New agents pesticides.
PATENT AS AFRICAN AND MALAGASY INDUSTRIAL PROPERTY P. 887 international Patent Classification yaoundê (Cameroon): 07 № 1900 for O-RO C. o A>m-I-P Request 20 January 1966 to 09 hr 10 min to lOAM.P.I. (G.P. no. 52331) by Company said: FBCN - company anonymous. resident of Switzerland. 4 February 1970 delivered Publishes official ballot № 1 of 1970 PRIORITY: patent application deposited in Swiss the 22 January 1965 no. 915/65/sec. 9 july 1965 and n° 9630/65/sec. on behalf of the applicant. Novel pesticidal agents. The present invention relates to pesticidal agents for combating especially insect pests, acarid, nematodes, preferably fungi and microorganisms and phytopathogenic bacteria, as well as 5 undesirable plants, these agents are characterized in that they contain as active ingredient at least one compound having the formula wherein R ^ is hydrogen or an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and R ^a aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic, the R ^ and RG can together form part of a saturated or unsaturated carbocyclic or heterocyclic ring, while and R ^ groups are negative and R, _ and RG represent. hydrogen, halogen, or alkyl groups, hydroxyl, acyloxy group, alkoxy group, aryloxy group, thiol group, acylthiol, alkylthio group, arylthio group, an amino, alkylamino or dialkylamino, or have the same meaning as R and R ^ ^, said pesticidal agents which may additionally contain the following additives: of dyestuff, dissolution agents, diluting, dispersing, wetting, fixing or fertilizers, as well as other pesticidal agents already known. The active compounds defined by general formula I represent to chemically oximéthers. These oximéthers may originate from aliphatic aldehydes and ketones, araliphatic, aromatic or heterocyclic, and quinones and ketones endocyclic, as fluorenone, indanone, 1 'acénaphténone, 1' like, n-methyl-pyridone derivative, n-methyl-piperidone, furfurol or nitrofurfurol, andc... As indiqué'indiqué' ci above, the two substituents R and Rj ^ ^ should represent negative groups. This expression designates in the frame of the invention groups that render the mobile halogen atom bonded ortho or para, as done for example nitro, a cyano, trifluoromethyl, formyl 1, possibly as acetal, or sulfamyl groups optionally having substituents, or carboxy groups or carboxyester. The remainder phenyl may further include still other substituents, for example halogen atoms, the alkyl radicals, alkoxy group, alkylthio group, c... Preferably, used oximéthers which derive from aliphatic aldehydes and ketones, aldehydes and ketones are araliphatic aldehydes and ketones or aromatic or heterocyclic. As aliphatic aldehydes, a very simple constitution of aldehydes, such as acetaldehyde, propionaldehyde, butyraldehyde and also of longer chain aldehydes, e.g. 1' heptaldehyde, the stéaraldéhyde, or unsaturated aldehydes, as crotonaldehyde, andc.... As aliphatic ketones, reporting the simple ketones, such as acetone, methyl ethyl ketone, the hexa-to-ηοη ℮ - (3), diisopropyl ketone, the mésityloxyde, the phorone, andc... As araliphatic or aromatic aldehydes and ketones, which enumerates the following: aldehyde einnamic, hydrocinnamic aldehyde, halogen adducts with the aldehyde einnamic, e.g. dibromocinnamic aldehyde, aldehyde diiodocinnamic, 1' acetophenone, the propiophenone, benzaldehyde, the benzaldehydes halogens in the core, alkylated, alkoxylated nitrated, et cetera, as cyclic ketones, it is reported for example cyclopentanone, cyclohexanone, cycloheptanone, and e.g. a cyano derivatives thereof• As heterocyclic ketones and aldehydes, mentioned are for example the aldehyde picolinic, nicotinic aldehyde, aldehyde isonicotinic, the n-alkylpipéridones, andc.. If these aldehydes or ketones include aromatic radicals, one can still use the corresponding substituted derivatives. The substituents may be non-functional in nature, for example halogen atoms, nitro or nitroso groups, or functional nature or come from functional substituents, such as hydroxy, acyloxy group, carbamoyloxy group, alkoxy group, aryloxy group, thiol group, acylthiol, an alkylthio, trifluoromethyl, a cyano, formyl 1, alkylamino, alkyl amino, dialkyl amino, arylamino group, arylamino, carboxyl, carbalkoxy, c... Novel agents have, due to their wide range biocidal, the particular advantage is suitable for a wide variety of pests of animal and plant. They are useful not only as herbicides, but also exert, when used at a concentration that does not causes phytotoxic phenomena, a very effective protection against harmful microorganisms, such as fungi, such as Alternaria solani or, Phytophthora infestans and Septoriaapii, as well as insect pests, acarid, nematodes and their eggs or larvae. Further, novel