1-CO-O-CO-R1< / BR>
in which R1has the above value,

optionally, in the presence of a diluent and an acid binding means.

This method is hereinafter referred to as "method B".

Pyrrolidinone the above formula (I), where G means

< / BR>
you can get due to the fact that the compounds of formula (Ia)

< / BR>
in which A, B, X, Y, Z and n have the above values,

subjected to interaction with complex ether of Harborview acid or tieferen Harborview acid of the formula (VII)

R2-M-CO-Cl,

in which R2and M have specified the>This method is hereinafter referred to as "method B".

Pyrrolidinone the above formula (I), where G means

< / BR>
you can get due to the fact that the compounds of formula (Ia)

< / BR>
in which A, B, X, Y, Z and n have the above values,

subjected to interaction

(a) esters of hormonestimulated acid or chartitemevent acid of the formula (VIII)

< / BR>
in which M and R2have the above values,

optionally, in the presence of a diluent and an acid binding means,

or

() with carbon disulphide and then with alkylhalogenide General formula (IX)

R2-Hal,

in which R2have the above significance and

Hal means chlorine, bromine or iodine,

optionally, in the presence of a diluent and of an auxiliary base.

This method is hereinafter referred to as "method D".

Pyrrolidinone the above formula (I), where G means-SO2-R3you can get due to the fact that the compounds of formula (Ia)

< / BR>
in which A, B, X, Y, Z and n have the above meanings, is subjected to the interaction with the sulfonic acid chlorides of the formula (X)

R3-CO2-Cl.

in which R3the ima is A.

This method is hereinafter referred to as "method D".

Pyrrolidinone the above formula (I), where G means

< / BR>
you can get due to the fact that the compounds of formula (Ia) or their enols

< / BR>
in which A, B, X, Y, Z and n have the above values,

subjected to interaction with phosphorus compounds of the formula (XI)

< / BR>
in which L, R4and R5have the above values and

Hal means halogen, in particular chlorine and bromine,

optionally, in the presence of a diluent and an acid binding means.

This method is hereinafter referred to as "method E".

Pyrrolidinone the above formula (I), where G means E, can be obtained due to the fact that the compounds of formula (Ia)

< / BR>
in which A, B, X, Y, Z and n have the above values,

subjected to interaction with the combination of metals or amines of the formulas (XII) and (XIII)

< / BR>
in which Me denotes a monovalent or divalent metal ion,

t represents the number 1 or 2,

R10, R11and R12mean independently from each other hydrogen or alkyl and

R13means hydrogen, hydroxy or alkoxy with 1 to 4 carbon atoms,

optionally, in the presence of razbaviteli (I), where G means

< / BR>
you can get due to the fact that the compounds of formula (Ia)

< / BR>
in which A, B, X, Y, Z and n have the above values,

subjected to interaction

(a) with compounds of the formula (XIV)

R6-N=C=L,

in which L and R6have the above values,

optionally, in the presence of a diluent and catalyst

or

(a) with acid chlorides to form carbamino acid or thiocarbamide acid of the formula (XV)

< / BR>
in which L, R6and R7have the above values,

optionally, in the presence of a diluent and an acid binding means.

This method is hereinafter referred to as "method C".

New derivatives of 1H-3-arylpyrimidine-2,4-dione of the formula (I) can be used as a means to combat the damaging plants by insects and mites, which is a further object of the invention. In addition to the active ingredient of this product contains more additives target.

If used according to the method of (A) ethyl ester of 4-(2,4-dichlorophenylethyl-amino-1-acetyl-piperidine-4-carboxylic acid, the course of the process according to the invention can be visualized in the following reaction scheme:

< / BR>
If the Prim is-2,4-dione and pivaloyloxy, the method according to the invention proceeds according to the following reaction scheme:

< / BR>
If used according to method (B) as a starting compound 3-(2,4,6-trimetilfenil)-5,5-ethylendiamine - pyrrolidin-2,4-dione and acetanhydride, then the method proceeds according to the following reaction scheme:

< / BR>
If used according to method (B) as a starting compound 3-(2,4,6-trimetilfenil)-5,5-ethylendiamine-pyrrolidin - 2,4-dione and ethoxyethyl ether of Harborview acid, the process proceeds by the following reaction scheme:

