DE2751317A1 - N,N-Di:substd. N'-substd. phenyl formamidine(s) - used as pesticides esp. insecticides and acaricides - Google Patents

Abstract

Phenyl-formamidine derivs. of formula (I) are new:- (where R1 is Me or Et; one of R2 and R3 is H and the other is Me). (I) are broad-spectrum pesticides, esp. insecticides and acaricides. They are also active against nematodes, viruses, bacteria and plant-pathogenic fungi. (I) are esp. active against plant-pathogenic biting insects (e.g. Spodoptera littoralis, Heliothis virescers, Leptinotarsa decemlineata and Myzus persical), and also have high activity against flies and mosquito larvae. (I) are pref. used in combination with synergists, e.g. piperonyl butoxide. (I) are more stable in solns. and slurries than the analogues of DT1542715. In an example, N,N-dimethyl-N'-(2,3-dimethyl-4-chlorophenyl)-formamidine was prepd. by reacting 2,3-dimethyl-aniline with DMF dimethyl-acetal then chlorinating.

Description

Phenylformamidine derivatives and -iLre- salts, process for their

Production and their use in pest control The present invention relates to phenylformamidine derivatives and their salts with inorganic and organic acids, processes for their production and their use in pest control. The phenylformamidines have the formula where R1 is methyl or ethyl, R2 is methyl and R3 is hydrogen or R2 is hydrogen and R3 is methyl.

Inorganic acids such as HC1, H2SO4, HEr and H3PO4 and as organic acids, for example, saturated or unsaturated mono-, di- and tricarboxylic acids such as formic acid, acetic acid, oxalic acid, Phthalic acid, succinic acid and citric acid into consideration.

The phenylformamidines of the formula I can be prepared by processes known per se, for example by adding the aniline of the formula a) in the presence of SOC12, POC13, PC13 or PC15 with elimination of water with an N-formamide of the formula or b) with an acetal of the formula implements.

In Formulas II and IV, R1, R2 and R3 have those for Formula I. given meaning and R stands for C1-C5-alkyl.

Phenylformamidines of the formula I can also be prepared by adding a phenylformamidine derivative of the formula in which R1 is methyl or ethyl, post-chlorinated.

The processes are preferred at a temperature of 0 to 1200C at 20 to 950C, at normal or elevated pressure and, if necessary, in a solution or diluents carried out. Suitable as a solvent or diluent e.g. ether and ethereal compounds like Diethyl ether, Dipropyl ether, dioxane, dimethoxyethane and tetrahydrofuran; Amides such as N, N-dialkylated Carboxamides; aliphatic, aromatic and halogenated hydrocarbons, in particular benzene, toluene, xylene, chloroform and chlorobenzene; Nitriles such as acetonitrile; Dimethyl sulfoxide and ketones such as acetone and methyl ethyl ketone. The starting materials of the formulas II to IV are known or can be prepared analogously to known methods will.

The compounds of the formula I are suitable for combating various types of disease animal and vegetable pests. They have nematicidal properties and can be used, for example, to combat phytopathogenic nematodes will. They are also suitable for combating viruses, bacteria and phytopathogens Mushrooms.

In particular, however, the compounds of the formula I show excellent properties Effect against insects and representatives of the order Akarina, surprisingly the stability in solutions or slurries compared to analog, from the German Patent No. 1,542,715 known compounds is higher.

The compounds of the formula I are therefore suitable for combating Insects, phytopathogenic mites and ticks e.g. of the order Lepidoptera, Coleoptera Homoptera, Heteroptera, Diptera, Acarina, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera.

In particular, compounds of the formula I are suitable for combating plant-damaging insects, especially plant-damaging feeding insects, in ornamental and useful plants, especially in cotton crops (e.g. against Spodoptera littoralis and Heliothis virescens) and vegetable crops (e.g. against Leptinotarsa decemlineata and Myzus persicae).

