GB2193212A - Pesticidal aromatic imine compounds - Google Patents

Description

SPECIFICATION Pesticidal compositions and process for the preparation of the active ingredient This invention relates to new compounds of the general Formula /I/

a process for the preparation thereof and pesticidal compositions comprising the same. According to an aspect of the present invention there are provided new compounds of the general Formula /I/ wherein X, stands for hydrogen or nitro;

alkyl), or C2-6 hydroxyalkyl, or C2-6 mercaptoalkyl, or C2-6 aminoalkyl, or C3-6 alkenyl, or C3-1 alkynyl, or phenyl, or substituted phenyl of the general Formula

wherein X3 stands for identical or different C1-4 alkyl, trifluoromethyl, hydroxy, mercapto, nitro, amino or halogen, preferably chlorine and n is an integer 1, 2 or 3; or aralkyl, C1-6 alkyl-phenyl or a group of the general Formula

wherein X, is as stated abpve and m is an integer 2, 3, 4, 5 or 6/. According to a further aspect of the present invention there there are provided pesticidal compositions comprising as active ingredient at least one compound of the general Formula

/wherein X, stands for hydrogen or nitro; X2 stands for: C1-18 alkyl (with the proviso that if X, represents nitro, X2 cannot stand for C1-6 alkyl), or C2-6 hydroxyalkyl, or C2-6 mercaptoalkyl, or C2-6 aminoalkyl, or C1-6 alkenyl; or C1-6 alkynyl, or phenyl, or substituted phenyl of the general Formula

wherein X3 stands for identical or different C1-4 alkyl, trifluoromethyl,hydroxy, mercapto, nitro, amino or halogen, preferably chlorine and n is an integer 1, 2 or 3; or aralkyl, C1-6 alkyl-phenyl or a group of the general Formula

wherein X, is as stated above and m is an integer 2, 3, 4, 5 or 6/. The new compounds of the general Formula /I/ are azomethine derivatives. The condensation of primary amines and carbonyl compounds was studied by H. Schiff for the first time [Ann. Chem. 131, 118 /1864/]. The said condensation products are generally called "Schiff-bases". A general review on the said condensation reaction is disclosed by M. M. Sprung [Chem. Rev. 26, 297 /1940/] and R. W. Layer [Chem. Rev. 63, 489 /1963/J. The compounds of the general Formula

used for the preparation of the new compounds of the general Formula /I/ are known /US-PS 4.306.900; DE-OS 30 17 795/. The amine starting materials of the general Formula H2N-X2 /III/ are known as well. From the substituted 5-phenoxy-2-nitro-benzaldehydes as starting material several new compound groups have already been prepared e.g. substituted phenoxy benzaldehyde acetales /EP-0 064 658/ and diacetates /DE-OS 30 44 810/, substituted phenoxy cinnamic acid derivatives /EP 0 053 321/, substituted phenoxy benzaldehyde oximes, -carboximes /DE-O$ 30 17 795/. In European Patent application No. 0 034 012 compounds having herbicidal effect are disclosed which may also be 5-[/2-chloro- or -2,6-dichloro-4-trifluoromethyl/-phenoxy]-2-nitro-benzaldehyde-C,_6 alkyl-imines. From these compounds, however, only the 5-[/2-chloro-4-trifluoro-

to the herbicidal effect thereof. According to the present invention it has been found that the new compounds of the general Formula /I/ obtained by the condensation of 3-[/2-chloro-4-trifluoromethyl/-phenoxy]-benzaldehyde or 5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitro-benzaldehyde /compounds of the general Formula /I/ and a primary amine of the general Formula /III/ exhibit an excellent pesticidal effect. According to a further aspect of the present invention there is provided a process for the preparation of new compounds of the general Formula /I/ which comprises reacting a substituted benzaldehyde of the general