< / BR>
If used according to method (G) as starting compound 3-(2,4,6-trimetilfenil)-5,5-ethylenoxide-pyrrolidin - 2,4-dione and methyl ether of hormonestimulated acid, the reaction according to the invention proceeds according to the following scheme:

< / BR>
If used according to method (G) as starting compound 3-(2,4,6-trimetilfenil)-5,5-ethylendiamine - pyrrolidin-2,4-dione, carbon disulphide and methyliodide, the reaction according to the invention proceeds according to the following scheme:

< / BR>
If used according to method (D) as the starting compound 3-(2,4,6-trimetilfenil)-5,5-methylene-DIPROPYLENE - pyrrolidin-2,4-dione and the acid chloride of methansulfonate, the course of the process according to the source compounds 3-(2,4-dimetilfenil) 5,5-ethylene-tietjen-pyrrolidin - 2,4-dione and 2,2,2-triptoreline ester acid chloride of meanti-phosphonic acid, the course of the process according to the invention can be visualized in the following reaction scheme:

< / BR>
If used according to method (G) as starting compound 3-(2,4,6-trimetilfenil)-5,5-ethylene-timetime - pyrrolidin-2,4-dione and the sodium hydroxide, the course of the process according to the invention can be visualized in the following reaction scheme:

< / BR>
If used according to method (C) as a starting compound 3-(2,4,6-trimetilfenil)-5,5-ethylenoxide - pyrrolidin-2,4-dione and utilitzant, the course of the process according to the invention can be visualized in the following reaction scheme:

< / BR>
If used according to method (C) as a starting compound 3-(2,4,6-trimetilfenil)-5,5-ethylenediamino-ethylene - pyrrolidin-2,4-dione and the acid chloride dimethylcarbinol acid, the course of the process according to the invention can be visualized in the following reaction scheme:

< / BR>
As a diluent can be used according to the method (A) all inert organic solvents. Preferably used are hydrocarbons, such as toluene and xylene, then ethers, as disutility ether, tetrahydrofuran, dioxane, simple dimethyl ether glycol and diglycol, except that the same alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, ISO-butanol and tert.butanol.

As reason (deprotonation funds) can be used in the process (A) all the usual acceptors of protons.

Preferably used oxides, hydroxides and carbonates of alkali and alkaline earth metals such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate, which can also be used in the presence of catalysts migration phases, such as, for example, triethylmethylammonium, tetrabutylammonium,RAdogen 464 (metyltrebutyl (C8-10)ammoniacal) or TDA 1 (Tris-(methoxyethoxymethyl)-Amin).

Hereinafter, can be used alkali metals such as sodium or potassium. Next, apply amides and hydrides of alkali and alkaline earth metals, such as sodium amide, sodium hydride and calcium hydride, and additionally also alkali metal alcoholate such as sodium methylate, sodium ethylate and tert.butyl potassium.

The reaction temperatures when carrying out process (A) can vary in a wide interval. Typically operate at temperatures between 0oC and 250oC, the P CLASS="ptx2">

In the process (A), the reaction components of the formulae (II) and deprotonation reason is usually introduced in equimolar amounts. However, you can also use one or another component in a larger excess (up to 3 mol).

As a diluent in the method (B) when applying golodnikov acids can be entered all inert with respect to these substances solvents.

Preferably used are hydrocarbons, such as benzine, benzene, toluene, xylene, tetralin, then, galoidovodorodami, such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, additionally ketones, such as acetone and methylisobutylketone, then, ethers, such as diethyl ether, tetrahydrofuran and dioxane, additionally, esters of carboxylic acids, such as ethyl acetate, and also cinnaprarie solvents, such as dimethylsulfoxide and sulfolane. If the resistance to hydrolysis of galodamadruga allows you to transform in the presence of water.

If apply the appropriate galodamadruga carboxylic acid, as an acid binding agent with transformation according to the proposed method (B) can plomin, pyridine, diazabicyclo (DABCO), diazabicyclo (DBU), diazabicyclo (DBN), the base Hunga and N,N-dimethylaniline, furthermore, the oxides of alkaline earth metals, such as magnesium oxide and calcium in addition, carbonates of alkali and alkaline earth metals such as sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal hydroxide such as sodium hydroxide and potassium.

