AMINE DERIVATIVES

Abstract: The present invention relates to a compound having formula (I) which has an excellent insecticidal activity, wherein R1 represents an optionally substituted 5-6 membered aromatic hetero ring containing nitrogen atom, except a non-substituted 2-pyridyl; X represents an optionally substituted C1-3 alkylene or alkylidene; R2 represents a hydrogen, a carbamoyl, a mono or di C1-5 alkyl carbamoyl, a thiocarbamoyl, a mono or di C1-5 alkylthiocarbamoyl, a sulfamoyl, a mono or di C1-5 alkylsulfamoyl, an optionally substituted C1-5 alkyl, an optionally substituted C2-5 alkenyl, an optionally substituted C2-5 alkynyl, an optionally substituted C3-8 cycloalkyl, an optionally substituted C3-8 cycloalkenyl, an optionally substituted aryl or -Y-R5; Y represents O, S(O)n, CO, CS or CO2; n represents 0, 1 or 2; R5 represents a hydrogen, an optionally substituted C1-5 alkyl, an optionally substituted C2-5 alkenyl, an optionally substituted C2-5 alkynyl, an optionally substituted C3-8 cycloalkyl, an optionally substituted C3-8 cycloalkenyl or an optionally substituted aryl; R3 represents a hydrogen, an optionally substituted C1-5 alkyl, an optionally substituted C2-5 alkenyl, an optionally substituted C2-5 alkynyl, an optionally substituted C3-8 cycloalkyl or an optionally substituted C3-8 cycloalkenyl; R4 represents a cyano or a nitro; and Z represents CH or N; or its salt.

Description: DESCRIPTION Amine Derivatives Technical Field: The present invention relates to new amine derivatives, the processes for the production thereof and insecticides containing the said derivatives as effective compounds. Background art: A large number of chemicals, for example, organophosphorus insecticides such as parathion and malathion and carbamate insecticides such as carbaryl and methomyl, have been developed and put to practical use by research and development on insecticides over many years. These insecticedes have played a very great role for the improvement of agricultural production. However, in recent years some of these insecticides are regulated on their use because of problems such as environmental pollution due to residue or accumulation, or cause infestitation of resistant insect pests as a result of long-term use. Therefore, it is demanded to develop new chemicals which have excellent insecticidal characteristics over various types of insect pests including these resistant insect pests and which can be used safely. The following compound is known as the analogous compound of this invention, which has no insecticidal activity. CN / (Boll. Chim. Farm., 1979 118(11)661-666) Further, the following compound is described in USP 4918088, which has insecticidal activities. CN N The compound however shows no insecticidal activity against lepidopterous insects and green rice leafhopper which are more serious pests on crops, though it shows the activity against cotton aphid. The purpose of this invention is to provide agricultural chemicals which can be advantageously synthesized industrially, have certain effects and are applicable safely. The compound of this invention has high insecticidal activity against both lepidopterous and hemipterous insects . Disclosure of Invention: The present invention relates to a compound having the formula I 4 wherein R, represents an optionally substituted 5 - 6 membered aromatic hetero ring containing nitrogen atom, except a non- substituted 2-pyridyl; X represents an optionally substituted c 1 _ 3 alkylene or alkylidene; R- represents a hydrogen, a carbamoyl, a mono or di C, ,. alkyl carbamoyl, a thiocarbamoyl, a mono or di alkylthiocarbamoyl, a sulfamoyl, a mono or di c ι_5 alkylsulfamoyl, an optionally substituted c ι _5 alkyl, a optionally substituted C ? ,- alkenyl, an optionally substitute C_ - alkynyl, an optionally substituted c 3 _ g cycloalkyl, a optionally substituted C 3_o cycloalkenyl, an optionall