/wherein X, has the same meaning as stated above/ or an acetale or acetate thereof with a primary amine of the generat Formula H2N-X2 /III/ /wherein X2 is as stated above/, if desired in the presence of an inert solvent and/or a catalyst, at a temperature between 0[deg]C and the boiling point of the reaction mixture and thereafter isolating the new compound of the general Formula /I/ thus obtained from the reaction mixture by known methods. The compounds of the general Formula /I/ may be prepared by methods known per se, thus e.g. as follows: a/ An acetale or acetate of a phenoxy benzaldehyde of the general Formula /II/ is reacted with a primary amine of the general Formula /III/ in the presence of an inert solvent at the boiling point of the reaction mixture. The reaction may also be carried out in the absence of a solvent by distilling off the alkanol or carboxylic acid formed. b/ According to a further form of realisation of the process of the present invention a phenoxy benzaldehyde of the general Formula /II/ is reacted with a primary amine of the general Formula /III/ in the presence or absence of an inert solvent, preferably in the presence of a catalyst, at a temperature between 0[deg]C and the boiling point of the reaction mixture. As reaction medium any suitable inert solvent may be used /e.g. methanol, ethanol, propanol, benzene, toluene, dichloro methane, chloroform, carbon tetrachloride etc/. The water formed in the reaction may be removed optionally by adding a solvent which forms an azeotropic mixture with water. As catalyst a mineral acid or Lewis-acid may be used /e.g. sulfuric acid, hydrochloric acid, boron trifluoride etherate, zinc chloride, phosphorous oxychloride etc/, but the reaction may successfully be carried out without catalyst as well. The aldehyde and the primary amine may be used in an equimolar amount but one may preferably proceed by applying one of the components /particularly the primary amine/ in an excess. The new compounds of the general Formula /I/ may be isolated from the reaction mixture by known methods /e.g. cooling the reaction mixture, filtering the product, etc/. The product obtained may be purified if necessary, by recrystallization from a suitable solvent /e.g. methanol, ethanol, isopropanol, petrolether etc/. Undesired plants /weeds/ and fungal pests of cultivated plants cause substantial damages in agriculture by decreasing the crops. Methods of increasing efficiency comprise the combating of weeds, decreasing the growth thereof and combating fungal pests. One group of the compounds of the general Formula /I/ possess herbicidal effect and an other group thereof exhibit fungicidal activity. Certain representatives of the compounds of the general Formula /I/ exert both herbicidal and fungicidal effect /pesticidal effect/. The compounds of the general Formula /I/ are not phytotoxical on cultivating plants /e.g. maize, sunflower, pea etc/. The absence of phytotoxicity /selectivity/ is of particular importance because in the case of compounds having pesticidal /herbicidal and fungicidal effect/ fungicides which possess also herbicidal activity are generally toxical towards cultivated plants. The new compounds of the general Formula /I/ are devoid of the above drawbacks. The following compounds of the general Formula /I/ exert particularly high herbicidal effect:

The following compounds of the general Formula /I/ exhibit particularly strong herbicidal activity:

The following compounds of the general Formula /I/ are particularly active fungicides: bis-{5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitrobenzaldehyde}-ethylene-diimine;

{5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitrobenzylidene}-3,4-dichloro-aniline. The following compounds of the general Formula /I/ are particularly excellent fungicides: {3-[/2-chloro-4-trifluoromethyl/-phenoxy]-benzylidene}-3-trifluoromethyl-aniline; {3-[/2-chloro-4-trifluoromethyl/-phenoxy]-benzylidene}-2-chloro-5-trifluoromethyl-aniline;

{5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitrobenzylidene}-4-hydroxy-aniline; {5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitrobenzylidene}-3,4-dichloro-aniline. The following compounds of the general Formula /I/ exert both herbicidal and fungicidal /pesticidal/ effect: {5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitrobenzylidene}-aniline; {5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitrobenzylidene}-2-chloro-5-trifluoromethyl-aniline;

The herbicidal compositions of the present invention can be applied by pre-sowing, preemergent and post-emergent treatment for combating weeds. The dose of the active ingredient may vary within a wide range depending on various factors /e.g. extent of weed coverage, type and species of the cultivated plants, type of the soil, meteorological conditions etc./ One must care not to exceed the phytotoxical threshold towards cultivated plants surpassed. It has been found that the dose of the active ingredient amounts to 0.1-10.0 kg.ha- , preferably to 0.2-2.0 kg.ha- . According to a preferred embodiment of the present invention the active ingredients of the general Formula /I/ are formulated in the form of a spray and are applied at a rate of 100-1200