The reaction temperature for the method (B) when applying golodnikov carboxylic acids can also vary in a wide interval. Typically operate at temperatures between -20oC and +150oC, preferably between 0oC and 100oC.

In the process (B) use of starting compound of the formula (Ia) and galoyanized formula (V) is usually in approximately equivalent amounts. However, you can also enter galoyanized carboxylic acid in a large excess (up to 5 mol). Processing is done in the usual way.

If method (B) as the reaction component of the formula (VI) apply the anhydride of the carboxylic acid as the diluent preferably apply the same diluents that when using golodnikov acids. However, it is possible takeout to vary in a wide interval using the anhydrides of carboxylic acids. Typically operate at temperatures between -20 and +150oC, preferably between 0 and 100oC.

In the process (B) educt of the formula (Ia) and the carboxylic anhydride of the acid of formula (VI) are usually in approximately equivalent amounts. However, it is also possible to introduce a carboxylic acid anhydride in a larger excess (up to 5 mol). The treatment is carried out in the usual way.

Usually do so that the diluent and excess carboxylic acid anhydride, and the resulting carboxylic acid is removed by distillation or by washing with an organic solvent or water.

If used, the corresponding esters or complex thiol esters of Harborview acid, as acid binding means are used during the interaction according to the method (C) all customary acid acceptors. Preferably used tertiary amines such as triethylamine, pyridine, DABCO, DBU, DBA, based Hunga and N,N-dimethylaniline, and the oxides of alkaline earth metals, such as magnesium oxide and calcium in addition, carbonates of alkali and alkaline earth metals, such as sodium carbonate, potassium carbonate and calcium carbonate, and hydroxide melts in method (C) when using esters and complex thiol esters of Harborview acid all inert to these compounds solvents. Preferably used are hydrocarbons, such as benzine, benzene, toluene, xylene, tetralin, then galoidovodorodami, such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, additionally ketones, such as acetone and methylisobutylketone, then ethers, such as diethyl ether, tetrahydrofuran and dioxane, additionally, esters of carboxylic acids, such as ethyl acetate, and also strongly polar solvents, such as dimethylsulfoxide and sulfolane.

When using esters or complex thiol esters of Harborview acid as a carboxylic acid derivative of the formula (VII), the reaction temperature in the process (C) can vary in a wide interval.

If you are in the presence of a diluent and a binder acid funds, the reaction temperatures are generally between -20oC and +100oC, preferably between 0oC and 50oC.

Method (C) is conducted usually under normal pressure.

When carrying out process (C) use the usual starting substances of the formula (Ia) and the corresponding esters of Harborview acid or complex thiol esters of Harborview acid FD is larger excess (up to 2 moles). Processing occurs in the usual ways. Usually do so that removing precipitated salt and the remaining reaction mixture is concentrated by removal of solvent.

Method for producing a (G) is subjected to transformation of one mole of the starting compound of formula (Ia) with approximately one mol of ester hormonestimulated acid or a complex ester of chartitemevent acid of the formula (VIII) at a temperature of from 0 to 120oC, preferably at temperatures from 20 to 60oC.

As added if necessary, the solvents used are all inert polar organic solvents, such as ethers, amides, alcohols, sulfones, sulfoxidov.

Preferably used dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, dimethyl sulphide.

If in a preferred form of execution of the get with the addition of a strong deprotonating means, such as, for example, sodium hydride, tertiary butyl potassium, enolate salt of the compound Ia, it is possible to waive the subsequent addition of acid binding means.

If injected linking the acid remedy, apply the usual inorganic or organic bases, the Reaction can be carried out at normal or at elevated pressure, preferably operate at normal pressure. Processing occurs in the usual way.

In the production method of (G) per mol of starting compound of the formula (Ia) was added an equimolar amount or an excess of carbon disulphide.

In this work, preferably at temperatures from 0oC to 50oC, in particular at 20-30oC.

It is often advisable to first obtain from the compounds of formula (Ia) additive deprotonating means (for example, tertiary butyl potassium or sodium hydride) in the appropriate salt. The compound (Ia) is subjected to transformation with carbon disulfide as long as you do not stop the formation of intermediate compounds, for example, after several hours of stirring at room temperature.

Further interaction with alkylhalogenide formula (IX) is preferably at temperatures from 0oC to 70oC and, in particular, at 20-25oC. using at least equimolar amount of alkylhalogenide.