substituted aryl or -Y-R-.; Y represents O, S(O) , CO, CS or C0 ; n represents 0,1 or 2; R,- represents a hydrogen, an optionally substituted C. g alkyl, an optionally substituted C_ ,_ alkenyl, an optionally substituted C„ _ alkynyl, an optionally substituted C 3_ « cycloalkyl, an optionally substituted 3 _„ cycloalkenyl or an optionally substituted aryl; R_. represents a hydrogen, an optionally substituted C., 5 alkyl, an optionally substituted 2_5 alkenyl, an optionally substituted __ 5 alkynyl, an optionally substituted C 3_g cycloalkyl or an optionally substituted C__ g cycloalkenyl; R. represents a cyano or a nitro; and Z represents CH or N; or its salt. Best Mode for Carrying Out the Invention: The compounds of this invention can be prepared in accordance with the following reaction schemes: (1) Preparation Method 1: Or R 1--X- > (ID (HI) (HI)' 1 2 where r and r represent a C,_-. alkyl; and R. , R 2 , R 3 , R. and X are as defined above . 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 acidic catalyst such as p-toluenesulfonic acid, if necessary, under reflux. (2) Preparation method 2: R.j (ID (IV) (I") 3 where r represents a C, ,_ alkyl: and R, , R-, , R 3 and X are as defined above. This reaction is carried out in an inactive organic solvent, preferably in an alcohol such as methanol, ethanol, between room temperature and the boiling point of the used solvent. (3) Preparation Method 3: CN CN N I + R 2 -Hal N I R χ -X-NHA \R R 1 -X- ^ \R 3 R 2 ( I ' " ) (V) ( I" ) where Hal represents a halogen; and R- , R- , R ~ and X are as defined above. This reaction is carried out in an inactive organic solvent, preferably DMF, THF, benzene acetonitrile, acetone, methylethylketone , in the presence of acid accepter such as potassium carbonate, NaH, triethylamine, between room temparature and the boiling point of the used solvent . (4) Preparation Method 4: where R» , R-, , R-., X and Hal are as defined above. This reaction is carried out in the same manner as that of Preparation Method 3. (5) Preparation Method 5: R 2 (VIII) (I' " ) where R- , R_ , R_ and X are as defined above. This reaction is carried out in an inactive organic solvent, preferably acetonitrile, carbon tetrachloride, dichloroethane , in the presence of nitration reagent such as nitronium tetrafluoroborate , between -20°C and the boiling point of the used solvent. After the reaction is completed, an usual after-treatment gives the intended compound. The structure of the compounds of this invention was determined by such means as IR, NMR, MASS, etc. When R ~ is hydrogen in a compound of this invention, tautomers represented by can exist. The syn - aniti isomers, when Z represents N, and the cis-trans isomers, when Z represents CH, as represented by, can also exist. The ratio varies depending on e.g. conditions of instrumental analysis. The following examples illuslrate the present invention. Example 1 : 2 - ( 2 -chloro-5-pyridylmethylamino ) - 1-nitro- l-butene : In 50ml of toluene, 4.2g of 2-chloro-5-pyridylmethylamine, 3.5g o l-nitro-2-butanone and O.lg of p-toluene sulfonic acid were mixe and the mixture was refluxed for 2 hours . The solvent was then distilled off and the residue was purified by column chromatography on silica gel to afford 4. lg of compound No. 368. .p. 95-98°C Example 2 : 2-( 2-chloro-5-pyridylmethylamino )-1-cyano-l-propene: 1.4g of 2-chloro-5-pyridylmethylamine and 0.8g of l-cyano-2- propanone were mixed and the mixture was stirred at room temperature over night . The solvent was then distilled off and the residue was purified by column chromatography on silica gel to afford 1.7g of compound No. 528. m.p. 95-98°C Example 3 : N-cyano-N 1 -( 2-chloro-5-pyridylmethyl)-N' -methylacetamidine: In 20ml of ethanol, 1.6g of N-methyl-2-cloro-5-pyridylmethylamine and 1.2g of ethyl-N-cyanoacetamidine were mixed and the mixture was stirred at room temperature