JPH0547540B2 - - Google Patents

Claims (2)

[Claims] [Claim 1] General formula: [Chemical formula 1] [ka] In the formula, R represents a hydrogen atom or a lower alkyl group, m represents 2, 3 or 4, and n represents 0, 1, 2 or 3, New diamines represented by [Claim 2] General formula: [Chemical formula 2] [Chemical formula] In the formula, R represents a hydrogen atom or a lower alkyl group, n represents 0, 1, 2 or 3, and X represents a halogen atom or a group -OSO ₂ R″, where _R ″ represents a lower alkyl group or _{an aryl group} ; Novel diamines represented by the following general formula: [Chemical formula 4] [Chemical formula] wherein R, m and n are the same as above. manufacturing method. Detailed Description of the Invention [0001] [Industrial Application Field] The present invention relates to novel diamines that are intermediates for producing insecticidal nitromethylene derivatives, and a method for producing the same. [0002] [Prior Art] West German Patent Publication No. 2514402, which was known before the filing date of the present application, contains 2-nitromethylene-imidazoline derivatives represented by the following general formula [0003] [Chemical formula 5] [Chemical formula] [0004], and 2-nitromethylene-
It is stated that hexahydropyrimidine derivatives have insecticidal activity. And n=2, R ₁ =
A phenyl ( _C1 - _C2 ) alkyl group and a case where _R2 = _R3 = hydrogen atom are included, and the compound represented by the following formula is described in the specification. [0005] [Case 6] [Case] [0006] Similarly, West German patent publication number 2732660
1-substituted benzyl-2- represented by the following general formula [0007] [Chemical formula 7] [Chemical] [0008]
It is stated that nitromethylene-imidazolidine derivatives have insecticidal activity. The specification describes a compound represented by the following formula. [0009] [Chemical formula 8] [Chemical formula] [Problem to be solved by the invention] In order to create a new useful compound with biological activity, the present inventors created a nitromethylene-tetrahydropyrimidine compound and a nitromethylene-tetrahydropyrimidine compound. We have performed synthesis and biological screening of methylene-imidazolidine compounds. [Means for solving the problem] The present inventors,
The insecticidal nitromethylene derivative of the following formula () was successfully synthesized and proposed separately. [0012] General formula: [0013] [Chemical formula 9] [Chemical formula] [Chemical formula] In the formula, R represents a hydrogen atom or a lower alkyl group, m represents 2, 3 or 4, and n represents 0, 1, Indicates 2 or 3. [0015] The compound of the above formula) is a compound represented by the general formula: [0016] [Chemical formula 10] [Chemical formula] [0017] In the formula, R, m and n are the same as above, and a compound represented by the general formula: [0018] [Chemical formula 11] [Chemical formula] [0019] In the formula, R' represents a lower alkyl or benzyl group, or two R's taken together
By reacting with a compound represented by a _C2 or higher lower alkylene group which may form a ring with adjacent sulfur atoms,
can get. [0020] The diamines of the above formula (), which are intermediates for the production of the compound of the general formula (), are new compounds that have not been described in known publications before the filing date of the present invention, and the present invention relates to these compounds. The compound of the general formula () can be produced by the following method, and the present invention also relates to this production method. [0021] Production method: - [Chemical formula 12] [Chemical formula] [Chemical formula] In the formula, R and n are the same as above, and X represents a halogen atom or a group -OSO ₂ R'', where R'' is lower alkyl or an aryl group, and a compound represented by the general formula: [0024] [Chemical formula 13] H ₂ N-(CH ₂ ) _n -NH ₂ (), where m is the same as above, and a compound represented by the following: A method for producing a compound of the general formula (), which comprises reacting. [0025] The compound of general formula () of the present invention can be easily produced by the following method. [Chemical formula 14] [Chemical formula] (In the formula, R, m, n and X are the same as above.) In the above reaction formula, R represents a lower alkyl group, specifically, methyl, Examples include ethyl, propyl, isopropyl, n-(iso, sec- or tert-)butyl and the like. m represents 2, 3 or 4, and n represents 0, 1, 2 or 3. Further, X represents a halogen atom such as fluoro, chloro, bromo, or iodo, or a group -OSO ₂ R'', where R'' is a lower alkyl group as exemplified above, or a lower alkyl group such as phenyl, p-tolyl, etc. Indicates a realyl group. [0028] In the method for producing the compound of the general formula () of the present invention shown in the above reaction formula, specific examples of the compound of the general formula () as a raw material include, for example, 2-chloro-5-pyridylmethyl chloride, 2 -(2-chloro-5-pyridyl)ethyl chloride, 1-(2-chloro-5-pyridyl)ethyl chloride 3-(2-chloro-5-pyridyl)propyl chloride, 2-chloro-5-pyridylmethyl p- Examples include toluene sulfonate. [0029] Similarly, specific examples of the compound of general formula () which is a raw material include ethylenediamine, trimethylenediamine, tetramethylenediamine, and the like. [0030] Next, the above manufacturing method will be specifically explained using representative examples. [0031] [Chemical formula 15] [Chemical formula] [0032] The method for producing the above-mentioned compound of the present invention can be carried out desirably using a solvent or a diluent.
