KR930008631B1 - Amine derivatives - Google Patents

Abstract

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Description

Amine derivatives

The present invention relates to novel amine derivatives, their preparation and pesticides containing the derivatives as effect compounds.

Numerous chemicals, for example, organic phosphorus insecticides such as parathion and malathion and carbamate insecticides such as carbaryl and methyl have been developed for many years and have actually been used in research and development of pesticides. The pesticides have played a large role in improving agricultural productivity. However, some of these pesticides in recent years cause their outbreak of resistant insect harm as a result of long-term use, or their use is controlled because of problems such as environmental pollution by residues or accumulation. Therefore, there is a need to develop new chemicals that can be used stably and have excellent insecticidal properties for various types of insects, including the insect insects.

The following compounds are known as analogous compounds of the present invention but do not have pesticidal activity.

In addition, the following compounds are described in USP 4 918 088, which have pesticidal activity.

The compound, however, shows activity against cotton aphids, but does not show pesticidal activity against insects of green rice anthracites and poultry species, which are more lethal pests of crops.

It is an object of the present invention to provide agricultural chemicals that can be industrially advantageously synthesized, have a definite effect and can be used safely.

The compounds of the present invention have a high pesticidal activity against both species of poultry and semipods.

The present invention relates to a compound of the general formula (I) or a salt thereof.

In the formula, R ₁ represents a 5-6 membered aromatic heterocycle (except for unsubstituted 2-pyridyl) containing an optionally substituted nitrogen-atom; X represents optionally substituted C _1-3 alkylene or alkylidene; R ₂ is hydrogen, carbamoyl, mono or di C _1-5 alkylcarbamoyl, thiocarbamoyl, mono or di C _1-5 alkylthiocarbamoyl, sulfamoyl, mono or di C _1-5 alkyl Sulfamoyl, optionally substituted C _1-5 alkyl, optionally substituted C _2-5 alkenyl, optionally substituted C _2-5 alkenyl, optionally substituted C _2-5 alkynyl, optionally substituted C _3-8 cyclo Alkyl, optionally substituted C _3-8 cycloalkenyl, optionally substituted aryl or —YR ₅ ; Y represents 0, S (O) m, CO, CS or CO ₂ ; n represents 0.1 or 2; R ₅ represents hydrogen, optionally substituted C _1-5 alkyl, optionally substituted C _2-5 alkynyl, optionally substituted C _3-8 cycloalkyl, optionally substituted C _3-8 cycloalkenyl or optionally substituted aryl ; R ₃ is hydrogen, optionally substituted C _1-5 alkyl, optionally substituted C _2-5 alkenyl, optionally substituted C _2-5 alkynyl, optionally substituted C _3-8 cycloalkyl or optionally substituted C _{3- 4} cycloalkenyl; R ₄ represents cyano or nitro; Z represents CH or N.

Compounds of the present invention can be prepared according to the following scheme.

(1) Manufacturing Method 1:

In the formula, r ¹ and r ² represent C _1-5 alkyl; R ₁ , R ₂ , R ₃ , R ₄ and X are as defined above. In an inert organic solvent, preferably in an aromatic hydrocarbon solvent such as xylene, toluene or benzene, the reaction is carried out under reflux if necessary in the presence of an acidic catalyst such as p-toluenesulfonic acid.

(2) Manufacturing Method 2:

In the formula, r ³ represents C _1-5 alkyl; R ₁ , R ₂ , R ₃ and X are as defined above. The reaction is carried out in an inert organic solvent, preferably in alcohols such as methanol, ethanol, between room temperature and the boiling point of the solvent used.

(3) Manufacturing Method 3:

In the formula, HaL represents halogen; R ₁ , R ₂ , R ₃ and X are the same as defined above. In an inert organic solvent, preferably DMF, HF, benzene, acetonitrile, acetone, methylethylketone, the reaction is carried out between room temperature and the boiling point of the solvent used in the presence of an acid acceptor such as potassium carbonate, NaH, triethylamine do.

(4) Manufacturing Method 4:

Wherein R ₁ , R ₂ , R ₃ , X and Hal are the same as defined above. The reaction is carried out in the same manner as in Preparation Method 3.

