RU2038352C1 - Amine derivatives or their salts and insecticide composition on their base - Google Patents

Abstract

FIELD: organic chemistry. SUBSTANCE: product: derivatives of amine of the formula (R₁X)(R₂)N-CR₃-Z-R₄, where R₁ pyridyl which can be substituted with halogen, C₁-C₄--alkyl, halide-substituted C₁-C₄--alkyl, nonobligatory halide-substituted C₁-C₄--alkoxy, C₁-C₄--alkylmercapto, C₁-C₄--alkylsulfonyl, phenoxy, cyano, nitro, di-C₁-C₄--alkylamino-group for exception with nonsubstituted 2-pyridyl, pyrazyl, pyrazolyl, pyridazyl or thiazolyl which can be substituted with C₁-C₄--alkyl or halogen; X linear or branched C₁-C₃--alkylene; R₂-H, H, di-C₁-C₅--alkylcarbamoyl which is nonobligatory substituted with C₁-C₅--alkyl, C₂-C₅-alkenyl, C₂-C₅--alkynyl, C₃-C₆--cycloalkyl, phenyl or radical -Y--Y-R₅;; Y O, SO₂,, CO or CO₂,; R₅ H which is nonobligatory substituted with C₁-C₅--alkyl, C₃-C₆--cycloalkyl or nonobligatory substituted phenyl; R₃- H, nonobligatory substituted C₁-C₅--alkyl, C₂-C₅--alkenyl, C₃-C₈--alkynyl, C₃-C₈--cycloalkyl or C₃-C₈--cycloalkenyl; R₄ cyano or nitro; Z CH or N, or their salts. Reagent 1: R₁X(R₂)-NH, where R₁ and R₂ as indicated above. Reagent 2: R₃COCH₂R₄ where R₃ and R₄ as indicated above. Reaction conditions: isolation as free form or as a salt. Synthesized compounds were used as insecticides. EFFECT: improved method of synthesis. 3 cl, 4 tbl

Description

 The invention relates to new amine derivatives, processes for their preparation and insecticides containing said derivatives as selective compounds.

 Over the years, an enormous amount of chemical products have been developed and put into practical use in the field of insecticide research, for example organophosphorus insecticides such as parathion and malathion, and carbamate insecticides such as carbaryl and methomyl. These insecticides have played a very large role in improving agricultural production. However, in recent years, some of these insecticides are under control due to environmental pollution due to residue or accumulation in nature, in addition, as a result of use over a long period of time, infection with resistant insect pests takes place. Therefore, it is necessary to develop new chemical agents that have excellent insecticidal characteristics against various types of insect pests, including these resistant pests, and which can be used safely.

CH₂-NH

Cl
(Boll. Chim. Farm, 1979 118/11/661-666).A compound is known that does not have any insecticidal activity.

CH ₂ -NH

Cl
(Boll. Chim. Farm, 1979 118/11 / 661-666).

CH₂-NH

CH₃
Однако данное соединение не проявляет инсектицидной активности против чешуекрылых насекомых и зеленой рисовой цикадки, которые являются более серьезными вредителями для сельскохозяйственных культур, хотя оно обнаруживает активность против хлопковой тли.The following compound is described in US patent N 4918088, and has insecticidal activity

CH ₂ -NH

CH ₃
However, this compound does not exhibit insecticidal activity against lepidopteran insects and green rice circad, which are more serious pests for crops, although it exhibits activity against cotton aphids.

 The purpose of the invention is to provide agricultural chemicals that can be successfully synthesized on an industrial scale, have a specific effect and are safely applicable.

 The proposed compound has a high insecticidal activity against both lepidopteran and semi-winged insects.