All inert solvents and diluents can be used for this purpose. [0033] Examples of such solvents or diluents include water; aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated) such as hexane, cyclohexane, petroleum ether,
Ligroin, benzene, toluene, kyrylene, methylene chloride, chloroform, carbon tetrachloride,
ethylene chloride and trichloroethylene,
Chlorobenzene; other ethers such as diethyl ether, methyl ethylether, di-
iso-propyl ether, dibutyl ether, propylene oxide, dioxane, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl-iso-propyl ketone, methyl-iso-butyl ketone; nitriles such as acetonitrile, propionitrile, acrylonitrile; alcohols such as Methanol, ethanol, iso-propanol, butanol, ethylene glycol; esters such as ethyl acetate, amyl acetate, acid amides such as dimethylformamide, dimethylacetamide; sulfones, sulfoxides such as dimethylsulfoxide, sulfolane, etc. . [0034] Furthermore, the above reaction can be carried out in the presence of an acid binder. Such acid binders include:
Commonly used alkali metal hydroxides, carbonates, bicarbonates and alcoholates, etc.
Examples of tertiary amines include triethylamine, diethylaniline, and pyridine. [0035] The above method can be carried out within a wide temperature range. It can generally be carried out between about -20°C and the boiling point of the mixture, preferably between about 0°C and the boiling point of the mixture.
It can be carried out at a temperature of about 100℃. Further, although it is preferable to carry out the reaction at room temperature, it is also possible to carry out the reaction under increased pressure or reduced pressure. [0036] In the compound of the former general formula (),
When R=H and n=0, in addition to the above-mentioned production method, it can be synthesized also by a method represented by the following general formula. [0037] Alternative method 1: - [0038] [Chemical formula 16] [Chemical formula] [0039] In the formula, m is the same as above. [0040] As shown in the above reaction formula, Schiff's base is synthesized by the reaction of 6-chloronicotinaldehyde and the compound of general formula (), and to this,
For example, by reacting with a reducing agent such as sodium borohydride (NaBH ₄ ),
can be synthesized. [0041] Furthermore, the compound of the above general formula (') can also be synthesized by the method shown by the following general formula. [0042] Alternative method 2: - [0043] [Chemical formula 17] [Chemical formula] [0044] In the formula, m is the same as above. [0045] As shown in the above reaction formula, nicotinamide is synthesized by the reaction of 6-chloronicotinoyl chloride and the compound of general formula (),
By reacting this with a reducing agent such as thirium aluminum hydride (LiAlH ₄ ),
A compound of general formula (') can be synthesized. [0046] Furthermore, in the case of R=H, n=0, and m=3 in the compound of the general formula (), as an alternative method, the synthesis can also be performed by the method represented by the general formula below. can do. [0047] Alternative method 3: - [0048] [Chemical formula 18] [Chemical formula] [Chemical formula] [0049] As shown in the above reaction formula, acrylonitrile is added to 5-chloropicolylamine,
