FI58773B - SAOSOM INSECTICIDE ANVAENDBARA CARBAMOYLOXIPYRIDINE- QUINOLIN- OCH -TETRAHYDROQUINOLINE-N-OXIDER - Google Patents

Description

I £ g «1 fftl ANNOUNCEMENT ς n„ „_ juarg ibj (11) utlaggninqsskkift bo773 C Patent granted 10 04 1901

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Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) P 2U32635.0 (71) Hoechst Aktiengesellschaft, 6230 Frankfurt / Main 80, Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (72) Adolf Studeneer, Kelkheim / Taunus, Gerhard Salbeck, Kelhard Salbeck, , Ludwig Emmel, Bergen-Enkheim, Werner Knauf, Eschborn / Taunus,

Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (7 * 0 Oy Kolster Ab (5 * 0 Carbamoyloxypyridine, quinoline and tetrahydroquinoline N-oxides useful as insecticides oxider

The invention relates to carbamoyloxy-pyridine, quinoline and tetrahydroquinoline N-oxides of the formula "ά" S5 1 1 0 in which one of the substituents R1 and R1 is a group of the formula S / CH3 which can be used as insecticides.

-0-C-N II

OF.

CH

2,57773 and the other is hydrogen, methyl or phenyl, R 6 is hydrogen or acetyl and and R 1 represent hydrogen or methyl or together form a tetramethylene or -CH = CH-CH = CH group which may be substituted by halogen, CH 2 , OCH 4, OCHF 3, CF or phenoxy.

Compounds of formula I may be prepared as a compound of formula R 3. rp

wT

R 1, in which R 2 -R 1, have the same meaning as above, are oxidized in a manner known per se.

Examples of suitable oxidizing agents are hydrogen peroxide addition peracids, for example performic acid, peracetic acid, halogeeniperetikkahapot, for example, pertrifluoroacetic acid, perpropionic acid, permaitohappo, monopermaleiinihappo, monopermeripihkahappo, perbenzoic acid, substituted perbenzoic acid, for example 3-chloroperbenzoic acid, diperftaalihappo, perkamferihappo or mixtures thereof. Of these peroxides, perforic acid, peracetic acid, monopermaleic acid, perbenzoic acid, monoperphthalic acid, 3-chloroperbenzoic acid and hydrogen peroxide are particularly preferred.

Said available peracids may be used as such or may be prepared in the course of a reaction, for example by reacting the starting carboxylic acids or their anhydrides with hydrogen peroxide. Excess carboxylic acids or their anhydrides can also act as a solvent.

In addition, a solvent unreacted under the reaction conditions, for example, water, ether, benzene or halogenated hydrocarbons, for example, chloroform, dichloroethane or chlorobenzene, can be used as the solvent for hydrogen peroxide or peracid. In general, the amount of oxidant used is based on one to several molar equivalents of the starting compound of formula III used. However, even larger amounts of oxidant can be used without inconvenience. The reaction proceeds rapidly at a temperature of -50 ° to 150 ° C. Generally, the reaction takes place at room temperature or under cooling.

The starting materials of the formula III are obtained, for example, by reacting the corresponding substituted 2- or U-hydroxypyridines or quinolines with a) the corresponding carbamoyl halides or b) phosgene or a chloroformic acid ester and then reacting with the appropriate secondary amine (cf.

FI patent application 352 ^ + / 7 ^).

The products according to the invention have considerably higher melting points 357773 than the starting compounds of the formula III and can thus be easily isolated from the latter, for example by recrystallization.

The new compounds of the formula I have a very good selective insecticidal action, in particular on aphids, and excellent systemic properties.

They act through both the above-ground parts and the roots of plants. Thus, they can be used in the effective control of aphid species latent in plant parts. The compounds are also effective against phosphorus ester-resistant aphid species.

Examples of aphids that can be successfully controlled by the compounds according to the invention are Brovicoryne hrassicae (powdered cabbage aphid), Myzaphis Rosarium, Aphis schneideri, aphids, for example Eriosoma lanigerum (blood aphid), aphids, for example Pemphigus spec, and Myzodes persicae. Even at high concentrations of active ingredient, beneficial species of beetles (e.g. ladybug), butterflies, straight-winged, double-winged, moths (e.g. parasitic mites) and mites are not destroyed. Likewise, the effect of the compounds on aquatic organisms is negligible. Only when very concentrated do the compounds affect the fish in the water.