For the combating of pests of plants and for the inhibition of fungal infection the most widespreadly used plant protecting methods are seed-dressing, spraying and dusting. The herbicidal and/or fungicidal compositions of the present invention-e.g. seed dressing agents, sprays, dusting powders etc.-are to be applied onto the host plant or to the environment thereof where the infection is developed or from where the pest spreads. Seed-dressing is used in order to obtain infection-free seeds and to combat fungi which infect the soil. Fungi which endanger the foliage and crops /fruit/ of the plants are combated by spraying or dusting the plants. The active ingredients of the general Formula /I/ are used for seed-dressing at a dose of

The pesticidal compositions of the present invention may be finished in forms generally used for plant protection, e.g. as wettable powders /WP/, suspension concentrates /SC/, watermiscible solution without water /S/, dusting powders /DP/, oily suspension concentrates /FO/, foils, preferably seed foils. The active ingredients may be finished in an ULV form as well. In the said compositions the active ingredient is admixed with solid or liquid inert carriers, solvents and optionally with other auxiliary agents. The said auxiliary agents may be e.g. wetting, suspending, dispersing and emulsifying agents, anti-coagulaing and anti-caking agents, adhesives, spreaders, agents facilitating penetration, agents maintaining or increasing biological activity, antifoam agents, etc. The suitable solid carriers and diluents may be e.g. inactive minerals such as China-clay, caoline, porcellaine earth, attapulgite, montmorillonite, mica slates, pyrophilite, bentonite, diatomaceous earth or highly dispersed synthetic silicic acids, calcium carbonate, calcinated magnesium oxide, dolomite, gypsum, tricalcium phosphate, Fuller's earth etc; ground stems of tobacco leaves, wood meal etc. As suitable liquid carriers and diluents e.g. the following solvents may be applied: water, mixtures of organic solvents or organic solvents and water, such as methanol, ethanol, npropanol, isopropanol, diacetone alcohol, benzyl alcohol, esters of the said alcohols e.g. methyl cellosolve, ketones e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone etc, esters e.g. ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, isopropyl miristate, dioctyl phthalate, dihexyl phthalate etc; aromatic, aliphatic, alicyclic hydrocarbons e.g. paraffin hydrocarbons, cyclohexane, cerosine, gasoline, benzene, toluene, xylene, tetraline, decaline; mixtures of alkyl benzenes; chlorinated hydrocarbons e.g. trichloro ethane, dichloro methane, perchloro ethylene, dichloro propane, chloro benzene etc; lactames e.g.N-methylpyrrolidone, N-cyclohexyl-pyrrolidone; acid amides e.g. dimethyl formamide etc; vegetable and animal oils e.g. sunflower oil, flax oil, rape oil, oliva oil, soya oil, castor oil, whale oil etc. Suitable wetting, dispersing, emulsifying, anti-adhesive, anti-aggregating and anti-caking agents may be of ionic or non-ionic character.As ionic surfactants e.g. the following compounds may be used: salts of saturated and unsaturated carboxylic acids; sulfonates of aliphatic, aromatic and aliphatic-aromatic hydrocarbons: sulphates of alkyl, aryl and aralkyl alcohols; sulfonates of aralkyl, aryl, and aralkyl carboxylic acids, esters and ethers; sulfonates of condensation products of phenol, cresol and naphthalene: sulfatated vegetable and animal oils; alkyl, aryl and aralkyl phosphate esters and salts of the said compounds formed with alkali or alkalkine earth metals or organic bases e.g. various amines and alkanol amines.Thus preferably sodium lauryl sulfate, sodium-2-ethyl-hexyl-sulfate; the sodium ethanol amine, diethanol amine, triethanol amine or isopropyl amine salt of dodecyl benzene sulfonic acid; sodium mono- or diisopropyl naphthalene sulfonate; the sodium or calcium salt of petroleum sulfonic acid; potash soaps; potassium, sodium, calcium, aluminium or magnesium stearate etc. can be used. The phosphate esters may be ethers of phosphatated alkyl phenols or fatty alcohols formed with polyglycol and forms thereof partially or completely neutralized with the above cations or organic bases. As further anionic surfactants disodium-N-octadecyl-sulfosuccinate, sodium-N-oleyl-N-methyl-tauride and various lignine sulfonates can be used. From the group of suitable non-ionic wetting, dispersing and emulsifying etc. agents the following compounds can be mentioned: ethers of ethylene oxide formed with C10-20 alkanols, such as stearyl-poly/oxyethylene/, oleyl-poly/oxy-ethylene/; ethers formed with alkyl phenols e.g. poly/glycol ethers/ formed with tert. butyl, octyl or nonyl phenol; esters formed with various organic acids e.g. esters of stearic acid or miristic acid formed with polyethylene glycol or polyethylene glycol oleate etc; block polymers of ethylene oxide and propylene oxide; partial esters of fatty and oleic acids formed with hexitol anhydrides e.g. partial esters of sorbitol formed with oleic acid or stearic acid; condensation products of such compounds formed with ethylene oxide; tertiary glycols e.g. 3,6-dimethyl-4-octin-3,6-diol or 4,7-dimethyl-5-decine-4,7diol;polyethylene glycol thioethers e.g. ether of dodecyl mercaptane formed with polyethylene