NZ202106A

NZ202106A - Insecticidal,acaricidal and veterinary parasiticidal compositions containing substituted hydroxy-malonic acid diamides

Info

Publication number: NZ202106A
Application number: NZ202106A
Authority: NZ
Inventors: K Findeisen; I Hammann; B Homeyer
Original assignee: Bayer Ag
Priority date: 1981-10-10
Filing date: 1982-10-07
Publication date: 1985-08-30
Also published as: ZA827369B; IL66943A0; AU551841B2; EG15762A; DD203678A5; BR8205906A; PL238572A1; GR77719B; IL66943A; ES8306994A1; EP0076957A1; OA07225A; PT75637B; PH18860A; ATE19058T1; CS241124B2; JPS5872547A; CS717682A2; PT75637A; DK444982A

Abstract

1. Substituted hydroxymalonic acid diamides of the formula (I) see diagramm : EP0076957,P17,F4 in which R represents alkyl with at least 2 C atoms and chlorine substituted alkyl, optionally substituted alkenyl, optionally substituted cycloalkyl, substituted aryl, or optionally substituted heteroaryl.

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £02106 202 o H «1MS Priority Date{s): " . . n-to-ez- Complete Specification .. rf-e>i sl 3yf.s f, rTk/. Class: Ac>(fJh-3/<p.9., Publication Date: P.O. Journal, No: 30 AUG 1985.,., i.2^tt. new zealand Patents Act, 1953 COMPLETE SPECIFICATION N.Z. No. -7 OCT19821"!: "Substituted hydroxy-maIonic acid diamides, a process for their preparation, and their use as pest combating agents." We, BAYER AKTIENGESELLSCHAFT, a Company registered under the laws of the Federal Republic of Germany, of Leverkusen, Germany, do hereby declare the invention, for which we pray that a Patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement -1- (Followed by 1A.) -1A- £o2iob Type lb The present invention relates to certain new substituted hydroxy-malonic acid diamides, to a process for their preparation, and to their use as pest-combating agents. It has already been disclosed that carbamates, such as 5,6-dimethyl-2-dimethylamino-4-pyrimidinyl dimethylcar-bamate or naphth-l-yl N-methylcarbamate, possess insecti-cidal activity (see U.S. Patent Specifications 3,493,574 and 2,903,478). However, their action is not always completely satisfactory, particularly when low concentrations are used. The present invention now provides a pesticidal composition characterised in that it contains as active ingredient a compound which is a substituted hydroxy-malonic acid diamide of the general formula conh I r-c-oh (i) I CONI^ in which unsubstituted R represents/alkyl with at least 2 carbon atoms, substituted alkyl, optionally substituted alkenyl, optionally substituted cycloalkyl; optionally substituted aryl or optionally substituted heteroaryl radical in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid di^aent or carrier containing a surface active agent. / According to the present invention we further provide a process for the production of a compound of the present invention, characterised in that a) a substituted trimethylsilyloxymalonic acid dinitrile of the general formula CN R-C-OSi(CH^), CN (II) in which R has the meaning given above, is hydrolysed with an organic acid, or b) hydroxy-malonic acid ester amides of the formula (III) COOR (III) R-C-OH CONH„ in which R has- the meaning indicated above and I R- represents optionally substituted alkyl or optionally substituted cycloalkyl, are reacted with ammonia, or c) hydroxy-malonic acid esters of the formula (IV) - 3 - 202106 coor' R-C-OH i00R2 (1W) in which R and R ^ have the meaning indicated above and 2 1 R has the meaning given for R , it being 1 2 possible for R and R to be identical or different, are reacted with ammonia, or d) hydroxy- or trimethylsilyloxy—malonic acid -amid-nitriles of the general formula (V) % conh2 R-c-o-x » in which R has the meaning indicated above and X represents hydrogen or SitCH^J^/ are hydrolysed with inorganic acids, or e) acyloxymalonic acid diamides of the general formula (VI) - 4 - 7021 0 6' CONH2 0 tl R-C-O-C-R (VI) CONH2 in which R has the meaning indicated above, are hydrolysed in the presence of bases, or f) acyloxymalonic acid dinitriles of the general formula (VII) CN O R-C-O-C-R (VII) CN in which R has the meaning indicated above are hydrolysed with inorganic mineral acids, or g) acyloxymalonic acid diesters of the general formula (VIII) COOR1 R-C-O-C-R (VIII) COOR1 dm ji' a i 0 4 1 rhv - 5 - 1021 in which R and R'1 have the meaning indicated above, are reacted with ammonia. Surprisingly, the substituted hydroxy-malonic acid diamides according, to the invention exhibit a substantially higher insecticidal action than the carbamates known from the prior art. and of the same direction of action. The substances according to the invention are thus suitable for combating pests. Compounds of the formula (I), in which R represents C^^-alkyl, C2_^-alkenyl or Cj_g-cycloalkyl, or represents -alkyl, C2_^-alkenyl or C^ g- cycloalkyl, which are substituted by one or more identical or different radicals selected from the following halogen, in particular fluorine, chlorine, bromine, C^_^-alkoxy, in particular methoxy or ethoxy, carboxyl, carbalkoxy, in particular methoxycarbonyl or ethoxycarbonyl, phenyl, phe-noxy or thiophenyl, it being possible for the phenyl, rings to be substituted by halogen or alkyl;: R furthermore, represents phenyl which is optionally. substituted by one or more identical or different radicals selected from the following: ■Lo ft 01 Jill 202106 halogen, in particular chlorine, bromine, fluo rine, nitro, amino, OH, CN, C^_4-alkyl, in par ticular methyl, C^._^-halogenoalkyl, in particu lar trifluoromethyl, trichloromethyl or penta-fluoroethyl, C^.^-alkoxy, C^_4-halogenoalkoxy, in particular trifluoromethoxy, pentafluoro-ethoxy, methylenedioxy, ethylenedioxy, difluo-romethylenedioxy or halogen-substituted ethylenedioxy, C^_4-alkylthio, C^_^-halogenalkyl-thio, in particular trifluoromethylthio, c2-4~ alkoxyalkyl, C2_g-halogenoalkoxyalkyl, C^_^-alkylsulphonyl, in particular methylsulphonyl, C^_4-halogenoalkylsulphonyl, carboxyl, carbal-koxy, in particular methoxycarbonyl, the radical C^_4~alkoxy-N=CH-, in particular CH3-0-N=CH-, also phenyl, phenyloxy, or thio-phenyl which may optionally be substituted by halogen or C^_4-alkyl, carboxylalkoxy with 2-4 C-atoms, such as carboxymethoxy, R furthermore represents heteroaryl such as pyridinyl, pyrimidinyl, triazinyl, isoxazolyl, thiazolyl, oxadiazolyl, imidazolyl, tr.iaz.olyl, furanyl or thiophenyl, which may optionally be substituted by one or more identical or different substituents, these being halogen,: in par ticular chlorine, C1_4-alkyl, in particular methyl or ethyl, or C^_4~alkoxy, in particular methoxy or ethoxy, particularly preferred. 