Working under normal or elevated pressure, preferably under normal pressure.

Processing is carried out by known methods.

Method for producing a IDA (X) at a temperature of from 0oC to 150oC, preferably at 20 to 70oC.

As a possible added diluents used all inert polar organic solvents, such as ethers, amides, NITRILES, alcohols, sulfones, sulfoxidov or halogenated hydrocarbons, such as methylene chloride.

Preferably used dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, dimethyl sulfide, methylene chloride.

If according to a preferred form of execution get enolate salt of the compound Ia by adding a strong deprotonating means (as, for example, sodium hydride or a tertiary butyl potassium), it is possible to refuse the further addition of acid binding means.

If they use an acid binding agent, then apply the usual inorganic or organic bases, as an example, include sodium hydroxide, sodium carbonate, potassium carbonate, pyridine.

The reaction can be carried out at normal or elevated pressure, preferably under normal pressure. Processing is performed in the usual way.

According to the method of obtaining (E) if necessary to work in the conditions of the transfer phase (Century. is inane formula (Ia) from 0.3 to 1.5 mole of sulfochloride (IX) preferably of 0.5 mole at a temperature from 0oC to 150oC, preferably at 20 to 70oC.

As catalysts for transfer phases can be Quaternary ammonium salts, preferably the bromide of tetraoctylammonium and chloride of benzyltriethylammonium. As the organic solvent can serve in this case, all non-polar inert solvents, preferably used benzene and toluene.

According to the method of obtaining (E) one mol of compound (Ia) is subjected to interaction with 1 to 2, preferably 1 to 1.3 moles of the phosphorus compounds of the formula (XI) at temperatures from - 40oC to 150oC, preferably from 10oC to 110oC.

As used optionally diluents used all inert polar organic solvents, such as ethers, amides, NITRILES, alcohols, sulfides, sulfones, sulfoxidov etc.

Preferably used acetonitrile, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, dimethyl sulphide.

As added if necessary, means connecting acid, apply the usual inorganic or organic bases, such as hydroxides, carbonates. As an example, should lead hydroxide nativesignal pressure, preferably operate at normal pressure. The treatment is carried out by conventional methods of organic chemistry. Purification spin-off of the final product occurs, preferably by crystallization, chromatographic purification or by so-called "distillation", i.e. removal of the volatile components in vacuo.

As a diluent in the method (G) can be used, preferably, ethers, such as tetrahydrofuran, dioxane, diethyl ether, or alcohols, such as methanol, ethanol, isopropanol, or water.

Method (G) is conducted usually under normal pressure. Reaction temperatures are typically in the range of 20oC and 100oC, preferably from 0oC to 50oC.

Method for producing (3) one mol of starting compound of the formula (Ia) is subjected to interaction with approximately one mol of isocyanate of the formula (XIV) at a temperature of from 0oC to 100oC, preferably at 20 to 50oC.

As an added optionally diluents can be used all inert organic solvents, such as ethers, amides, NITRILES, sulfones, sulfoxidov.

If necessary, may be added catalysts to accelerate realadinsert. Preferably operate at normal pressure.

Method for producing (3) one mol of starting compound of the formula (Ia) is subjected to transformation with approximately one mol of the acid chloride carbamino acid of the formula (XV) at a temperature of from 0oC to 50oC, preferably at 20 to 70oC.

As an added optionally diluents used all inert polar organic solvents, such as ethers, amides, alcohols, sulfones or sulfoxidov.

Preferably apply dimethyl sulfoxide, tetrahydrofuran, dimethylformamide or methylene chloride.

If according to the preferred form by adding a strong deprotonating means (e.g., sodium hydride or a tertiary butyl potassium) get enolate salt of compound (Ia), it is possible to waive the subsequent addition of acid binding means.

If injected linking the acid remedy, apply the usual inorganic or organic bases, for example, include sodium hydroxide, sodium carbonate, potassium carbonate, pyridine, triethylamine.

The reaction can be carried out at normal or at elevated pressure, predpochtiteljno to combat damaging plants by insects and mites can be translated in the usual form, such as solutions, emulsions, wettable powders, spray powders, suspensions, powders, pastes, soluble powders, granules, suspension-emulsion concentrates, impregnated with active substances of natural and synthetic substances, as well as microencapsulated in a polymer substances. The proposed product contains in General from 0.1 to 95 wt.% the active ingredient, mainly from 0.5 to 90%.