glycol etc. As adhesion increasing agent e.g. alkaline earth metal, soaps, salts of sulfosuccinic esters, natural or artifical water-soluble macromolecules e.g. caseine, startch, Arabian resin, cellulose ethers, methyl cellulose, hydroxy cellulose, polyvinyl pyrrolidone, polyvinyl alcohol may be used. As antifoam agent e.g. lower poly/oxy-ethylene/, poly/oxy propylene/, block polymers /the number of octyl, nonyl, phenyl-poly/oxy-ethylene/ethylene oxide units is 5/ and longer chained alcohols /e.g. octyl alcohol/ and special silicone oils can be used. By using suitable additives the formulated compositions of the present invention can be rendered colloidal chemically compatible with various fertilizer compositions. The compositions of the present invention can also comprise known pesticides and/or nutritive materials. Wettable sprayable powders /WP/ can be prepared by admixing the active ingredient/s/, auxiliary agent/s/, surfactant/s/ with the carrier/s/, grinding the mixture thus obtained and finally homogenizing the same. Liquid surfactants can be applied onto the solid organic or inorganic diluent/s/ or onto the powder mixture comprising a solid active ingredient e.g. by spraying. The latter procedure can be applied for liquid active ingredients as well. In the case of liquid surfactants one may also proceed by suspending the previously ground solid components in an organic solvent comprising a liquid surfactant. The suspension thus obtained is dried e.g. by pulverizing. Thus the surfactant is applied onto the surface of the solid active ingredient and solid diluent. Self-emulsifiable concentrates /EC/ suitable for the formation of an emulsion in aqueous dispersed medium can be prepared by dissolving the active ingredient/s/ and one or more of the above surfactants in a water-nonmiscible solvents. The emulsifiable concentrate thus obtained formes with water spontaneously or under slight mechanical effect a sprayable emulsion which remains unchanged even after longer storage. A water miscible solution concentrate /SL/ can be prepared by preparing a solution of the active ingredient and suitable water-soluble auxiliary agents in water and/or a water miscible solvent. On .diluting with water a spray having the desired concentration can be obtained. By appropriate selection of a suitable emulsifier the aqueous solution concentrate of the active ingredient can be dispersed in a water non-miscible liquid too to yield a so-called inverse emulsion. Thus by appropriate selection of the solvent and surfactants compositions can be obtained which-on admixing with water or a water non-miscible liquid-yield an even molecularly dispersed phase, the latter dispersed phase remaining unchanged even after storage for a longer period of time. Suspension concentrates /SC/ can be prepared by dissolving the wetting and dispersing agents in a mixture of water /preferably ion-exchanged water/ and an antifoam component /preferably ethylene glycol or glycerol/, if necessary under heating. To the solution thus obtained the solid /powdered or crystalline/ active ingredient/s/ and-if necessary-the anti-caking component /e.g. Aerosil 200/ are added under constant stirring. The slurry thus obtained is ground in a suitable wet grinding apparatus /e.g. closed Dyno mill/ to the desired particle size /i.e. to a maximal particle diameter of 5 /Microm/. After stirring if necessary an antifoam or thickening agent /e.g. Kelzan S/ is added during homogenization. One may also proceed by changing the order of succession of the addition of the components or adding further components too /e.g. a dyestuff/.In addition to a solid active ingredient as combination partner liquid water non-miscible active ingredients can also be used. Solid active ingredients having a lower melting point can be introduced in the form of a melt too, in the absence or in admixture with an emulsifier. ULV compositions can be prepared similarly to EC or SC compositions. Granules suitable for direct use /G/ can be prepared by means of extrusion or lamination by absorbing on a granular carrier /e.g. ground limestone/ or a liquid component in a carrier having a high sorption capacity. Granules applicable for spraying purposes /WG/ can be prepared from WP and/or SC forms with the aid of an agglomerating technology /e.g. in a dragee pan by using a binding agent/. A spray or dusting powder directly applicable, in agriculture can be prepared from the above compositions by known methods by diluting with water or an inert solid diluent. The active ingredient content of the ready-for-use compositions is generally below 5% by weight and amounts preferably to 0.01-3% by weight. One may also proceed by admixing several compositions, each containing one active ingredient, to yield a spray directly before use. Further details of the present invention are to be found in the following Examples without limiting the scope of protection to the said Examples. In Examples 1-24 the preparation of the active ingredients of the general Formula /I/ is disclosed. Examples A-D are directed to the preparation of chemically related compounds which serve as reference compounds in the biological tests /Table 1/. In the 'H-NMR spectroscopical data disclosed in some of the Examples the mode of identification corresponds to that shown on Formula