R₃ (I) где R₁ необязательно замещенное 5-6-членное ароматическое гетерокольцо, содержащее атом азота, за исключением незамещенного 2-пиридила;
Х необязательно замещенный С₁-С₃-алкилен или алкилиден;
R₂ водород, карбамоил, моно- или ди-С₁-С₅-алкилкарбамоил, тиокарбамоил, моно- или ди-С₁-С₅-алкилтиокарбамоил, сульфамоил, моно- или ди-С₁-С₅-алкилсульфамоил, необязательно замещенный С₁-С₅-алкил, необязательно замещенный С₂-С₅- алкенил, необязательно замещенный С₂-С₅-алкинил, необязательно замещенный С₃-С₈-циклоалкил, необязательно замещенный С₃-С₈-циклоалкенил, необязательно замещенный арил или -Y-R₅;
Y O, S(O)n, CO, CS или СО₂;
n 0, 1 или 2;
R₅ водород, необязательно замещенный С₁-С₅-алкил, необязательно замещенный С₂-С₅-алкенил, необязательно замещенный С₂-С₅-алкинил, необязательно замещенный С₃-С₈-циклоалкил, необязательно замещенный С₃-С₈-циклоалкенил или необязательно замещенный арил;
R₃ водород, необязательно замещенный С₁-С₅-алкил, необязательно замещенный С₂-С₅-алкенил, необязательно замещенный С₂-С₅-алкинил, необязательно замещенный С₃-С₈-циклоалкил, или необязательно замещенный С₃-С₈-циклоалкенил;
R₄ циано или нитро;
Z СН или N; или его соли.The present invention relates to compounds having the formula
R ₁ -X-

R ₃ (I) where R _{1 an} optionally substituted 5-6 membered aromatic hetero ring containing a nitrogen atom, with the exception of unsubstituted 2-pyridyl;
X optionally substituted C ₁ -C ₃ alkylene or alkylidene;
R ₂ hydrogen, carbamoyl, mono- or di-C ₁ -C ₅ -alkylcarbamoyl, thiocarbamoyl, mono- or di-C ₁ -C ₅ -alkylthiocarbamoyl, sulfamoyl, mono- or di-C ₁ -C ₅ -alkylsulfamoyl, optional substituted C ₁ -C ₅ alkyl, optionally substituted C ₂ -C ₅ alkenyl, optionally substituted C ₂ -C ₅ alkynyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₃ -C ₈ cycloalkenyl, optionally substituted aryl or —YR ₅ ;
YO, S (O) n, CO, CS or CO ₂ ;
n is 0, 1 or 2;
R ₅ hydrogen, optionally substituted C ₁ -C ₅ alkyl, optionally substituted C ₂ -C ₅ alkenyl, optionally substituted C ₂ -C ₅ alkynyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₃ -C _8- cycloalkenyl or optionally substituted aryl;
R ₃ hydrogen, optionally substituted C ₁ -C ₅ alkyl, optionally substituted C ₂ -C ₅ alkenyl, optionally substituted C ₂ -C ₅ alkynyl, optionally substituted C ₃ -C ₈ cycloalkyl, or optionally substituted C ₃ - C ₈ cycloalkenyl;
R ₄ cyano or nitro;
Z CH or N; or its salt.

 The compounds of this invention may be suspended in accordance with the following reaction schemes.

-

+ R

R₄ или R

_____→

где r₁ и r₂ С₁-С₅-алкил;
R₁-R₄ и Х имеют указанные значения.1. The method of obtaining 1:

-

+ R

R ₄ or R

_____ →

where r ₁ and r _{2 is} C ₁ -C ₅ alkyl;
R ₁ -R ₄ and X have the indicated meanings.

где r₃ С₁-С₅-алкил;
R₁-R₃ и Х имеют указанные значения.The reaction is carried out in an inactive organic solvent, preferably in an aromatic hydrocarbon solvent such as xylene, toluene or benzene, in the presence of an acid catalyst such as n-toluenesulfonic acid, if necessary when heated under reflux (under reflux) (2). Production Method 2:
R

where r ₃ C ₁ -C ₅ -alkyl;
R ₁ -R ₃ and X have the indicated meanings.

 This reaction is carried out in an inert organic solvent, preferably in an alcohol such as methanol, ethanol, at a temperature between room temperature and the boiling point of the solvent used.

NH

R₃

R₁-X-

R₃
где Наl галоген;
R₁-R₃ и Х имеют указанные значения.3) Production Method 3:

NH

R ₃

R ₁ -X-

R ₃
where Hal is halogen;
R ₁ -R ₃ and X have the indicated meanings.

