IE45341B1 - Novel oxime carbamates and their use as insecticides acaricides and nematicides - Google Patents

Abstract

The test equipment is for supplying either alternating or direct voltages which can be varied under a programme controller to examine the behaviour of equipment being tested under conditions of supply voltage intermittency or variation. The equipment comprises two main channels, one for providing a variable, programmed alternating voltage (A1) and the other for providing a variable programmed direct voltage (A2). In the case of the alternating voltage, an input alternating voltage (E1) is fed to three variable ratio transformers (N1W, N2W, N3W) the outputs of which are set to suitable values. These outputs are fed to the equipment output (A1) via switches (S1W, S2W, S3W) in a sequence controlled by a programme control unit incorporating an input voltage monitor (UW), a clock generator (TG) and selector counter (VW). Intermittent voltage failure can be simulated by setting one of the transformer outputs to zero.

Description

The present invention relates to certain netv oximecarbamates and their salts and metal complexes, to a process for their preparation and to their use as arthropodicides (especially insecticides and acaricides) and as nematicides.i The present invention also relates to oximes which are used as intermediates for the preparation of said oximecarbamates .

It has already been disclosed that certain U-cyanooxime-carbamates, such as, for example, l-cyano-2-methylpropanaldoxime-N-methylcarbamate and l-cyano-butanaldoxime-N-methylcarbamatc, possess pesticidal, especially insecticidal and nematicidal, properties (see German ' Offenlegungsschrift (German Published Specification) Is56?j142). However, their action is not always satisfactory, especially when low amounts are used.

The present invention now provides, as new compounds, the oxime-carbamates of the general formula /1 (I), - 0-C0 - N, in which R represents optionally substituted alkyl, cycloalkyl, aryl or aralkyl, R? represents hydrogen or alkyl, I R represents halogen, alkyl, alkenyl, alkynyl, halogenalkyl, halogenalkenyl or alkoxyalkyl, and R represents a pyrazolyl-(l), imidasolyl-(l), 1,2,4triazolyl-(i), l,2,3-triazolyl-(l), 1,3,4-triazolyl-(l), indazolyl-(l), benzim±dazolyl-(1) or benztriazolyl-(l) radical, which may be optionally substituted, or represents the group - 2 1 ίϊ 3 j I R4 ir R·’ in which 4 5 R and R are identical or different and represent hydrogen or alkyl, or conjointly represent a penta-1 $ methylene or tetramethvlene group, and R° represents a pyrazolyl-(1), imidazolyl-(1), 1,2,4triazolyl-(l), l,2,3-triazolyl-(l), l,3,4-triazolyl-(l), indazolyl-(1), benzimidazolyl-(1) or benztriazolyl-(l) ring, which may be optionally substituted, and their salts and metal complexes.

The present compounds have been found to exhibit powerful insecticidal, acaricidal and nematicidal properties.

The compounds of the formula (l) can be present in the syn-form or anti-form, but predominantly arise as a mixture 15 of both forms.

Preferably, R represents straight-chain or branched alkyl with 1 to 6 carbon atoms, phenyl which can optionally be substituted by halogen (especially fluorine, chlorine or bromine), phenylalkyl with 1 to 4 carbon atoms in the alkyl part and wiiich is optionally substituted in the phenyl part by halogen (especially fluorine, chlorine or bromine), or cycloalkyl with 5 to 7 carbon atoms which is optionally substituted by methyl or ethyl; R represents hydrogen or straight-chain cr branched alkyl with 1 to 4 carbon atoms; R~ represents hydrogen, straight-chain or branched alkyl with 1 to 12 carbon atoms, alkenyl and alkynyl each with 2 to 4 carbon atoms, halogenalkyl with up to 2 carbon atoms and up to 5 halogen atoms (especially fluorine and chlorine atoms, as in, for example, trifluoromethyl), halogenalkenyl with up to 3 carbon atoms and. up to 5 halogen atoms (especially fluorine and chlorine atoms) or alkoxyalkyl with up to 2 carbon atoms in each alkyl part; and - 3 4 5 3 41 η RJ represents an optionally substituted pyrazolyl-(1), imidazolyl-(1), ljZH-triazolyl-il), l,2,3-triazolyl-(l), 1,5.4-triazolyl-(1), indazolyl-{1), benzimidazolyl-(1) or benztriazolyl-(1) radical, the substituents being selected from halogen (especially fluorine, chlorine and bromine), alkyl with 1 to 4 carbon atoms, halogenoalkyl with up to 2 carbon atoms and up to 5 halogen atoms (especially fluorine and chlorine atoms, as in, for example, trifluoromethyl), alkoxy and alkylthio, each with up to 4 carbon atoms, and R* » ( -N-R° I R5 λ ς in which R and R^ are identical or different and represent hydrogen or alkyl with 1 to 2 carbon atoms, or Λ c Ic and R conjointly represent a pentamethylaie or tetramethylene group, and R^ represents an optionally substituted pyrazolyl-(1), imidazolyl-(1), 1,2,4-triazolyl-(1), 1,2,3triazolyl-(1), 1,3,4-triazolyl-(1), indazolyl-(1), benzimidazolyl-(1) or benztriazolyl-(1) radical, the substituents being selected from halogen (especially fluorine, chlorine and bromine), alkyl with 1 to 4 carbon atoms, halogenoalkyl with up to 2 carbon atoms and up to 5 halogen atoms, (especially fluorine and chlorine atoms as in, for example, trifluoromethyl), alkoxy and alkylthio, each with up to 4 carbon atoms, and the nitro group .

The present invention also provides a process for the preparation of an oxime-carbamate of the formula (I) in which an oxime of the general formula „ HOH nitro, or R·’ represents the group C I R^ (II), in which R and R5 have the abovementioned meanings, - 4 ά 3 3 4 ί ίο (a) provided is hydrog.;·!, is reacted with an isocyanate of the general formula a2 - n = c = o (in), in which o H4 has tae abovemen tioned meaning, in the cresence of a diluent- and optionally in the presence of a catalyst, or (b) is reacted with a carbamoyl cnloride of the general formula H1 z . .

Cl - CO - NZ (IV), ri4· in which R' and R2 have the afcovementioned meanings, either in the presence of a diluent and of an acid-binding agent or in the presence of a diluent and sodium hydride, or (c) is reacted with phosgene and subsequently with an amine of the general formula -R H - N( (V), in which O R' and R4- have the abovementioned meanings, either in the presence of a diluent and of an acid-binding agent or in the presence of a diluent and sodium hydride, or (d) in the case where R1 and R2 denote hydrogen, is reacted with an alkali metal cyanate cf the general formula MOON (VI), in which M represents sodium, potassium or ammonium, - 5 ·« 4 S 3 '11 « in the presence of hydrochloric acid and of a diluent.

Surprisingly, the oxime-carbamates according to the invention exhibit a greater insecticidal, acaricidal and nematicidal action than the known ra-cyano-oxime-carbamates, such as, for example 1-c,vano-2-methylpropanaldoxime-N-methyl carbamate and 1-cyano-butanaldoxime-H-methylcarbamate, which are chemically, and in respect of their action, the nearest compounds. They thus represent an enrichment of the art.

If 5,3-dimethyl-2-oxiraino-1-[l,2,4-triazolyl-(1)]butane and methyl isocyanate are used as starting materials in process variant (a), the course of the reaction can be represented by the following equation; (CH,),0-0 b 3 , /OH CH„ N-O-CO-Ui II OH (CH,),0-0 3 3 , CH, I 2 + CH5-N=C=O If 3»3-dimethyl-1-imidazolyl-(1 )-2-oximino=butane and dimethylcarbamoyl chloride are used as starting materials in process variant (b), the course of the reaction can be represented by the following equation; (CH,),0-0 > ·> I HOH CH, 1 ά (ch3)3o-c' N-O-CO-/ // \ GH, CH, + Cl-CO-lKCH^g - 6 4 5 3 -11 If 3»3-dimethy'i-2-oxiiaino-1-tl ,2,4-triazolyl-(1 )]butane, phosgene and dimethylamine are used as starting materials in process variant (c), the course of the reaction can be represented by the following equation: ,NOH N-0-C0-C1 55 ! CH, 1 ά N Ο (CH,),C-C 5 5 I CH, 1 * 1} o —-> + COCI. £ 1 j- J CH5 + HI*/ _ CH5 N-0-C0-N(CH,)p , (CH,),0-0 3 3 , Cil2 i ύ If 3j3-dimethyl-2~oximino-1~pyrazolyl-(1)-butane and sodium cyanate in hydrochloric acid are used as starting materials in process variant (d), the course of the reaction can be represented by the following equation: ΝΟΗ (CH5)5C-/ N-O-CO-HHg (CH,)-0-9 CH.. 1 * % ττ ( c Q - + NaOCN/HOl Suitable salts of the compounds of the formula (I) are salts with physiologically tolerated acids. These preferentially include the hydrogen halide acids, such as, for example, hydrobromic acid and, especially, hydrochloric acid, 3 3-11 phosphoric acid, nitric acid, monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, and 1,5-naphthalene-disulphonic acid.