agents can be used as microbicides for combating organisms. from Aspergillus, as well as as insecticides against mosquitoes and flies. For preparing solutions directly sprayable compounds having the general formula (I-), can be used, for example, mineral oil fractions of high boiling or means, waste oil such as diesel or kerosene, the coal oil and vegetable or animal oils, as well as hydrocarbons, such as alkylated naphthalenes and tetrahydronaphthalene, optionally using mixtures of xylenes, of cyclohexanol derivatives, ketones, and chlorinated hydrocarbons, such as trichloroethane and tetrachlorethane, trichloroethylene or the tri and tetrachlorobenzenes. Advantageously, organic solvents are used whose boiling point is greater than 100 °c. Are prepared from aqueous solutions to the application advantageously from concentrates emulsified, pastes or powders to be nebulized wettable by adding water. As emulsion or dispersion, nonionic agents are used, such as the condensation products of alcohols or amines aliphatic carboxylic acids with long-chain hydrocarbon group of about 10 to 20 carbon atoms to ethylene oxide, as the condensation product of octadecyl alcohol with 25 to 30 moles of ethylene oxide, or that of the fatty acid soybean with 30 moles of ethylene oxide or that of the oleyiàmine technology with 15 moles of ethylene oxide, or that of the dodecyl mercaptan with 12 moles of ethylene oxide. Among the emulsification to usable active anion, reported to the sodium salt of the sulfuric ester of the dodécylalcool, the sodium salt of dodecylbenzenesulfonic acid, the potassium salt or triethanolamine oleic acid or abietic acid or mixtures of these two acids, or the sodium salt of an acid petrolosulfonic. As dispersants cation-active, use can be made of quaternary ammonium compounds, such as cetylpyridinium bromide or chloride dihydroxyéthylbenzyldodécylammonium. For the spraying agent preparation for spreading, can be used as solid supports talc, kaolin, bentonite, calcium carbonate, calcium phosphate, but also the coal, cork flour, wood flour and other materials. It is also advantageous in preparing the products in a granular form. The various application forms may further contain conventional additives, which improve the distribution, the attachment and resistance to rain or the throwing power; these substances are usually fatty acids, resins, glues, alginates or casein. Pesticidal agents can be used according to the invention separately or in conjunction with other agents known and common, as insecticides, miticides, nematocides, bactericides or fungicides or herbicides complementary agents. Herbicides particularly useful are formed by compounds which contain as active substance the product having the formula The n (I-d) wherein R ^ is hydrogen or an aliphatic radical and RG an aliphatic radical or a phenyl radical which is optionally substituted, whereas a denotes a group - N0 in2 , - CH0, - C00HCOOAlkyl and b - or hydrogen or a group - the NOG, C00H -, - COOAlkyl or chlorine. The phenyl radical carrying various RG§substituent such as halogen atoms, nitro groups, alkyl groups, hydroxy or alkoxy and/or carbamyloxy groups. Herbicides particularly effective are formed by compounds having the formula (I-d) above, wherein R ^ and RG are as below: H HR LEC-TO-HN-COO Hr - IF iC (following) the R ^ r2 Hr (the X=brr or j) H CH, 5G 2H 5 HR ' C.2H5 0 - Are particularly suitable as acaricidal agents containing as active ingredient a compound of formula where R1 and RG is hydrogen radical phenyl optionally having halogen atoms as substituents, or alkyl or alkoxy groups, or wherein R ^ and RG are radicals alkyl or are part of a core isocyclic. Particular effect returns to compounds having the formulae H LC H H H H ^ O Z-CH-HR/VS. HM, HM - 3.5. HM - HM, 0 - The active compounds may be prepared for formula 1 as follows: Reacting a salt of a ketoxime or aldoxime of formula R 1 ≈ Prefecture wherein R ^ and RG have the meaning already indicated and me is a metal atom, preferably alkaline, on a halobenzene of the formula wherein R ^, ^ ^ d or the R, the rg are as defined above and hal denotes fluorine, chlorine, bromine or iodine. This reaction can be carried out in a solvent, such as ethanol, methanol, 1' acetonitrile, dioxane, andc... it takes place in general at ordinary temperature and, in many cases, with spontaneous heat release. Can be isolated simply oximéthers the so obtained in diluting with water the reaction mixture. The ethers precipitate then and if necessary they can be recrystallize. The method lends itself to variations of the fact that after the formation of the oximether can be still further modifying one or more of groups R ^, the R ^, R., _, the rg. In particular, which is exchangeable for the