Compounds according to the invention are applied by known methods, for example by watering, spraying, spray and globular spray.

Compounds according to the invention can be applied before emergence of the plants or after germination. They can also enter into the soil before sowing.

The consumption rates used active substances can vary in a large range. They essentially depend on the desired effect. Usually consumption rates are from 0.01 to 10 kg of active substance per hectare of soil surface, preferably from 0.05 to 5 kg per 1 hectare

The preparation and use of compounds according to the invention are illustrated in the following examples.

Examples of making

Example 1.

to 49.9 g of tert.the butyl potassium purestorm 65 g of methyl ester of N-(2,4,6-trimetilfenil)-acetyl-tetrahydrothiophene-3-amino-carboxylic acid in 420 ml of dry toluene and refluxed for 90 minutes After cooling, the reaction solution is treated with 650 ml of water, the aqueous phase is separated. The organic phase is again washed with 300 ml of water. The aqueous phase are combined acidified with 70 ml of concentrated hydrochloric acid, the precipitate is sucked off and dried.

Get 56 grams (96% of theory) of the compound from so pl. > 230oC, having the formula

< / BR>
Similarly receive connections, are given in table. 1.

Example 9.

5.8 g of the compound of example 1 are mixed in 70 ml of dry methylene chloride with 2.8 ml of triethylamine and added dropwise at 0oC 1.5 ml of acetylchloride in 5 ml of dry methylene chloride. The reaction solution is washed twice with 200 ml of 0.5 N. caustic soda, dried over magnesium sulfate and the solvent is distilled off. Remains of 1.7 g (26% of theory) of the compound from so pl. 211oC, having the formula

< / BR>
Similarly receive connections, are given in table. 2.

Example 38.

5.8 g of the compound of example 1 is treated with 70 ml of dry methylene chloride with 2.8 ml of triethylamine and added at a temperature of from 0 to 10oC 2.7 g Deut. butyl ether of Harborview acid in 5 ml of dry methylene chloride. The reaction solution is washed with twice 200 ml of 0.5 N. caustic soda, dried over magnesium sulfate and the solvent is distilled off. OST the tion, summarized in table. 3.

Example 66.

5.8 g of the compound of example 1 is treated with 70 ml of dry methylene chloride with 2.8 ml of triethylamine and added at a temperature of from 0 to 10oC 1.7 g of acid chloride of methansulfonate in 5 ml of dry methylene chloride. The reaction mixture was twice washed with 200 ml of 0.5 N. caustic soda, dried over magnesium sulfate and the solvent is distilled off.

Remains of 3.2 g (56 % of theory) of the next connection so pl. 220oC, having the formula

< / BR>
Similarly receive the connection formulas

< / BR>
Example 67.

< / BR>
< / BR>
Example 69.

3 g of compound of example 1 are placed in 20 ml of dry tetrahydrofuran, mixed with 1.5 ml of triethylamine and then add 2.1 g Deut.butylthiourea acid chloride enantiomorphous acid. Stirred for one day at 50oC, evaporated the solvent and chromatographic the residue on silica gel with hexane/acetone 9:1 as eluent. After evaporation of the solvent to obtain 1.1 g (23% of theory) of the above compounds with so pl. 216oC.

Similarly receive the following connection so pl. 208oC.:

< / BR>
Example 70.

5.8 g of the compound of example 1 are mixed in 70 ml of dry methylene chloride with 6,24 ml Enie 15 minutes The reaction solution is concentrated and the residue by the addition of simple diisopropyl ether is brought to crystallization. After the extraction of the sediment remains of 5.4 g (99% of theory) of the next connection so pl. 110oC:

< / BR>
Example 71.

5.8 g of the compound of example 1 is mixed with 70 ml of dry methylene chloride with 2.8 ml of triethylamine and added at a temperature of 0 to 10oC 1,76 ml of acid chloride morpholinylcarbonyl acid in 5 ml of dry methylene chloride. The reaction solution is washed twice with 200 ml of 0.5 N. caustic soda, dried over magnesium sulfate and the solvent is distilled off. Remains of 1.2 g (19% of theory) of the next connection so pl. 198oC:

< / BR>
Examples obtain the intermediates of formula III

Example 72.

