IL98014A - Amine derivatives their preparation and insecticidal compositions containing them - Google Patents

Description

Amine derivatives , their preparation and insecticidal compositions containing them NIPPON SODA CO. , LTD.

C. 83425 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 insecticides 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 infes titation 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. 98014/2 CN / 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 where in A complates a 5 or 6 membered aromatic ring selected from the group .consisting of pyridyl, pyridyl substituted with Cj-salkyl, C i-s haloa Iky1, C i-.alkoxy, C t-5 a 1ky1 thio, d-salkyl's u I fonyl. cyano, halogen, phenoxy or C i _ s d i a Iky I ami no, pyraziny 1, · pyrazinyl substituted with C i - s a 1 ky 1 o r ..halogen, pyrazolyl substituted with C i-3a Iky 1, pyridazyl substituted with 'halogen, and thiazolyl substituted with halogen or C i-salky 1. provided, however, that the ring is not unsubstituted 2-pyridyl; Γ is d-aaikylene or Ct _aalky1 idene; j is hydrogen, monoalky {carbamoyl. C i -sd ialkyl carbamoyl, ^d-salkyl. .C x _ 5 alkyl substituted with halogen, C i-3alkoxy. C i-.alky 1 thio. C t - 3 alkoxycarbonyl, cyano, phenyl, haloaryl, C i-.alkoxyaryl, furyl. thienyl, pyridyl, halopyridyl, thiazolyl or halothiazolyl; , C3 _3a 1ksn 1. Ca-5 alkynyl, C3-acycloalkyI, phenyl or the radical - Y - s wherein Y is 0, CO, C02 or S02 , Rs is hydrogen, Cx-3aIky1. phenyl or ha lopheny1 ; R. is hydrogen, Cx -δ a1ky I. C i -saIky1 substituted with halogen, C t-salkoxy, C i _s a1ky 1 thio, d-.alkoxycarbonyl, cyano, .phenyl, ha lopheny 1. amino, monoalky laniino, C i-adialkylamino, cyano imino, -halopy idy 1 — C x _ 3 alkylamino or N-(ha lapyr idy 1- C i -B a I ky 1 ) -N- C i a"l ky famino or C 3 - 3 cycloalky1 ; R4" is cyano or nitro; Z is CH or N; and an insecticidai acceptable salt thereof.

Best Mode for. Carrying Out the Invention: The compounds of this invention can be prepared accordance with the following reaction schemes: Preparation Method where r' and r' represent a C^_5 alkyl; and A, R2 ' R3 ' R4 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: 3 where r represents a C1_5 alkyl: and A, R2 ' R3 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.

Preparation Method where Hal represents a halogen; and A, R2 » 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.

) Preparation Method 4: where A, R3 ' 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: nitration reagent (VIII) where A, R2 , H3 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 R2 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- 1-butene : In 50ml of toluene, 4.2g of 2-chloro-5-pyridylmethylamine , 3.5g of l-nitro-2-butanone and O.lg of p-toluene sulfonic acid were mixed 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. m.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 -cyano- ' - ( 2-chloro-5-pyridylmethyl ) - ' -ethylacetamidine 0.7g of sodium hydride (purity 60%) was added to the solution of 3.0g of N-cyano- '-( 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 1 -methylacetamidine : 0.6g of sodium hydride (purity 60%) was added to the solution of 1.3g of N-cyano-N 1 -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 on silica gel to afford 1.5g of compound No.22 m.p. 101-103°C Reference Example : N- ( 2-chloro-5-pyridylmethyl ) -N-methylacetamidine hydrochloride : To 40ml of ethanol was added 5. lg 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-N1 -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.

Ta b l e 1 98014/2 4 5 98014/2 1 1 H-NMR(CDC13) c5;ppm 3.32 (s,3H), 4.63 (s,2H), 7.37 (d, IH), 7.62 (dd, IH), 8.37 (d,lH) 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 , dimethylformamxde , 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 water into suspensions or emulsions of a prescribed concentration, before they are actually sprayed on plants in the field. In the case of dusts or granules, they are directly applied without further process ing .