halogen atoms of R ^ and/or RG against compounds having active hydrogen atoms, for example against a group - NHg, primary or secondary amines or aliphatic, araliphatic or aromatic, alcohols, phenols, alkanethiols, thiophenols, andc... The oximéthers, that make it possible to prepare, can exist in the form syn and anti. In general, they are obtained in the preparation state of a mixture of isomers, that may be separated into two forms by conventional methods, for example crystallization, 1' adsorbing, andc... To prepare the agents according to the invention, it suffices to use the mixture of isomers such as occurs. The present invention also relates to novel oximéthers of general formula wherein R ^ and Rg have the meanings already mentioned and R ^ is a trifluoromethyl radical, optionally esterified carboxyl or formyl 1 * sulfamyl optionally alkylated ^ and R represents hydrogen or a group - the NOG, also being a group of R ^ - ^ the NOG and R an optionally esterified carboxyl group. The invention concerns in particular oximéthers of general formula wherein R1 is hydrogen or an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and RG an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic, or the R ^ and RG may be part of a carbocyclic or heterocyclic. Further, the invention relates to novel compounds of the category NO., THE R, : c=n - 0 COCR THE R, wherein R ^ and Rg have the meanings already mentioned and R is an alkyl or lower cycloalkyl, for example methyl, ethyl, propyl methacrylamide, butyltin, hydroxyamyl, phenylcyclopentyltrimethylammonium or cyclohexyl, or hydrogen. Further, the invention concerns novel oximéthers of general formula wherein R ^ and RG are as defined above. •specifically disclosed novel oximéthers of general formula wherein R ^, Rg and R have also defined as above. In addition, it relates to novel oximéthers of general formula wherein R ^ and RG are as defined above and X is a halogen atom or a group aminogenic primary, secondary or tertiary aliphatic, araliphatic or aromatic group which is etherified or esterified hydroxy or thiol. Finally, the invention provides oximéthers of general formula in which R - ^, Rg and R have the above meaning, and also novel oximéthers of general formula where R1 denotes hydrogen and RG represents a phenyl radical substituted with at least two halogen atoms and optionally a hydroxy group. EXAMPLE 1 1.) ^ O Ch HM=n 0 - ^ - the NOG NR Is added to a solution of 2.) To a solution of 82 parts of O-methoxybenzaldehyde and 115 parts 4-chloro-L, 3-dinitrobenzene in 1000 parts by volume of acetonitrile, is added dropwise, in 1/2 hour at room temperature, a solution of sodium ethoxide prepared from 13.1 parts sodium and 300 parts by volume of absolute ethanol. 4 - After hours, the mixture is diluted with 3000 parts by volume of water, is separated by filtration and is recrystallized in a mixture of toluene-acetone. Melting point: 184 - l84,5° * To a solution of 90 parts cyclohexanone oxime and 162 parts 4-chloro-L, 3-dinitrobenzene in 500 parts by volume of acetonitrile, is added dropwise, in l/2 hour and at room temperature, a solution of sodium dlsthylate sputtering prepared from 18.5 parts of sodium and 500 parts by volume of absolute ethanol. After 4 hours, the mixture is diluted with water, removed by filtration the precipitated product and is recrystallized in acetonitrile. Melting point: 105.5 - 106°. EXAMPLE 4 HM - 4.) (CH-^)2 CH C.=/ - N - 0~VBE1) - FOR N0, no.2 Is dissolved 50.5 parts of methyl-isopropylcétonoxime and 101.5 parts 4-chloro-L, 3-dinitrobenzene in 400 parts by volume D.1 acetonitrile derivative. Is added dropwise with stirring, at room temperature, a solution of sodium ethoxide prepared from 12 parts sodium and 250 parts by volume of absolute ethanol, the precipitate is separated by filtration and is recrystallized in of 11 acetonitrile. Melting point: 85 - 86 degrees. A solution is prepared of salt oxime from 380 parts of 2.6 to-dichlorobenzaldéhydoxime, 46.3 parts sodium in 4000 parts by volume of absolute ethanol and introducing this solution within one hour, with stirring and cooling, in 405 parts 4-chloro-L, 3-dinitrobenzene dissolved in 500 parts by volume of acetonitrile, this at a rate such that the temperature is maintained between -5 et + 10 °c. After 3 hours of stirring the mixture, it is diluted with ice water, the precipitate is separated by filtration and is recrystallized in a mixture of dimethylformamide and acetonitrile. Melting point: 177 - 178°• Added to 93 parts 4 fluoro-L-, 3-dinitrobenzene in 200 parts by volume of acetonitrile, to -5° and stirring, within half an hour, a salt solution of oxime prepared from 43.5 parts of isobutyraldoxime, 10.5 parts sodium in 300 parts by volume of absolute ethanol. After that, the mixture is stirred for 3 hours at room temperature, diluted with ice water, the precipitate is separated by filtration and is recrystallized in acetonitrile. Melting point: 80 - 82°. 