+ R

al _____→

где R₁-R₃, Х и Hal имеют указанные значения. Данная реакция осуществляется таким же образом, как реакция способа получения 3.This reaction is carried out in an inert organic solvent, preferably in DMF, THF, benzene, acetonitrile, acetone, methyl ethyl ketone, in the presence of an acid acceptor such as potassium carbonate, sodium hydride, triethylamine, between the room temperature and the boiling point of the solvent used
4) Production Method 4:

+ R

al _____ →

where R ₁ -R ₃ X and Hal have the indicated meanings. This reaction is carried out in the same manner as the reaction of the production method 3.

R₃

R₁-X-

где R₁-R₃ и Х имеют указанные значения.(5) Production Method 5:
R

R ₃

R ₁ -X-

where R ₁ -R ₃ and X have the indicated meanings.

This reaction is carried out in an inert organic solvent, preferably acetonitrile, hydrocarbon tetrachloride, dichloroethane, in the presence of a nitrating reagent such as nitronium tetrafluoroborate, between ^-20 ° C and the boiling point of the solvent used.

 After the reaction is complete, ordinary post-treatment gives the title compound. The structure of the compounds of this invention was determined using such means as IR, NMR, mass spectra, etc.

R₃ R₁-X-N

R₃
Могут также существовать синантиизмеры, если Z N, и цистрансизомеры, если Z СН, представленные
R₁-X-

R₃ R₁-Z-

R₃
Соотношение варьирует в зависимости от, например, условий инструментов для проведения анализа.If R _{2 is} hydrogen in the compound of this invention, tautomers present as
R ₁ -X-NH

R ₃ R ₁ -XN

R ₃
There may also exist synantiomers if ZN, and cystransisomers if Z CH represented
R ₁ -X-

R ₃ R ₁ -Z-

R ₃
The ratio varies depending on, for example, the conditions of the analysis tools.

 The following examples illustrate the invention.

CH₂NH₂+C₂H₅COCH₂NO₂ ____→

CH₂NH

В 50 мл толуола смешивали 4,2 г 2-хлор-5-пиридилметиламина, 3,5 г 1-нитро-2-бутанона и 0,1г n-толуолсульфоновой кислоты, смесь нагревали с обратным холодильником в течение 2 ч. Растворитель затем отгоняли и остаток очищался с помощью хроматографии на колонке на силикагеле, давая 4,1 г соединения N 368, (табл. 1) т.пл. 95-98^оС.PRI me R 1. 2- (2-Chloro-5-pyridylmethylamino) -1-nitro-1-butene

CH ₂ NH ₂ + C ₂ H ₅ COCH ₂ NO ₂ ____ →

CH ₂ NH

4.2 g of 2-chloro-5-pyridylmethylamine, 3.5 g of 1-nitro-2-butanone and 0.1 g of n-toluenesulfonic acid were mixed in 50 ml of toluene, the mixture was heated under reflux for 2 hours. The solvent was then distilled off. and the residue was purified by column chromatography on silica gel, giving 4.1 g of compound N 368, (table. 1) so pl. 95-98 ^about S.

CH₂NH₂+CH₃COCH₂CN ____→

CH₂NH

1,4 г 2-хлор-5-пиридилметиламина и 0,8 г 1-циано-2-пропанола смешивали и смесь перемешивали при комнатной температуре на протяжении ночи. Растворитель затем отгонялся и остаток очищался с помощью хроматографии на колонке из силикагеля, давая 1,7 г соединения N 528. (табл. 1). Т.пл. 95-98^оС.PRI me R 2. 2- (2-Chloro-5-pyridylmethylamino) -1-cyano-1-propene

CH ₂ NH ₂ + CH ₃ COCH ₂ CN ____ →

CH ₂ NH

1.4 g of 2-chloro-5-pyridylmethylamine and 0.8 g of 1-cyano-2-propanol were mixed and the mixture was stirred at room temperature overnight. The solvent was then distilled off, and the residue was purified by silica gel column chromatography to give 1.7 g of compound N 528. (Table 1). Mp 95-98 ^about S.