To a 51.2 g of 3-amino-3-cyano-Tirana in 600 ml of dry tetrahydrofuran was added 56 ml of triethylamine and at 0oC was added dropwise a solution of 78.6 g of acid chloride of mesitylenesulfonic acid in 80 ml of dry tetrahydrofuran. The reaction mixture is poured into 1.2 l of ice water, add 200 ml of 1 N. hydrochloric acid, the precipitate is sucked off and dried. Get to 89.5 g (78% of theory) of the next connection so pl. 174-175oC.

< / BR>
Similarly receive connections, are given in table. 4.

Use the 500 ml of methylene chloride was added to the 152,4 g of concentrated sulfuric acid, stirred for 2 h and added dropwise at 40oC 218 ml of methanol. Continue to mix at 40-70oC for 6 hours the Reaction solution served in 1.5 l of ice water, extracted with 500 ml of methylene chloride, methylenchloride phase is dried and the solvent is distilled off.

Get 65 g (65% of theory) of the compound from so pl. 111-113oC the following formula:

< / BR>
Similarly receive connections, are given in table. 5.

In the application examples used the following known from the above-mentioned application EP N 0 456 063 comparative connections:

< / BR>
Example 91.

Test Myzus

Solvent: 7 weight. hours of dimethylformamide

Emulsifier: 1 weight. including simple alkylarylsulphonates ether

To get suitable for use mix 1 part weight. including the active substance with the specified amount of solvent and a specified amount of emulsifier; the concentrate is diluted with water to the specified in table 6 concentration.

Cabbage leaves (Brassica oleracea), strongly affected peach aphid (Myzus persicae) are processed by immersion in composition of the desired concentration.

After 6 days assess the degree of destruction in %. 100% means that all aphids destroyed, and 0% means that there is SS="ptx2">

Example 92.

Test Myzus

Solvent: 7 weight. hours of dimethylformamide

Emulsifier: 1 weight. including simple alkylarylsulphonates ether

To get suitable for use mix 1 part weight. including the active substance with the specified amount of solvent and a specified amount of emulsifier; the concentrate is diluted with water to the specified table. 7 concentration.

Cabbage leaves (Brassica oleracea) are treated by dipping into the active substances required concentration and load caterpillars (Plutella macullipennis) as long as the leaves do not become wet.

After 3 days assess the degree of destruction in %. 100% means that all caterpillars destroyed, and 0% means that it is not destroyed, none of the caterpillar.

Active substances, their concentrations and the results of the experiment are given in table. 7.

Example 93.

Test Nephotettix

Solvent: 7 weight. hours of dimethylformamide

Emulsifier: 1 weight. including simple alkylarylsulphonates ether

To obtain a usable composition mix 1 weight part of the active substance with the specified amount of solvent and a specified amount of emulsifier; the concentrate is diluted into and infect green rice Cicada (Nephotettix cinticeps) as long until the sheets become wet.

After the desired period of time assess the degree killing in %. 100% means that all cicadas destroyed; 0% means that it is not destroyed, none of the Cicada.

In this experiment, the compounds of examples 51 and 53 at a concentration of 0.01% shows 100% killing.

Example 94.

The Tetranychus test (resistance to esters of orthophosphoric acid)

Solvent: 3 weight. hours of dimethylformamide

Emulsifier: 1 weight. including simple alkylarylsulphonates ether

To get suitable for use mix 1 part weight. including the active substance with the specified amount of solvent and a specified amount of emulsifier; the concentrate is diluted with water to a concentration equal to 0.02%.

Bean plants (Phaseolus vulgaris), which are affected by spider mites (Tetranychus urticae), is dipped in the composition of the active substance concentration required.

After 7 and 14 days to determine the effectiveness of the action in %. 100% means that all the mites are killed, 0% means that the ticks are not affected at all.

In this experiment, the compounds according to examples 6, 20 and 53 are 100% killing after 14 days, and the compounds of examples 7, BR>
Solvent: 3 weight. hours of dimethylformamide

Emulsifier: 1 weight. including simple alkylarylsulphonates ether

To get suitable for use mix 1 part weight. including the active substance with the specified amount of solvent and a specified amount of emulsifier; the concentrate is diluted with water to the specified table. 8 concentration.