20210 6 Compounds of the formula (I), in which R represents C2_4-alkyl and halogen- (in particular fluorine or chlorine), phenyl- or phe-noxy-substituted C^_4-alkyl or C^_g-cycloalkyl, optionally carboxyl-substituted C2_4-alkenyl and also phenyl which is optionally substituted by halogen, in particular fluorine or chlorine, C^ ^-alkyl, in particular methyl, C^_4-alkoxy, C1_4-halogenalkoxy, C1_4-halogenoalkyl, NH2, ch3o-n=ch-, are particularly preferred. Very particularly preferred compounds of the present invention are those in which R represents a phenyl radical which is optionally monosubstituted or polysubstituted by chlorine or fluorine. The following may be mentioned individually as new active compounds of the present invention: pheny1-hydroxy-malonic acid diamide, o-, m- and p-chloropheny1-hydroxy-malonic acid diamide, 2,3-dichloro-phenyl-hydroxy-malonic acid diamide, 3,4-dichloropheny1-hydroxy-malonic acid diamide, 3,5~dichlorophenyl-hydroxy-malonic acid diamide, 2,4-dichlorophenyl-hydroxy-malonic acid diamide, 2,5-dichlorophenyl-hydroxy-malonic acid diamide, 2,6-dichlorophenyl-hydroxy-malonic acid diamide, o-, m- and p-nitrophenyl-hydroxy-malonic acid diamide, o-chloromethyIphenyl-hydroxy-malonic acid diamide, o-, m-and p-trifluoromethyIphenyl-hydroxy-malonic acid diamide, ' ^ $2106 - 8 - o~j m- and p-methoxypheny1-hydroxy-malonic acid diamide, 2,6-dimethoxypheny1-hydroxy-malonic acid diamide, o-, m-and p-tolyl-hydroxy-malonic acid diamide, o-, m- and p-trifluoromethoxyphenyl-hydroxy-malonic acid diamides}. o-, m-and p-fluoropheny1-hydroxy-malonic acid diamides, cyclohexy1-hydroxy-malonic acid diamide, benzy1-hydroxy-malonic acid diamide, buty1-hydroxy-malonic acid diamide, tert.-butyl-hydroxy-malonic acid diamide, fluoro-tert.-butyl-hydroxy-maIonic acid diamide, chloro-tert.-butyl-hydroxy-malonic acid diamide, difluoro-tert.-buty1-hydroxy-malonic acid diamide and trichloromethy1-hydroxy-malonic acid diamide. If in process variant a) trimethylsilyloxy-phenyl-maIonic acid dinitrile is used as the starting material and 96 % strength sulphuric acid is used as the hydroly-sing agent the course of the reaction according to the present invention is illustrated by the following equation: CN - CONK. ' i 2 ,-\^C-0Si(CH,), ;> ^ ,.C-0H [Oj CN h2S04 [O^ CQNH2 Some of the trimethylsilyloxymalonic acid dinitriles of the formula II which are used as starting materials are known (Chem. Ber. 106 , 587 (1973) 3 and Tetrahedron Letters No. 17, 1449 - -1450; (1973 )). New compounds can readily be synthesised by the methods given in these papers, according to the following equation: CN R-C0C1 + 2 (CH^SiCN* R-C-OSi (CH3) 3 + (CH^SiCl CN Le A 21 341 - RTF wherein R has the above mentioned meaning. In formula (II) , R preferably represents a straight-chain or branched alkyl radical having 2 to 6 carbon atoms. As well as for alkyl radicals having up to 6 carbon atoms which are substituted by halogen (such as fluorine, chlorine or bromine), alkoxy, carboxyl or carbalkoxy groups. R furthermore preferably represents alkenyl radicals having 2 to 7 carbon atoms, which can be substituted by halogen (such as fluorine, chlorine or bromine), alkoxy, carboxyl or carbalkoxy groups, and furthermore preferably represents cycloalkyl radicals having 3 to 6 carbon atoms, ■which can be substituted by halogen (such as fluorine, chlorine or bromine), alkoxy, carboxyl or carbalkoxy groups, and furthermore preferably represents aryl radical especially phenyl which can be substituted by alkyl having 1 to 4 carbon atoms, substituted alkyl which can be substituted by halogen (such as fluorine or chlorine) , and alkoxy groups, by halogen (such as fluorine, chlorine or bromine), by alkoxy having 1 to 4 carbon atoms, by chlorine-substituted or fluorine-substituted alkoxy or by amino or'nitro groups, and, preferably, heteroaryl radicals which can be substituted by alkyl having 1 to 4 carbon atoms, alkoxy groups or halogen (such as fluorine, chlorine and bromine). In general, water is used as the diluent in the hydrolysis according to process a). The acid hydrolysis can be carried out in anhydrous or water-containing acids, and even small amounts of water are frequently sufficient to obtain the desired end products. However, the amount of water can be varied within a relatively wide range, between 2 % and 75 %, relative to the amount of acid employed. Furthermore, it is possible initially to dissolve 202106 the starting material of the formula (II) in an anhydrous acid and to add the required amount of water at a later point in time. The following may be preferably mentioned as suitable acids: sulphuric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid and boric acid. Sulphuric acid (E^SO^) and hydrochloric acid (HCl) are particularly preferred. In some cases,, the end products of the general formula (I) are somewhat water-soluble and must therefore be removed from this with the aid of an extracting agent... Suitable extracting agents are any of the inert organic ' solvents which are immiscible, or only slightly miscible, with water. These include toluene, xylene, chloro-benzene, dichlorobenzene, ethyl acetate, methylene chloride, chloroform, carbon'tetrachloride and ether. However, an extracting agent is generally not required. The reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried, out .at a temperature between about -15°C and 100°C, preferably between 0 and 80°C, especially between 20 and 60°C . The reaction is normally carried out under normal pressure, but it can also be carried out under elevated pressure. In general, the reaction is carried out under pressures of between about 1 bar and about 10 bar, preferably between 1 bar ana 5 bar. Generally, the process according to variant a is carried out as follows: about 0,5 to 20 mol, preferably 1 to 5 mol, of inorganic acid are employed per mol of the substituted trimethylsilyloxy-malonic acid dinitrile of formula (II); the compound of the formula (II), which is dissolved in the acid is poured onto ice after the solution has been Q'luNfri 1 H'PE' - 11 - 2 1 stirred for 30 minutes to two hours, and is obtained either by filtering off under suction or extraction. In general, the purification is carried out by recrystallisation. Process b is carried out by reacting hydroxymalonic acid ester amides (III) with ammonia according to the following equation: COOR R-C-OH CONH NH- -R^ OH CONH, i « R-C-OH CONH III Compounds of the formula (III) in which R represents the preferred definitions given above and 1 R represents C^_4~alkyl which is optionally substituted by halogen, in particular chlorine, or CT_4-alkoxy, are preferred. In particular 1 R represents methyl, ethyl or propyl. In genera,1, the process is carried out in solvents which are inert towards the educts and products. Preferred solvents are alcohols such as methanol, ethanol, propanol, isopropanol, hydrocarbons such as toluene or xylene, halogenated hydrocarbons such as chloro-benzene, methylene chloride or carbon tetrachloride and ethers such as diethyl ether or dioxane. Mixtures of the solvents are of course also suitable. The alcohols are particularly preferred. 