CH₂NHCH₃+C₂H₅O

H₃ ______→

CH

H₃
В 20 мл метанола смешивали 1,6 г N-метил-2-хлор-5-пиридилметиламина и 1,2 г этил-N-цианоацетамидина, смесь перемешивали при комнатной температуре в течение ночи. Растворитель затем отгонялся и остаток очищался с помощью хроматографии на колонке на силикагеле, давая 1,8 г соединения N 22 (табл. 1) Т.пл. 101-103^оС.PRI me R 3. N-Cyano-N- (2-chloro-5-pyridylmethyl) -N-methylacetamidine

CH ₂ NHCH ₃ + C ₂ H ₅ O

H ₃ ______ →

CH

H ₃
1.6 g of N-methyl-2-chloro-5-pyridylmethylamine and 1.2 g of ethyl N-cyanoacetamidine were mixed in 20 ml of methanol, and the mixture was stirred at room temperature overnight. The solvent was then distilled off, and the residue was purified by silica gel column chromatography to give 1.8 g of compound N 22 (Table 1) mp. 101-103 ^about S.

CH₂NH

H₃ + C₂H₅I ______→

CH

H₃
0,7 г Гидрид натрия (чистота 60% 0,7 г) добавляли к раствору 3 г N-циано-N-(2-хлор-5-пиридилметил)ацетамидина в 20 мл N,N-диметилформамида при температуре ледяной бани. После перемешивания смеси при той же температуре в течение 1 ч к смеси добавляли 2,7 г иодистого этила с последующим перемешиванием в течение 5 ч при комнатной температуре. Реакционную смесь затем выливали в смесь льда с водой, экстрагировали этилацетатом, сушили над безводным сульфатом магния и концентрировали при пониженном давлении. Полученный остаток очищался с помощью хроматографии на колонке на силикагеле, давая 1,6 г соединения N 51 (табл. 1). Т.пл. 100-101^оС.PRI me R 4. N-Cyano-N '- (2-chloro-5-pyridylmethyl) -N'-ethylacetamidine

CH ₂ NH

H ₃ + C ₂ H ₅ I ______ →

CH

H ₃
0.7 g Sodium hydride (purity 60% 0.7 g) was added to a solution of 3 g of N-cyano-N- (2-chloro-5-pyridylmethyl) acetamidine in 20 ml of N, N-dimethylformamide at an ice bath temperature. After the mixture was stirred at the same temperature for 1 hour, 2.7 g of ethyl iodide was added to the mixture, followed by stirring for 5 hours at room temperature. The reaction mixture was then poured into a mixture of ice and water, extracted with ethyl acetate, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to give 1.6 g of compound N 51 (Table 1). Mp 100-101 ^about C.

H₃ +

______→

Нитрид натрия (чистота 60% 0,6 г) добавляли к раствору 1,3 г N-циано-N'-метилацетамидина в 20 мл N,N-диметил- формамида при температуре ледяной бани. После перемешивания смеси при той же температуре в течение 1 ч к смеси добавляли 2,2 г 2-хлор-5-пиридилметилхлорида с последующим перемешиванием в течение 5 ч при комнатной температуре. Реакционную смесь затем выливали в смесь лед-вода, экстрагировали этилацетатом, сушили над безводным сульфатом магния и концентрировали при пониженном давлении. Полученный остаток очищался с помощью колонной хроматографии на силикагеле, давая 1,5 г соединения N 22 (табл. 1). Т.пл. 101-103^оС.PRI me R 5. N-Cyano-N- (2-chloro-5-pyridylmethyl) -N'-methylacetamidine
CH ₃ NH

+ ₃ H

______ →

Sodium nitride (purity 60% 0.6 g) was added to a solution of 1.3 g of N-cyano-N'-methylacetamidine in 20 ml of N, N-dimethylformamide at an ice bath temperature. After the mixture was stirred at the same temperature for 1 hour, 2.2 g of 2-chloro-5-pyridylmethyl chloride was added to the mixture, followed by stirring for 5 hours at room temperature. The reaction mixture was then poured into ice-water, extracted with ethyl acetate, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to give 1.5 g of compound N 22 (Table 1). Mp 101-103 ^about S.

⁺

К 40 мл этанола добавляли 5,1 г N-(2-хлор-5-пиридилметил)-N-метиламина, а затем 4 г хлоргидрата этилацетамидата при 0^оС. После перемешивания в течение часа реакционная смесь оставлялась подогреваться до комнатной температуры и перемешивалась на протяжении ночи. Растворитель затем отгонялся. Полученный белый остаток промывался диэтиловым эфиром, давая 7,3 г целевого соединения. Т.пл. 192-197^оС.Reference example. N- (2-chloro-5-pyridyl) -N-methylacetamidine hydrochloride

⁺

To 40 ml of ethanol was added 5.1 g of N- (2-chloro-5-pyridylmethyl) -N-methylamine, and then 4 g of ethyl hydrochloride at 0 ^C. After stirring for one hour the reaction mixture was allowed to warm to room temperature and stirred throughout the night. The solvent was then distilled off. The resulting white residue was washed with diethyl ether to give 7.3 g of the target compound. Mp 192-197 ^about S.