The active ingredients of formula 1 also show a very beneficial effect against flies such as Musca domestica and mosquito larvae.

The acaricidal or insecticidal effect can be reduced by adding other insecticides and / or acaricides widen significantly and given Adjust circumstances. Organic phosphorus compounds, for example, are suitable as additives; Nitrophenols and their derivatives; Formamidine; Ureas; pyrethrin-like compounds as well Carbamates and chlorinated hydrocarbons.

Compounds of the formula I are also particularly advantageous with substances combined, which have a reinforcing effect. Examples of such compounds include: piperonyl butoxide, propynyl ether, propinyloxime, propynyl carbamate and Propynyl phosphonate, 2- (3,4-methylenedioxyphenoxy ) -3,6,9-trioxaundecane, S, S, S-tributyl phosphorotrithioate.

The compounds of the formula I can be used alone or together can be used with suitable carriers and / or additives. Suitable carriers and aggregates can be solid or liquid and correspond to those used in formulation technology common substances such as natural or regenerated substances, solvents, dispersants, Wetting agents, adhesives, thickeners, binders and / or fertilizers. For application you can the compounds of formula I to dusts, emulsion concentrates, granules, Dispersions, sprays, solutions or slurries in the usual formulation, which are part of general knowledge in application technology. Furthermore, there are "cattle dips", i.e. cattle baths, and n spray races ", i.e. spray courses, in which aqueous preparations are used.

The agents according to the invention are prepared in a manner known per se Way by intimately mixing and / or grinding active ingredients of the formula I with the suitable .carriers, optionally with the addition of the active ingredients inert dispersants and solvents.

The active ingredients can be in the following working-up forms and are used: Solid processing forms: dusts, grit, granulates (Coated granules, impregnation granules and homogeneous granules); Liquid processing forms: a) Active substance concentrates dispersible in water: wettable powders, pastes, Emulsions; b) Solutions.

The content of active ingredient in the agents described above is between 0.1 to 95%.

The active ingredients of the formula I can, for example, be formulated as follows : Dusts: For the production of a) 5% and b) 2% dust the following substances are used: a) 5 parts of active ingredient, 95 parts of talc; b) 2 parts of active ingredient, 1 part of highly disperse silica, 97 parts of talc.

The active ingredients are mixed and ground with the carrier substances.

Granules: The following are used to produce 5% granules Substances used: 5 parts of active ingredient, 0.25 parts of epichlorohydrin, 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, 91 parts of kaolin (grain size 0.3-0.8 mm).

The active ingredient is mixed with epichlorohydrin and added 6 parts Dissolved acetone, then polyethylene glycol and cetyl polyglycol ether are added. The solution obtained in this way is sprayed onto kaolin and then the acetone evaporated in a vacuum.

Wettable powder: For the production of a) 40%, b) and c) 25% d) 10% wettable powder, the following ingredients are used: a) 40 parts of active ingredient, 5 parts of lignin sulfonic acid, sodium salt, 1 part of dibutylnaphthalenesulfonic acid, sodium salt, 54 parts of silica; b) 25 parts of active ingredient, 4.5 parts of calcium lignosulfonate, 1.9 Parts of champagne chalk / hydroxyethyl cellulose Mixture (1: 1), 1.5 Parts of sodium dibutyl naphthalene sulfonate, 19.5 parts of silica, 19.5 parts of champagne chalk, 28.1 parts of kaolin; c) 25 parts of active ingredient, 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1.7 parts of Champagne-Krelde / llydroxyethylcellulose mixture (1: 1), 8.3 parts of sodium aluminum silicate, 16.5 parts of kieselguhr, 46 parts of kaolin; d) 10 parts of active ingredient, 3 parts of mixture of Sodium salts of saturated fatty alcohol sulfates, 5 parts of naphthalenesulfonic acid / Formaldehyde condensate, 82 parts of kaolin.