The salts of the compounds of the formula (I) can be obtained in a simple manner in accordance with the customary methods of forming salts, for example by dissolving the base in an ether, for example diethyl ether, and adding the acid, for example nitric acid, and can, using known methods, be isolated, for example by filtration, and be purified if required.

Suitable complexes of the compounds of the formula (I) are complexes with metal salts. In this context, metals of main group II to IV and of sub-group I, II and IV to VIII, especially copper, zinc, manganese, magnesium, tin, iron and nickel, should be mentioned. Suitable salts are salts with physiologically tolerated acids, preferably the hydrogen halide acids, such as, for example, hydrochloric acid and hydrobromic acid, phosphoric acid, nitric acid and sulphuric acid.

The metal complexes of the compounds of the formula (I) can be obtained in a simple manner in accordance with customary processes, such as, for example, by dissolving the metal salt in an alcohol, for example ethanol, and adding the solution to the base. They can be Isolated by known methods, for example by filtration, and be purified, if required, by re crystallisation.

Preferred diluents for the raaction according to process variant (a) are all inert organic solvents, especially ketones, such as diethyl ketone, and especially acetone and - 8 I 3 3 J ί methyl ethyl ketone; nitriles, such as propionitrile and especially acetonitrile; alcohols, such as ethanol or isopropanol; ethers, such as tetrahydrofuran or dioxan; formamides, such as, in particular, dime thylformamide; and halogenated hydrocarbons, such as metlyl?ne chloride, carbon tetrachloride or chloroform.

The following may be used preferentially as catalysts for process variant (a): tertiary bases, such as triethylamine and pyridine, and organo-tin compounds, such as dibutyl-tin dilaurate.

In carrying out the process variant (a), the reaction temperatures can be varied within a fairly wide range. In general, the reaction is carried out at between 0° and 100°C, preferably between 20° and 35°C, In carrying cut process variant (a), 1 to ? mol of isocyanate of +he formula (III) are normally employed per mol of the compound of the formula (II). To Isolate the compound of the formula (I), the solvent is distilled off and the residue is worked up in accordance with customary methods.

Preferred diluents which can be used for carrying out the reaction according to process variants (b) and (c) are all inert organic solvents, especially the solvents recited in connection with process variant (a). When using sodium hydride as an auxiliary material, polar organic solvents, such as, in particular, hexamethylphosphoric acid triamide, are used preferentially.

If the reaction according to process variant (b) or (c) i3 carried out in the presence of an acid-binding agent, any inorganic and organic acid-binding agent customarily usable may be added, especially an alkali metal carbonate, 5341 such an, for example, sodium carbonate, potassium carbonate and sodium bicarbonate, or a lower tertiary alkylamine, cyeloalkylamine or aralkylamine, such as, for example, triethylamine, ϊΓ,Η-dimethyl-benzylamine and dicyclohexylmethylamine, as well as pyridine and diaaabicyclooctane.

The reaction temperatures of process variants (b) and (c) can be varied within a fairly wide range. In general, the reaction is carried out at between 0° and 100°C, preferably between 0° and 85°0.

Xn carrying out process variants (b) and (c), preferably 1 to 2 mol of carbamoyl chloride of the formula (IV) or 1 to 1.5 mol of phosgene and 1 to 1.5 mol of amine of the formula (V) are employed per mol of the compound of the formula (II).

It has proved advantageous to employ the acid-binding agent in a slight excess (of up to about 30 per cent by weight) and, if appropriate, to employ the sodium hydride in an excess of up to about 50 per cent by weight. The com- | pounds of the formula (I) are isolated in the usual manner.

Preferred suitable diluents for the reaction according to process variant (d) are inert organic solvents or their mixtures with water. The preferred inert solvents include the solvents recited in connection with process variant (a).

The reaction temperatures for carrying out process variant (d) can be varied within a fairly wide range. In general, the reaction is carried out at between 0° and 50°C, preferably between 0° and 30°C.

In carrying out process variant (d), preferably 1 to 2 mol of sodium cyanate are employed per mol of the compound of the formula (II). To isolate the compounds, the organic phase is separated off, the solvent is distilled off and the - 10 4 u 3 *2 1 residue is worked up in accordance with customary methods.

In part, it is also possible to carry out the individual stages of the preparation of the oximes of the formula (II), and their reactions to give the compounds according to the invention, without isolation of the particular intermediate products, in a so-called one-vessel reaction.

The following may be mentioned as examples of starting materials of the formula (II): 3,3-dimethyl-2-oximino-1pyrazolyl-(1 )-butar.e, 3,3-di3>ethyl-1-imidazolyl-(1 )-2cximino-butane. 3,3-dimetfcyl-2--oxiffiino-1-[l ,2,4-triazolyl(1) ]-butane, 3,3-dimetnyl-2—cximino-1-[l ,2,3-triszolyl-(1) ]butane, 3,3-dimethyl-2-oximinc-1-[l, 3,4-triazoly 1-(1) ]butane, 3,3-diraethyl-1-indaz olyl-(1)-2-oximino-butane, 1benzimidazolyl-(1)-3,3-dimethyl-2-oximino-butane, 1benztriazolyl- (1 )-3,3~dimethyl-2-oximino-butane, 2-oximino-1 pyrazolyl-(1)-propane, 2-oximino-1-[l,2,4-fcriazolyl-(1)]propane, 1-imidazolyl-(1)-2-oximinc-propane, 3~methyl-2oximino-1 -pyrazolyl- (1) -butane, 1 -imidazoiyl-3-methyl-2oximino-butane, 3-methyl-2-oximino-1-[l,2,4- triazolyl-(1)]butane, 2-oximino-2-phenyl-1-pyrazolyl-(1)-ethane, 1imidazolyl-(1)-2-oximino-2-phenyl-ethane, 2-oximino-2-phenyl1 —[1,2,4-triazoiyl-(1)]-ethane, 2-oximino-2-phenyl-1[1,2,3-triazoly1-(1)]~ethane, 2-oximino-2-phenyl-1-[l,3,4triazolyl-(1)]-ethane, 2-(4-chlorophenyl)-1-imidazolyl-(1)2-oximino-ethane, 2-(2,4-dichlorophenyl)-2-oximino-1[1,2,4-triazolyl-(1)]-ethane, 2-oximino-3-phenyl-1-pyrazolyl(1)-propane, 3-(4-bromophenyl)-1-imidazolyl-(1)-2-oximinopropane, 3,3-diraethyl-2-oximino-3-phenyl-1-[l,2,4-triazoly1(1)]-propane, 2-cyclopentyi-1-imidazolyl-(1)-2-oximinoethane, 2-cyolohexyl-1-imidazolyl-(l)-2-cximino-ethane, 2-cyclohexyl~2-oximino-1-pyrazolyl-(1 )-ethane, 2-oyolohexyl- 11 4S3<11 2-oximino-1-[l,2,4-triazolyl-(1 )]-ethane, 1-benzimidazolyl-(l)2-cyclohex,yl~2-oximino-ethane, 2-cycloheptyl-2-oximino-1pyrazolyl-(1)-ethane, 1-imidazolyl-(1 )-2-(methylcyolohexyl)2-oximino-ethane, 1-[4-chlorop.yrazolyl-(1)]-3,3-dimethyl-25 oximino-bu.tane, 1-[3-acetylpyrazolyl-(1) ]-3»3-dimethyl-2oximino-butane, 1-[2-bromoimidazolyl-(1)3—3,3-dimethyl-2oximino-butane, 5,3-dimethyl-1-[2-methylimidazolyl-(1 )]2-oximino-butane, 3,5-dimethyl-2-oximino-[4-trifluoromethylimidazolyl-(1)]-butane, 3,3-dimethyl-1-[4-nitroimidazolyl10 (1)]-2-oximino-butane, 1-[3-chloro-1,2,4-triazolyl-(1)]3,3-dimethyl-2-oximino-butane, 1-[3-ethyl-1,2,4-triazolyl-(1)] 3,3-dimethyl-2-oximino-butane, 5,3-dimethyl-1-methyl-2oximino-1-pyrazolyl-(1)-butane, 3,3-dimethyl-1-imidazolyl(1 )-1-methyl-2-oximino-butane, 3,3-dimethyl-1-methyl-215 oximino-1-[l,2,4-triazolyl-(l)]-butane, 1,1-dimethyl-2oximino-1-[1,2,4-triazolyl-(1)]~propane, 1,1-dimethyl-2I oximino-1-pyrazolyl-(1)-propane, 1,1-dimethyl-3-methyl-2oximino-1-[l,2,4-triazolyl-(1)]-butane, 3,3-dirtethyl-1[5-methyl-4-nitro-imidazolyl-(1)]-2-oximino-butane, 3,320 dimethyl-2-oximino-1-[3-trichloromethyl-1,2,4-triazolyl(1)]-butane, 1-[3-bromo-1,2,4-triazolyl-(l)]-3,3-dimethyl-2oximino-butane, 3,3-dimethyl-2-oximino-1-[2,4,5-tribromoimidazolyl-(1)]-butane, 2,2-dimethyl-1-oxiraino-pyrazolyl(1)-propane, 2,2-dimethyl-1-imidazolyl-(1)-oximino-propane, 2,2-dimethyl-1-oximino-1-[1,2,4-triazolyl-(1)]-propane, 2,2dimethyl-1-oximino-1-[1,2,3-triazolyl-(1)]-propane, 2,2-diraethyl-1-oximino-1~[1,3,4-triazolyl-(1)]-propane, 2,2-dimethyl-1-indazolyl-(1)-1-oximino-propane, 1-benzimidazolyl(1)-2,2-dimethyl-1-oximino-propane, 1-benztriazolyl-(1)30 2,2-dimethyl-1-oximino-propane, 1-oximino-1-pyrazolyl-(1)ethane, 1-oximino-1-[1,2,4-triazolyl-(1)]-ethane, 1- 12 4 y 3 j ί imi dazolyl-(1)-1 -oximinc-ethane, 2-methyl ~1 -oximino-1 pyrazolyl- (1) ~ propane, 1 -imi.dazolyl-2-methyl-1 -oximinopropane, 2-methyl-1-oxin:ino-1-[l ,2,4-triazolyl-(1 )]-propane, ’5 oximino-phenyl-pyrazol.yl-( 5 )-raethane, imidazolyl-(1 ία ximino-phenyl-methane, oximino-phenyl-[l,2,4-triazolyl-(1)]methane, oximino-phenyl-[ 1,2,3-triazolyl-(1)]-methane, oximino-phenyl-[1,3,4-triazolyl-(1)]-methane, (4-chlorophenyl)-imidasolyl-(1)-oximino-methane, (2,4-diehlorophenyl1-oximino-[l,2,4-triazolyl-(1)]-methane, 1-oximino-2pheriy1-1-pyrazolyl-( 1)-ethane, (4-bromophenyl)-1imidazolyl-(1 )-1-oximino-ethane, 2,2-dimethyl-1-oximino-2jhenyl-1-[ 1 ,2,4-triazolyl-(l)]-ethane, cyclopentyl-imidazolyl(i)-oximino-methane, cyelohexyl-imidazolyl-O)-oximinomethane, cyclohexyl-oximino-pyrazolyl-(1)-methane, cyclohexyl-oximino-[l,2,4-triazolyl-(1)]-methane, benzimidazolyl(1J-oyclohexyl-oximino-methane, cycloheptyl-oximinopyrazciyl- (1) -methane, imidazolyl- (1)-(methyl cyclohexyl)2C oximino-cethane, 1 -[4-chloropyrazolyl-(1)]-2,2-dimethyl-1oximino-propane, l-[3-acetylpyrazolyl-{1)]-2,2-dimethyl-1oximino-propane» 1-[2-bromoimidazolyl-(1)]-2,2-dimethyl-1oximino-propane, 2,2-dimethyl--1-[2-methylimidazolyl-(l) ]-1oximino-propane, 2,2-dimethyl-1-oximino-[4-trifluoromethylimidazolyl-(1)j-propane, 2,2-dimethyl-l-[4-nitroimidazolyl(1)3-1-oximino-propane, 1-[3-ohloro-1,2,4-triazolyl-(1)]2,2-diraethyl-1-oximino-propane, i-[3-ethyl-1,2,4-triazolyl(1)]-2,2-dimethyl-1-oximino-propane, 2,2-dimethyl-1-methyl-1oximino-1-pyrazolyl-(1)-propane, 2,2-dimethyl-1-[5-methyl-4nitro-imidazolyl-(1)3—1-oximino-propane, 2,2-dimethyl-1oximino-1-L3-trichloromethyi-1,2,4-triazolyl-(1)]propane, 1-[3-bromo-1,2,4-triazolyi-(1)]-2,2-dimethyl-1oximino-propane and 2,2-dimethyl-1-oximino-1-[2,4,5-tri30 - 13 43341 broino-lmldnznly |-(1) j-propane. •z The nxiini’n of tha formula (II) in which RJ represents an optionally substituted N-contalning heterocyclic radical have not previously been described inlhe literature. They ’> can be prepared by reacting, hydroxamie aeid halides of the general formula . MOH R - C (VII), .1 Γ Hal in which R has the abovementioned meaning and 10 Hal represents halogen, especially chlorine or bromine, with azoles of the geneial formula R6 - Η (VIII), in which R® has- the abovementioned meaning, in the presence of an organic solvent, for example tetrahydrofuran, and in the presence of an acid-binding agent, for example trimethylamine or excess azole, at temperatures between 0° and 80°C, preferably between 0° and 40°C. The compounds of the formula (II) are isolated by adding water to the reaction mixture, filtering off and drying the resulting precipitate, and purifying it, if appropriate, by recrystallisation.