Thus the designation of the site of certain protons differs from that according to the official nomenclature but the method used in the present specification enables a uniform spectroscopical evaluation. The 'H-NMR spectroscopical data disclosed in the Examples relate to the X2 moiety of the general Formula /I/. Due to the weak inductive effect of the X2 moiety the protons of the diphenyl ether part appear at the same chemical shift values.

In the IR spectrum of the compound according to the present invention the vC=0=1700 cm-1 band characteristic of the formyl group disappear and a vC=N=1580 cm-1 band appear. The

cm-1.

Example 1 Table 1 Substituents and melting point of the active ingredients shown in the Examples

C ontinued

5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitrobenzaldehyde-octylimine /Compound No. 1 5 g /0.0145 mole/ of 5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitro-benzaldehyde and 1.9 g /0.0145 mole/ of n-octyl amine are dissolved in 15 ml of isopropanol. The solution is refluxed for half an hour and the reaction mixture is cooled. Thus 4.6 g of the crystalline desired compound are obtained, yield 69%.

Example 2 Molecular weight 456. The pale yellow crystals melt at 55-56[deg]C. Characteristic fragments of the mass spactrum: m/e/r.i./=

5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitrobenzaldehyde allyl imine /Compound No. 2/ To 6.9 g /0.02 mole/ of 5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitro-benzaldehyde 1.14 g /0.02 mole/ of allyl imine are added and the reaction mixture is heated on a hot water bath for an hour. After cooling the oily residue is crystallized from 10 ml of ethanol. Thus 4.84 g of the desired compound are obtained, yield 63%. Molecular weight 384. The yellowish brown light-sensitive crystals melt at 38-41 [deg]C. Characteristic fragments of the mass spectrum:

/mp/, CH=6,0 ppm /mp/.