(5) Manufacturing Method 5:

Wherein R ₁ , R ₂ , R ₃ and X are as defined. The reaction is carried out in an inert organic solvent, preferably in acetonitrile, carbon tetrachloride, dichloroethane, in the presence of a nitration reagent such as nitronium tetrafluoroborate, at a temperature between −20 and the boiling point of the solvent used.

After the reaction is complete, conventional post-treatment affords the intended compound. The compound structure of the present invention was determined using IR, NMR, MASS and the like. In the compound of the present invention, when R ₂ is hydrogen, tautomers represented by the following formula may be present.

When Z represents N, the cis-trans isomer may also be present when Z represents CH, as shown by the formula below.

The ratio depends, for example, on the conditions of the instrumental analysis. The following examples illustrate the invention.

2- (2-Chloro-5-pyridylmethylamino) -1-nitro-1-butene:

In 50 ml of toluene, 4.2 g of 2-chloro-5-pyridylmethylamine, 3.5 g of 1-nitro-2-butanone and 0.1 g of p-toluene sulfonic acid are mixed and the mixture is refluxed for 2 hours. . The solvent was then distilled off and the residue was purified by column chromatography on silica gel to yield 4.1 g of compound number 368. m.p. 95-98 ℃

Example 2

2- (2-chloro-5-pyridylmethylamino) -1-cyano-1-propene

1.4 g 2-chloro-5-pyridylmethylamine and 0.8 g 1-cyano-2-propanone are mixed and the mixture is stirred overnight at room temperature. The solvent is then distilled off and the residue is purified by column chromatography on silica gel to give 1.7 g of compound number 528. m.p. 95-98 ℃

Example 3

N-cyano-N '-(2-chloro-5-pyridylmethyl) -N'-methylacetamidine:

In 20 ml of ethanol, 1.6 g of N-methyl-2-chloro-5-pyridylmethylamine and 1.2 g of ethyl-N-cyanoacetamidine are mixed and the mixture is stirred at room temperature overnight. The solvent is then distilled off and the residue is purified by column chromatography on silica gel to give 1.8 g of compound number 22. m.p. 101 ~ 103 ℃

Example 4

N-cyano-N '-(2-chloro-5-pyridylmethyl) -N'-ethylacetamidine:

0.7 g sodium hydride (60% purity) was added 3.0 g of N-cyano-N '-(2-chloro-5-pyridylmethyl) acetami in 20 ml of N, N-dimethylformamide at ice bath temperature. To the solution of dean. After stirring for 1 hour at the same temperature, 2.7 g of ethyl iodine are added to the mixture and then stirred for 5 hours at room temperature. The reaction mixture is then poured into ice water, extracted with ethyl acetate, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue is purified by column chromatography on silica gel to give 1.6 g of compound number 51. m.p. 101 ~ 109 ℃

Example 5

N-cyano-N- (2-chloro-5-pyridylmethyl) -N'-methylacetamidine:

0.6 g sodium hydride (purity 60%) is added to a solution of 1.3 g N-cyano-N'-methylacetamidine in 20 ml N, N-dimethylformamide at ice bath temperature. After stirring for 1 hour at the same temperature, 2.2. G of 2-chloro-5-pyridylmethylchloride was added to the mixture, followed by stirring at room temperature for 5 hours. The reaction mixture is then poured into ice water, extracted with ethyl acetate, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue is purified by column chromatography on silica gel to give 1.5 g of compound number 22. m.p. 101 ~ 103 ℃

[Reference Example]

N- (2-Chloro-5-pyridylmethyl) -N-methylacetamidine hydrochloride:

To 40 ml of ethanol is added 5.1 g of N- (2-chloro-5-pyridylmethyl) -N-methylamine at 0 ° C., followed by 4 g of ethylacetimidade hydrochloride. After stirring for 1 hour, the reaction mixture is warmed to room temperature and stirred overnight. Next, the solvent is distilled off. The white residue obtained is washed with diethyl ether to give 7.3 g of the title compound. m.p. 192 ~ 197 ℃

Example 6

N- (2-Chloro-5-pyridylmethyl) -N-methyl-N'-nitroacetamide:

To a suspension of 1 g of N- (2-chloro-5-pyridylmethyl) -N-methylamidine hydrochloride in 10 ml of anhydrous acetonitrile, 0.7 g of DBU is added dropwise under nitrogen at room temperature. After stirring for 30 minutes, the solution is added dropwise to a suspension of 0.6 g nitronium tetrafluoroborate in 5 ml of anhydrous acetonitrile under nitrogen with cooling with ice water and stirred for 4 hours. The mixture is then poured into ice water and extracted several times with chloroform. The collected chloroform layers are dried over magnesium sulphate, filtered and distilled off. Crude oil is purified by column chromatography on silica gel to yield 0.3 g of compound number 236.