5 - 100 g, preferably 10 - 70 g of hydroxymalonic acid ester amide are preferred used per 100 ml of solvent. The reaction is carried out at temperatures of -20 °C to 100 °c, preferably at temperatures of 0 to 80 °C, and particularly preferably at temperatures of 20 to 60 °C. In general, ammonia is passed in the form of a gas into the solution of the starting compound of the formula (III), it being necessary to employ an at least stoichiometric amount of ammonia. The process is however preferably carried out. with an excess of ammonia. It may be necessary to conduct the process under pressure. It is however equally possible to mix a solution of the starting product with an optionally aqueous NH^-solution. The process may also be carried out in a two-phase system, in the customary manner. The reaction proceeds quickly and the working up step can be carried out almost immediately after the introduction of ammonia has ended. If the sparingly soluble end product does not already precipitate during the reaction or by cooling and can be filtered off by suction, the solution is concentrated by evaporation and the almost pure product of formula (I) is obtained - if appropriate, after being freed from traces of impurities by means of recrystallization. The compounds of formula (III) are new. They are obtained by hydrolysing hydroxy- or silyloxy-malonic ester nitriles of the general formula (IX). with inorganic acids according to the following equation: - 13 - COOR COOR R-c-qx ♦ h2o h2s04 .. r-c-oh CN IX c ^nh2 III Preferred-compounds of the formula (IX) are those in which 1 the radicals R and R have the preferred definition indicated above and X represents hydrogen. That said for the hydrolysis of the compounds of formula (II) (cf. process a)) applies for carrying out the hydrolysis. It is advantageous to carry out the working up step at temperatures below 10 °C in order to prevent the possible hydrolysis of the ester group in the acidic/aqueous medium. The compounds of the formula (IX) are new. They are obtained by reacting Of-ketocarboxylic acid esters of the general formula (X) COOR T, ' ' R-C = 0 wherein R and have the meaning indicated aboye, with HCN or compounds releasing HCN or with trimethylsilyl cyanide. Lia ft ai 3.11 RTF - 14 - 2/ This may be illustrated by the following 3 reaction equations COOR R-C=0 + HCN COOR R-C-OH I CN 1 COOR1 R-C=0 + (CH3)3SiCN COOR 1 R-C-OSi(CH-J I J 3 cn ■ COOR1 R-C=0 + ■ .CH3 CH3-C-OH CN COOR 1 R-C-OSi (CH-, ) I J J CN (ch3)2co Cyanohydrins are used as HCN-releasing substances, acetone-cyanohydrin or benzaldehyde-cyanohydrin may be mentioned as example. The reaction of X to give IX is carried out by the methods known in the literature in the presence of small amounts of alkaline catalysts, for example sodium cyanide, potassium cyanide or tertiary amines such as triethyl-amine or hydroxides or carbonates of alkali metals and alkaline earth metals. Whereas the addition of molar amounts of HCN or trimethylsilyl cyanide already proceeds slightly exothermi-cally at room, temperature and is complete after the addition of the reagents has ended, the reaction mixture must be heated slightly when using cyanohydrins in order to achieve complete conversion. Here it is also advisable to use more than 1; mol of cyanohydrin per mol of the oC -keto- 1*1 A-Q1 341 IRiy 20 1 - 15 - esters of the formula (X). 1.1 - 3 mols, and most particularly preferably 1.2 -2 mols of cyanohydrin are preferably used. The excess is, distilled off again when the reaction has ended. The reactions proceed in general without the presence of solvents, however, the use of solvents which are inert towards the products and educts, such as for example methanol, ethanol, isopropanol, toluene, chlorobenzene, methylene chloride, carbon tetrachloride and diethyl ether may indeed be appropriate in some cases. The reaction conditions for the reactions are very variable. Thus, for example, HCN and trimethylsilyl cyanide can also be used in higher than stoichiometric amounts, but a more than 10 % molar excess does not produce any further advantages. The reaction temperature can also be varied within wide limits, the process can be conducted in a temperature range of -50 to 30 °C, the reactions being conducted under pressure either in the gasphase or in the liquid phase when higher temperatures within the above range are used. However, here as well no significant advantage is achieved oyer the preferred process conditions first described. Compounds of the formula (X) are known or can be prepared according to known methods (S.Hiinig, R.Schaller, Angewandte Chemie (Applied Chemistry) 9_4 , 10 (1982) ). Process c is carried out by reacting hydroxy-malonic acid diesters of the formula (IV) with ammonia according to the following equation: T.(b B ?T ^41 2021 16 R-C-OH + 2 NH ' 2 COOR COOR 3 C0NH2 R-C-OH + 2 R1OH CONH 2 IV That said for the reaction of the compounds of formula (III) (cf. process b) applies for carrying out the amidation. Some of the compounds of the formula (IV) are known (Chimica e. Industria 1964 , _5, 509-517). Preferred compounds of the formula (IV) are those in i which the radicals R and R have the preferred meanings 2 indicated above. R has the same preferred meanings given 1 1 2 above for R - R and R can be identical or different. They are obtained either according to C1 by hydrolysing compounds of the formula (IX) COOR I (IX) R-c-ox I CN in which 1 R and R have the meaning indicated above with an alcohol of the formula R 2 OH in which 2 R has the meaning indicated above, - 17 - ■? 0? ..