over night. The solvent was then distilled off and the residue was purified by column chromatography on silica gel to afford 1.8g of compound No. 22. m.p. 101-103°C Example 4 : N-cyano-N'-(2-chloro-5-pyridylmethyl)-N' -ethylacetamidine: 0.7g of sodium hydride (purity 60%) was added to the solution of 3.0g of N-cyano-N' -(2-chloro-5-pyridylmethyl)acetamidine in 20ml of N.N-dimthylformamide at ice bath temperature. After stirring it at the same temperature for 1 hour, 2.7g of ethyl iodide 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 pressre. The residue obtained was purified by column chromatography on silica gel to afford 1.6g of compound No. 51. m.p. 100-101°C Example 5 : N-cyano-N-(2-chloro-5-pyridylmethyl)-N' -methylacetamidine: 0.6g of sodium hydride (purity 60%) was added to the solution of 1.3g of N-cyano-N' -methylacetamidine in 20ml of N,N- dimethylformamide at ice bath temperature. After stirring it at the same temperature for 1 hour, 2.2g of 2-chloro-5- pyridylmethylchlride was added to the mixture, followed by stirring for 5 hours at room temperature. The reaction mixture was then poured into ice-water, extrated with ethyl acetate, dried over anhydrous magnesium sulfate and concentrated under reduced pressre The residue obtained was purified by column chromatography o silica gel to afford 1.5g of compound No.22 m.p. 101-103 C C Reference Example : N-(2-chloro-5-pyridylmethyl)-N-methylacetamidine hydrochloride : NH-HC1 NH'HCl . T" » cl Qr c cH3 To 40ml of ethanol was added 5.1g of N-(2-chloro-5-pyridylmethyl)- N-Methylamine and then, 4g of ethyl acetimidate hydrochloride at 0°C. After stirring for an hour, the reaction mixture was allowed to warm to room temperature and stirred over night. The solvent was then distilled off. The obtained white residue was washed with diethyl ether to afford 7.3g of the title compound m.p. 192-197°C Example 6 : N-(2-chloro-5-pyridylmethyl)-N-methyl-N'-nitroacetamidine: To a suspension of lg of N-(2-chloro-5-pyridylmethyl)-N- methylamidine hydrochloride in 10ml of dry acetonitrile was added dropwise 0.7g of DBU under nitrogen at room temperature. After stirring for 30 minutes, the solution was added dropwise to a suspension of 0.6g of nitronium tetrafluoroborate in 5ml of dry acetonitrile under nitrogen on cooling with ice-water and let stir for 4 hours. After which time, the mixture was poured into ice- water, then extracted several time with chloroform. The combined chloroform layer was dried over magnesium sulfate, filtered and distilled off. The crude oil was purified by column chromatgraphy on silica gel to afford 0,3g of compound No. 236. N 25 1.5808 D Typical examples of this invention including those described above are listed in Table 1. R.X R. R» R. [ 3 m.p.°C CHa 25 5 CH 2 CI -L CIi 3 CN n D 1.5910 C£ N CHaCHa C II 25 5 CHs n D " 1.6162 = \ II // CHs [115-117 3 OCHs II CHs [110-112 3 CHO II CHs 25. 5 COCHs II n D 1.5475 CHs [ 84- 86 3 SO2 2CI1I13 H [160-163 3 CHa -C.C C0 \_/ CHs [112-114 J No. R.X Rs Rs R, C 3 ID. P. °C 212 Calis CN 21. 5 213 CHs n D 1.5665 214 CHaCi 215 Calls 216 CSIITO) 217 CHa 218 CZaHπEs // // 219 COCIIs // 220 CHs 221 SOa 2C WHill 222 // CHs * 1 'H-NMR(CDCls) cAppm 3.32 (s,3H), 4.63 (s.2H). 7.37 (d, 111), 7.62 (dd, HI), 8.37 (d, 111) The compounds of this invention exhibit high insecticidal activities against various species of insect pests such as cutworms , diamondback moth, aphids , leafhoppers and planthoppers . In recent years the decrease of the control effects of organophosphorus and carbamate insecticides , which is caused by the development of resistance to these insecticides, has become serious problem. In such situations, the development of new insecticides which is effective on the resistant pests has been desired. The compounds of this invention possess superior insecticidal activities against not only susceptible strains but also resistant ones . The