7.) (CH-^)2 N S02 - -=0 N Added to 106 parts 4 chloro-3-nitrate benzenesulfonyl - (I)- dimethylamide 50° contained in parts by volume of dioxane dropwise and at room temperature, while stirring and in half an hour, a solution prepared from 54 parts of the sodium salt of cyclohexanonoxim in 800 parts by volume of dioxane, thereby elevating the temperature up to 2 hours after 35°•, the mixture is heated for half an hour to, 50 degrees, then diluted with ice water, the product is separated by filtration and is recrystallized in ethanol. Melting point: 124 - 125°. 8.) OgN - 0 n=- CH2 - V-no., 2 To a solution of 42 parts of 5 chloro-2.4 dlnltro-to-anillne °0 in 5 parts by volume of acetonitrile, is added dropwise, at room temperature under stirring for half an hour, a solution of the salt of oxime which was prepared from 50 parts 2 a-chlorobenzaldéhydoxime, 4.5 parts sodium in 400 parts by volume of absolute ethanol. After 6 hours of reaction, the mixture is diluted with ice water, the precipitate is separated by filtration and is recrystallized in of 1' acetonitrile. Melting point: 166 - l67 °C. Is introduced dropwise into a solution of 69 parts of cuminaldéhydoxime-a 0 / - 5 chloro-2.4 a-dinitrophényléther7 in After one hour, the mixture is diluted with ice water, the precipitate is separated by filtration and is recrystallized in a mixture of ethanol and dimethylformamide. Melting point: 6 ΐ ΐ - l62 degrees. To a solution of 77 parts fluorénonoxime-a 0 a-z5-chloro 2.4 a-dinitrophényléther7 in 1500 parts by volume of dioxane, is added dropwise to, within one hour and 50 degrees, a solution of isopropylamine in 25 parts 100 parts of dioxane. Continuing to heat the mixture for 5 hours at reflux at 80 degrees, again added 20 parts isopropylamine and preserves all further 5 hours at 80 degrees, which was then diluted with ice water, the precipitate is separated by filtration and the fact digesting hot in dimethylformamide. Melting point: 240 - 241° (with decomposition). 11.) To a solution of 150 parts of isopropyl - / 5 chloro-2.4 a-dinitrobenzoic phényl7-sulfide in 400 parts by volume of acetonitrile, is added dropwise, at room temperature by stirring, in a period of half an hour, a salt solution of oxime which was prepared from 86 5 parts5 4 a-dichlorobenzaldoxime, 10.3 parts sodium in 600 parts by volume of absolute ethanol. After 3 hours of reaction, the mixture is diluted with ice water, the precipitate is separated by filtration and is recrystallized in acetonitrile. Are introduced into a solution of 63 parts of 2 a-méthoxybenzaldéhydoxime-a 0 / - 5 chloro-2.4 a-dinitrophényléther/in 1000 parts by volume of dioxane dropwise and stirring, while passing in the recipient a nitrogen stream, a solution comprised of sodium methylate and 29 parts of 4 chloro-thiophenol in 800 parts by volume of dioxane, this solution being added thiophenoxide within half an hour, and the mixture is heated for one hour to 40 degrees, diluted with ice water and the precipitate is separated by filtration, and then recrystallized product in a mixture of dioxane-dimethylformamide. Melting point: 197 - 198°• As described ODBC examples given in the above, can be prepared also oximéthers the ,, 2 4 a-dinitrophenol listed on the following table: TABLE 1• As described in the examples, can be obtained *' *•" -... the oximéthers 2 of theJ 4 a-dinitrobenzoic 5 a-ohlorophénol hereinafter: TABLE 2 Can be obtained analogously the oximéthers The•- ^ 2-nitrate 4 a-Garbométhoxy-to-CTB " nol-to-.iüd.lques on the board - cr after: - ^ tabUe '&u.-a 3 - - The oximéthers of 2.4 to-dinitrobenzoic 6 a-carbométhoxyphénol can be obtained in a similar manner :.• TABLE 4•• The; oximéthers of 2.4 to-dinitrobenzoic 6 a-carbocyclohexoxyphénol may be prepared " a manlèr'manlèr' e-to-analoguerTABLE 5 "'"' Further, are prepared oximéthers hereinafter which are derived from 2-nitrate 4-formyl phenol: TABLE 6 It has also prepared the oximéthers of 2-nitrate 4-trifluoromethyl-phenol hereinafter: The 2.6 to-dinitrobenzoic 4-trifluoromethyl phenyl ether of 11 acetone oxime melts at 80 - 8 l °C (compound no. 10 125). The oximéthers hereinafter of the 2, 4, 6 a-trinitrophenol were also prepared: It was also prepared the oximéthers of 2-nitrate 4 n, n-dimethyl-sulfamylphénol hereinafter: The oxime-to-2-nitrate 4 n-methyl-sulfamyl-phenyl-éttier melts at 129 - 130 °c (compound no. 10 ij54). It was also prepared the oximéthers of 2.4 and the Dini-to-ORR-to-5-amino phenol hereinafter: Further, are prepared oximéthers of 2.4 to-dinitrobenzoic 5 isopropylamino-phenol: The fluorénonoximéther