The hydroxamie acid halides of the formula (VII) used as starting materials are in general known (see H.Ulrich The Chemistry of Imidoyl Halides, pages 157-172, Plenum Press, New York 1968, and the literature references cited there). Those that have not previously been disclosed specifically can easily be prepared in accordance with the process described in the cited reference, for example by chlorination - 14 4 5 3 41 of the corresponding aldcxirces.

The oximes of the formula (II5 in which RJ represents the group I n5 Λ have not previously been described in the literature. They can be prepared by reacting azolyl-ketones of the general formula _ R4 | R - C - C - R6 (IX), »u it/ in which A R £ R, R , R and P. have the abovementioned meanings, with hydroxylamine- in the presence of a solvent, preferably an alcohol cr aqueous alcohol, at temperatures between 20° and 100°0, preferably between 50° and 80°C. The hydroxylamine is preferably employed in the form of one of its salts, especially as the hydrochloride, in the presence of an acidbinding agent,such as, for example, sodium carbonate. The compounds of the formula (II) are isolated by working up the product, formed during the reaction, in accordance with customary methods, after distilling off the solvent.

The azolyl-ketones of the formula (IX) are in some cases known (see German Offenlegungsschrift (German Published Specification) 2,431,407). They can be prepared by reacting halogenoketones of the general formula r5 0 I R- G - 0 - Hal (X), I R4 in which - 15 4ΰ3'ϋ 4- 5 R, R and R have the abovementioned meanings and Hal represents chlorine or bromine, with azoles of the formula (VIII) in the presence of a diluent, for example methyl ethyl ketone, and in the presence of an acid-binding agent, for example potassium carbonate, at temperatures between 20° and 150°G, preferably between 60° and 12O°C. The compounds of the formula (X) are isolated by filtering off the salt formed during the reaction and concentrating the filtrate by distilling off the solvent.

The solid which hereupon remains is dried and purified by recrystallisation.

Further, it has been found that the new oximes of the general formula (II) ia which R^ represents the group R* -C- R6 ) R^ are obtained by reacting oximes of the general formula r4r I I Hal-C-C=N-QH (XI), R5 in which R, R^ and R^ have the abovementioned meanings and Hal represents halogen, especially chlorine or bromine, with azoles of the general formula R6 - Η (VIII), in which r6 has the abovementioned meaning, in the presence of a diluent and in the presence of an acidbinding agent.

If 3,5-dimethyl-1-[1,2,4-triazolyl-(1)]-butan-2-one - 16 45 3 11 and hydroxylamine hydrochloride are used as starting materials, the coarse of the reaction can be represented by the following equation: ,Tf—j (GH,), G-C-Crk-if | + [I® (OH)]C1 3 5 2 v-t; 3 Acid-binding (CH,),C-C=HOH agent 3 9 ' -* CH...

- HOI ' “ “ V Λ H_ii If 1-chloro-5,5-dimethyl“2~oximino-butane and pyrazole are used as starting materials, the course of the reaction can be represented by the following equation: (CH,),G-C=NOH H Acid-binding agent ---- HGl (OH,),C-C=HOH 3 3 1 0H2 /% IO Preferred possible diluents for the reaction in which the oximes according to the invention, of the formula (II), are prepared from azolyl-ketone3 of the formula (IX) and hydroxylamine are protic solvents, especially alcohols, such as ethanol and isopropanol, or formamides, such as dimethylformamide, as well as their mixtures with water.

If this reaction is carried out in the presence of an acid-binding agent, any customarily usable inorganic and organic acid-binding agent can be added, especially an alkali metal carbonate, such as, for example, sodium carbonate, potassium carbonate and sodium bicarbonate, or a lower tertiary alkylamine,cycloalkylamine or arylalkylamine, such as, for example, triethylamine, Η,Ν-dimethyl-benzylamine, dicyclohexylmethylamine and also pyridine and diazabicyclooctane.

The reaction temperatures can be varied within a fairly wide range. In general, the reaction is carried out at between 20° and 100°C, preferably between 50° and 80°C.

In carrying out the reaction, preferably 1 to 2 mol of hydroxylamine or hydroxylamine hydrochloride and 1 mol of acid-binding agent are employed per mol of the azolylketone of the formula (IX). The compounds of the formula (II) are isolated iii the usual manner.

Preferred possible diluents for the reaction in which the oximes according to the invention, of the formula (II), are prepared from .oximes of the formula (XI) and azoles of the formula (VIII) are all inert organic solvents, especially ketones, such as diethyl ketone and especially acetone and methyl ethyl ketone} nitriles, such as propionitrile and especially acetonitrile; alcohols, such as ethanol or isopropanol; ethers, such as tetrahydrofuran or dioxan; formamides, such as, in particular, dimethylformamide; and halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride or chloroform.