By reducing this adduct in the same manner as Alternative Method 1 above, the target compound N-(2-chloro-5-pyridylmethyl)trimethylenediamine shown in Compound No.-2 below can be synthesized. can. [0050] Furthermore, in the case of m=2 in the compound of the general formula (), it can alternatively be synthesized by a method represented by the following general formula. [0051] Alternative method 4: - [0052] [Chemical formula 19] [Chemical formula] [0053] In the formula, R and n are the same as above. [0054] As shown in the above reaction formula, by reacting 2-chloro-5-pyridylalkylamine of the general formula () with ethyleneimine,
Compounds of general formula (') can also be synthesized. [0055] The insecticide nitromethylene derivative of the general formula () produced from the compound of the general formula () of the present invention has an accurate control effect on harmful insects without causing any chemical damage to cultivated plants. demonstrate. Furthermore, the compounds of the present invention can be used to control a wide variety of pests, such as harmful sap-sucking insects, biting insects, and other plant-parasitic pests, storage pests, sanitary pests, etc., and can be applied to exterminate them. [0056] Examples of such pests include the following pests. Insects include Coleoptera pests such as Callosobruchus chinensis, Sitophilus zeamais, Tribolium castaneum, Epilachna vigintiocntomaculata,
Agriotes
fuscicollis), Anomala
rufocuprea), Colorado potato beetle (Leptinotarsa decemkineata), Diabrotica (Diabrotica spp), Monochamus alternatus, rice weevil (Lissorhoptrus oryzophilus), flattened beetle (Lyctus bruneus); lepidopteran insects, such as gypsy moth (Lymantria dispar), Malacosoma neustria, Pieris.
rapae), Spodoptera litura,
Mamestra brassicae, Chilo suppressalis, Pryausta nubiloalis, Ephestia cautella, Adoxophyes orana, Carpocapsa pomonella, Agrotis fucosa, Galleria
mellonella), diamondback moth (Plunella maculipennis),
Citrus moth (Phyllocnistis citrella);
Hemiptera, such as Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzus persicas, Aphis
pomi), cotton aphid (Aphis gossypii), and false radish aphid (Rhopalosiphum).
pseudobrassicas), nasigunbai (Stephanitis)
nashi), green stink bugs (Nazara spp.), bed bugs (Cimex lectularius), trialurodes vaporariorum, wood lice (Psylla spp.); orthoptera, e.g.
Cockroach (Blatella germanica), American cockroach (Periplaneta americana), Mole cricket (Gryllotalpa africana), Locusta (Locusta)
migratoria migratoriodes); Isoptera, such as Deucotermes speratus, Coptptermes formosanus; Diptera, such as Musca domestica, Aedes aegypti, hylemia platura, Culex
pipiens), Anopheles
slnensis), Culex tritaenior
hynchus) etc. [0057] Furthermore, in the medical field of veterinary medicine,
The novel compounds of the present invention are useful against a variety of harmful animal parasites (endo- and ectoparasites), such as insects and helminths. Examples of these harmful animal parasites include the following pests. [0058] Examples of insects include Gastrophilus spp., Stomoxys spp.
spp.), house lice (Trichodectes spp.), assassin bugs (Rhodnius spp.), and dog fleas (Ctenocephlides canis). [0059] Next, the content of the present invention will be specifically explained with reference to Examples, but the present invention should not be limited to these. [0060] [Example] Example 1 [0061] [Chemical formula 20] [Chemical formula] [Chemical formula] [0062] 2-chloro-
A solution of 5-chloromethyl-pyridine (16.2 g) in 30 ml of acetonitrile is added dropwise over 1 hour. After the dropwise addition, the mixture was stirred at room temperature for 1 hour and at 40°C for 2 hours, then acetonitrile was distilled off under reduced pressure, and ether was added to the residue.