of 2.4 to-dinitrobenzoic 5 a-morpholinophénol melts with decomposition 229 - 250 °c (compound no. 10 145). Is the derivative of formula in the manner described in the example 11. The product melts at 155 - 155 °c (compound no. 10 144). EXAMPLE 15 a) is finely 50 g of the active ingredient no. 10 14, together with 20 g of "Hisil" (si0 preparation2 ) and 25 g of kaolin clay by adding 5 * 5 g of a suspending agent (e.g. of the condensation product of 1 mole of p-octylphenol with 6 to 10 moles of ethylene oxide) and 1.5 g of a wetting agent (e.g. L-benzyl 2 a-heptadecyl-benzimidazole sodium dodecyl diphenyloxide disulfonate); this provides a "wettable powder" containing 50 $of active substance. There is a similar preparation with the active substance NO 21, but using, instead of 25 g of kaolin clay, 25 g of chalk. A formulation identical to that obtained with the substance NO 14 is obtained also with the substance NO 4. b) mixed each time 500 grams substances Nos. 5 or 67 with 110 g of ammonium lignosulfonate, 45 g of dicrésylméthane disulfonic acid, 10 g of a mixture of 40 EXAMPLE 14 a) substances Nos. 26, 15, 17, 29, and 27 show l8 for custom emergence effective against various dicotyledenous plants. The treatment is carried out using 5.0 kg of the substance according to the invention 12 days after planting when plants carry 1 or 2 true leaves. The results obtained are as follows: (used amount of each produced kg of active substance) 0=not affected 5 ^=damage observed 5 ^=heavily damaged, causing destruction. 10=the plant is completely destroyed. Similar effects are observed with compounds Nos. 1, 2, 13, 14, 19, 21, 32, 33, 36, 37 * 4l, 43 * 46, 47, 62, 65, 71 * 72 * 77 * 97 * 98, 100, 121, 130 and 131. b) for a greenhouse test, has been sprayed on the earth the active substances Nos. 5 and 67 of the example 13 and b) in amounts of 4.0, 2.0, 1.0 and 0.3 kg per ha. immediately after planting plants for the treatment of various early ., plants sown and results follow from the following table: 0=not effect 10=complete destruction of plants The two materials of the invention, taken in an amount of 4.0 kg/acre, show a wide range of efficiency, while with 0.5 kg of substance only, few plants are heavily damaged (especially of Avena, AOP, Dactylis, Lactuca), while others are not or little, as Triticum, of Hordeum, Brassica plant, soybean and galactosidases. This can allow both substances as herbicide sum to early treatment to a suitable concentration for selectively eliminating weeds, for example in wheat (Fermented Triticum and Hordeum), the cabbage (Brassica plant) and vegetables (soybean paste and Phaseoulus). EXAMPLE 15 50 G of each ground active substance of our. 16, 20, 22, 4 and 66 with 3 * 5 g of a wetting and dispersing agent and 1.5 g of nonionogenic anion active agent, together with 50 g of a carrier substance. This gives wettable powders, which can be diluted in any ratio with water. EXAMPLE 16 10 To 40 combined g of active ingredient compounds 68, 73 * 75 * 98, 76, 9 ^ with appropriate amounts of emulsifier (mixture of sulfonate with a non ionic) in xylene to a volume of 100^CrN material. These emulsifiable concentrates may be diluted with water to the appropriate concentration and used as fungicides. EXAMPLE 17 The compounds according to the invention, for example No. 16, are also distinguished not their action against mildew (English language "powderymildew"). To this end, grown in greenhouse plants "Zucchetti" (Cucumis OPOP), then sprayed prophylactically once with a liquid, which contains 0.2 $of the active substance contained in the preparation made according to example 15•two days after watering, infecting plants with Erysiphe cichoracearum spore and reviewing the development of fungi after 12 - 14 days. As compared to the untreated control (=0 $efficiency), the destruction reaches 90 $on plants sprayed, this without any phytotoxicity. The effect is similar to that of the 17 in Erysiphe cichoracearumexempie against with a good tolerance for the "Zucchetti" using the following compounds: No. 10 20 80 $effect NO 4,100 $ 49 NO No. 10/00 66 80 EXAMPLE 18 The effectiveness of the compounds of the invention against rust-sheets (English language "Curled spotlight") is confirmed on the celery (Nosemosis apium graveoles) against the fungus Septoriaapii. Celery plants are cultivated in a greenhouse and weeds are sprayed, 2 days prior to infection with the fungus Septoriaapii, separately with liquids containing 0.2 $of the substances indicated further away. After infection, placing the plants during 2 weeks in a greenhouse to 5 high-humidity incubation of 11 air and then examined the effect obtained as compared to the untreated control (0 $effect). The results obtained are as follows: EXAMPLE 19 herbicidal observed in greenhouse Slab material. 