The reaction is carried out in the presence of an acidbinding agent. Any customarily usable inorganic or organic acid-binding agent may be added, such as an alkali metal carbonate, for example sodium carbonate and sodium bicarbonate, or such as lower tertiary alkylamines, cycloalkylamines or aralkylamines, for example triethylamine and dimethylbenzyl- 18 4 6 3 41 amine, or 3uch as pyridine and diazabicyclooctane. Furthermore, an appropriate excess of the asole can be used.

The reaction temperatures can be varied within a fairly wide range. In general, the reaction is carried out at from 0° to 100°C, preferably from 0° to 80°C.

In carrying out the reaction, 1 to 1.1 mol of azole of the formula {VIII) and to 1.1 mol of acid-binding agent is preferably employed per mol of the oxime of the formula (XI). The .compounds of the formula (II) are isolated in the usual manner.

The halcgcnoketones of the formula (X) used as starting materials are in general known (see Bulletin de la Society Chimique de France 1955. pages 1365-1583; Houben-Weyl Methoden der Organischen Ohemie (Methods of Organic Chemistry), Volume VT'/2a, page 117; Beilstein Handbuch der Organischen Chemie (Handbook of Organic Chemistry”), K 1, page 703, E I, page 350, 561 and 364, E II, page 738, 756 and 757, and E III, 2 .842 and 2,843). The compounds that hevs not previously been described specifically can be prepared in accordance with the processes described in these references.

The following may be mentioned as examples of starting materials of the formula (III) to be used in process variant (a): methyl isocyanate, ethyl isocyanate, i-propyl isocyanate, t-butyl isocyanate, heptyl isocyanate, dodecyl isocyanate, allyl isocyanate, propargyl isocyanate, trifluoromethyl isocyanate, chloromethyl isocyanate, chloroethyl isocyanate, trichlorovinyl isocyanate, methoxymethyl isocyanate, ethoxymethyl isocyanate, «ethoxyethyl isocyanate and cyclohexyl isocyanate.

The isocyanates of the formula (III) are known or can be - 19 4 3 3-11 prepared in accordance with generally customary and known processes, for example by reacting amines with phosgene and subsequently heating the product. These processes are known from the general textbooks of organic chemistry.

The following may be mentioned as examples of starting materials of the formula (IV) to be used in process variant (b) : dimethylcarbamoyl chloride, methylethylcarbamoyl chloride, allylmethylcarbamoyl chloride, methoxymethylmethylcarbamoyl chloride, methyltrifluoromethylcarbamoyl ,0 chloride and ethylvinylcarbamoyl chloride.

The carbamoyl chlorides of the formula (IV) are known or can be prepared in accordance with generally customary and known processes, for example by reacting amines with phosgene. These processes are known from the general text15 books of organic chemistry.

The following may be mentioned as examples of starting materials of the formula (V) to be used in process variant (c) : ammonia, methylamine, ethylamina, dimethylamine, methylethylamine, allylmethylamine, methoxymethyl20 methylamine, methyl-trifluoromethylamine and ethylvinylamine.

The amines of the formula (V) are generally known compounds.

As already mentioned, the active compounds according to the invention are distinguished by excellent insecticidal, acaricidal and nematicidal activity. In addition, they also possess a certain fungicidal action.

The active compounds are well tolerated by plants, have a favourable level of toxicity to warm-blooded animals, and can be used for combating arthropod pests, especially insects and arachnids, and nematode pests which are encountered in agriculture, in forestry, in the protection of stored pro- 20 .45 3 1 ducts and of materials, and in the hygiene field. They are active against normally sensitive and resistant species and against all or some stages of development. The abovementioned pests include: from the cl? ' of the fsopoda, for example Oniscus asellus, Armadilliiium vulgare and Porcellio scaber; from the class of the Dlplopoda. for example Blanlulus guttulatus; from the class of the Chilopoaa, for example Geophilus carpophagua and Scutigera spec.; from,the class of the Symphyla, for example Seutigeralla immaculata; from the order of the Thyganura. for example lepisma saccharine; from the order of the Colj embola. for example Onychiurus armatus: from the order of the Orthoptera, for example Blatta orientalls, Periplaneta americana, Deucophaea maderae. Blattella germanica. Acheta domesticus. Gryllotalpa spp., locusta migratoria mlgratorioideg. Melanoplus differentialis and Schistooerca gregaria; from the order of the Dermaptera, for example Porfieula auricularia: from the order of the Isoptera. for example Reticulitermea spp.; from the order of the Anoplura. for example Phylloxera vastatrix. Pemphigus spp.. Pediculus humanus corporis. Baematopinus spp. and linognathus spp.; from the order of the Mallophaga. for example i'riohodeet&s spp, and Damalinea spp.; from the order of the Thysanoptera. for example Hercinothrips femoralls and Thrips tabaci; from the order of the Heteroptera for example Eurygaster spp., Dysdercus intermediua, Pieema quadrata. Olmex leotularius. Rhodnius prollxus and Triatoma spp.; from the order of the Homoptera. for example Aleurodes brassicae. Bemisia tabaci. Trialeurcdes vaporarlorum. Aphis goaeypli. Breviooryne brassicae. Cryptomyzus ribis. Derails a 3 4 i· f abae. Doralis pomi. Briosoma lanigerum. Hyalopterus arunainis. Ifeorosiphum avenae, Myzus spp., Ehorodon humuli. Rhopalosiphum padi, Bmpoasca spp., Euscelis bilobatuB, Hephotettix cinotioeps. Becanium coral, Salssetia oleae.

Baodelphax striatellus, Eilaparvata lugens, Aonidiella aurantii. Aspidiotus hederae, Pseudococcus spp., and Psylla spp., from the order of the Bepidoptera. for example Pectinophora gossypiella. Bupalus piniarius, Cheimatobia brumata. Bithocolletis blancardella. Hyponomeuta padella.

Plutella maculipenais., Malacosoma neustria. Euproctis Qhrysorrhoea. Bymantria spp., Bucculatrlx thurberlella. Phylloonistis citrella. Agrotis spp., Euxoa spp., Peltia spp., Barias iasulana. Heliothis spp., Baphygma exiaua, Mamestra brassicae. Panolis flammea. Prodenia litura. Spodoptera spp., Srichoplusia ni, Carpocapsa pomonella, Pieris spp., Philo spp., Pyrausta aubilalis. Bphestia kughnlella. Galleria mellonella. Gaooeoia podaaa. Capua reticulaaa. Ohoristoheura fumiferana. Clysia ambiguella. Homoaa maaaaalma and Sortrlx vlridanag from the order of the Coleontera. for example Anobium punctatum, Rhizopertha dominlca, Bruohidius obteotus.

Acanthoscelides obteotus. Hylotrupes ba.lulus, Agelastica alnl. Beptinotarsa decemlineata. Phaedon cochleariae, Diabrotlca Bpp., iirysocephala, Epilaohna varivestis. Atomaria spp., hub surlnamensis. Anthonomus spp., Sltophilus spp., Otiorrhynohus suloatus. Cosmopolites sordidus. Ceuthorrhynchus assimllis, Hypera postica. Permeates spp., Trogoderma spp., Aathrenus spp., Attagenus spp., Byctus spp., Meligethes aensus. Ptinus spp., Hiptus hololeuous, Gibbium psylloldes. Triboliuffl spp., Senebrio molltor. Agriotes spp., Conoderug spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra zealandicas from the order of the Hymenoptsra. - 22 4 5 3 41 for example Diprion spp., Hoplocampa spp., Dasius spp., Monomorium pharaonis and Vespa spp.; from the order of the II Dlptera. for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster. Musca spp., Farrnia spp., Calliphora erythrocaphala. Ducilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus. Osoinella frit. Phorbia spp., Pegomyia hyoscyami. Oeratitis capitata. Dacus oleae and Tipula paludosa; from the order of the Siphonaptera, for example Xenopsylla oheopis and Oeratophyllus spp.; from the class of the Arachnida, for example, Scorpio maurus and Datrodectus mactans; and from the order of the Acarlna, for example Acarus siro. Argaa spp., Ornithodoros spp., Permanyssus gal3.ir.ae, Eriophyes ribis. Phyllocoptruta olelvora, Boophilus spp., Rhipioephalus spp., Amblyomma spp., Hvalomma spp., Ixodes spp., Psoroptes spp., Ohorioptes spp., Sarcoptes spp., Tarsoneaus spp., Bryobia praetiosa. Panonychus sap. and Tetranychus spp..

The plant parasite nematodes include Pratyjenchas spp., Radopholus simllis. Ditylenchus dipsaci. Tylenchulus semlpenetrans, Heterodera spp., Meloidogyne spp., Aphelencholflss spp., Donflidorus spp., Alnhlnema spp. and Trichodorus spp..

The active compounds can be converted to the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed-treatment powders, natural and synthetic materials impregnated with active compound, very fine capsules in - 23 4 S 3 '1 i polymeric substances and in coating compositions, for use on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils as well as U/V (ultra-low-volume) cold mist and warm mist formulations.