«is or according to C2 by hydrolysing compounds of the formula (II) CN R-C-OSi(CH-), (II) T 3 J CN Process C1 for the preparation of the compounds of formula (IV) is carried out by following the method of Pinner (A.Pinner, Die Imidoether und ihre Derivate (Imido-ethers and their derivatives) Berlin 1882). In this, in general, the compound containing nitrile groups is reacted either with hydrochloric acid or with sulphuric acid in an alcoholic solution (R2OH) and water. In the following both methods are described by way of example without thus limiting the universality of the processes. a.) Hydrolysis with hydrochloric acid: In this the compound of formula (IX) is treated, with a 2-20 times molar excess of absolute alcohol, of the formula R^OH, and with 1.1-20 mol of HCL-gas at -10 to 5 °C. Then the mixture is stirred for about 1 hour at below 30 °C and then a stoichiometric amount of H^O is added and the mixture is stirred for a further hour at 0-50 °C. The mixture is then filtered with suction and the filtrate is concentrated with evaporation. The residue is taken up in an inert solvent, eg. 18 02 1 0 the compound of the formula (IX) is introduced into an alcohol/Hydrochloric acid solution at between -20 and +10 °C. b.) Hydrolysis with sulphuricacid: 100 - 1000 g of sulphuric acid monohydrate, 2-25 2 mols of the alcohol of the formula R OH and 1 mol of water are used per mol of the compound of the formula (IX). Losses in yield are caused if there is marked deviation from stoichiometry in the introduction of the amount of water. If the starting products (alcohol and sulphuric acid) contain any water this must be taken into account with regard to the amount of water to be added. The starting solution is stirred at temperatures of 0 - 150 °C, preferably 20 - 100 °C, and particularly preferably 60 - 90 °C, for 1-20 hours. If appropriate, the reaction can be carried out under elevated pressure. Then the mixture is stirred into ice-water, extracted in the cold state with a customary organic solvent, such as, for example, methylene chloride, toluene, or ethyl acetate and the product is, if appropriate, purified by distillation . Process C2 for the preparation of the compounds of the formula (IV) is conducted according to the method of Pinner (cf. process CI), already described, it being necessary, however, when using hydrochloric acid, to conduct the process by the inverse method since it is not possible to initially introduce the compounds of formula (II) in the alcohol. -19 - "2 021 In this case the compounds of the formula (II) would be decomposed. In the following, an example of carrying out the reaction for the inverse Pinner esterification is described, without the general practicability of the reaction being limited thereby: 2 2 The absolute alcohol of the formula R OH (wherein R has the meaning given further above) is initially introduced in a 2-20 times molar excess - based, on the compound of the formula II - and is saturated with HCL-gas at -10 to +10 °C. For this purpose at least 2 mols of HC1 have to be taken up per mcl of the compound of the formula II. At -20 to +10 °C, preferably at -10 °C, the reaction component of the formula (II) is added dropwise and the mixture is then stirred, for about 1 hour at a maximum of 30 °C before the stoichiometric amount of water - based on the CN groups used -, optionally diluted in the alcohol, is added. An amount of water which is too far above or below the stoichiometric amount leads to losses in yield. After the mixture has been stirred for about a further 1 hour at 0 - 50 °C the working up is carried out as in process C1. If the process C2 is conducted in sulphuric acid, it is conducted as in the sulphuric acid variant described for process CI. In this, however, that process variant in which the alcohol, acid and water are initially introduced and then the compounds of the formula (II) are added is paricularly preferred. Distillation of compounds of formula (IV) should be omitted if their boiling points under distillation conditions considerably exceed 160 °c. Process d) is conducted by hydrolysing hydroxy- or trimethylsilyloxy-malonic acid amide nitriles of the general formula (V) with inorganic acids, according to the following equation: //^ C ^ NH R-C-O-X CN h2O H2S°4 ■> NH, R-C-OH ,U° V NH, That- said for the hydrolysis of the compound of the formula (II) (cf. process a)) applies for carrying out the hydrolysis. Compounds of the formula (V) are new. Compounds of the formula (V) in which R has the preferred definition given further above are preferred. They are obtained by reacting -keto acid amides of the general formula (XI) 202106' o NH- R-C=0 (XI) wherein R has the meaning indicated above with HCN or HCN-releasing agents or with trimethylsilyl cyanid. This may be illustrated by the following 3 reaction equations: ^0 ? v mu CONH- I NH_ , R-C=0 + HCN > R-C-OH CN 0 C ^ ° cf NH I NH I 2 R-C=0 + (CH3)3SiCN > R-C-O-Si(CH3)3 c?° CN I -MU CHT C0NHn ■ CH, I NH_ ,3 ,2 ,3 R-C=0 + CH-.-C-OH > R-C-OH + CH -C=0 J I | J CN CN 20210S For this cyanohydrins are used as HCN-releasing substances, acetocyanohydrin or benzaldehyde cyanohydrin may be mentioned as examples. The reaction of (XI) to give (V) proceeds according to methods known in the literature, in the presence of small amounts of alkaline catalysts, for example sodium cyanide, potassium cyanide or tertiary amines such as tri-ethylamine, as well as hydroxides and carbonates of alkali metals or alkaline earth metals. Whereas the addition of molar amounts of HCN or trimethylsilyl cyanide already takes place slightly exother-mically at room temperature and is complete after the addition of the reagents has ended, when using cyanohydrins the reaction mixture has to be heated for some time in order to achieve a complete conversion. For this it is also appropriate to use more than 1 mol of cyanohydrin per mol of -ketoamide of the formula (XI). Preferably 1,1 -3 mols, and particularly preferably 1,2 - 2 mols of cyanohydrin are used. The excess is distilled off again when the reaction is complete. The reactions take place in general without the presence of a solvent, however, the use of solvents which are inert towards the products and educts such as for example methanol, ethanol, isopropanol., toluene, chlorobenzene, methylene chloride, carbon tetrachloride and diethylether can indeed be appropriate in some cases. The reaction conditions for the reactions are very variable. Thus for example HCN and trimethylsilyl cyanide can also be used in higher than stoichiometric amounts, however a more than 10 % molar excess does not produce any further advantages. The reaction temperature can also be varied within wide limits, the process can be conduc- 202106 ted in a temperature range of -50 to 300 °C, the reaction being conducted under pressure either in the gas phase or in the liquid phase when higher temperatures within the above range are used. However, here as well no significant advantage is achieved over the preferred reaction parameters first described. Compounds of the formula (XI) are known or can be prepared according to known methods. (S.Hiinig, K.Schaller, Angewandte Chemie, 94_, 10 (1982).) . Process e is carried out by hydrolysing acyloxy-malo-nic acid diamides of the general formula (VI) in the presence of bases. The reaction can be illustrated by the following equation: conh 0 conh- ' " Raoa 1 * r-c 0-c-r base > r-c-oh conh2 conh2 vi Compounds of the formula (VI) in which R has the preferred meaning given above are preferably used. The reaction is conducted by mixing 1 mol of the compound of the formula (VI) in an inert diluent with an approximately equimolar amount of a base. Water, alcohols such as methanol, ethanol or tert.