99 present at 2 * 0 kg of substanceet more tetrazolinones total. Lesser aquantities * for example to 0 * 25 kg of substanceconforme * the invention to transplant may be deleted entirely or substantially controls entièrementdétruire e.g. beans or soybean deAvec doses even smaller * combatting wild oats growing in barley. The compound no. 10 93 is effective at a dose of 2.5 kg of active against numerous dicotyledenous and Panicum virgatum, while the various kinds of wheat are not harmed by the active substance according to the invention. EXAMPLE 20 In a field of winter wheat, which has undergone its first pushes and wherein the weeds have reached the stage of 4 sheets, sprayed NO compounds 18 and No. 26 according to the invention, a dose of 8.0 kg of active substance. 3 weeks after treatment, the destruction of the weed is very good (it is to say 1 or 2). On the contrary, the wheat has not undergone damage (no.' tee 1 or 2 or L). Four weeks after seeding a lettuce (to 3 - 4 sheets) and after pushing of a rosette important weeds, sprayed the compound no. 10 27 according to the invention at a dose of 8.0 kg of active substance. The effectiveness against the weed is good (score 3) and the salad is neither intended damaged by the herbicide according to the invention. Immediately after planting cabbage plants and before growth of weeds, sprayed on the soil surface the substances according to the invention and 5 NO no.67 at a dose of 2.0 or Note: weeds: 1=very well 9=any action for tolerance with respect to the culture: 1=very well 9=complete destruction. EXAMPLE 21 Is prepared in the usual manner a composition containing the compound no. 10 21. To examine the acaricidal effect, is infesting plants of Phaseolus two sheet 12 hours before treatment by applying pieces of leaves infested by the Tetranychustelarius or "Range Per moth". After 12 hours, there is post-emergence test the population of insects at all stages. Spraying the active substance in the form of an emulsion with a pulverizer very thin on the plant, to form on the surface of the sheets a uniform mist of droplets. After 7 days and 2, the level of mortality is expressed in For an active substance concentration of 0.08 $, it was found the kill rate hereinafter: A similar effect is similarly cleaned good with the compounds Nos. 1, 2, 3, 4, 13, l4, 29 and 45. EXAMPLE 22 The compound no. 10 4 shows applied concentrations of 0.05 $good killing effect against the spiders, e.g. the Panonychus-ulmi, the Eotetranychustiliae, this either against the eggs that against post embryonic stages. Effects are obtained just as good with the compounds our. 21 and 3 · EXAMPLE 23 Is poured on of freshly products worm flour polymorphic Ephestia Kühniella deposited each time to 20 copies into pleated filters the compound no. 10 36 emulsion form, and then allowed to desiccate the filters open at ordinary temperature. After drying the filter, is covered each larva of a wire mesh and thus it is maintained until hatching of the untreated control. Braking control is carried out under a binocular telescope and gives the kill rate hereinafter: (the substance effective being indicated in ppm) Amount used in ppm: 1000, 500 25062.5 100,100 100100 New oxime ethers and pesticidal and herbicidal preparations containing them are disclosed. The oxime ethers correspond to the formula WHEREIN R1 is a hydrogen atom or a lower alkyl radical; R2 is an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radical; or wherein R1 and R2 form part of a saturated or unsaturated carbocycle or a 5-, 6- or 7-membered heterocycle; R3 is a nitro, trifluoromethyl, formyl, lower carbalkoxy, sulfamyl or mono- or di-lower alkyl sulfamyl radical; R4 and R5 each is a hydrogen or halogen atom, an amino, mono- or di-lower alkyl amino, lower alkoxy, cycloalkoxy, lower alkythio, nitro, lower carbalkoxy, arythio, lower aralkylthio, or lower alkyl group, or 5-, 6- or 7-membered heterocycle. 1 Degrees - they consist of a herbicidal composition as above, which contain as active ingredient at least one compound of formula wherein R. ^ is hydrogen or an aliphatic radical and RG an aliphatic radical or a phenyl radical which is optionally substituted, while a represents the NOG -, - CHO-, C00HCOOAlkyl and b - or hydrogen, the NOG - group, - C00H, - COOAlkyl or chlorine; 2 - Degrees acaricidal agents as has, containing as active ingredient at least one compound of formula where represents hydrogen and RG phenyl optionally substituted by a radical as substituents of halogen atoms or alkyl or alkoxy groups, the R ^ and RG indicating residues alkyl or forming part of a core isocyclic; B. - a method of obtaining oximéthers having the general formula wherein is hydrogen or an