К суспензии 1 г N-(2-хлор-5-пиридилметил)-N-метиламинхлоргидрата в 10 мл сухого ацетонитрила добавляли по каплям 0,7 г ДВV в атмосфере азота при комнатной температуре. После перемешивания в течение 30 мин раствор добавляли по каплям к суспензии 0,6 г тетрафторбората нитрония в 5 мл сухого ацетонитрила в атмосфере азота при охлаждении с помощью cмеси льда с водой и оставляли перемешиваться в течение 4 ч. После этого смесь выливалась в смесь лед-вода, затем экстрагировалась несколько раз хлороформом. Объединенный хлороформный слой сушился над сульфатом магния, фильтровался и отгонялся. Неочищенное масло очищалось с помощью колоночной хроматографии на силикагеле, давая0,3 г соединения N 236 (табл. 1).N_D ²⁵ 1,5808.PRI me R 6. N- (2-Chloro-5-pyridylmethyl) -N-methyl-N-nitroacetamidine

To a suspension of 1 g of N- (2-chloro-5-pyridylmethyl) -N-methylamine hydrochloride in 10 ml of dry acetonitrile was added dropwise 0.7 g of DBV in a nitrogen atmosphere at room temperature. After stirring for 30 minutes, the solution was added dropwise to a suspension of 0.6 g of nitronium tetrafluoroborate in 5 ml of dry acetonitrile in a nitrogen atmosphere while cooling with ice-water and allowed to mix for 4 hours. After that, the mixture was poured into ice-ice water, then extracted several times with chloroform. The combined chloroform layer was dried over magnesium sulfate, filtered and distilled off. The crude oil was purified by silica gel column chromatography to give 0.3 g of compound N 236 (Table 1). N _D ²⁵ 1.5808.

 Typical examples of the compounds of this invention, including the compounds described above, are listed in table. 1.

 The compounds of this invention exhibit high insecticidal activity against various types of insect pests, such as scoops, cabbage moths, aphids, cicadas and delphacides. In recent years, a decrease in the regulatory effect of organophosphorus and carbamate insecticides, which is caused by the development of resistance to these insecticides, has become a serious problem. In this situation, the development of new insecticides that are effective against resistant pests is very necessary. The compounds of this invention have superior insecticidal activity not only against susceptible strains, but also against resistant organisms.

 The insecticides of the present invention contain, as active ingredients, one or more types of compounds expressed by the general formula (1). These active ingredients can be used as they are, but are usually used in any of the forms common to conventional agricultural pesticides, namely, in the form of a wettable powder, dust, emulsifiable concentrate, suspension concentrates, fumigation chemicals, fumigants, granules or other finished formulations. Soy flour, wheat flour or other types of vegetable flour, diatomaceous earth, apatite, gypsum, talc, pyrophyllite clay or other finely divided mineral powders, when solid formulations are needed, are used as additives and carriers.

 When liquid formulations are required, then kerosene, mineral low, oil, naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, water, etc. are used as solvents. If necessary, surface-active agents can be added. to obtain a homogeneous and suitable formulation. Wettable powders, emulsifiable concentrates, suspension concentrates, etc. obtained in this way are diluted with water to obtain suspensions or emulsions of a given concentration, before they are actually sprayed onto the plants in the field. Dusts or granules are applied directly without additional processing.

 The compound of this invention is effective, but they can be used when mixed with various types of insecticides, acaricides and fungicides.

 Typical examples of acaricides and insecticides that can be used when mixed with the compounds of this invention are as follows.