These formulations are produced in known manner, for example by mixing the active compounds with extenders, that is, liquid or solid or liquefied gaseous diluents or carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.

.Is liquid diluents or carriers, there are preferably used aromatic hydrocarbons, such as xylenes, toluene, benzene or alkyl naphthalenes, chlorinated aromatic or aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers ahd esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethyl formamide, dimethyl sulphoxide or acetonitrile, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperatures and pressures, for example aerosol propellants, such as halogenated hydrocarbons, for example Freon (Trade Mark).

As solid diluents or carriers, there are preferably used ground natural minerals, such as kaolins, clays, talc. - 24 & CJ 3 i 1 chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, or ground synthetic minerals, such as highly-dispersed silicic acid, alumina or silicates.

Preferred examples of emulsifying and foam-forming agents include ncr—ionic snd anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylarylpclyglycol ethers, alkyl sulphonates, alkyl sulphates and aryu sulphonates as well as albumin kydrolyzation products; and preferred examples of dispersing agents include lignin sulphite waste liquors and methyl cellulose.

Adhesives such as carbcxymethyicelluiose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arable, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or aetal-phtliaiocyaoine dyestuffs, and trace nutrients, such as salts cf iron, manganese, boron, copper, cobalt, molybdenum and sine.

The formulations m general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent.

The ac+iva compounds according to the invention may be used in the form of their formulations of the types that are commercially available or in the use forms prepared from these formulations.

The active compound content of the use forms prepared from the formulations of the types that are commercially available can vary within wide ranges. The active compound concentration of the use forms can be from 0.0000001 to 1005¾ by weight of active compounds, preferably between 0.01 and 10/ by weight.

The compounds are employed in a customary manner appropriate for the particular use forms.

When used against pests harmful to health and pests of stored products, the active compounds are distinguished by an excellent residual activity on wood and clay as well as a good stability to alkali on limed substrates.

The present invention also provides a nematicidal or arthropodicidal composition containing as active ingredient a compound of present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surfaceactive agent.

The present invention also provides a method of combating arthropods(especially insects or acarida) or nematodes which comprises applying to the arthropods or nematodes, or to a habitat thereof, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.

The present invention further provides crops protected from damage by nematodes or arthropods by being grown ia areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier.

It will be seen that the usual methods of providing a harvested crop may be improved by the present invention. - 26 4 S3 4 I The insecticidal, acaricidal and nematicidal activity of the compounds of this invention is illusti’ated by the following biotest Examples, in which the compounds according to this invention are each identified by the number, in parentheses, of the corresponding preparative Example given later in the text.

Examnle A Critical concentration test Test nematode: Heloldogyne incognita Solvent: 5 parts oy weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether Tc produce a suitable preparation of active compound, part by weight of active compound was mixed with the stated amount of solvent, the stated amount of emulsifier was added and the concentrate was diluted with water to the desired concentration.

The preparation of active compound was intimately mixed with soil which was heavily infested with the test nematodes. The concentration of the active compound in the preparation was of practically no importance} only ths amount of active compound per unit volume of soil, which is given hereinafter in ppm (= ag/l),was decisive. The soil was filled into pets, lettuce was sown in and the pots were kept at a greenhouse temperature of 27°G.

After 4 weeks, the lettuce roots were examined for infestation with nematodes (root galls), and the degree of effectiveness of the active compound was determined as a percentage. The degree of effectiveness was 100% when infestation had been completely avoided; it was 0% when the infestation was exactly the same as in the case of the - 27 4 3 3 41 control plants in untreated soil which had been infested in the same manner.

The active compound, the amounts applied and the results can be seen from the following table: Table A Hematicides Meloidogyne incognita Active compound Degree of destruction in / at an active compound concentration of ppm .CH ch-c<. ' ^n-o-co-hk-ck(known) ch3^ ch5^ CH ΟΗ-Οζ ^H-O-CO-EH-GHj (known) (14) (1) (16) · (17) (5) 100 100 100 100 100 Degree of destruction in / at an active compound concentration of PPa (39) 100 Example E Critical concentration test/root-syatemie action Test insects Ehaedon cochleariae Solvents 3 parts by weight of acetone Emulsifiers 1 part by weight of alkylaryl polyglyool ether To produce a suitable preparation of active compound, - 28 4 5 3 j i part by weight of active compound was mixed with the stated amount of solvent, the stated amount of emulsifier was added and the concentrate was diluted with water to the desired concentration.

The preparation of active compound was intimately mixed with the soil. The concentration of the active compound in the preparation was of practically no importance; only the amount of active compound per unit volume of soil, which is given hereinafter in ppm (= mg/l),was decisive.

The treated soil was filled into pots and these were planted with cabbage (Brassica oleracea). The active compound could in this way be taken up from the soil by the plant roots and be transported into the leaves.

To demonstrate the root-systemic effect, only the leaves were infestsd with the abcre-mentioned test insects after 7 days. Aftci’ a further 2 days, the results were evaluated by counting or estimating the dead insects. The root-systemic action of the active compound was deduced from the destruction data. It was 100% when all the test insects had been killed and 0% when just as many test insects were still alive as in the case of the untreated control.

The active compounds, the amounts used and the results can te seen from the following table: Table B Eoot-systeaic action Phaedon oochleariae larvae Active aoapound Begree of destruction in % at an active compound concentration of ppm °5H7“c%.0-C0-SK-CfI» 0 (known) J - 29 11 Table B (continued) Root-systemic action Phaedon cochleariae larvae Active compound Degree of destruction in % at an active compound concentration of _____________ 10 PPm_ CH, ON CH-C 0Uil3 N-O-CO-NH-CH^ (known) (7) 95 (1) 100 (5) 100 (39) 100 (33) 100 (40) 100 Example 0 Critical concentration test/root-systemic action Test insects Mvzus persicae Solvents 3 parts by weight of acetone Emulsifiers 1 part by weight of alkylaryl polyglyool ether To produce a suitable preparation of active compound, part by weight of active compound was mixed with the stated amount of solvent, the stated amount of emulsifier was added and the concentrate was diluted with water to the desired concentration.

The preparation of active compound was intimately mixed with the soil. The concentration of the active compound in the preparation was of practically no importance; only the amount of active compound per unit volume of soil, which is given hereinafter in ppm (= mg/l),waa decisive. The treated soil was filled into pots and thesewsre planted with cabbage - 30 4 3 3 Ί 1 (Brassica oleracea). The active compound could in this way he taken up from the soil by the plant roots and be transported into the leaves.

To demonstrate the root-systemic effect, only the leaves were infested with the above-mentioned test insects after 7 days, After a further 2 days, the results were evaluated by counting or estimating the dead insects. The root-systemic action of the active compound was deduced from the destruction data. It was 100% when all the test insects had been killed and C% when just as many test insects were still alive as in the case of the untreated control.

The active compounds, the amounts used and the results can be seen from the following table: i a d 1 e ΰ Rost-syatemio action ilyzus persicac Active compound Degree of destruction in % at an active compound concentration of ppm ^.CS η ρ π (known) CH. ..CI’ > * o Gild ^N-C’-CO-SH-CK,, (known) (7) 95 (i) 100 (5) 90 Example D Kyzua test (contact action) Solvent; 3 parts by weight of dimethylfcrmamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether S 3 3 Ί1 To produce a suitable preparation of active compound, part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.

Cabbage plants (Brassica oleracea) which had been heavily infested with peach aphids (Myzus persicae) were sprayed with the preparation of the active compound until dripping wet.

After the specified periods of time, the degree of destruction was determined as a percentage: 100# meant that all the aphids were killed, whereas 0# meant that none of the aphids were killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following table: Table D (Insects which damage plants) Kvzus Test Active compounds Active compound Degree of deconcentration struction in ............ # after 1. day (33) 0.1 0.01 99 98 (36) 0.1 100 0.01 100 (38) 0.1 100 0.01 95 (37) 0.1 100 0.01 99 (39) 0.1 100 0.01 100 (40) 0.1 100 0.01 99 - 32 4 3 3 41 Example 2 laphygma test Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglyool ether To produce a suitable preparation of active compound, part by weight of the active compound was mixed with the stated amount of solvent and the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.

Cotton leaves (flossypium hirsutua) were sprayed with the preparation of the active compound until dew-moist and were then infested with caterpillars of the owlet moth (laphygma exigua).

After the specified periods of time, the destruction in % was determined. 100% meant that all the caterpillars had been killed, whereas 0% indicated that no caterpillars had been killed.

The active compounds, the concentrations of the active compound, the evaluation times and the results can be seen from the following table; labia Ξ {Insects which damage plants) LaphVgma Tast Active compounds Active compound Degree of deconcentration struction in % after 5 days 0.1 100ΰ5νΊ(ί^^-(>-ΰ6-ϋΆ-ΰϊΙ^ 0,01 0 (known) (35) 0.1 100 0,01 80 (3©) 0.1 100 0.01 100 (39) 0.1 100 0.01 100 ·. 4 3 3 41 Solvent: Emulsifier: teat (resistant) parts by weight of dimethylformamide 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, part by weight of the active compound was mixed with the stated amount of solvent and the stated amount of emulsifier and tho concentrate was diluted with water to the desired concentration.