It goes without saying that the compound(s) of this invention 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): chlorobenz ilate , chloropropylate , proclonol, bromopropylate , dicofol, dinobuton, binapacryl, chlordimeform , amitraz , propargite , PPPS , benzoximate, hexythiazox, fenbutatin oxide, polynactine , chinomethionat , thioquinox, chlorfenson, tetradifon, phenproxide, avermectins , clofentez ine , flubenz imine , 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, dihydrostreptomycin, 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, tetramethrin , 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 , flufenoxuron , 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 in 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, which 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.

Table 2 Comparative compound A: CN I Comparative compound B: CN 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 . 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 33 100 35 100 36 100 44 100 48 100 "50 100 51 100 53 100 57 100 60 100 62 100 66 100 68 100 72 100 73 100 Comparative compound A and B: The same as test 1 Compound C : S O ( CH30)2P-SCHCOC2H5 ^ II 0 ( 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 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. 98014/2 83 Table 4 Comparative compound A and B: The same as Test 1 Compound D: ( chlordimeform ) Passages of the description which are not within the scope of the claims do not constitute part of the invention.

Claims (9)

98014/2 84 Claims

1. A compound having the formula wherein A computes a 5 or 6 membered aromatic ring selected from the group .consisting of pyridyl, pyridyl substituted with Cj-.alkyl, d _a a 1 oa Iky 1 , C!-salkoxy, Ci -3 a Iky 1 thio, C i -5 a Iky 1 su 1 f onyl, cyano, halogen, phenoxy or Cj -6 d ialky lamino, pyrazinyl, pyrazinyl substituted with Ci-5alkyl or .halogen, pyrazolyl substituted with Cj-Salkyl, pyridazyl substituted with halogen, and thiazolyl substituted with halogen or Ci-salkyl, provided, however, that the ring is not unsubstituted 2-pyridyl; X is Ci-aalkylene or Ci-8alky 1 idene; Rg is hydrogen, monoalky lcarbamoyl. Ci-sdialkylcarbamoyl, Cx-salkyl. .Ci-» a Iky 1 substituted with halogen, d-salkoxy, Ci-.alkylthio. Ci-s alkoxycarbonyl, cyano, phenyl, haloaryl, Ci-5alkoxyaryl, furyl. thienyl, pyridyl, halopyridyl, thiazolyl or halothiazoly 1; . C»-Salkenyl. Ca-5 alkynyl, 'ca-«cycloalkyl, phenyl or the radical - Ϊ - R3 wherein Y is 0, CO, C02 or S02, 85 98014/3 R3 is hydrogen, Ci-. alkyl. phenyl or halop enyl; R3 is hydrogen, C1-.alkyl. C,-3alky 1 substituted with halogen, C.-3alkaxy, d-salkylthio, C1-salkoxycarbonyl, cyano, phenyl, halophenyl, amino, monoalkylaraino, C i -5 d i a 1 ky 1 am i no, cyanoimino, N-halopyr idy alkylamino or N- (ha lop r 1 dy I -C , -6 a 1 ky I ) -N-C t -3 1 k 1 ami no or C3-3_ cycloalkyl; R4 is cyano or nitro; Z is CH or N; and an insecticidal acceptable salt thereof.

2. A compound according to claim 1, wherein R2 represents a hydrogen; a mono or di alkylcarbamoyl; C 5 alkyl; Q_s alkyl substituted with halogen; Q.5 alkenyl; Q.j alkynyl; C3_6 cycloalkyl; phenyl or the radical -Y-R5; Y represents 0, CO, CO2 or SO2; R5 represents Cj_5 alkyl; phenyl or halophenyl; R3 represents a hydrogen; C 5 alkyl; alkyl substituted with halogen; or Q-e 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 98014/2 86 which comprises reacting a compound having the formula with a compound having the formula Or1 R3-.COCH-2R4. or R3, 1 2 wherein r and r are a C^_5 alkyl , respectively; and A, R2 ' 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 98014/2 87 with a compound having the formula 3, Ir" R3 3 wherein r represents a C-j__5 alkyl and A, R2 , 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 R2-Hal wherein Hal represents a halogen atom; and A, R2 , R3 and X are as defined above.

8. 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 98014/2 wherein A, R2 ' R3' x and Hal ar^ as defind above.

9. A process for the preparation of a compound having the formula which comprises reacting a compound having the formula with nitration reagent , wherein A, , and X are as defined above For the Applicants