aliphatic, araliphatic, aromatic or heterocyclic and KG an aliphatic, araliphatic, aromatic or heterocyclic or, when R ^ and RG together form a portion of a saturated or unsaturated carbocyclic or heterocyclic and R ^ ^ and R groups are negative and RG ^ and R represent hydrogen, halogen, alkyl, hydroxyl, acyloxy group, alkoxy group, aryloxy group, thiol group, acylthiol, alkylthio group, arylthio group, an amino -, alkylamino or dialkylamino or have the same meaning and that R and R ^ ^, the method being characterized by the fact that a salt of a ketoxime or aldoyime having the general formula The n=- for OMe wherein R ^ .and RG have the meaning already indicated and me is a metal atom, preferably alkali metal, on a halobenzene of the formula wherein R ^, the R ^, the R ^ and RG have the meaning already mentioned and hal represents fluorine, chlorine, bromine or iodine; when R, - and/or RG are halogen atoms, which is exchangeable for, after formation of the oximether, these halogen atoms against to compounds containing active hydrogen atoms; this method can further have the following features, based on which to: C. - novel oximéthers of general formula wherein and Rg have the meanings already mentioned under A and R ^ stands for a trifluoromethyl, formyl 1 ., optionally esterified carboxyl or sulfamyl optionally having substituents alkylated and R ^ denotes hydrogen or a group - the NOG, or R ^ the NOG - group and R,, optionally esterified carboxyl group; 3 Degrees - novel oximéthers of general formula wherein R ^ represents hydrogen or an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and RG an aliphatic, cycloaliphatic, araliphatic or heterocyclic, while R ^ and RG may be part of a core carbocyolic or heterocyclic; 4° to - novel oximéthers having the formula The NOG THE R. C=N - 0 * // - \ α-Y-COOH wherein R ^ and RG have the meaning already indicated under a and R denotes LED ' is hydrogen or lower alkyl or cyoloalkyl, as the radicals methyl, ethyl, propyl methacrylamide, butyltin, hydroxyamyl, phenylcyclopentyltrimethylammonium, the cyclohexyl; 5 Degrees - novel oximéthers of general formula Rthe n THE R, NO., ' C=n - 0 / - / - CHO-FV wherein R1 and R2 have the meanings given under has; 6° to - novel - n0 oximéthers of general formula THE R, R ER R. * wherein R ^, Rg and R have the meanings given under has; 7 Degrees - novel oximéthers of general formula in which R and R ^2 have the meanings given under a and X represents a halogen atom or a group aminogenic primary, secondary or tertiary aliphatic in nature, araliphatic or aromatic, or a hydroxy or thiol etherified or esterified; 8° to - novel oximéthers having the formula wherein R ^ and Rg have the meanings given under a and R denotes hydrogen or alkyl or lower cycloalkyl; 9 Degrees - novel oximéthers of general formula wherein R1 represents from 1' hydrogen and R2 a phenyl radical substituted with at least two halogen atoms and optionally a hydroxy group; 10° to - more particularly the compounds listed below: Proxy company called FBCN corporaton anonymous BUGNION-TO-UBAF ITS P. 4038 - Nlongkak/Yaounde Cameroon** Compound.■no. '! . ' THE R, - > Melting point 13 LC - HM=^ C.T- 165 - 166 14 hereinafter the c ^ - HM * 195 - 196 15 LC CI-ls ^ HSC, 197 - 197, 5 16 (hM3 )2 n 0 ^=- OH- 186 - 187 17 N0~ 189 - 190, 5 18 HM5 NH 8 AND 0 -<^>THE C -!=HR 181 - 182 19 H0 O-CH2= 185 - 186 20 C10H 199.5 200 21 cïï5 ^ - CH-CH=1•CHH0, 3 165 - 166 22 o=0= 164 - 165 23 osh3 r0 -<^=U-O-ch-•** 202 - 203 1 N02 24 C1 - LC<^^CH= 1.84 - 185 25 HM5 0 -<> - j-P-ch=0 206.5 - 207 çr? * T-ÏÏ02 - 26 <0>- HM= 142 - 144 27 HM, HM / ^=C., 3 71 - 71, 5 28 (c.2 hr5 )2 the n -<S>- hM= 141 - 142 : -: - r. 8fr The O -=5 (2 ho) -ee an HO * HS 8Ê L6T - 961 Λ℮ " an HO - ^ - OH-<Jtg S * 68 - 68 The O -=GBP an HO HSO £1 9Ê 102 - 002 - * - ^ ; ≈ HS TO VERBS 6Ê If 96l Τ - 66 2 0K=0 AN HO Κ θ ΐτηΐΐ aurvef ^0=0 - Η) - ¾) sîô £ 0 - 1 θ ΐ 181 = DEGREES_<S> 00' * HS 2 £ 6 τ•δ τ - ≤ 9 the HO 1 C. T-GBP if SLTs - SLTs ■=\ -<Ç>0Ê HS SlOO 0 £ m - s ' 00 N. KD=^ - ^ - 00 - ovo-Η jrfT - 62 The £θ - ΐ θ >H0 above 0% '/ 2 j-c/o VBE1 degrees "2/ "C H0 - \7 CD 11 - IF % D H0 -2 (GBP H0)=■CR39? VBE1 7, C.C. H0 - H0 - (tM HS) 061 - 881 r=h0 -<^>- 0:00 F. CD 601 - 101 VO=JhoOCf (GBP HO). D.2 / H0 HO OF THE £"* HQ IN (^ uofSOduidosp) 902 - s02 AN HO=<^>- LO ITs THE III - 16, 1" tDC 1•SïoyHO ≈ d=o7 VBE1? \ / 0 £ 6 £ 46 DEGREES * E, ■0= 91 - 92 47 OH-CHl 13 HM, HM - C. - - - * C.3 the I2 " O 91 - 92 1, 48 f. 3 YF■' ch-ch-Ch ^ - - -=C. 36 - 37 49. HC, HC,, 3 -, 3 HM5 - cH2 - (CH22 )2 -=C. 56 - 58 50 THE O *the OH=> 177 - 178 (dëoomp.) 51 HC=C.>! 161 - 163 52 136 - 138 53 HM, HM, 13 P-OH, - CH2 - 0==C. 130 - 131 54 THE OH, |3 <£3>- CH-CH-A-C== 136 - 142 55 THE OH, . p-O-<^=CHBi CHBr-C. 183 - 184% (décomp.). 