The compounds of the invention or compositions containing them can be used in many ways. The treatment can be applied to the leaves and / or their contaminated parts or to the soil surrounding the plants.

comparison Tests

The anti-aphid activity of the new and known compounds of similar structure was investigated by treating the roots of the plants with the test compounds. The following compounds were compared with each other: o-co-n (ch3) 2 o-co-n (ch3) 2 I (1) rS (2) h3c in3 "3C J, kn3 0 0 -CO-N (CH) | J o -CO-n (CH 3) 2

and vA A

CH3 V CH

J '' 0, 58773 o-co-n (ch3) 2 o-co-n (ch3) 2

(5> (6> CX A and kJLX

CH3 O 0 -CO-N (CH3) 2 0-CO-N (CH3) 2 "'YyS m. -IfY,., 3 4 3 0 0-CO-N (CH) O-CO-N ( CH) I * d I 3 2 C0CH3 ^ "'> ^' coce-3 t 3 (9) ΓΤ (io> CH3 Ln3 Cff3 I CH3 0 CH0 I 3? H3 (n). ΛΛ ^ 12)

l | I and I

O-CO-N (CH3) 2 O-cO-N (CH3) 2

X

0 (f ^ S (13). F ^ X (1U) A— O-CO-N (CH_) o ^ 8, 4 3 2 ^ N> -O-CO-N (CH3) 2 i 0 5 58773

The compounds denoted by even numbers are novel compounds from Examples 1, 2, 3, 5, 15, 1 and 18 (respectively) and the compounds denoted by odd numbers are known from FI application 352U / TU from Examples 3, 1, 2, 25, 60 and 1 + 6 (in that order). Only compound 13 is not specified in the said FI application, however, it falls within the scope of the claims.

The experiments were performed as described below in Example II by treating the rhizomes of pot-grown kidney bean plants with the test compounds by varying the concentrations of the compounds. Bean aphids (> 200 aphids per plant) were infected with the plants before the experiment. After 8 days, evaluation was performed by determining the concentration (mg of active ingredient per rhizome) at which 95% of aphids died, i.e. LC ^ ·

The results are shown in the following table.

Compound LCQ Compound LCOI- yy yy (mg / l) (mg / l) 1 0.5 2 0.03 3 0.5 k 0.125 5 0.5 6 0.06 T 0.125 8 0.03 9 0.125 10 0, 03 11> 2 12 0.5 13 0.5 11+ 0.125

It is found from the results that the N-oxides according to the invention are at least 1+ times more effective compared to the known compounds when carrying out the treatment on the roots of the plants. The compounds according to the invention are therefore very well suited for the treatment of ornamental plants by treating the soil surrounding the plant with an insecticide; for when the plant is sprayed with an insecticide, an ugly residue sometimes remains on the leaves and petals, which is why the spray treatment is less desirable.

6 58775 Substances containing these compounds may be in the form of dusts, powders or granules in which the active ingredient is in powder or granular form mixed with solid extenders or carriers, e.g. unreacted substances. These substances generally have a concentration of 3 to 75%. Suitable solid extenders or carriers are, for example, kaolin, bentonite, diatomaceous earth, dolomite, calcium carbonate, talc, ground magnesium oxide (chalk), effervescent clay, gypsum, diatomaceous earth and clay. The substances can also be used in the form of spray powders, which in addition to the active ingredients can, as is known, contain wetting agents and / or dispersing agents and, if appropriate, further fillers and / or emulsifying agents.

The agents may also be in the form of liquid emulsion concentrates for rolling solutions, which usually contain the active ingredient and one or more wetting agents, dispersing aids and emulsifying agents. Organic solvents can also be used in the preparation of liquid compositions.

Wetting, dispersing and emulsifying agents can be cationic, anionic or also non-ionic.

The compounds of the formula I can also be used as smoke active ingredients.

Example 1 2 <6-Dimethyl-4-dimethylaminocarbo [3] bipyridinyl-1-oxide (ch5) 2 CH3 4, ^ H3 0

19.4 g (0.1 mol) of 2,6-dimethyl-4-dimethylaminocarbonyloxypyridine were dissolved in 150 ml of anhydrous and non-alcoholic chloroform. Under ice-water cooling, Huob with 23 g of 70% chloroperbenzoic acid in 400 ml of chloroform was added dropwise with stirring.

Kim was allowed to stand for four days at room temperature. The chloroform solution was shaken three times with 100 ml portions of 2N sodium bicarbonate solution and once with 100 ml portions of distilled water, and all aqueous extracts were discarded.