Typical embodiments of the invention, including those described above, are listed in Table 1.

TABLE 1a

TABLE 1b

TABLE 1c

TABLE 1d

TABLE 1e

TABLE 1f

Table 1g

Table 1h

TABLE 1i

TABLE 1j

Table 1k

TABLE 1L

[Table 1m]

TABLE 1n

Table 1o

Table 1p

TABLE 1q

TABLE 1r

Table 1s

Table 1t

TABLE 1u

Table 1v

TABLE 1W

Table 1x

Table 1y

TABLE 1z

Table 1aa

Table 1ab

Table 1ac

Table 1ad

TABLE 1ae

Table 1af

Table 1ag

Table 1ah

Table 1ai

Table 1aj

Table 1ak

Table 1al

^{* 1} H-NMR (CDCl ₃ ) δ ppm; 3.32 (s, 3H), 4.63 (s, 2H), 7.37 (d, 1H), 7.62 (dd, 1H), 8.37 (d, 1H).

The compounds of the present invention exhibit potent pesticidal activity against various types of pests such as cutworms, diamondback moths, aphids, leafhoppers and planthoppers. Recently, the reduction of the control effect of such insecticides caused by the development of resistance to organophosphorus and carbamate insecticides has become a serious problem. In this situation, development of new pesticides effective against resistant pests has been desired. The compounds of the present invention have excellent pesticidal activity against resistant strains as well as resistant strains.

The pesticide covered by the present invention contains at least one type of compound represented by the general formula (1) as an active ingredient. The active ingredient may be used as produced, but is usually in any form normally agrochemicals can take, namely wettable powders, dusts, emulsifiable concentrates, suspension concentrates, smoking chemicals, fumigants, granules, or other It can be used in formulation form. If a solid formulation is intended, soy flour, flour or other vegetable flours are used for the additives and carriers, diatomaceous earth, apatite, gypsum, talc, pyrophyllite, clay or other mineral powders.

If a liquid formulation is intended, kerosene, mineral oil, petroleum, solvent naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, water and the like are used as the solvent. If desired, surface active agents may be used to obtain a uniform and suitable formulation. Before actual spraying on crops in paddy fields, the wettable powders, emulsifiable concentrates, suspension concentrates and the like thus obtained are diluted with water and diluted with suspensions or emulsions of the prescribed concentrations. In the case of dust or granules, it can be used directly without further processing.

Needless to say, the compound (s) of the present invention are effective alone, but may be used in combination with various types of pesticides, acaricides and fungicides.

Typical examples of acaricides and fungicides that can be used in combination with the compounds of the invention are described below.

Acaricides (Fungicides):

Chlorobenzylate, Chloropropylate, Proclool, Bromopropylate, Dicopol, Dinobutone, Binapacryl, Chlodimeform, Amitraz, Propargite, PPPS, Benzoxymate, Hexythiazoox, Fenbutatin oxide, polynactin, quinomethionate, thioquinox, chlorphenone, tetradipon, fenproxide, avetmectins, clofentazine, flubenzimine, phenazakine, pyridaben, phenoxymate, Chlorophenetol, thiophanate-methyl, benomil, tiram, ifprobenfos, edifeneforce, phthalide, probenazole, isoprothiolane, chlorothalonyl, captan, polyoxine-B, blastitidine- S, sangagamycin, validamycin, tricyclazole, pyroquilon, phenazine, oxide, mepronil, flutolanyl, pencicuron, iprodione, himmezazole, metallaxyl, triflumizole, diclomezin, teccle Loft alarm, vinclozoline, procmidone, Vitertanol, triadimefon, prochloraz, pyrifenox, phenarimal, fenpropormorph, triporin, metallaxyl, oxycarboxycin, peprazoate, diclomethin, fluazinam, oxadixyl, Etoquinolak, TPTH, propamocarbo, pocetyl, dihydrostreptomycin, anilazine, dithianon, dietofencarb.