Example 3 5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitrobenzaldehyde propargyl imine /Compound No. 3/ One proceeds according to Example 2 except that allyl amine is replaced by propargyl amine. Thus 8.9 g of the desired compound are obtained, yield 78%. Molecular weight 382. The body-coloured crystals melt at 63[deg]C. Characteristic fragments of the mass spectrum:

Example 4

8CH=2,48 ppm bis-{5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitro-benzaldehyde}-ethylene diimine /Compound No. 4/ 5.2 g /0.0151 mole/ of 5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitro-benzaldehyde and 0.45 g /0.0076 mole/ of ethylene diamine are dissolved in 15 ml of isopropanol. The solution is refluxed for half an hour, whereupon the mixture is cooled. Thus the desired compound is obtained with a yield of 84%. The pale yellow crystals melt at 136-138[deg]C. Molecular weight 714. Characteristic fragments of the mass spectrum:

pound No. 5/ One proceeds according to Example 4 except that ethylene diamine is replaced by hexamethylene diamine. Thus 4.82 g of the desired compound are obtained, yield 83%. Molecular weight 770. The pale yellow crystals melt at 142-144[deg]C. Characteristic fragments of the mass spectrum:

CH2= 1,25-1,75 ppm.

Example 6 5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitro-benzaldehyde-ethanol imine /Compound No. 6/ One proceeds in an analoguous manner to Example 2 except that allyl amine is replaced by ethanol amine. Thus 4.94 g of the desired compound are obtained, yield 82%. Molecular weight 388. The beige crystals melt at 81-83[deg]C. Characteristic fragments of the mass spectrum:

Example 7

5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitrobenzaldehyde-benzyl imine /Compound No. 7/ One proceeds according to Example 2 but allyl amine is replaced by benzyl amine. Thus 6.94 g of the desired compound are obtained, yield 80%, molecular weight 434. The yellowish brown crystals melt at 62-66[deg]C. Characteristic fragments of the mass spectrum:

Example 8

5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitrobenzaldehyde-/a-methyl/-benzyl imine /Compound No. 8/ One proceeds according to Example 2 except that allyl amine is replaced by /a-methyl/-benzyl amine. Thus 6.72 g of the desired compound are obtained, yield 75%. Molecular weight 448. The light brown crystals melt at 48[deg]C. Characteristic fragments of the mass spectrum:

8CH=4,57 ppm /q, J=7Hz/.

Example 9 5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitrobenzylidene-aniline /Compound No. 9/ One proceeds according to Example 2 except that allyl amine is replaced by aniline. Thus 6.8 g of the desired compound are obtained, yield 81%. Molecular weight 420. The lemon yellow crystals melt at 91-92[deg]C. Characteristic fragments of the mass spectrum:

180/ 550/=C6H4CHNC6H5 77/ 920/=C6H5 'H-NMR /CDCI3/: =8.92 ppm.

Example 10 {5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitrobenzylidene}-3-trifluoromethyl-aniline /Compound No. 10/ One proceeds according to Example 2 except that allyl amine is replaced by 3-/trifluorome-

488. The yellow crystals melt at 92-94[deg]C. Characteristic fragments of the mass spectrum:

145/ 820/ =F3CC6H4

11/ One proceeds according to Example 2 except that allyl amine is replaced by 3,4-dichloro aniline. Thus 6.64 g of the desired compound are obtained, yield 68%. Molecular weight 488. The beige coloured crystals melt at 102-103[deg]C. Characteristic fragments of the mass spectrum:

145/ 220/ =CsH3Cl2 'H-NMR /CDCI3/: CH=8.92 ppm.

Example 12 {5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitrobenzaldehyde}-2-chloro-5-/trifluoromethyl/-aniline /Compound No. 12/ One proceeds according to Example 2 except that allyl amine is replaced by 2-chloro-4trifluoromethyl-aniline and the product is crystallized from isopropanol. Thus 8.14 g of the desired compound are obtained, yield 78%. Molecular weight 522. The light yellow crystals melt at 88-89[deg]C. Characteristic fragments of the mass spectrum:

179/ 950/ =F3C/CI/C6H3 H-NMR /CDCI3/: CH=8,95 ppm.