Bean plants (Phaseolus vulgaris) which were heavily infested with the spider mite (Tetranychus urticae) in all stages of development were sprayed with the preparation of the active compound until dripping wet.

After the specified periods of time, the degree of destruction was determined as a percentage: 100/ meant that all the spider mites were killed, whereas 0/ meant that none of the spider mites were killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following table: Table ff (Insects which damage plants) TetranychuB Test Active Active compound Degree of deseoapounds concentration truction in / in / _after 2 days OH η ι n « w „nx 0.1 0 u3 7 ’•IT-O-CO-HH-CSj (known) CH^CH-O CHy'' (known) /CH ^H-O-CO-HH-CH 0.1 (39) 0.1 99 - 34 '3 ΰ 3 j ι Example & Metamorphosis-inhibiting action/ingestion test Test insects: Plutella maculipennis (caterpillar in the 4th stage cf development) 20 insects Phaadon cochleariae (larvae in the 4th stage of development) 20 insects Peed plant: Cabbage plants (Brassica oleracea) Solvent: 10 parts by weight of acetone Bmulsifier; 1 part by weight of polyoxyethylene-(20)sorbitan monolaurate To produce a suitable preparation of active compound, parts by weight of active compound were mixed with the stated amount cf solvent -old emulsifier and with sufficient water to give a i% strength mixture, which was diluted with water to the wssirsd concentration.

The test insects were fed with leaves of the feed plant, whicn were provided with a uniform spray coating of the active compound mixture of the chosen concentration, until the imago developed.

As a control, leaves treated only with solvent and emulsifier of the stated concentration were used for feeding. The sum of the morphologically malformed insects and of the dead insects, aa a percentage of the insects employed, ia quoted, 100% means that all. the insects were malformed or dead and 0% that no insect was malformed or dead. The results can be seen from the table which follows: ο *d φ ο •p a o -p ¢1 o •rl «Ρ ω © tb Q) H cd e* β ο •Η •Ρ Ο CJ ο ο «ΜΟ 3' •gtsj □ ra°. Ο Ο ΟΟΟΟΟΟΟΟΙΛ ο ο οοοοοσιοοονο II <π> ν™ r» *“* <· Ο Ο Ο Ο Ο Ο Ο Ο OOQQ ο ο οοοοοδ ο δ δ δ ο ο ooQOoggooQin ο ο οοδοοδδον>δν> ο ο oogogoogogo ο ο οοδοοοοδωδδ 6« «· ΰ (Q Ο I ο ο ,ξ σ» tn tn tn ο Μ* H— χ—S χ—* k0 οο σ\ >CI οο Ci (15) •3.5341 The process of this invention is illustrated by the following preparative Examples. Example 1 (CHS )SC -CO - NHCHj 7¾ If (1) Process variant (a) 18.2 g (0,1 mol) of 3,5-di5iethyl-2-oximiiiO-1-[1,2,410 triazolyl-(1)]-butane were dissolved in 100 ml of methylene chloride and 11.4 g (©·' mol) of methyl isocyanate were added, whilst stirring, The mixture was left to stand overnight at room to.r- srature and the volatile constituents were then distill off in vacuo. The oily residue was caused to crystallise by trituration with petroleum ether. After recrystalliaation from ethyl acetate/petroleum ether, 19.2 g (QOfr of theory) cf 3,3-dimethyl~2-methylcarbamoyloximino-l-i.1,2,4-triazolyl-(1 )1-cut' ’ie of melting point 94-90°C were obtained.

Example 2 (CH, s,),c ,. X ° ·“ - W: CH, XN' (2) ?N li Process variant (¾) 18.2 g (0.1 mol) of 3,3-dimethyl-2-oximino-1-[l,2,4triazolyi-(1)]~butane in 100 ml cf anhydrous hexamethylphosphoric acid triamide were slowly added, at room tempera20 ; ¢3341 ture, to a mixture of 50 ml of hexamethylphosphoric acid triamide and 3.5 g of sodium hydride. The mixture was then heated to about 80°C and after the evolution of hydrogen had ceased 11.2 g (0.1 mol) of dimethylcarbamoyl chloride were added dropwise. After two hours, the cooled reaction mixture was poured into watei' and repeatedly extracted with methylene chloride. The combined methylene chloride phases were dried over sodium sulphate. The mixture was concentrated by distilling off the solvent in vacuo and the oily residue was then distilled. 9.5 g (37.8$ of theory) of 3t3“4imethyl-2-dimethylcarbamoyloximino-1-[l ,2,4triazolyl-(1)]-butane with a boiling point of 160°0/0.4 mm 8 Hg and a refractive index nDJ of 1.5015 were obtained as a colourless oil.

Process variant (c) g (0.12 mol) of phosgene were passed slowly into a solution of 18.2 g (0.1 mol) of 3j3-dimethyl-2-oximino-1[1,2,4-triazolyl-(1)]-butane and 13.5 g (0.1 mol) of Η,Ηdimethyl-benzylamine in 150 ml of absolute methylene chloride at 0 to 5°C, whilst stirring. The mixture was left to stand for 5 hours, whilst stirringj and excess phosgene was then driven out of the reaction mixture by means of a dry stream of carbon dioxide. The salt which had separated out during the reaction was separated off and the solution was mixed with 15 ml of a 40$ strength solution of dimethylamine in water at 0° to 5°C, whilst stirring. Stirring was continued for 3 hours at room temperature and the salt which had separated out was then filtered off. The filtrate was washed twice with 20 ml of water, dried over sodium sulphate and concentrated by distilling off the solvent in vacuo.

The oily residue was then also distilled. 11.2 g (44.5$ of - 38 3341 theory) oi' 3,3-dimethyl-2-dimsthyl.carbamoyl-oximino-1 [1,2,4-triazolyl-(-1 )]-butane with a boiling point of 16O°C 22 5 /0,4 mm Hg and a refractive index of 1.5015 were obtained as a colourless oil.

Example 5 H /K - 0 - CO - Nt v {CH,)SC-CX XCH(CH,)a (3) Process variant (a) 9.05 g (0.05 mol) cf 3«3“dimethyl-2-oximino-1-pyraKolyl-O)-butane vers dissolved in 100 ml of chloroform and 8.5 g (0.1 mol) o” isopropyl isocyanate were added slowly, whilst stirring. The mixture was left to stand at room temperature for about 5 hours and the solvent was then distilled off in vacuo. The crystalline residue was recrystallised from petroleum ether. 11.5 g (86.5% of theory) oi 3,3-dimethyi-2~lscpropylearbamoyloximino-1pyraE0iyl-{1'-butane of melting point 66-67°Ciere obtained. Example 4 (CHS)SC-C .•κ - o - co - n: ,CX pH, XCH,- 0 - CH, (4) Process variant (a) 8.7 g (0.1 mol) of methoxymethyl isocyanate were added to a suspension cf 12 g (0.05 mol) of 3,3-dimethyl-1-[2methyl-4~nitro-imidazolyl-(1)j-2-cximino-butane in 100 ml - 39 4 3 3 41 of methylene chloride and the mixture was stirred at room temperature until the oxime had completely dissolved. The solvent was then distilled off in vaouo and the residue was recrystallised from ethyl acetate. 12.0 g (73.5/ of theory) of 3s3“dimethyl“2=methoxymethylearbamoyloximino-1-[2-methyl4=nitro-imidazolyl-(l)]-butane of melting point 149-52°C were obtained.

Example 5 (CH,)SC - C' CHj, (5) Salt formation 8.5 g (0.035 mol) of 3»3-dimethyl-2-methylcarbamoyloximino-1-[1,2,4-triazolyl-(1)]-butane (see Example 1) were dissolved in 50 ml of acetone and an excess of naphthalene1 i5-disulphonic acid was added in portions. The resulting precipitate was filtered off and washed with acetone. 11.3 g (83/ of theory) of 3,3-dimethyl-2-methylcarbamoyloximino-1-[l,2,4-triazolyl-(1)]-butane naphthalene-1,5disulphonic acid of melting point 17O-75°O (with decomposition) were obtained.

Example 6 r - 40 «53-41 Complex formation 11.95 g (0.05 mol} of 5,3-dimethyl-2-methylcarbamoyloximino-1-[l,2,4-triazolyl-(1)]-butane (see Example 1) were dissolved in 50 ml of ethanol and a solution of 3.41 g (0.025 mol) of dry zine dichloride in 30 ml of ethanol was added dropwise. The mixture was left to stand overnight and the solvent was then distilled off in vacuo. Bis-[3,3-dimethyl-2-methylcarbamoyloximino-1-[1,2,4triazolyl-(1)]-butane]zinc(II) dichloride of melting point 1O5-11O°C (with decomposition) was obtained quantitatively.

The compounds in Table I which follows were obtained analogously.