The active ingredients are mixed with the additives in suitable mixers intimately mixed and ground on appropriate mills and rollers. Spray powder is obtained which can be diluted with water to form suspensions of any desired concentration.

Emulsifiable concentrates: For the production of a) 10% b) 25% and c) 50% emulsifiable concentrate, the following substances are used: a) 10 Parts active ingredient 3.4 parts epoxidized vegetable oil, 3.4 parts of a combination emulsifier, consisting of fatty alcohol polyglycol ether and alkyl aralkyl sulfonate calcium salt, 40 parts of dimethylformamide, 43.2 parts of xylene; b) 25 parts of active ingredient, 2.5 parts of epoxidized vegetable oil, 10 parts of an alkylarylsulfonate / fatty alcohol polyglycol ether mixture, 5 parts of dimethylformamide, 57.5 parts of xylene.

c) 50 parts of active ingredient, 4.2 2 parts of tributylphenol polyglycol ether, 5.8 parts of calcium dodecylbenzenesulfonate, 20 parts of cyclohexanone, 20 parts of xylene.

Such concentrates can be diluted with water to produce emulsions of any desired concentration.

Spray: For the production of a> 5% and b) 95% spray the following ingredients are used: a) 5 parts of active ingredient, 1 part of epichlorohydrin, 94 parts of gasoline (boiling limits 160-1900C); b) 95 parts of active ingredient, 5 parts of epichlorohydrin.

Example 1 Preparation of N, N-Dimethyl-N '- (2'3-dimethyl-4-chlorophenyl) -formamidine.

a) 60.5 g of 2,3-dimethylaniline are mixed with 75 g of dimethylformamide dimethylacetal Heated in a still for 5 hours after the forming Methyl alcohol is largely distilled off, the reaction product is in vacuo distilled.

The compound of the formula is obtained with a boiling point of 78-80 C / 0.2 Torr.

b) 58 g of N, N-dimethyl-N '- (2,3-dimethylphenyl) formamidine are in 250 ml of chloroform are mixed with 11.5 g of hydrochloric acid gas.

After adding 0.7 g of iodine, 23 g of chlorine gas are passed in at 5-10 ° C. for two hours, the mixture is left to stand for 15 hours at room temperature, the batch is poured onto ice, 10 g of sodium bisulfite are added and the reaction mixture is made after a short period of tubing strongly alkaline with caustic soda. The organic phase is separated off and distilled. The compound of the formula is obtained with a distillation point of 105 ° C / 0.2 Torr and a melting point of 540C.

The following connections are also established in the same way: Bp: 90 ° C / 0.08 torr Sdp .: 1080C / 0.07 Torr Bp: 130 ° C / 0.15 Torr Example 2 A) Insecticidal food poison effect Cotton plants were sprayed with a 0.05% aqueous active ingredient emulsion (obtained from a 10% emulsifiable concentrate>.

After drying the covering, the cotton plants were each with Spodoptera littoralis and Heliothis virescens larvae L3 occupied. The attempt was made carried out at 24 0C and 60% relative humidity.

Compounds according to Example 1 showed in the above test one good insecticidal feeding poison action against Spodoptera and Heliothis larvae.

B) Systemic insecticidal effect To determine the systemic Effect were rooted bean plants (Vicia faba) in an 0.1% aqueous solution Active ingredient solution (obtained from a 10% emulsifiable concentrate) set. After 24 hours, aphids (Aphis fabae) were found on the above-ground parts of the plant. set. Thanks to a special device, the animals were protected from contact and gas effects protected. The experiment was carried out at 24 ° C. and 70% relative humidity.

Compounds according to Example 1 showed systemic insecticides in the above test Effect against Aphis fabae.

Example 3 Action against Chilo suPpressalis 6 rice plants each of the Caloro variety were transplanted into plastic pots with an upper diameter of 17 cm and raised to a height of approx. 60 cm. The infestation with Chilo suppressalis Larvae (L1: 3-4 mm long) took place 2 days after the addition of the active ingredient in granulate form (Application rate 8 kg of active substance per hectare) in the paddy water. The evaluation insecticidal action took place 10 days after the addition of the granules.