Tree plum (Prunus domestica) with a height of about 30 cm, which is strongly affected by mites of fruit (Panonychus ulmi), are sprayed with the active ingredients of the desired concentration.

After 14 days determine effectiveness of action in %. 100% means that all the mites are killed, 0% means that the ticks are not affected at all.

Active substances, their concentrations and the results of the experiment are given in table. 8.

1. Derivatives of 1H-3-aryl-pyrrolidin-2,4-dione of the formula I

< / BR>
in which a and b denote, together with the carbon atom to which they relate, which is interrupted by at least one heteroatom 5-6-membered spirits, which contains nitrogen, oxygen or sulfur as heteroatom and may be substituted at the nitrogen atom of the group R1or COR1;

X - alkyl or halogen;

Y is alkyl or halogen;

Z - alkyl;

n = 0 or 1;

G - in lceil, alkoxyalkyl, cycloalkyl, substituted phenyl or heteroaryl;

R2- alkyl, phenyl or benzyl;

R3, R4and R5independently from each other - alkyl, alkylthio;

R6and R7- alkyl or together with the nitrogen atom to which they are linked, a cycle that may be interrupted by oxygen.

2. Derivatives of 1H-3-aryl-pyrrolidin-2,4-dione under item 1, having the following formulas Ia - If

< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
where A, B, E, L, M, X, Y, Z, R1, R2, R3, R4, R5, R6, R7and n have the above values.

3. Derivatives of 1H-3-aryl-pyrrolidin-2,4-dione under item 1 of the formula I in which A, B and the carbon atom to which they relate, mean 5-6-membered spiractin, which contains a group

< / BR>
oxygen or sulfur;

X is alkyl with 1-6 carbon atoms or halogen;

Y is alkyl with 1-6 carbon atoms or halogen;

Z is alkyl with 1-6 carbon atoms;

G is hydrogen or a group

< / BR>
< / BR>
< / BR>
in which E - ion ammonium;

L and M each is oxygen or sulfur;

R1- alkyl with 1-20 carbon atoms, alkenyl with 2-10 carbon atoms, alkoxyalkyl with 1-8 carbon atoms in the alkyl and parts of the CNS, cycloalkyl with 3-8 atoms in the ring, phenyl, Samedan is displaced phenyl or benzyl;

R3, R4and R5independently from each other - alkyl with 1-8 carbon atoms, alkylthio with 1-8 carbon atoms,

R6and R7- alkyl with 1-10 carbon atoms or together with the nitrogen atom to which they relate, signify 3-7-membered ring which may be interrupted by oxygen,

R9- R1or COR1and R1can't take those specified in paragraph 3 for R1value;

n = 0 or 1.

4. Derivatives of 1H-3-aryl-pyrrolidin-2,4-dione under item 1 of the formula I in which A, B and the carbon atom to which they relate, mean 5-6-membered spirits, which contains a group

< / BR>
oxygen or sulfur;

X is alkyl with 1-4 carbon atoms or halogen;

Y is alkyl with 1-4 carbon atoms or halogen;

Z is alkyl with 1-4 carbon atoms;

G is hydrogen or a group

< / BR>
< / BR>
< / BR>
in which E - ion ammonium;

L and M each is oxygen or sulfur;

R1- alkyl with 1-16 carbon atoms, alkenyl with 2-8 carbon atoms, alkoxyalkyl with 1-6 carbon atoms in the alkyl and parts of the CNS, cycloalkyl having 3-7 atoms in the ring, substituted by halogen phenyl, unsubstituted or substituted with chlorine furanyl, thienyl, pyridyl;

R2- alkyl 1-16 carbon atoms, unsubstituted phenyl or benslimane carbon;

R6and R7- alkyl with 1-8 carbon atoms or together with the nitrogen atom to which they are bound, form a 4-7-membered ring which may be interrupted by oxygen;

R9- COR1'and R1'is alkyl with 1-6 carbon atoms;

n = 0 or 1.