- 1 0 6 24 butanol, hydrocarbons such as toluene, carbon tetrachloride, or methylene chloride, or ether such as diethyl ether, or dioxane are used as diluents. Water, methanol or ethanol are preferred. The process can also be conducted, in a customary manner, in a two-phase system. Hydroxides, carbonates, bicarbonates or alcoholates of alkali metals and alkaline earth metals, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium methylate or sodium ethylate, as well as ammonia or amines, for example triethy1amine, pyridime or di-methylamine, are used as bases. The reaction is carried out at between -10 °C and +60 °C, preferably at between 0 and 30 °C. The working up step after the reaction has ended is carried out in the customary manner. Some of the compounds of the formula (VI) are known. They can be prepared according to known processes (J. Am. Chem. Soc., 71 page 34 (1949)). Process f is carried out by hydrolysing acyloxy-malo nic dinitriles of the formula (VII) with inorganic acids. The reaction can be illustrated by the following equation CN 0 CONH- .. I ^ I II R-C-O-C-R R-C-OH CN CONH 2 VII Compounds of the formula (VII) in which R. has the meaning given further above, 202106 - 25 - are preferred. Some.of the compounds of the formula (VII) are known. They can be prepared according to processes known per se (cf. Journal fur prakt. Chemie (Journal of Practical Chemistry) /2/ 39, page 260 (1889) , Chemistry and Industry 1970, page 1408). Process f is conducted by heating the compounds of the formula (VII) with concentrated sulphuric acid and 2 - 10 % of water, based on the amount of sulphuric acid used, for several hours at temperatures between 50 and 150 °C, preferably 6 0 - 100 °C. Process g is conducted by reacting acyloxy-malonic acid diesters of the formula (VIII) with ammonia according to the following reaction equation: c coor o iv nh- 0 1 II ' ^ ^ r-c 0-c-r + nh., > r-c-oh + r-c ^ „7tt i 3 ^ ^ nh- coor In c XNH2 viii II That said for the amidation of the hydroxy-malonic acid diesters of the formula (IV) according to process c applies for carrying out the reaction. It is merely the working up step which is made somewhat more difficult by the fact that the two amides forming during the amidation of compounds of the formula (VIII) are somewhat difficult to separate by crystallization because of their similar solubilities. - 26 - 202106 Compounds of the formula (VIII) are new. They are obtained by esterifying dimeric acyl cyanides of the formula (VII) according to the method of Pinner. The conditions are the same as already described for the esterification of the compounds of the formula (IX) (cf. processes Cl and C2). The only difference is that the distillation has to be omitted in the case of some of these compounds owing to their high boiling points. In this case, however, further processing can be carried out without difficulties with the crude product. 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 arachniaa which are encountered in agriculture, in forestry, in the protection of stored products 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 above-mentioned pests include: from the class of the 'Isopoda, for example Oniscus asellus, Armadillidium vulgare and Porcellio scaber; from the class of the Diplopoda, for example Blaniulus guttulatus; from the class of the Chilopoda, for example Geophilus carpophagus and Scutigera spec.; from the class of the Symphyla, for example Scuti-gerella immaculata; from the order of the Thysanura, for example Lepisma saccharina; from the order of the Collembola, for example Onychiurus armatus; , I 0 6 27 from the order of the Orthoptera, for example Elatta orientalis,' Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllo-talpa spp., Locusta migratoria migratcrioides, M-elanoplus dif.ferentialis and Schistocerca gregaria; from the order of the Dermaptera, for example Forficula auricularia; from the order of the Isoptera, for example Reticulitermes' spp.; from the order of the Anop.lura, for example Phylloxera vastatrix, Pemphigus spp. , Pediculus humanus corporis, Haematopinus" spp. and"Linognathus spp.; from the order of the Mallophaga, for example Trichodectes spp. and Damalinea spp.; from the order of the Thysanoptera, for example Hercinothrips femoralis and Thrips tabaci; from the order of the Heteroptera, for example Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.; from the order of the Homoptera, for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma ' lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, ■Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp.; from the order of the Lepidoptera, for example Pectinophora gossypiell-a, Bupalus. piniarius , Cheimatobia brumata., Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis 202H0 6 - 28 - chrysorrhoea, Lymantria'spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrctis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia .ku.ehn.ie 1.1a, Galleria'mellonella, Tineola bissel.liel.la, Tinea pellionella, Hof marinophi'la pseudospretella, Cac.oecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima and Tortrix viridana; from the order of the Coleoptera, for example Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorr-nynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra. zealandica; from the order of the Hymenoptera, for example Diprion spp., Hoplocampa spp., Lasiirs spp., Monomorium pharaonis and Vespa spp.; from the order of the Diptera, for example Aedes spp., Anopheles spp.,- Culex spp., Drosophila melano-.gaster, Musca spp., Fann-ia. spp. , Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastro-philus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, C.scinella frit, Phorbia spp.., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula - 29 - paludosa; from the order of the Siphonaptera, for example Xenopsylla cheopis' and- Ceratophyllus spp.; from the class of the Aracnnida, for example Scorpio maurus and Latrodectus mactans; from the order of the Acarina, for example Acarus siro, Argas spp., Ornithodoros spp., Dermanys.sus gallinae, Eriophyes ribis, Phyilocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Kyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.. The active compounds can be converted to the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances and in coating compositions for seed, and in formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils, as well as ULV cold mist and warm mist formulations. These formulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say 