Compounds according to Example 1 acted against chilo in the above test suppressalis.

Example 4 Acaricidal activity Phaseolus vulgaris plants were 12 Hours before testing for acaricidal activity with an infected piece of leaf the end a mass breeding of Tetranychus urticae. The defected movable Stages were made from a chromatography nebulizer with the emulsified test preparations sprayed in such a way that the spray liquid did not run off. After two and seven days larvae, adults and eggs were examined under the dissecting microscope for living and dead individuals evaluated and the result expressed as a percentage. Stood during the "hold time" the treated plants in greenhouse cabins at 250C.

Compounds according to Example 1 were effective in the above test against adults, Larvae and eggs of Tetranychus urticae.

Example 5 Effect due to soil nematodes To test the effect against Soil nematodes became the active ingredients in through root cell nematodes (Meloidogyne arenaria) infected soil and mixed thoroughly. In the earth prepared in this way were planted immediately after tomato seedlings in a series of experiments and In another series of experiments, tomatoes were sown after a waiting period of 8 days.

The nematicidal activity was assessed 28 days after planting or after sowing the galls present on the roots are counted. In this test Active ingredients according to Example 1 showed a good effect against Meloidogyne arenaria.

Example 6 Action against ticks A) Rhipicephalus bursa. 5 adults each Ticks or 50 tick larvae were counted in a glass tube and counted for 1 to 2 Minutes in 2 ml of an aqueous emulsion from a dilution series of 100 each. 10, 1 or 0.1 ppa test substance submerged. The tube was then closed with a standardized cotton ball and turned upside down so that the Active ingredient emulsion could be absorbed by the cotton wool.

The evaluation was carried out in the adults after 2 weeks and in the Larvae after 2 days. Two repetitions were run for each attempt.

B) Boophilus microplus (larvae) With an analogous dilution series as in test A) were each with 20 sensitive resp. OP-resistant larval trials carried out. (The resistance relates to the tolerance of Diazinon). Compounds according to Example 1 were active in these tests against adults and larvae of Rhipicephalus bursa and sensitive or 0P-resistant larvae of Boophilus microplus.

Example 7 Action against Erysishe graminis on Hordeum vulgare Ca.8 cm high barley plants were made with a wettable powder of the active ingredient Spray mixture (0, eyelet active substance) sprayed. After 48 hours the treated Plants pollinated with conidia of the fungus. The infected barley plants were placed in a greenhouse at about 220C and assessed the fungal attack after 10 days.

Compounds according to Example i were effective against Erysiphe in this test graminis.

Claims (10)

Claims 1. A phenylformamidine derivative of the formula where R1 is methyl or ethyl, R2 is methyl and R3 is hydrogen or R2 is hydrogen and R3 is methyl. 2. The phenylformamidine derivative according to claim 1 of the formula 3. The phenylformamidine derivative according to claim 1 of the formula 4. The phenylformamidine derivative according to claim 1 of the formula 5. The phenylformamidine derivative according to claim 1 of the formula 6. Process for the preparation of a phenylformamidine derivative according to claim 1, characterized in that a) a phenylformamidine derivative of the formula in which R1 is methyl or ethyl, post-chlorinated or b) a compound of the formula wherein R2 and R3 have the meaning given in claim 1, with a compound of the formula reacted, in which R is Cl-C5-alkyl and R1 has the meaning given in claim 1. 7. A pesticide that acts as the active component a compound according to claim 1 and suitable carriers and / or other additives contains. 8. Use of a compound according to claim 1 for combating various animal and vegetable pests. 9. Use according to claim 8 for combating insects and representatives of the order Akarina. 10. Use according to claim 8 for combating phytopathogens Nematodes.