5. Derivatives of 1H-3-aryl-pyrrolidin-2,4-dione under item 1 of the formula I in which A, B and the carbon atom to which they relate, mean 5-6-membered spirits, which contains a group

< / BR>
oxygen or sulfur;

X is methyl or chlorine;

Y is methyl or chlorine;

Z - methyl;

G is hydrogen or a group

< / BR>
< / BR>
< / BR>
in which E - ion ammonium;

L and M each is oxygen or sulfur;

R1is alkyl with 1 to 14 carbon atoms, alkenyl with 2-6 carbon atoms, alkoxyalkyl with 1-4 carbon atoms in the alkyl part and 1 to 6 carbon atoms in the CNS part, cycloalkyl with 3-6 carbon atoms, substituted by chlorine, phenyl, unsubstituted or substituted with chlorine thienyl, furanyl or pyridyl;

R2- alkyl 1-14 carbon atoms, unsubstituted phenyl or benzyl;

R3, R4and R5independently of each is alkyl with 1-4 carbon atoms, alkylthio with 1-4 carbon atoms;

R6and R7is alkyl with 1-6 carbon atoms or together with the nitrogen atom, with 1' and R1'is alkyl with 1-4 carbon atoms;

n = 0 or 1.

6. Esters of N-acylaminoacyl formula II

< / BR>
in which A, B, X, Y, Z and n are specified in paragraph 1 values;

R8- alkyl,

representing the initial products to obtain the compounds of formula I under item 1.

7. Derivatives aminonitriles formula III

< / BR>
in which A, B, X, Y, Z and n are specified in paragraph 1 values representing intermediate products for preparing compounds of formula I under item 1.

8. The way to combat the damaging plants by insects and mites, including the active ingredient, a derivative of pyrrolidone and the target additives, characterized in that the active ingredient is a derivative of pyrrolidone contains a compound of the formula I

< / BR>
in which A and B denote, together with the carbon atom to which they relate, 5-6-membered spirits, which contains nitrogen, oxygen or sulfur as heteroatom and may be substituted at the nitrogen by lower alkyl or acyl;

X is alkyl with 1-6 carbon atoms or halogen;

Y is alkyl with 1-6 carbon atoms or halogen;

Z is alkyl with 1-4 carbon atoms;

n = 0 or 1;

G is hydrogen or the group - COR1where R1means alkyl with 1m nitrogen form a 6-membered cycle, interrupted by an oxygen atom, or

< / BR>
where M is an oxygen atom or sulfur;

R4is alkyl with 1-4 carbon atoms.

 

Same patents:

The invention relates to imidazopyridine, in particular, there are some derivatives of 4-substituted-1-/2-methylimidazo [4,5-C]pyrid-1-yl)-benzene and alkylbenzene

-n-performatic-3n, 6n-tiain with inotropic action, and method thereof" target="_blank">

The invention relates to organic chemistry, namely to a new connection, 4,5-dimethyl-2-n-propylthio-2--H-PERFLUORO - butyl-3N, 6N-Ticino and method thereof

The invention relates to imidazopyridine, in particular, there are some derivatives of 4-substituted-1-/2-methylimidazo [4,5-C]pyrid-1-yl)-benzene and alkylbenzene

The invention relates to new derivatives aminouksusnoy acid, which can be used for the production of biologically active peptides, and more particularly to aminouksusnoy acid derivative of General formula

< / BR>
where

Z - remains-O-, -S(O)n- where n means the number of O - 2,where R3means hydrogen, alkyl, alkenyl, quinil, cycloalkyl, cycloalkenyl, razmeshanny or substituted aryl, unsubstituted or substituted heteroaryl, fluorenylmethyl or group CX3where X represents halogen or aryl, -CH2)-mwhere m represents the number 1 - 4, -(CH2)n-CH=CH(CH2)n- where n has the above value, the formulas group

,

where

n has the above meaning,

,

where

R and n have the abovementioned meaning,

,

where

R and n have the abovementioned meaning,

-(CH2)n-CC-(CH2)n, ,

where

n has vysheukazannoe the specified value, and

,

where

R3has the above value,

R is hydrogen, methyl, trifluoromethyl, methoxy, hydroxyl, chlorine, bromine, fluorine, iodine, 2,4-dibromo, 2,4-dichloro, 2,4-debtor,

R1is hydrogen, alkyl, alkenyl, quinil, cycloalkyl, cycloalkenyl, unsubstituted or substituted aryl, arylalkyl, unsubstituted or substituted heteroaryl and fluorenylmethyl

The invention relates to compounds of the following formula 1, which inhibit the enzyme glycinamide ribonucleotide the formyl transferase (GARFT)
Up!