 Acaricides (fungicides): chlorobenzylate, chloropropylate, proclonol, bromopropylate, dicofol, dinobuton, binapacryl, chlordemeform, amitraz, propargite, PPPS, benzooximate, hexithiazox, phenbutatin phosphonetene, chlorofenzoimphenonefenonefenonefenonefenonefenonefenonefenonefenonefenonefenonefenonefenonefenonefenonefenonefenonefenonefenotenefontefonimonetonefenotenefentonomethinonefenonefenotenefenotenefentone , phenazachine, pyridaben, fenproximate, chlorphenetol, thiofanatmethyl, benomyl, thiram, iprobenfos, edifenfos, phthalide, probenazole, isopropiolan, chlorothalonil, captan, polyoxin-B, blastidin-S, casolamycin, pyrolamycin, pyrogamycin, pyrogamycin, pyrogamycin, pyrogamycin, pyrogamycin, zinoxide, mepronil, flutalonil, pencicuron, iprodion, gimexazole, metalaxyl, triflumisole, diclomesine, teclofthalam, vinclozolin, procymidone, bitertanol, triadimefon, prochloraz, pyrifenoxin oximerfin oxoflorfoximorphin triphoric oxflorfox aminoforfinoxin triphosphoric acid triforum oxiflorfoxin triphosphoric acid triforum oxiflorfin oxorphin triphosphoric acid triforum oxiflorfin oxiforfin oxiforfinoxin triphosphoric acid triforficfromfinformin triphoric acid triforficfromfinoxin triphosphoric acid peroxidine, dichloromethane, etoquinolac, TPTH, propamocarb, fosetil, dihydrostreptomycin, anilazine, dithianon, dietofencarb.

 Insecticides (acaricides): organophosphorus and carbamate type; for example fenthion, phenytrotion, diazinon, chloripyrifos, oxydeprofos, vamidothion, fentoate, dimethoate, formotion, malathion, trichlorfon, thiometon, phosphmet, menazone, dichlorvos, acephate, EPBP, dialiphos, parathionomethyl, ethydebomethoxymethoxybimethoxybenzo, , VRMS, pyraclophos, monocrotophos, salition, cartap, carbosulfan, carbofuran, benfuracarb, metolcarb, carbaryl, pyrimicarb, etiofencarb, phenoxycarb.

 Pyrethroid insecticides (acaricides): permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropatrin, pyrethrins, allethrin, tetramethrin, resmethrin, partrin, dimethrin, propratrin, bifentrin, protrin, fluvalinate, cyfluthrin, cyclotrin troprin, cyflotrin tetrin, cyclotrin tetrin .

 Benzoylphenylurea type insecticides and other types: diflubenzuron, chlorofluazuron, triflumuron, teflubenzuron, buprofesin, pyriproxifen, flufenoxuron, machine oil.

 The following are some examples of formulations. Carriers of surface-active agents and others that are added are not limited to these examples.

 PRI me R 7. Emulsifiable concentrate, hours

The compound of this invention 10 Alkylphenolpolyoxyethylene 5 Dimethylformamide 50 Xylene 35
The components are mixed and dissolved. For use in spraying or spraying, the liquid mixture is diluted with water to form an emulsion.

 PRI me R 8. Wettable powder, hours

The compound of the present invention 20
Sulfuric acid ester of higher alcohol 5 Diatomaceous earth 70 Silicon dioxide 5
These components are mixed and crushed to obtain a fine powder, which for use by spraying is diluted with water to obtain a suspension.

PRI me R 9: Dust, h:
The compound of the present invention 5 Talc 94.7 Silica 0.3
These ingredients are mixed and crushed, used in crushed form when sprayed.

 PRI me R 10. Granules, h

The compound of this invention 5 Clay 73 Bentonite 20
Sodium Dioctyl Sulfosuccinate 1 Sodium Phosphate 1
These compounds are granulated and used when used as they are.

 Industrial applicability.

 The following tests show the insecticidal activity of the compounds of this invention.

 Trial 1. Efficacy against cotton aphids.

30-50 cotton aphid insects were inoculated per plot (tray) using a small brush on the leaves of cucumbers, which were sown in trays, 10 cm in diameter, 10 days old. after germination. After a day, the affected insect pests (injured) were removed, a chemical solution was sprayed, which was prepared so that the emulsifiable concentrate described in Example 7 was diluted with water to a concentration of compound 125 ppm. as prescribed. The trays were placed in a thermostatic chamber at ²⁵ ° C and 65% RH After 7 days the number of living pests was counted, control or destruction efficiency was calculated in comparison with the case of untreated tray. The results are shown in table. 2.