After the chloroform phases were dried over calcium chloride, the chloroform was removed by distillation on a rotary evaporator under a water suction pump vacuum. The maximum temperature of the bath was 40 ° C. the oily residue and n-hexane were triturated to initiate crystallization.

7 58773 In this way 13 * 2 g of a goat fermentation product * were obtained in which the thin layer of the thin layer chromatography still contained some starting carbamate. Therefore, it was crystallized twice from acetonitrile slurry * to finally give 5 * 9 g of product with very little starting carbamate * m.p. 1Θ9-190 ° ((starting carbama- + in m.p. 75-76 ° C).

Example 2 2-Methyl-4-dimethylamino-carbonyl-oclyl-1-oxide (ch5) 2 5 0

23 g (0 * 1 mol) of 2-methyl-4-dimethylaminocarbonyloxy-quinoline were dissolved in 150 ml of anhydrous and non-alcoholic chloroform. With stirring and cooling with ice water, 25 g of 70 # 3-chloroperbenzoic acid was added dropwise to 400 ml of equal chloroform.

After standing for five days at room temperature, the chloroform solution was shaken three times with 100 ml portions of sodium bicarbonate solution and once with 100 ml portions of distilled water, and the aqueous phase was discarded.

The chloroform was dried over calcium chloride and removed by distillation on a rotary evaporator.

The crystalline residue * which, according to thin-layer chromatography, contained traces of the starting carbamate * was purified by crystallization from n-hexane-toluene * with a little activated carbon. 152 ° C (starting carbamate is liquid at room temperature).

Example 3 2-Methyl-4-dimethylaminocarbonylloxy-5,6,8,8-tetrahydroquinolinyl-1-oxide (ch5) 2 CH, i 0 5 8 7 7 3 θ

As described in Examples 1 and 2, 18 g (0.077 moles) of 2-methyl-4-dimethylaminocarbonyloxy-5,6,7,8-tetrahydroquinoline in 13.5 g of 70% 3-chloroperheenoic acid were oxidized in chloroform and the oxidation product was isolated above. as described.

The residue formed after removal of chloroform obtained by crystallization from n-hexane-benzene 9.5 g of a uniform N-okide, m.p.

197-198 ° C (m.p. 89 ° C of the starting carbamate).

Example 4 2-Methyl-6H-methoxy-4-dimethylaminocarbonyloxyquinoline-1-oxide (ch5) 2 -Ml OH, 0

33 * 5 g (0.13 mol) of 2-methyl-6-methoxy-4-dimethylaminocarbonyloxyquinoline 280 were dissolved in any glacial acetic acid, and 30 ml of hydrogen peroxide was added dropwise to this solution at about 0 to 8 ° C.

After standing for 40 days at room temperature, 2% sodium bicarbonate solution was added to the reaction mixture under ice-water cooling to a pH of 5. The precipitated crystalline oxidation product was filtered off, washed with cold water and sucked dry.

37 g of crude product were obtained. To remove the starting carbamate, it was crystallized from ethanol, acetonitrile and benzene to give 8 g of a uniform N-oxide, m.p. 172-173 ° C (m.p.

80-81 ° C).

Example 5 2-Methyl-6-netoxy-4-dimethylaminocarbonyl-5,6,7,8-tetrahydro-cyclo-11-yl-oxide.

OCON (CH 2) 2 CH-0 I

| 0 5 o 9 58773

25.5 g (0.096 mol) of 2-methyl-6-methoxy-4-dimethylaminocarbonyloxyquinoline were dissolved in 75 ml of anhydrous and non-alcoholic chloroform and, as described in Examples 1 and 2, a solution of 30 g of 3-chloroperbenzoic acid in 230 ml was oxidized: in chloroform.

After removal of chloroform in a similar manner, 31 g of an oily crude product were obtained, which was triturated in n-hexane to give 13 g of crystalline material. This was crystallized from n-hexane-benzene to give 6 g of a uniform N-oxide, m.p. 121-122 ° C (m.p. 49-51 ° C of the starting material).