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. As liquid diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, 'such as xylene, toluene or- alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene fee—ftf—£H'" 34 1 - RTP 2 021iQ)% - 30 - chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone' or cyclo-hexanone, or strongly polar solvents, such as- dimethy1-.formamide and dimethylsulphoxide, as'well as water. By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. As solid carriers there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers for granules there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks. As emulsifying and/or foam-forming agents there may be used non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphon-ates as well as albumin hydrolysis products. Dispersing agents include, for example, lignin sulphite waste liquors and methyIcellulose. Adhesives such as carboxymethylcellulose 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. lmi 311 —rp 21 06 - 31 - It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, ana organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc. The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight. The active compounds according to the invention can be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with other active compounds, such as insecticides, baits, sterilising agents, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. The insecticides include, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenyl^reas and substances produced by microorganisms . The active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with synergistic agents. Synergistic agents are compounds which increase the action of the active compounds, without it being necessary for the synergistic agent added to be active itself. The active compound content of the use forms prepared from the commercially available formulations can vary within wide limits. The active compound concentration of the use forms can be from 0.0000001 to 100$ by weight of active compound, preferably between 0.0001 and 1% by weight. The compounds are employed in a customary manner appropriate., for the use forms. When used against pests harmful to health and pests ae.ii.ii!Ku#4 -i' nroa 32 of stored products, the active compounds are distinguished by an excellent residual action on wood and clay as well as a good stability' to alkali and limed substrates. of combating pests (especially insects or acarids) which comprises applying to the pests, 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 pre.sent invention in admixture with a diluent or'carrier. The present invention also provides a method of . freeing or protecting domesticated animals from parasites which comprises applying to said animals a compound according to the present invention, in admixture with a diluent or carrier. The present invention further provides crops protected from damage by pests by being grown in 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. The present invention further provides domesticated animals whenever freed or protected from parasites by the ' application to said animals of a compound according to the present invention, in admixture with a diluent or carrier. Preparative Examples: Example la The present invention also provides a method CONH 2 C-OH CI 202106 - 33 - 600 g of sulphuric acid (96$ strength) were initially introduced into a 1 litre four-necked flask with a reflux condenser, a stirrer,, a thermometer and a dropping funnel, and the flask was cooled externally. 299 g of 3,4-dichlorophenyl-trimethylsilyloxy-malonic acid dinitrile (1 mol) were then added dropwxse to the sulphuric acid in the course of 30 minutes, and the internal temperature was not allowed to exceed 50°C. After the exothermic reaction had ended, the mixture was stirred for a further. 15 minutes. The reaction mixture was poured into ice-water the reaction product was precipitated, and was filtered off under suction, washed neutral and dried, and the residue was recrystallis.ed from ethanol. Yield: 242 g of 3,4-dichloropheny1-hydroxy-malonic acid diamide (= 92% of theory) melting point: 175 to 177°C Example lb As described in Example 1, 200 g of concentrated hydrochloric acid were initially introduced into the reactor, and 74.75 g of 3,4-dichlorophenyltrimethy1-silyloxy-malonic acid dinitrile were added dropwise. The reaction mixture was warmed to 4o°C, an exothermic reaction occurring. The internal temperature was kept at 40 to 50°C by cooling. The mixture went into solution-, and some of it was precipitated towards the end of the reaction. The mixture was introduced onto ice-water, the precipitated reaction.,, product was filtered off under suction and rinsed with ice-water and the residue was recrystallised from ethanol. Yield: 57.8 g of 3,4-dichloropheny1-hydroxy-malonic acid diamide (= 88% of theory) melting:point: 176 to 177°C Example 2 ?H3XC0NH~ C1CH9-OC-OH 1 \ CH3 C0NH2 20210 6 - 34 - As described in Example 1, 200 g of sulphuric acid (96$ strength) were initially introduced, and a mixture of 244 g of chloro-tert.-buty1-trimethy1-silyloxy-malonic acid dinitrile (1 mol), dissolved in 150 ml of methylene chloride at 0 to 5°C, was added dropwise. Cooling was then discontinued, and the internal temperature increased to- 30°C.- After'30 minutes, the mixture was warmed for a short time until the methylene chloride refluxed. The methylene chloride was removed by distillation, and the residue was stirred into 2 litres of ice-water. The precipitated product was filtered off under suction, washed neutral with, water, dried, and recry stallised from ethanol. Yield: l8l g of chloro-tert.-buty 1-hy-droxy-malonic acid diamide (= 87$ of theory) melting point: 183 to l85°C Example 5 CONH2 01 \Q C0NH2 CI As described in Example 1, 200 g of sulphuric acid (96$ strength) were initially introduced, and 98 g of 3,5-dichloropheny1-trimethy1-silyloxy-malonic acid dinitrile (0.33 mol) were added dropwise at 40 to 50°C, while cooling. ■ The mixture was then stirred for a further hour at 60°C. The reaction mixture was introduced onto water at 50 to 60°C, and was filtered off under suction, washed neutral, and recrystallised from acetonitrile. Yield: 75 g of 335-dichloropheny1-hydroxy-malonic acid ■ diamide (= 87$ of theory) melting point: 181 to l83°C 202106 - 35 - Example 4 conh. F^CO -oh conh, As described in Example 1, 106.5 g of 4—trifluoro- methoxypheny1-trimethylsilyloxy-malonic acid dinitrile (0.34 mol) were added dropwise to 400 g of sulphuric acid (92% strength). The mixture was then stirred for 30 o minutes at 50 . C, and was then introduced onto ice. The greasy react.i.on product "was taken up in methylene chloride, the solution was dried over sodium sulphate and concentrated, and the residue was recrystallised from toluene. Yield: 79 g of 4-trifluoromethoxypheny1-hydroxy-malonic acid diamide (= 85% of theory) melting point: 119 to 121°C The following substituted hydroxy-malonic acid diamides were synthesised as described in Example 1 to 4: Example n.o... .". C omp ound Melting point .oh for' \ (c0nh2)2 159 -161 c (from ethanol) CI \ OH (conh2)2 135 - 137 C (from chlorobenzene ) / \ oh (conh2)2 138 - 139 c (from xylene' - 36 - Example No.. Compound 202 1 0 Melting point oh 'CI . \conh2)2 ci 165 - l67°c (from ethanol) CI OH \ CI (c0nh2)2 199 - 201 C (from ethanol) .oh 10 11 12 CI o2n \ CI / (c0nh2)2 oh \ (c0nh2)2 oh cf- \ (c0nh2)2 149 - 151°C (from o-dichloro-benzene) 166 - l67°C (from ethanol) 185 - 187°c' (from ethanol) oh 13 H •(c0nh2)2 245 - 247°C 14 ? 