Insoluble inorganic salts are filtered off. Ether and excess ethylenediamine were distilled off under reduced pressure to obtain the desired colorless oily N-(2-chloro-5-pyridylmethyl)ethylenediamine (16 g) represented by the above formula. n ²⁰ _D 1.5627 According to the same method as in Example 1 above, N-(2-chloro-5-pyridylmethyl)trimethylenediamine represented by the following formula was synthesized. [0063] [Chemical formula 21] [Chemical formula] [0064] Further, Table 1 shows compounds of the general formula () of the present invention that can be synthesized by a method substantially similar to that in Example 2 above. [0065] [Table 1] ■■■ Turtle shell [0066] ■■■ [0066] Synthesis reference example (synthesizing agent for compound of formula ()) [0067] [Chemical formula 22] [Chemical formula] [0068] N-(2 -chloro-5-pyridylmethyl)ethylenediamine (18.6g) 1-nitro-
2,2-bis(methylthio)ethylene (16.5g)
Methanol (100 ml) is mixed at room temperature and the contents are gradually warmed with stirring, then stirred at 50°C until the evolution of methyl mercaptan has ceased. After the reaction is completed, the crystals are cooled to room temperature and the formed crystals are collected by filtration to give the target 1-(2-chloro-
5-pyridylmethyl)-2-(nitromethylene)-
Imidazolidine (19 g) is obtained. mp.165～
166°C [0069] 1-(2-chloro-5-
Pyridylmethyl)-2-(nitromethylene)-tetrahydropyridine was synthesized. [0070] [Chemical formula 23] [Chemical formula] [0071] Example 2 (biological test) Preparation of test sample solution against organic phosphorus agent-resistant black leafhopper Solvent: 3 parts by weight of xylene Emulsifier: 1 weight by weight of polyoxyethylene alkyl phenyl ether To prepare a suitable active compound formulation, 1 part by weight of the active compound is mixed with the above amount of solvent containing the above amount of emulsifier and the mixture is diluted with water to the prescribed concentration. [0072] Test method: Rice plants with a plant height of about 10 cm were planted in pots with a diameter of 12 cm.
10 ml of the active compound diluted in water at a predetermined concentration prepared as above was sprayed per pot. After the sprayed chemical solution had dried, a wire mesh with a diameter of 7 cm and a height of 14 cm was covered, and 30 female adult leafhoppers of a strain that is resistant to organic phosphorus agents were released into the mesh, and the number of dead insects was counted after 2 days by placing them in a constant temperature room. The insect killing rate was calculated. [0073] The results are shown in Table 2. [0074] [Table 2] ■■■ Turtle shell [0067] ■■■ [0076] [Chemical formula 24] [Chemical value] [0077] [Chemical formula 25] [Chemical value] [0078] Example 3 (Biological test) Against planthoppers Test test method: Rice was planted in a pot with a diameter of 12 cm and the plant height was about 10 cm.
10 ml of an active compound diluted with water at a predetermined concentration prepared in the same manner as in Example 2 was sprinkled per pot. After the sprayed chemical solution had dried, a wire mesh with a diameter of 7 cm and a height of 14 cm was placed over the mesh, and 30 female adult brown planthoppers of a strain that is resistant to organic phosphorus agents were released into the mesh, and the number of dead insects was counted after 2 days by placing them in a constant temperature room. The insect killing rate was calculated. [0079] In the same manner as the above method, the insecticidal rate against the white-legged planthopper and the organophosphorus-resistant brown planthopper was calculated. The results are shown in Table 3. [0080] [Table 3] ■■■ Turtle shell [0068] ■■■ [0082] Example 4 (biological test) Test against organic phosphorus agent and carbamate agent resistant peach aphid Test method: In a clay pot with a diameter of 15 cm Approximately 200 peach aphids resistant to organic phosphorus agents and carbamate agents were inoculated to each seedling of eggplant seedlings (deep black long eggplants) with a height of about 20 cm, and one day after inoculation, they were inoculated as in Example 2. A sufficient amount of an active compound diluted with water at a predetermined concentration was sprayed using a spray gun. 28 after spraying
It was left in a greenhouse at ℃, and the insect killing rate was calculated 24 hours after spraying. The test was repeated twice. [0083] The results are shown in Table 4. [0084] [Table 4] ■■■ Turtle shell [0069] ■■■