 T rticle 2. Efficiency in relation to the green rice circad.

Rice seedlings after germination of 7 days. immersed in a chemical solution, which was prepared so that the emulsifiable insecticide concentrate described in example 7 was diluted with water to a concentration of compound 125 parts. / million for 30 s. After air drying, the treated seedlings were placed in experimental tubes and 10 insects of the 3rd stage of green rice cicadas resistant to organophosphate and carbamate insecticides were inoculated with larvae. Tubes coated gauze and placed in a thermostat at 25 ^{° C} and humidity of 65% after 5 days. checked mortality.

 The results are shown in table. 3.

 And with the test 3. Efficiency against rice scoops.

Test compounds were converted to a wettable powder formulation in the same manner as in Example 8. The compounds were diluted with water to a concentration of 125 ppm. Corn leaves were immersed in a chemical solution for 30 s. After air drying, the treated sheet was placed in a Petri dish and five larvae of the rice scoop of the 3rd age stage were inoculated. Petri dishes closed by glass lids and placed in an incubator with temperature ^of 25 C and relative humidity of 65% mortality was checked after 5 days. Each experiment was repeated twice. The results are shown in table. 4.

Claims (2)

1. Derivatives of the amine of the General formula

where R _{1 is} pyridyl which may be substituted with halogen, C ₁ –C ₄ -alkyl, halogen-substituted C ₁ –C ₄ -alkyl, C ₁ –C ₄ -alkoxy, C ₁ –C ₄ -alkyl mercapto, C ₁ –C ₄ -alkylsulfonyl, phenoxy, cyano, di-C ₁ -C ₄ -alkylamino, with the exception of unsubstituted 2-pyridyl, pyrazyl, pyrazolyl, pyridazyl or thiazolyl, which may be substituted with C ₁ -C ₄ -alkyl or halogen;
X is straight or branched C ₁ C ₃ alkylene;
R ₂ hydrogen, di-C ₁ C ₅ -alkylcarbamoyl, optionally substituted C ₁ C ₅ -alkyl, C ₂ C ₅ -alkenyl, C ₂ - C ₅ -alkynyl, C ₃ C ₆ -cycloalkyl, phenyl or radical Y - R ₅ , where YO, SO ₂ , CO or CO ₂ , and R _{5 is} hydrogen, optionally substituted C ₁ C ₅ alkyl, C ₃ - C ₆ cycloalkyl or halogen substituted phenyl;
R _{3 is} hydrogen, optionally substituted C ₁ C ₅ alkyl or C ₃ C ₆ cycloalkyl;
R ₄ cyano or nitro;
Z CH or N,
or their salts. 2. An insecticidal composition containing an amine derivative and target additives as an active ingredient, characterized in that a compound of the general formula is used as an amine derivative

where R _{1 is} pyridyl which may be substituted with halogen, C ₁ –C ₄ -alkyl, halogen-substituted C ₁ –C ₄ -alkyl, C ₁ –C ₄ -alkoxy, C ₁ –C ₄ -alkyl mercapto, C ₁ –C ₄ -alkylsulfonyl, phenoxy, cyano, di-C ₁ -C ₄ -alkylamino, with the exception of unsubstituted 2-pyridyl, pyrazyl, pyrazolyl, pyridazyl or thiazolyl, which may be substituted with C ₁ -C ₄ -alkyl or halogen;
X is straight or branched C ₁ C ₃ alkylene;
R ₂ hydrogen, di-C ₁ C ₅ -alkylcarbamoyl, optionally substituted C ₁ C ₅ -alkyl, C ₂ C ₅ -alkenyl, C ₂ - C ₅ -alkynyl, C ₃ C ₆ -cycloalkyl, phenyl or radical Y - R ₅ , where YO, SO ₂ , CO or CO ₂ , and R _{5 is} hydrogen, optionally substituted C ₁ C ₅ alkyl, C ₃ C ₆ cycloalkyl or halogen substituted phenyl;
R _{3 is} hydrogen, optionally substituted C ₁ C ₅ alkyl or C ₃ C ₆ cycloalkyl;
R ₄ cyano or nitro;
Z CH or N,
or their salts in an amount of 5 to 20 wt. targeted additives rest.

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