3 oh 1 / f-ch -c-c | (conh-)~ ch3 * ^ 215 - 217 c (from ethanol) fciji 'A "3111 nir - 37 - 202106 Example N.o. Compound Melting point 15 fh2f oh ch^-c - c. ch2f (c0nh2)2 204 - 206 C (from ethanol) 16 ci3c-c> oh' (conh2)2 264°c (decomposition) 17 c*' CHjCf oh ~(conh2)2 109 - 111 c (from chlorobenzene) 18 oh c-(com2 )2 212 - 215 c (from ethanol) 19 conh- conh- 207 - 209 °c (from ethanol) 20 ch3on=ch/' oh conh- X 134 - 135°C (from ethanol) conh- - 38 - 2°2 Example No. Compound Melting point 21 o2N. OH ToT CONH. s. CONH- CI 1 236 - 23 9 °C (from butanol) 22 OH CONH CONH 231 - 233 °C 23 -N ji ?H CONH., Cl" C 2 \ CONH. 200 - 203 °C (from isopropanol) 24 OH , ^ CONH, HOOC-CH=CH-C \ CONH- 160 - 162 °C (from acetonitrile) 25 ?HX CONH-CH -C CONH2 105 - 107 °C (from ethanol) Lu,-A-L 3 4 >1' - 39 - 2021 0 Example No. Compound Melting point 26 oh -ch0-c 2 v conh, conh. 173 - 1 75 °C (from ethanol) 27 oh ^ conh2 x conh- ch_, ci 178 - 179 °C In the following further examples for the preparation of the compounds of formula (I) and for the preparation of their starting products are given: I) Preparation of the compounds of formula (IX) and the further reaction thereof to give compounds of the formula (III) and the further reaction thereof to give compounds of the formula (I) according to process b: Example Ia^ OSi(CH3)3 c i ~\(~) Vc -cooch3 / cn CI 6 2.8 g of trimethylsilyl cyanide are added dropwise to 40 - 202 1 06' 147.8 g of 3,4-dichlorophenylglyoxylic acid methyl ester and 0.5 ml of triethylamine at not more than 55 °C while cooling with ice. 210 g of 3,4-dichlorophenyltrimethyl-silyloxy-malonic acid methyl ester nitrile were obtained. IR, NMR and MS confirm the presence of this substance. Example la^ 210 g of 3, 4-dichlorophenyl-trimethylsilyloxy-malonic acid ethyl ester nitrile were added dropwise to 4 00 g of sulphuric acid (96 % strength) at not more than 4 0 °C. The mixture was stirred for another hour at room temperature and then stirred into ice-water. The precipitate, which was first of all greasy and then crystallized, was taken up in ethyl acetate, washed, dried and the solution was concentrated. 130 g of crude product were obtained. By recrystallization from isopropanol 3,4-dichloro-phenyl-hydroxy-malonic acid methyl ester amide with a melting point of 132 - 133 °C was obtained. Example Ia^ 27.8 g of 3,4-dichlorophenyl-hydroxy-malonic acid methyl oh - 41 - 207 % ester amide were dissolved in 150 ml of methanol and ammonia was passed in. The reaction temperature increased to 4 0 °C at the same time. The mixture was concentrated and recrystallized from isopropanol. 2 2 g of 3,4-dichloropheny1-hydroxy-malonic acid diamide remained. Example Ib^ OSi(CH-). 1 * (CH ) C-C-C N°CH3 Following the same procedure as in Example Ia^ 19 7.8 g of tert.-butyl-trimethylsilyloxy-malonic acid methyl ester nitrile were prepared from 116.8 g of o( -keto-3 ,3-dimethyl-butyric acid methyl ester, 0.5 ml of triethylamine and 81 g of trimethylsilyl cyanide. Example Ib2 (CH-) 0-C'C ^0 oh I 3 ' 3_<r " ^och C0NH2 3 Following the same procedure as in Example Ia2 55 g of tert.-butylhydroxy-malonic acid methyl ester amide are prepared from 187 g of tert.-butyl-trimethylsilyloxy-malonic acid methyl ester nitrile by hydrolysis in 500 g of H2S04. Melting point 102 - 103 °C (from wash benzene) ll. 'a 21 311 42 Example IC| OH CN OCH 3 13.5 g of hydrocyanic acid were added dropwise to 82 g of phenylglyoxylic acid methyl ester and 1 ml of triethylamine at 25 - 30 °C. Based on the spectroscopic data phenyl-hydroxy-malonic acid methyl ester nitrile had formed . Example Ic2 9 5 g of phenyl hydroxy-malonic acid methyl ester nitrile were added dropwise to 500 g ^SO^ at 30 °C. After the mixture was stirred for 30 minutes at room temperature it was stirred into ice water, taken up in methylene chloride, washed and concentrated. The residue -was recrystallized from toluene. 72 g of phenyl-hydroxy-malanic acid methyl ester amide having a melting point of °C were obtained. II. Preparation of compounds of the formula (IV) and the further reaction thereof to'give compounds of the formula (I) according to process c: - 43 - 205106 Example Ila \ °H O )-c-cooch3 cooch3 100 ml of absolute methanol were saturated with about 80 g of hydrochloric acid at 10 °c. Then at between -10 and -5 °c 131-5 g of phenyl-trimethylsilyloxy-malonic acid methyl nitrile were added dropwise. The homogeneous solution was then stirred at 10 - 15 °c for 1 hour, during which it became two-phased. Then 9 g of water, diluted with 50 ml of methanol, were added dropwise and the mixture was stirred for 2 hours at 20 °c. The misture was concentrated, taken up in methylene chloride, washed with water, dried, concentrated and distilled . 84 g of phenyl-hydroxy-malonic acid bis methylester having a b.p.Q ^ = 126 - 28 °c. Example Ilb^ 3 20 ml of absolute methanol were saturated with about 210 g of hydrochloric acid at 10 °c. 300 g of 3,4-dichlo-rophenyl-trimethylsilyloxy-malonic acid dinitrile were added dropwise at -10 °C, the mixture was stirred for 1 hour at 10 - 15 °c and 36 g of water, diluted with 50 ml of methanol, were added at 15 °c. Then the mixture 3 CI - 44 - 202106 was stirred for 1 hour at not more than 30 °C, filtered off from the precipitated crystals and the filtrate was concentrated. The concentrate was taken up in methylene chloride, washed with ice water, dried, concentrated and the residue was distilled. 