insecticides covered by this invention contain as active ingredients one or more types of the compounds as expressed by the general formula (1). These active ingredients, may be used as- produced but normally they are used in any of the forms which ordinary agricultural chemicals can take, namely wettable powder, dust, emulsifiable concentrate, suspension concentrates, smoking chemicals, fumigant, granule, or other formulations. For additives and carriers are used soybean flour, wheat flour or other vegetable flours, diatomaceous earth, apatite, gypsum, talc, pyrophyllite, clay or other fine mineral powders, when solid formulations are intended. When liquid formulations are intended, then for solvents are used kerosene, mineral oil, petroleum, solvent naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, water, etc. A surface active agent may, if necessary, be added in order to give a homogeneous and suitable formulation. The wettable powders, emulsifiable concentrates, suspension concentrates, etc. thus obtained are diluted with wate into suspensions or emulsions of a prescribed concentration, befor they are actually sprayed on plants in the field. In the case o dusts or granules, they are directly applied without furthe processing. It goes without saying that the compound(s) of this inventio is effective even alone, but it can be used by mixing with various types of insecticides, acaricides and fungicides. Typical examples of acaricides and insecticides which can be used by mixing with the compounds of this invention are described below: Acaricides ( fungicides) : chlorobenzilate, chloropropylate, proclonol, bromopropylate, dicofol, dinobuton, binapacryl, chlordimeform, amitraz , propargite, PPPS, benzoximate, hexythiazox, fenbutatin oxide, polynactine , chinomethiona , thioquinox, chlorfenson, tetradifon, phenproxide, avermectins , clofentezine , flubenzimine , fenazaquin, pyridaben, fenproximate, chlorfenethol, thiophanate-methyl, benomyl, thiram, iprobenfos, edifenfos, fthalide, probenazole, isoprothiolane, chorothalonil, captan, polyoxin-B, blasticidin-S, kasugamycin, validamycin, tricyclazole, pyroquilon, phenazine oxide, mepronil, flutolanil, pencycuron, iprodione, hymexazole, metalaxyl, triflumizole, diclomezine, tecloftalam, vinclozolin, procymidone , bitertanol, triadimefon, prochloraz , pyrifenox, fenarimal, fenpropimorph, triforine , metalaxyl, oxycarboxin, pefrazoate, diclomedine, fluazinam, oxadixyl, ethoquinolac, TPTH, propamocarb, fosetyl, dihydrostrepto ycin, anilazine, dithianon, diethofencarb. Organophosphorus-type and carbamate-type insecticides( acaridides) : fenthion, fenitrothion , diazinon, chlorpyrifos , oxydeprofos , vamidothion, phenthoate, dimethoate, formothion, malathion, trichlorfon, thiometon, phosmet , menazon, dichlorvos , acephate , EPBP, dialifos, parathion-methyl, oxydemeton-methyl, ethion, aldicarb, propoxur, methomyl, fenobucarb, BPMC, pyraclofos , monocrotophos , salithion, cartap, carbosulfan carbofuran, benfuracarb, metolcarb, carbaryl, pirimicarb, ethiofencarb, fenoxycarb, Pyrethroide-type insecticides (acaricides): permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropathrin, pyrethrins, allethrin, tetramethri , resmethrin , parthrin, dimethrin, proparthrin, bifenthrin, prothrin, fluvalinate, cyfluthrin, cyhalothrin, flucythrinate, ethofenprox, cycloprothrin, tralomethrin, silaneophan. Benzoylphenylurea-type and other types insecticides: diflubenzuron, chlorfluazuron, triflumuron, teflubenzuron, buprofezin, pyriproxyfen, flufenoxuro , Machine oil. Same examples of the formulations are given below. The carriers, surface-active agents, etc. that are added, however, are not limited to these Examples. Example 7 : Emulsifiable concentrate The compound of this invention 10 parts Alkylphenyl polyoxyethylene 5 parts Dimethyl formamide 50 parts Xylene 35 parts These components are mixed and