Organophosphorus-type and carbamate-type insecticides (salvases):

Pention, Phenythrothione, Diazinon, Chloropyriphos, Oxidedefoss, Bamidothione, Pentoate, Dimethoate, Formomoone, Malathion, Trichlorphone, Thiomethone, Phosmet, Menazone, Dichlobos, Acetate, EPBP, Dialilifos, Parathion-methyl, Oxidemetone-methyl, Ethion, Aldicarb, Propoxur, Methomil, Fennobucarb, BPMC, Pycloclofos, Monochrome Tophos, sality, cartab, carbosulphan, carbofuran, benfuracarb, metholcarb, carbaryl, pyrimikab, ethiophencarb, phenoxycarb,

Pyrethroid-type insecticides (fertilizers):

Fermetrin, cipermethrin, deltamethrin, fenvalate, phenpropatrine, pyrethrin, alletrin, tetramethrin, resmethrin, partin, dimethrin, propartrin, bifenthrin , Protrin, fluvalinate, cyfluthrin, sihalothrin, flucitrinate, etofenprox, cycloprotrin, tralomethrin, silaneophan.

Benzoylphenalurea-type and other types of insecticides:

Diflubenzuron, chlorfluazuron, triflumuron, teflubenzuron, buprofezin, pyriproxyfen, flufenoxuron, mechanical oil.

The same examples of formulations are given below. However, the carrier, surface-active agent, etc. to be added are not limited to the above embodiments.

Example 7

: Emulsifiable Concentrate

10 parts of the compound of the present invention

Alkylphenyl polyoxyethylene 5 parts

Dimethyl formamide 50 parts

Xylene Part 35

For spraying, the components are mixed and dissolved, and the liquid mixture is water-diluted to form an emulsifier.

Example 8

: Wettable powder

20 parts of the compound of the present invention

Higher Alcohol Sulfur Ester Part 5

Diatomite 70 parts

5 parts silica

For spraying, the components are mixed and ground to a fine powder which is water-diluted to form a suspension.

Example 9

: dust

5 parts of a compound of the present invention

Talc 94.7

0.5 parts of silica

These are mixed and ground to use as ground when spraying.

Example 10

Granules

5 parts of a compound of the present invention

Clay Part 73

Bentonite Part 20

1 part sodium dioctylsulfosuccinate

1 part sodium phosphate

The mixtures are granulated and used as they are.

The following tests show the pesticidal activity of the compounds of the present invention.

Test 1: Effect on Cotton Aphids

30 to 50 cotton aphid worms per plot are placed on a 10-day-old cucumber leaf after germination, seeded in a 10 cm diameter pot. One day later, the damaged pests are removed and, according to the prescription, the chemical solution prepared by diluting the emulsifier concentrate described in Example 7 of the above example with water to a compound concentration of 125 ppm is sprayed. Place the pot in the thermostat room at a temperature of 65% humidity and 25 ° C. After 7 days, the number of surviving pests is counted and the control effect is calculated by comparison with that of the untreated float. The results are shown in Table 2.

TABLE 2a

TABLE 2b

TABLE 2c

Comparative Compound A:

Comparative Compound B:

Test 2: Effect on Green Rice Anchovy

Insecticide According to the formulation, the emulsifiable concentrate described in Example 7 of the above example was diluted with water and soaked 7 days old rice seedlings for 30 seconds after germination in a chemical solution prepared at a compound concentration of 125 PPM. After air drying, the treated seedlings are placed in a test tube and 10 third-layer larvae of green rice larvae resistant to organic phosphorus and carbamate insecticides are placed. The test tube is covered with a gauze and placed in a thermostat at 65% humidity and 25 ° C. Check the mortality rate after 5 days. The results are shown in Table 3.