165 g of 3,4-dichlorophenyl-hydroxy-malonic acid dimethyl ester were obtained. B.p.0 3 =154 - 58 °C. Example Hb2 / \ Cl-(0 / C-C0NH2 cl>-y C0NH2 30 g of 2,4-dichlorophenyl hydroxy-malonic acid dimethyl ester were dissolved in 80 ml of methanol and NH^ was passed in. During this introduction the solution warmed to 50 °C. After concentrating the solution 26 g of 3,4-dichlorophenyl-hydroxy-malonic acid diamide having a melting point of 175 - 77 °C remained. The pesticidal activity of the compounds of this invention is illustrated by the following.biotest Examples. In these Examples, the compounds according to the present invention are each identified by the number (given in brackets) of the corresponding preparative Example. Example A Phaedon larvae test Solvent: 3 parts by weight of dimethy Iformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amount of solvent and the stated amount of emulsifier, and - 45 - 202106 the concentrate was diluted with water to the desired concentration . Cabbage leaves (Brassica ols.racea) were treated by being dipped into the preparation of the active compound of the desired concentration and were infested with mustard beetle larvae (Phaedon cochleariae), as long as the leaves were still wet. After the specified periods of time, the destruction in % w-as determined. 100% meant that all the be.et.le larvae had been killed; 0% meant that none of the beetle larvae had been killed. In this test, for example, the following compounds showed a superior activity compared to the prior art: (1) , (3) (5) , (6) and (7) . Example B Tetranychus test (resistant) Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of 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. Bean plants (Phaseolus vulgaris) which were heavily infested with the common spider mite or two-spotted spider mite (Tetranychus urticae) in all stages of development were treated by being dipped into the preparation of the active compound of the desired concentration. After the specified periods of time, the destruction in % was determined. 100% meant that all the spider mites had been killed; 0?o meant that none of the spider mites had been killed. In this test, for example, the following compounds showed a superior activity compared to the prior art: (6), (1) , (3) , (7) and (12) . </div>

Claims

<div class="application article clearfix printTableText" id="claims"> - 46 - 2021 G-6 Example C Critical concentration test / soil insects Test insect: Phaedon cochleariae larvae (in the soil) Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 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. The concentration of the active compound in the preparation was of practically no importance, only the amount by weight of active compound per unit volume, of soil, which was given in ppm (= mg/1) being decisive. The soil was filled into pots and the pots were left to stand at room temperature. After 24 hours, the test animals were introduced into the treated soil, and after a further 2 to 7 days the degree of effectiveness of the active compound was determined in % by counting the dead and live test insects. The degree of effectiveness was 100?^ if all the test insects had been killed and was 0% if just as many test insects were still alive as in the case of the untreated control. In this test, for example, the following compounds showed a superior action compared to the prior art: (7), (1) , (3), (6) and (8) . I5&-'A 2-"IVrff - 47 - WHAT WE CLAIM IS: 1. A pesticidal composition characterised in that it contains as active ingredient a compound which is a substituted hydroxy-malonic acid diamide of the general formula conh I R-C-OH (I) I conh2 in which unsubstituted R represents/alkyl with at least 2 carbon atoms, substituted alkyl, optionally substituted alkenyl, optionally substituted cycloalkyl; optionally substituted aryl or optionally substituted heteroaryl radical in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface active agent. 2. A composition according to claim 1 wherein in compound (I) R represents C2_^-alkyl, C2_7-alkenyl or C3_g-cycloalkyl, or represents C^_4~alkyl, C2_^-alkenyl or C^ ^-cycloalkyl, which are substituted by one or more identical or different radicals selected from the following: halogen, C^_^-alkoxy, carboxyl, carbalkoxy, phenyl, phenoxy or thiophenyl, it being possible for the phenyl rings to be substituted by halogen or alkyl; 48 202106 R furthermore represents phenyl which is optionally substituted by one or more identical or different radicals selected from the following: halogen, nitro, amino, OH, CN, C^_^-alkyl, C^_^-halo-genoalkyl, C^_^-alkoxy, C^_^-halogenoalkoxy, methylenedioxy, ethylenedioxy, difluoromethylenedioxy or halogen-substituted ethylenedioxy, C^_^-alkylthio, C^_^-halogenoalkylthio, C2_g~alkoxyalkyl, C2-Q~ halogenoalkoxyalkyl, C^^-alkylsulphonyl, halogenoalkylsulphonyl, carboxyl, carbalkoxy, the radical C1_4~alkoxy-N=CH-, also phenyl, phenyloxy or thiophenyl which may optionally be substituted by halogen or C1_4~alkyl, carboxylalkoxy with 2-4 C-atoms, R furthermore represents heteroaryl, which may optionally be substituted by one or more identical or different substituents, these being halogen, C^_4~alkyl, or C^ ^-alkoxy. A composition according to claim 1 wherein in compound (I) R represents a pyridinyl, pyrimidinyl, triazinyl, isoxazolyl, oxadiazolyl, imidazolyl, triazolyl, furanyl or thiophenyl radical. - 49 - 202106 4. A composition according to claim 1 wherein in compound (I) R represents C2_4~alkyl and halogen-, phenyl- or phenoxy-substituted C^_^-alkyl or C^_g-cycloalkyl, optionally carboxyl-substituted C2_4~alkenyl and also phenyl which is optionally substituted by halogen, halogenoalkoxy, C^_^-halogenoalkyl, NH2, CH-jO-N^H-, or nitro. 5. A composition according to claim 1 wherein in compound (I) R represents a phenyl radical which is optionally monosubstituted or polysubstituted by chlorine or fluorine. 6. A composition according to claim 1 substantially as hereinbefore described or exemplified. 7. A composition according to any one of the preceding claims, characterised'in that it contains from 0.1 to 95% of the active % compound, by weight. 8. A method of combating pests, characterised in that there is applied to the pests, or to a habitat thereof, a composition according to any of claims 1 to 6 with the proviso that the method does not include a method of treatment of the human body. 9. A method of freeing or protecting domesticated animals from parasites, characterised in that there is applied to said animals a composition according to any one of claims 1 to 6 in admixture with a diluent or carrier. 10. A method according to claim 9, characterised in that a composition is used containing from 0.0000001 of the ' active compound, by weight. r Cl_4~alkyl, Ci_4~alkoxy, C^_4~ Xcn/fS 202106 - 50 - 11. A method according to claim 10, characterised in that a composition is used containing from 0.0001 to 1% of the active compound, by weight. 12. A method according to any of claims 8 to 11, characterised in that the pests or parasites are insects or acarids. BAYER AKTIENGESELLSCHAFT By Their Attorneys HENRY HUGHES LIMITED Per: (I </div>