56 " 0=o ' 214 - 215 57 N02 <^>- 0:00= 185 - 186 58 02 - f.<O>- hM= 210 - 211 59 THE O-CH-CH-CH-==- 187 - 189 60 HM, ο 155 - 156 61 0 - - 0 Η Η=5 95 - 96, 5 Compound no.. Point j of produc>•°C I 62 ch-O-ch-ch-*3 . 130 - 131 63 JXQ <-S THE II 92 - 94 64• <J> 85 - 87 65 OOHj 168 - 169 66 CH 13 0 ^ - 0 - r 1 cm. - C. 67 LC <^j>HM * of Cl -. 186 - 187 (décomp.) 68 yF degrees "2/ aTO3 )2 R-CH2 - 0:002 . . 126 127 r. 69. <^>- - CH=0 175 - 176 70 The OH * Osh5 169 - 170 71' 01<C £63" HM * 182 - 183" 72 01 to-an HO " HM * 202 - 203 73 0 Η ^ CH OH C=5 the I is OH, 68 - 69 74 DEGREES / ^HM 3 /"TDC 2NR THE OH, \ Α=02 0 ≈ < the OH-therein. σ ¾. 110 - 112 75 F.3/0:00 2 - CH-VBE1 DEGREES, THE OH,, 0=0 0 V-V-OH-VBE1 Η, ^ " i-104 - 105 76 fii HM3 - (OH-2 )6 HI " hti ' it ^ hnune. 77 <S>- OH-O= 165 - 166 78 The L? σ ΐ>- 00 - HM=■ 181 - 183 79 •SF 1 brown oil 80 brown oil 81 HM, _ 13 <C>- ch-ch-a-c== 155 - 165 82 ** F.•YF oa-lus oï-to-oHj O " · brown oil 83 128 - 131 84 0 * 132 - 133 ' 85 The OH=ό 148,149 86 sF SF CHj-to-VOLT-to-OHgC= brown oil 87 HM, |5 O 0hbi~chbr c= 186 - 187 88 Ο π Ο ο-II 214 - 215 Compound no.. C=t "/R 2 Point.de melting °C - 89 68 - 69 90. 0CH3 <^-CH * 135 - 137 91 hereinafter c3> - HC ". 134 - 136 92 LC LC - ^ - HM * 169 - 171 93 J IS THE J 185 - 186 94 HM, the I5 . 68 - 69 95 f2H 5, 0 - 0=^ brown oil < 96 HM - HM - ^> *. 143 - 144 Compound * no.. THE R, I-1 =-C-R2 Fusion pointI c." 97 Ç1 -<I>HM - " 124 - 126 98 <1> 50 - 51 01, 1 99 c5 Ch " 105 - 107 101 100 LC 123 - 124|■■; 1 101 JCH,<D 0H= ' 133 - 135 102 ; yF chlorophyll-C." 65 - 67 105 Ch - ch-: I-3 13 - CHj-C. brown oil ! 104 : sF fii CHj OH - HC2 THE C - " • brown oil.. 105 0 CH CIH3=" 141 - 143 106 0 - ∞= 119 - 120 107 RC -: 121 - 122 108 0 Η=6 131 - 132 109 no.2 156 - 157 110 aHj-to-toHjjj O. oil " brown. 111 the R>, the R *:CHyGlHCH! - ^ - C. oil, brown 112 OjHj O. oil-brown 113 F.3 <~O-CH-CH 0 *" 141 - 143 114 sF. F. *. OjHj-CB-a-OOTW a-c - 1 brown oil Compound 7" subscribed not 9.ï1 "-C-R2 The point fusio):;I c.. 115 LC LC T->" ch *. 130 - 132 116 ©■% ^ - HM - HM "/ CHj 117 CONCERNS-HC " 111 - 113 118 OH-HM, 1 P- oil - brown 119 "Aces 0"® has' brown oil 120 HM, the I5OjHç O - . " ee 75 - 76 Compound no.. R 1 RG is Melting point °C J 121 Η 0 - 0=^ - Η 197 - 198 J 122 C1< v3~=HC 143 - 144 Compound no.. R 2^ Melting point °C HUMAN GH 3<I 123 Cthe OHK 0~VBE1 - / - HM=2 ^ / VBE1 143 - 144 124 f3/HM 2/C VBE1 C.R2/H 2/=X HM - ^ deg. C., " the BH, 3, 3 83 - 85 Compound no.. •^ * VI Melting point °C 126 <ii)= l64 - 165 127 II-O-O-O/W-m-VBE1 ll4 - 115 Lu 128 rl Ch<= 147 - 148 i-n02 129 HM 157 - 158 132 /0:00 3 ¾ / HM0CH_yC Ch, VBE1=C.2/2 3 CH-CH-/2 l42 - 144 133 HM -, - 1, 1 - HM=c-ch-ch-a-j ^ ^ 111 - 113 Compound no.. Melting point °C 135 0 -. 210 (décomp.) 136 (C.2H5 )2 N -<QY between Ch= 149 - 150 137 CH, CH=- C.1, 1 5 HM, HM^3 199 - 200 138 CH, CH - (HC ")9 - C=3 1, 2 2, CH-CH-^3 113 - 114 139 187 - 188 140 Osh, the j 3 158 (décomp.) Compound V Melting point No.. °C 0C THE EL. 5 l4l fWs< 146 - 147 HM, |^ 142 CH-CH-VBE1 /=C.2 - hC2 ℮Η, ^ Η, 5, 5 Nature of the plant Compound no. 10 15 17 NO NO l8 No.26 27 NO 29 NO Beta-vulg. 9. 10 10 10 10 10 OfCalendula 10 10 10 10 10 9 Linum usitatissimum 10 10 10 10 10 10 The Brassica 9 10 10 10 10 10 Daucus 2 .8 10 9 1 2 Lactuea 2 5 10 10 1 2 Medicago sativa 6 10 10 10 10 10 Soybean 1 8 4 1 1 Galactosidases 2 6 5 4 4 1 Fermented Triticum 0 0 0 1 1 1 Of Hordeum 2 3 3 3 3 1 Sorghums 1 2 4 2 2 1 5 NO material 67 NO material 4 2 1 0.5 kg 4 2 1 0.5 kg Fermented Triticum 10 10 9 2 10 7 7 2 Of Hordeum 10 5 5 2 10 4 5 2 Of Avena 10 10 10 10 10 10 10 8 AOP 10 10 10 10 10 10 10 10 Dactylis 10 10 10 10 10 10 10 10 Linum usitatissimum 10 10 10 3 10 9 8 3 The Brassica 10 10 5 3 10 4 2 1 Lactuca 10 10 10 10 10 10 10 10 Medicago sativa 10 10 10 4 10 10 10 8 Soybean 10' 7 4 1 9 4 2 1 Galactosidases 5 1 1 1 4 1 0 0 Compound no.. Effect 20 93 $ 22 80 $ 4 93 $ 66 100 $ 68 94 $ 73 100 $ 75 95 $ 98 94 $ 76 100 $ 94 87 $ 8o 100 $ Pre-emergence no.99 compound Post emergence compound no. 10 95 kilograms the O < •ER 1.0 0.5 0 * 25 5.0 2.5 Fermented Triticum 10 10 9 7 0 0 Of Hordeum 10 9 7 4 0 0 Of Avena 10 10 10 10 1 1 Sorghums 8 4 2 1 2 1 Panicum virgatum 10 10 8 1 10 8 AOP 10 10 10 1 8 6 2 Dactylis 10 10 10 10 4 2 Crusgalli 10 10 4 1 7 4 Beta- 10 10 10 10 10 10 OfCalendula 10 10 10 10 10 10 Linum usitatissimum 10 10 10 5 1C 10 The Brassica 10 10 7 8 10 10 Daucus 10 10 10 10 10 10 Lactuea 10 10 10 10 10 10 Soybean 10 8 2 0 4 5 Phaseoulus 10 10 1 0 8 5 Test planting wheat free field.
Test planting lettuces free field.
Test on cabbage plants on foot free field.
Used amount kg. 5 Compound no. 10 67 Compound no. 10 2.0 3.0 4.0 3.0 4.0 Activity against weeds 3 3 2 2 2 Crop tolerance 2 2 2 3 5 2 days Eggs 100 $Larvae 100 $Adult 7 days 100 $ 100 $ 100 $