TABLE 3a

TABLE 3b

TABLE 3c

Comparative Compound A or B: Same as Test 1

Compound C:

Test Example 3: Effect on rice armywarm

Test compounds were formulated into wettable powders in the same manner as in Example 8. Dilute the compound with water to 125 ppm. Soak corn leaves in chemical solution for 30 seconds. After air-drying, the treated leaves are placed in a glass dish and 5 worm-larvae larvae are added. Cover the plate with a glass lid and cover 65% relative humidity and 25? Into the temperature control room. Check the mortality rate after 5 days. The test is carried out in two replicates for each test. The results are shown in Table 4.

Comparative compound and: same as test 1

Compound D:

(Chlordime form)

Claims (9)

Compound of the following general formula or its salt [Wherein, R ₁ represents a 5 to 6 membered aromatic heterocyclic ring (except for unsubstituted 2-pyridyl) containing an optionally substituted nitrogen atom; X represents optionally substituted C _1-3 alkylene or alkylidene; R ₂ is hydrogen, carbamoyl, mono or di C _1-5 alkylcarbamoyl, thiocarbamoyl, mono or di C _1-5 alkylthiocarbamoyl, sulfamoyl, mono or di C _1-5 alkyl Sulfamoyl, optionally substituted C _1-5 alkyl, optionally substituted C _2-5 alkenyl, optionally substituted C _2-5 alkynyl, optionally substituted C _3-8 cycloalkyl, optionally substituted C _3-8 cyclo Alkenyl, optionally substituted aryl or -YR ₅ ; Y represents O, S (O) _n , CO, CS or CO ₂ ; n represents 0, 1 or 2; R ₅ is hydrogen, optionally substituted C _1-5 alkyl, optionally substituted C _2-5 alkenyl, optionally substituted C _2-5 alkynyl, optionally substituted C _3-8 cycloalkyl, optionally substituted C _{3- 8} cycloalkenyl or optionally substituted aryl; R ₃ is hydrogen, optionally substituted C _1-5 alkyl, optionally substituted C _2-5 alkenyl, optionally substituted C _2-5 alkynyl, optionally substituted C _3-8 cycloalkyl or optionally substituted C _{3- 8} cycloalkenyl; R ₄ represents cyano or nitro; Z represents CH or N.] The compound of claim 1, wherein R ₁ is C _1-5 alkyl, C _1-5 haloalkyl, C _1-5 alkoxy, C _1-5 alkylthio, C _1-5 alkylsulfonyl, cyano, halogen or di C Pyridyl, pyrazyl, pyrazolyl, pyridazyl or thiazolyl, each of which may be substituted with _{1 to 5} alkylamino, except for unsubstituted 2-pyridyl; R ₂ is hydrogen, mono or di C _1-5 alkylcarbamoyl, optionally substituted C _1-5 alkyl, optionally substituted C _2-5 alkenyl, optionally substituted C _2-5 alkynyl, optionally substituted C _3-6 cycloalkyl, optionally substituted aryl or -YR ₅ ; X represents O, CO, CO ₂ or SO ₂ ; R ₅ represents optionally substituted C _1-5 alkyl, or optionally substituted aryl; R ₃ represents hydrogen, optionally substituted C _1-5 alkyl or optionally substituted C _3-6 cycloalkyl; Z is N, characterized in that the compound. An insecticide composition comprising the compound of claim 1 as an active ingredient. An insecticide composition comprising the compound according to claim 2 as an active ingredient. Compound of the formula With a compound of the formula A compound of the formula characterized by the reaction How to prepare. [Wherein, r ¹ and r ² are each C _1-5 alkyl; R ₁ , R ₂ , R ₃ , R ₄ and X are the same as defined above] Compound of the formula With a compound of the formula A compound of the formula characterized by the reaction How to prepare. [Wherein, r ³ is C _1-5 alkyl; R ₁ , R ₂ , R ₃ and X are the same as above definition] Compound of the formula Formula: A compound of the formula characterized by reacting with a compound of R ₂ -Hal How to prepare. [Wherein Hal represents a halogen atom; R ₁ , R ₂ , R ₃ and X are the same as above definition] Compound of the formula Formula: A compound of the formula characterized by reacting with a compound of R ₁ -X-Hal How to prepare. [Wherein R ₁ , R ₂ , R ₃ , X and Hal are the same as defined above] Compound of the formula A compound of the formula characterized by reacting with a nitration reagent How to prepare. [Wherein R ₁ , R ₂ , R ₃ and X are the same as defined above]