(Iix) 'es V in ia I I C£< , •P G •rl Pi •HO *P H ω S »£> %$ oi f ΙΛ a (Λ I so os - 42 (continued) a fc « (CH5)5S H CHs Η n viscous oil ed - 43 4S3 ii CH, NO. «3341 ¢.3341 Example 52 χ N - Ο - CO - NHCHj (CH3)3C -.(/ (52) Process variant (a) 8.4 g (0.05 mol) of 2,2-dimethyl-1-oximino-1-[1,2,35 triazolyl-(1)]-propane and 5.7 g (0.1 mol) of methyl isocyanate in 100 ml of methylene chloride were heated for 12 hours under reflux. The resulting clear solution was subsequently concentrated in vacuo by distilling off the solvent.

The solid residue was recrystallised from ethyl acetate/petroleum ether. 7.8 g (69.5% of theory) of 2,2dimethyl-1-methylcarbamoyloximino-1-[1,2,3-triazolyl-(1)] propane were obtained as colourless crystals of melting point 128-131 °C.

Example, 32 N - 0 - CO - HHCHs (CHS)SC - CZ * (55) Prooess variant (a) 8.55 g (0.05 mol) of 2,2-dimethyl-1-oximino-1pyrazolyl-(l)-propane were dissolved in 150 ml of methylene chloride and 5.7 g (0.1 mol) of methyl isocyanate were added. The mixture was left to stand for 24 hours at room temperature and was then concentrated by distilling off - 46 4 3 3 4 1 the solvent in vacuo. On trituration with petroleum ether, the residue crystallised throughout. 8.2 g (73$ of theory) of 2,2-dimethyl-1-methylcarbamoyl-1-pyrazolyl-(1 )-propane of melting point 95-97°C were obtained.

Example 34 /H - 0 - CO - Νζ(CH3)3C - CH. -CH«CH2 ( ίΜ λ SOsH Salt formation g (0.06 mol) of 2,2-dimethyl-1-oximino-1-[1,2,4triazolyl~(1)3-propane and 7 g (0.085 mol) of allyl iso10 cyanate in 150 ml of methylene chloride were heated for 12 hours under reflux. She mixture was then allowed to cool and after distilling off the solvent in vacuo. 14 g of 1-allylcarbamoyl-oximino-2,2-dimethyl-1-[1,2,4-triazolyl(Dj-propane were obtained as a non-crystalline, yellowish oil. This was dissolved in 50 ml of acetone and an excess of naphthalene-1,5-disulphonie acid was added. The resulting precipitate was filtered off and washed with acetone. 14.8 g (62.5$ of theory, based on the oxime) of 1-allylcarbamoyloximino-2, 2-dimethyl-ϊ- [ΐ,2,4-triazolyl-(1)] -propane napthalene-1,5-disulphonic acid of melting point 175°C (with decomposition) were obtained.

Example 35 - 47 4 83 41 Ν - Ο - CO (CK3)5C - C CHS χ ZnCl2 (35) Complex formation 11.25 g (O.O5 mol) of 2,2-dimethyl-l-methylcarbamoyloximino-1-[l,2,4-triazolyl-(l)]-propane were dissolved in 50 ml of absolute methylene chloride and a solution of 3.41 g (0.5 mol) of dry zinc dichloride in 50 ml of absolute ethanol was added dropwise. After brief standing, colourless crystals separated out from the solution, and were filtered off and rinsed with a little methylene chloride. 9.6 g (65.5% of theory) of bis»(2,2-dimethyl-l-methylcarbamoyloxiaino-1 -[1,2,4-triazolyl- (1)] -propane -zinc (II) dichloride of melting point 190-S2°C (with decomposition) were obtained in the form of colourless crystals.

The compounds in Table 2 whioh follows were obtained analogously. ¢-48o o I o I z \' I cd S '3 3 J i oi I o I d* S a? o a” o I coo tn m m CJ ω r4 ώ EH Φ W σ\ <*> O r- OJ *ι< 3341 3 3 11 Table 2 (continued) 3 *4 A The preparation of the starting materials of the formula (II) is illustrated by the following Examples. Example I .NOH (CHj )3 C A solution of 102 g (1 mol) of sodium carbonate in 400 ml of water was added dropwise, at room temperature, to 167 g (1 mol) of 3,3-dimethyl~1-[1,2,4-triazolyl-(1)]butan-2-one and 140 g (2 mol ) of hydroxylamine hydrochloride in 400 ml of ethanol. After completion of the addition, the reaction solution was heated for 12 hours under reflux. The mixture was then concentrated by distilling off the solvent and the residue was poured into 1 1 of water. The resulting crystalline precipitate was filtered off and dried. 114 g (62.5# of theory) of 3,3-dimethyl-215 oximino-1-[1,2,4-triazolyl-(1)]-butane of melting point 121-23°0 were obtained.

The compounds in Table 3 which follows were obtained analogously. - 52 4 3 311 NOH S311 (continued) υ ΒΊ ο δ η Η Η Η Η !» Η Η W Κ Μ X (CH3 JaCH-CHj- Η Η —Ν , viscous oil -P £ Ή O $ •P H K£> & (continued) H GO in 1 •rt O in rH W 3 © O 03 £ Pco I in m KO Γ CM O Table 5 (continued) Example XXI (CHj)jC NOH A solution of 135.5 g (1 mol) of pivalohydroxamic acid chloride in 100 ml of absolute tetrahydrofuran was added dropwise, at 0 to 3°C, to a mixture of 69 g (1 mol) of 1,2,3-triazole and 101 g (1 mol) of triethylamine in 500 ml of absolute tetrahydrofuran. After completion of the dropwise addition, the mixture was stirred for a further 24 hours at about 20°C. 1.5 1 of water was then added to the reaction mixture, and the precipitate was filtered off, dried and recrystallised from cyclohexene/ethyl acetate. 106.5 g (63# of theory) of 2,2-dimethyl-1-oximino-1-[1,2,3-triazolyl-(1)]-propane were obtained as colourless needles of melting point 165-167°C (with decomposition).

Example XXII (CHj)sC g (1.1 mol) of pyrazole and 101 g (1 mol) of triethylamine were dissolved in 500 ml of absolute tetrahydrofuran and the solution was cooled to 0°0. 135«5 g (1 mol) of pivalohydroxamic acid chloride in 100 ml of absolute tetrahydrofuran were added dropwise. The mixture was then stirred for a further 12 hours at about 20°C. - 57 633 41 The salt which had separated out was filtered off, the filtrate was concentrated by distilling off the solvent in vacuo and the residue was also distilled. 88.5 g (53% of theory) of 2,2-dimethyl-l-oximino-1-pyrazolyl-(1) propane with, a boiling point of 82-85°C/0.12 mn Hg and a melting point of 68-71 °C were obtained.

The compounds of Table 4 which follows were obtained analogously. - 58 «3311 H H H X X o o o o « m z> s“»» z—\ V) in wi X X X X o O o o o «1 ί *«z H M H H H X > r* H X X X X X X X X X Φ H Xi d 3 41 oo o o ss o o P S3 H »rt *2 2 KV w •ϋ Φ d *8 o o Pi pH J g3| Em| o d VO H CM rH in I σι CM 1 O <$ CO H rt ra il I 8 o eq «< n £ ? £ 3 3 41 The preparation of the intermediates of the formula (IX) is illustrated by the following Examples.

Example Ia CH, 67.3 g (0.5 mol) of monochloropinacoline were added dropwise to a vigorously stirred and boiling mixture of 35 g (0.5 mol) of 1,2,4-triazole and 70 g (0.5 mol) of potassium carbonate in 250 ml of methyl ethyl ketone. The mixture was heated for 6 hours under reflux, the resulting inorganic salt was filtered off and the filtrate was concentrated by distilling off the solvent. The residue was triturated with petroleum ether, whereupon the product crystallised out. After recrystallisation from petroleum ether/ethyl acetate (2/1), 50 g (60% of theory) of 3,315 dimethyl-i~[1,2,4~triazolyl-(1)]-butan-2-one of melting point 65-67°C were obtained.

The compounds of Table 5 which follows were obtained analogously. - 62 <053 ί ι ** -- i.

Villa (CHS)SC Η Η N| ΊΓΊΙ 82-85 3 3-11 (continued) (CH3)2CH- Η H viscous oil

Claims (46)

1. CLAIMS:Oxime-carbamates of the general formula (I) (I) in which R represents optionally substituted alkyl, cycloalkyl, aryl or aralkyl, R 1 represents hydrogen or alkyl, R represents hydrogen, alkyl, alkenyl, alkynyl, halogenoalkyl, halogenoalkenyl or alkoxyalkyl, and R represents a pyrazolyl-(1), imidazoiyl-(1), 1,2,4triazo!yl-(1), l,2,3-triazolyl-(l), 1,3 s 4-triazolyl-(1), indazolyl-(l), benzimidazolyl-(1) or benztriazolyl-(1) radical, which may be optionally substituted, or represents the group in whieh R^ and r5 are identical or different and represent hydrogen or alkyl, or conjointly represent a pentamethylene or tetramethylene bridge, and 6 R represents a pyrazolyl-(1), imidazolyl-(1), 1,2,4triazolyl-(l), 1,2,3-triazolyl-(1), 1,3,4-triazolyl-(l), indazolyl-(1), benzimidazolyl-(1) or benztriazolyl-(1) ring, which may be optionally substituted.