In a similar manner, the following N-oxides of pyridine and chlorolinecarbamate pathways were prepared: 10 58773

Sul * »iePiete» lant (solvent) OCON (CH3) 2

c * h, o> XVL

, 1 T 2 1 * 1 - lU2 c i ocon (ch3) a 7 ζθ-CH,

OCH, J

O C (OCH) 2

Cl 16U - ^ 6 ° c 8 'OsAch, Λ ocon (ch3) 2

165 DEG-167 DEG C.

CHj i ocon (ch3) 2 i I I .., 168 ° 10 i OCON (CHj) a 90 -,.,

0C6 Hj ^ O

11 58773

Example Structural formula Melting point (solvent) OCON (CH) 165 ° C (H-hexane / benzene) N CH 3

CF

* 0 CH3 130-131 ° C I (n-hexane / benzene) N 2 OCON (CH 3) 2 OCON (CH 3) 2

123-12 * C +

15 JC jj ^ ° Η3 cis l o 0 ^ -N (CH_) o li 3 2 o CXi 0 CH3

7 115-122 ° C

WA, 1 N0- € - »(CH3) 2 O o 12 58773

Example Structural formula Melting point (solvent) Q * - »·«.

* N> -c-n (ch?) O o 3

Br Jf ~ 0 ~ N <CH3} 2 1? 5 ° C (decomposes) 19 ΓιΓί

O

Beigögridcl_A

A readily water-dispersible, wettable powder is obtained by grinding 12 parts by weight of 2-methyl-4- * diethylaminocarbonyloxyquinoline-1-oxide as the active ingredient and 3 parts by weight of Ca-Mg-Al silicate and mixing 45 parts by weight of a premix containing 10 parts by weight of laLlus lignin sulfonic acid, 49 parts by weight of diatomaceous earth (quartz and kaolinite), Θ parts by weight of colloidal silicic acid, 7 parts by weight of polypropylene oxide / colloidal silicic acid 1: 1 and 1 part by weight of sodium oleoylmethyluridide.

Example B

The emulsifiable sealant contains, for example, 1.5 parts by weight of 2-methyl-4-dimethylaminocarbonyloxy-5,6,7,8-tetrahydroquinoline-1-oxide, 6.5 parts by weight of cyclohexane as solvent and 2.0 parts by weight ethoxylate nonylphenol.

Example I

Persistent strains of black bean aphid (Soralle fabae) on potted kidney beans (Yioia faba) were sprayed dripping wet with water-diluted emulsion concentrates of the preparation of Example 2 using decreasing concentrations.

After three days, mortality rates were determined by counting live and dead animals. * The results are shown in Table I, which compares two compounds with similar structure or mode of action. The formulations of Examples 1-6, Θ, 10 and 13-19 have virtually the same potency.

58773 13

Table I

Structural formula Weight # active ingredient Mortality # in spray liquid AC0N (civ) 2 0.000375 100 0.00019 75 1 0.000095 40 _0___

KnNE-0S 6,606,695 ~ 0.003 98 0.0015 60 0CO (CH3) 2 0.0006 20

Isolane CH (CHal 0.005 100 '0 An 0.0025 96 (0¾) 2-N-C-O - / ff 0.0012 60 j [CH3 0.0006 20

Example II

The rhizomes of bull beans in pots contaminated with the stem of a pin bean (Doralla fabae) were covered with a film and a glass funnel was inserted into the center of the rhizome.

The preparation of Example 2 in the form of aqueous dilutions of the emulsion concentrate with a decreasing concentration was then uniformly poured into the root zone of the test plants via a funnel. After eight days, dead sex percentages were determined by counting dead and live aphids from the plants.

mg of active substance 0.5 0.25 0.125 0.06 per rhizome

Mortality io 100 100 92 43

The other preparations mentioned in Example I have practically the same effect.

U 58773

Example III

Hard-to-control aphid species (e.g. Myzodes persioae) can also be successfully controlled with these preparations. Myzodes perslca strains on pepper wells (Capsicum annuum) are sprayed wet with dripping emulsion concentrates diluted with the water of Example 2 using decreasing concentrations.

After three days, the mortality percentage was determined by counting live and dead animals.

$> active ingredient 0.003 0.0015 0.00075 0.000375 in spray broth

Mortality <$> 100 100 92 50

The potency of said other compounds was approximately the same.

Claims (1)

58773 Claim: Carbamoyloxypyridine, quinoline and tetrahydroquinoline N-oxides of the formula R 5] R 10 in which one of the substituents R 1 and is a group of the formula 0 ^ ch3 and the other is hydrogen, methyl or phenyl, R2 is hydrogen or acetyl and R1 and R1. represent hydrogen or methyl or together form a tetramethylene or -CH = CH-CH = CH group which may be substituted by halogen, CH 2 O, OCH 2, OCHF 4, CF 2 or phenoxy.