dissolved and, for use i spraying, the liquid mixture is water-diluted into an emulsion. Example 8 : Wettable powder The compound of this invention 20 parts Higher alcohol sulfuric ester 5 parts Diatomaceous earth 70 parts Silica 5 parts These components are mixed and ground to fine powder, whic for use in spraying, are water-diluted into a suspension. Example 9 : Dust The compound of this invention 5 parts Talc 94.7 parts Silica 0.3 parts These are mixed and ground and used as-ground in spraying. Example 10 : Granule The compound of this invention 5 parts Clay 73 parts Bentonite 20 parats Sodium dioctylsulfosuccinate 1 part Sodium phosphate 1 part The above compounds are granulated, and applied as it is when used. Industrial applicability: The tests below show the insecticidal activity of the compounds of this invention. Test 1 Efficacy for cotton aphid 30 to 50 insects of cotton aphid per plot were inoculated using a small brush on cucumber leaves which were seeded in pots, 10cm in diameter, and 10 days old after germination. A day later, wounded insect pests were removed, and a chemical solution, which was prepared in the way that the emulsifiable concentrate described in Example 7 of the above example of insecticide was diluted with water to 125 ppm of compound concentration according to the prescription, was sprayed. The pots were placed in a thermostatic room at temperature of 25°C and humidity of 65%. The number of survival pests was counted 7 days later and the control efficacy was calculated by comparing with that of untreated plot. The results are shown in Table 2. 16 100 20 100 21 100 22 100 23 100 24 100 25 100 27 100 29 100 31 100 32 100 33 100 38 100 44 100 48 100 50 100 51 100 53 100 57 100 60 100 62 100 64 100 66 100 68 100 70 100 72 100 150 100 Comparative compound A: Comparative compound B: Test 2 Efficacy for green rice leafhopper Rice seedlings of 7 days old after germination were immersed in a chemical solution, which was prepared in the way that the emulsifiable concentrate described in Example 7 of the above example of insecticide was diluted with water to 125 ppm of compound concentration according to prescription, for 30 seconds. After dried in air, the treated seedlings were placed in test tubes and 10 insects of 3rd-instar larvae of green rice leafhopper resistant to the organophosphorus and carbamate insecticides were inoculated. The tubes were covered with gauze, and placed in a thermostatic room at temperature of 25°C and humidity of 65%. The mortality was checked 5 days later. The results are shown in Table 3. Table 3 % mortality (5 days later) Compound No. 125 ppm 1 100 % 2 100 4 100 6 100 8 100 10 100 16 100 18 100 20 100 21 100 22 100 23 100 24 100 25 100 27 100 28 100 29 100 31 100 32 100 Compound No . % Mortality 213 100 236 100 366 100 368 100 369 100 381 100 Comparative Compound A 0 B 0 C 0 Comparative compound A and B: The same as test 1 Compound C; (malathion ) Test 3 Efficacy for rice armyworm The test compounds were formulated into the wettable powder in the same manner as Example 8. The compounds were diluted with water to 125 ppm. A maize leaf was immersed in the chemical solution for 30 seconds. After air-dried, the treated leaf was placed in a petri dish and five 3rd-instar larvae of rice armyworm were inoculated. The petri dishes were covered with glass lids, and placed in a thermostatic room at 25 C C and 65% relative humidity. The mortality was checked 5 days later. Two replications were conducted in the each test. The results are shown in Table 4. Table 4 Comparative compound A and B: The same as Test 1 Compound D: (chlordimeform)