2. The salts and metal complexes of the oxime-carbamates according to claim 1.

3. Compounds according to claim 1 or 2, in which R represents straight-chain or branched alkyl with 1 to 6 carbon atoms, phenyl which can optionally be substituted by halogen, phenylalkyl with 1 to 4 carbon atoms the alkyl part and 4. S 3 4 I which is optionally substituted in the phenyl part by halogen, or cycloalkyl with 5 to 7 carbon atoms which -t is optionally substituted by methyl or ethyl; R represents hydrogen or straight-chain or branched alkyl with 1 to 4 carbon atoms; R represents hydrogen, straight-chain or branched alkyl with 1 to 12 carbon atoms, alkenyl and alkynyl 5. Each with 2 to 4 carbon atoms, halogenoalkyl with up to 2 carbon atoms and up to 5 halogen atoms, halogenoalkenyl with up to 3 carbon atoms and up to 5 halogen atoms or alkoxyalkyl with up to 2 carbon atoms in each alkyl part; R^ represents an optionally substituted pyrazolyl-(1), 10 imi dazolyl-(1), 1,2,4-triazolyl-(1), 1,2,3-triazOlyl-(1), 1,3 s4-triazolyl-(1), indazolyl-(1), benzimidazolyl-(1) or benztriazolyl-(1) radical, the substituents being selected from halogen, alkyl with 1 to 4 carbon atoms, halogenoalkyl wiefch up to 2 carbon atoms and up to 5 halogen atoms, alkoxy 15 and alkylthio, each with up to 4 carbon atoms, and nitro, or R represents the group R« -A - R 6 R5 in which R snd R^ are identical or different and represent hydrogen or alkyl with 1 or 2 carbon atoms or R* and P? 20 conjointly represent a pentamethylene or tetramethylene group, and R^ represents an optionally substituted pyrazolyl(1), imidazolyl-(1), 1,2,4-triazolyl-(1), 1,2,3-triazolyl(1), 1,3,4-triazolyl-(1), indazolyl-(1), benzimidazolyl-(1) or benztriazolyl-(l) radical, the substituents being 25 selected from halogen, alkyl with 1 to 4 carbon atoms, halogenoalkyl with up to 2 carbon atoms and up to 5 halogen atoms, alkoxy and alkylthio, each with up to 4 carbon atoms, and the nitro group. - 68 4 ΰ 3·ί 1

4. The compound of the formula ^,n-g-cg-nhch t 3 Luj (1)

5. The compound of the formula (oh 3 ) 3 o-c ^N-O-OO-KHCHS J (5)

6. The compound of the formula N-O-CO-IOICH, (ch 3 ) 3 g - C x-n ά \=K o 2 i 5 (16)

7. The compound of the formula , li-O-CO-NHCH. (ck 3 ) 3 c — c „N (33)

8. The compound of the formula ji-o-co-nhch 3 3 ) 3 c - s' A j (36) - 69

9. The compound of the formula JI-O-CO-BHCH, (CH,),0 - / Jk N (59) Lji

10. The compound of the formula ..Ii-O-CO-NHCH~-OCH_ (CH^J^C - CT 2 3 (40) 5

11. The compounds that are disclosed in Examples 2-4, 6-15, 17-32, 34-37 and 40-47.

12. A process for the preparation of an oxime-carbamate according to claim 1, in which aa oxime of the general formula xNQH R/ in which R and R have the meanings stated in claim 1 i (a) provided R is hydrogen, is reacted with an isocyanate of the general formula 15 r 2 -h=c=o (iii), in which o R has the meanings stated in claim 1, in the presence of a diluent and optionally in the presence of a catalyst, or 20 (b) is reacted with a carbamoyl chloride of the general formula , /R 1 Cl-CO-N 2 (IV), ^R in which - 70 1 2 R and R have the meanings stated in claim 1, either in the presence of a diluent and an acid-binding agent or in the presence of a diluent and sodium hydride, or (c) is reacted with phosgene and subsequently with an amine of the general formula R 1 Η~Ν Ζ \ (V), in which 1 9 R and R 1 have the meanings stated in claim 1, either in the presence of a diluent and an acid-binding agent or in the presence of a diluent and sodium hydride,or 1 2 (d), in the case where ? and R both denote hydrogen, is reacted with a cyanate of the general formula MOCK (VI), in whioh M represents sodium, potassium or ammonium, in the presence of hydrochloric acid and of a diluent.

13. A process according tc claim 12(a), in which the reaction is effected in the presence of an inert organic solvent.

14. A process according to claim 12(a) or 13 in which the reaction is effected in the presence, as a catalyst, of an organotin compound or a tertiary base.

15. A process according to claim 12(a), 13 or 14, in which the reaction is effected at between 0° and 100°C.

16. A process according to claim 15, in which the reaction is effected at between 20° and 85°C.

17. A process according to any of claims 12(a) and 13 to 16, in which 1 to 2 moles of the isocyanate (III) are used 4S341 per mole of the compound (II).

18.. A process according to any of claims 12(a) and 13 to 17, in which the isocyanate (III) is one that is hereinbefore specifically mentioned.

19. A process according to claim 12(b) or 12(c), in which the reaction is effected in the presence of an inert organic solvent.

20. A process according to claim 12(b), 12(c) or 19* in which the reaction is effected in the presence, as an 10. · acid-binding agent, of an-alkali metal carbonate of a tertiary amine.

21. A process according to claim 12(b) cr 12(e) in which the reaction is effected in the presence of sodium hydride and a polar organic solvent. 15

22. A process according to claim 21, in which the solvent is hexamethylphosphoric acid triamide.

23. A process according to any of claims 12(b), 12(c) and 19 to22, in which the reaction is effected at between 0° and 100°C. 20

24. A process according to claim 23, in which the reaction is effected at between 0° and 85°C.

25. A process according to any of olaims 12(b), 12(c) and 19 to 24, in which-1 to 2 moles of the carbamoyl chloride (IV) or 1 to 1.5 moles of phosgene and 1 to 1.5 moles of 25 the amine (V) are used per mole of the oompound (II).

26. A process according to any of claims 12(b), 12(c) and 19 to 25, in which the carbamoyl chloride (IV) or the amine . (V) is one that is hereinbefore specifically mentioned.

27. A process according to claim 12(d), in which the 30 reaction is effected in the presence of an inert organic - 72 solvent, which is optionally in admixture with water.

28. A process according to claim 12(d) or 27', in which the reaction is effected at between 0° and 50°C·

29. A process according to claim 28, in which the reaction 5 is effected at between 0° and 30°C.

30. A process according tc any of claims 12(d) and 27 to 29, in which 1 tc 2 moles of the cyaiate (VI) are used per mole of the compound (II).

31. A process according tc any of claims 12 to 30, in 10 which the compound (II) is one that is hereinbefore specifically mentioned,

32. A process for the preparation of a salt according to claim 2, in which a compound according to claim 1 is dissolved in an ether and an acid is added thereto. 15

33. , A process according to claim ?2, in which the acid ie a physiologically tolerated acid.

34. A process according to claim 33, in whieh the acid is hydrochloric acid, hydrobromic acid, a monobasic or dibasic carboxylic or hydroxycarboxylic acid or 1,52C naphthalene-dieulphonic acid.

35. A process fcr the preparation of a complex according to claim 2, in which a metal Balt, dissolved in an alcohol, is added to a compound according to claim 1.

36. A process according to claim 35, in which the salt is 25 a copper, zinc, manganese, magnesium, tin, iron or nickel salt of a physiologically tolerated acid.

37. A process according to claim 36, in which the acid is hydrochloric acid, hydrobromic acid, sulphuric acid, nitric acid or phosphoric acid. 30

38. A process for the preparation of a compound according - 73 45341 to claim 1 or 2, substantially as described in any of ., f Examples 1 to 6 and 32 to 35.

39. Compounds according to claim 1 or 2 whenever prepared by a process according to any of claims 12 to 33. i ς

40.’ A nematicidal or arthropodicidal composition containing ' as active ingredient a compound according to any of claims 1 to 11 and 59 in admixture with a solid or liquefied gaseous diluent or carrier or in 1 admixture with a liquid diluent or carrier containing a surface-active agent. 10 ·

41. A composition according to claim 40 containing from 0.1 to 95% of the active compound, by weight.

42. A method of combating nematodes or arthropods which comprises applying to the nematodes or arthropods, or to a habitat thereof, a compound according to any of claims 1 to 15 11 and 39 alone or in the form of a composition containing a3 active ingredient a compound according to any of claims 1 to 11 and 39, in admixture with a diluent or carrier.

43. A· method according to claim 42 in which a composition is used containing from 0.0000001 to 100% of the active 20 compound, by weight.

44. A method according to claim 43 in which a composition l is used containing from 0.01 to 10% of the active compound, by weight.

45. A method according to claim 42, 43 or 44 in which the 25 active compound is applied to insects oraoarids or to a habitat thereof.

46. Crops protected from damage by nematodes or arthropods ; . by being grown in areas in which immediately prior to and/or 1 during the time of the growing a compound according to any 30 of claims 1 to 11 and 39 was applied alone or in admixture with a diluent or carrier. - 7.4 -