Claims: Claims 1. A compound having the formula wherein R- represents an optionally substituted 5 - 6 membered aromatic hetero ring containing nitrogen atom, except a non- substituted 2-pyridyl; X represents an optionally substituted C., ., alkylene or alkylidene; R 2 represents a hydrogen, a carbamoyl, a mono or di C, ,- alkyl carbamoyl, a thiocarbamoyl, a mono or di c ι _5 alkylthiocarbamoyl, a sulfamoyl, a mono or di c _ς alkylsulfamoyl, an optionally substituted c ι c alkyl, an optionally substituted C_ -. alkenyl, an optionally substituted C__ ι - alkynyl, an optionally substituted -. β cycloalkyl, an optionally substituted "- T . Q cycloalkenyl, an optionally substituted aryl or -Y-R g ; Y represents O, S(O) , CO, CS or C0 2 n represents 0,1 or 2; R- represents a hydrogen, an optionally substituted C 1 _ r - alkyl, an optionally substituted c - ? _ t ; alkenyl, an optionally substituted C_ - alkynyl, an optionally substituted C 3_ Q cycloalkyl, an optionally substituted C 3 _„ cycloalkenyl or an optionally substituted aryl; R-. represents a hydrogen, an optionally substituted C, -. alkyl, an optionally substituted C 2- n alkenyl, an optionally substituted c - j c alkynyl, an optionally substituted C T _ Q cycloalkyl or an optionally substituted C 3 _ R cycloalkenyl; R. represents a cyano or a nitro; and Z represents CH or N; or its salt. 2. A compound according to claim 1, wherein R.. represents a pyridyl, a pyrazyl, a pyrazolyl, a pyridazyl or a thiazolyl, which may be substituted by a C., 5 alkyl, a C. .. haloalkyl, a C- ,. alkoxy, a C, g alkylthio, a C., 5 alkylsulfonyl, a cyano, a halogen or a di C. _ alkylamino, respectively, except a non-substituted 2-pyridyl; R_ represents a hydrogen, a mono or di C,_ c- alkylcarbamoyl, an optionally substituted C._-. alkyl, an optionally substituted C- ,- alkenyl, an optionally substituted c - < =, alkynyl, an optionally substituted C 3_ Λ cycloalkyl, an optionally substituted aryl or -Y-R-.; Y represents 0, CO, C0_ or SO.,; R,- represents an optionally substituted . 5 alkyl, or an optionally substituted aryl; R 3 represents a hydrogen, an optionally substituted C., _ alkyl or an optionally substituted C 3 _, cycloalkyl; Z represents N; 3. An insecticidal composition comprising a compound according to claim 1 as an active ingredient. 4. An insecticidal composition comprising a compound according to claim 2 as an active ingredient. 5. A process for the preparation of a compound having the formula R1, which comprises reacting a compound having the formula R--X-NH 1 I R 2 with a compound having the formula Or 1 I R3-,COCH_2R4. or R3-. H2-R4. wherein r 1 and r2 are a C., -. alkyl, respectively; and R, , R- , R~ , R- and X are as defined above. 6. A process for the preparation of a compound having the formula which comprises reacting a compound having the formula R.-X-NH 1 I R 2 with a compound having the formula r 3 0^\ R 3 3 wherein r represents a C. ,_ alkyl; and R, , R 2 , R 3 and X are as defined above. 7. A process for the preparation of a compound having the formula which comprises reacting a compound having the formula with a compound having the formula R 2 -Hal wherein Hal represents a halogen atom; and R,, R 2 , R, and X are as defined above. 8. A process for the preparation of a compound having the formula CN which comprises reacting a compound having the formula CN I N R 2 H / \R 3 with a compound having the formula R 1 -X-Hal wherein R, , R 2 , R 3 , X and Hal are as defind above. 9. A process for the preparation of a compound having the formula NO- I 2 N R-^X-N ^ \ R 3 R 2 which comprises reacting a compound having the formula with nitration reagent. wherein R, , R 2 , R., and X are as defined above,

Inventors: HATANO RENPEI, ISHIMITSU KEIICHI, OHISHI HARUHITO, SUZUKI JUNJI, YAMADA TOMIO, HATANO, RENPEI, ISHIMITSU, KEIICHI, OHISHI, HARUHITO, SUZUKI, JUNJI, YAMADA, TOMIO
Applicants: NIPPON SODA CO, NIPPON SODA CO., LTD.
Application year: 1990
Main classification: C07D417
IPC codes: A01N33, A01N37, A01N43, A01N47, A01N51, C07C209, C07C211, C07C261, C07C311, C07D213, C07D231, C07D237, C07D239, C07D241, C07D277, C07D307, C07D405, C07D409, C07D417, C07D521