Example 13 {5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitrobenzylidene}-2-hydroxy-aniline /Compound No. 13/ 5 g /0.0145 mole/ of 5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitro-benzaldehyde and 1.58 g /0.0145 mole/ of 2-hydroxy-aniline are dissolved in 15 ml of isopropanol. The solution is refluxed for half an hour and cooled. Thus 5.5 g of the desired crystalline compound are obtained, yield 87%, molecular weight 436. The yellow crystals melt at 139-142[deg]C. Characteristic fragments of the mass spectrum:

'H-NMR /CDCI3/: CH=9.1 ppm.

Example 14 {5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitrobenzylidene}-4-hydroxy-aniline /Compound No. 14/ One proceeds according to Example 13 except that 2-hydroxy-aniline is replaced by 4-hydroxyaniline. Thus 6.0 g of the desired compound are obtained, yield 95%. Molecular weight 436. The lemon yellow crystals melt at 91-93[deg]C. Characteristic fragments of the mass spectrum:

Example 15

196/1000/ =C6H3OC6H3NO

One proceeds according to Example 13 except that 3-hydroxy-aniline is replaced by 3-nitroaniline. Thus 5.80 g of the desired compound are obtained, yield 86%. Molecular weight 465. The pale yellow crystals melt at 112-114[deg]C. Characteristic fragments of the mass spectrum:

'H-NMR /CDCI3/: CH=8.95 ppm.

Example 16

No. 16/ One proceeds according to Example 13 except that 2-hydroxy-aniline is replaced by 3-ethyl-6methyl-aniline. Thus 5.63 g 6f the desired compound, are obtained, yield 84%. Molecular weight 462. The lemon yellow crystals melt at 92.5-93.5[deg]C. Characteristic fragments of the mass spectrum:

133/ 330/ =NC6H3/CH3/C2H5 'H-NMR /CDCI3/: CH=8.63, CH3=1,05 /tr, J=7Hz/, CH3=2,1, CH2=2,45 ppm /q, J=7Hz/.

Example 17

17/ One proceeds according to Example 13 except that 2-hydroxy-aniline is replaced by 2,6diethyl-aniline. Thus 5.11 g of the desired compound are obtained, yield 74%. Molecular weight 476. The lemon yellow crystals melt at 64-65[deg]C. Characteristic fragments of the mass spectrum:

147/ 430/ =NC6H3/C2 H5/2 132/ 700/ =NC6H3/CH2/ CH3 117/ 650/ =NC6H3/ CH2/CH2

CH2=2,45 ppm /q, J=7Hz/.

Example 18 3-[/2-chloro-4-trifluoromethyl/-phenoxy]-benzaldehyde-isopropyl imine /Compound No. 18/

of isopropyl amine are added. During addition the reaction mixture is intensively stirred and a slightly exotermix reaction takes place. The solution is allowed to stand overnight and then diluted with ether. The etheral solution is dried over magnesium sulfate and evaporated. The residue is distilled off in vacuo. Thus 5.4 g of the desired compound are obtained, yield 79%. Molecular weight 342. The boiling point of the yellow liquid amount? to 135-150[deg]C/1 Hgmm.

CH=3,42 ppm /oct., J=7Hz/.

Example 19 3-[/2-chloro-4-trifluoromethyl/-phenoxy]-benzaldehyde-allyl imine /Compound No. 19/ One proceeds according to Example 18 except that isopropyl amine is replaced by 2.284 g /0.04 mole/ of allyl amine. Thus 5.6 g of the desired compound are obtained, yield 83%. Molecular weight 339. The boiling point of the yellow liquid amounts to 105-135[deg]C/I Hgmm.

4,95-5,20 /mp./, CH=5,94 ppm /mp./.

Example 20 3-[/2-chloro-4-trifluoromethyl/-phenoxy]-benzylidene-aniline /Compound No. 20/

mole/ of aniline are added. The reaction mixture is stirred for an hour and the water formed is removed in vacuo. Thus 18,2 g of the desired compound are obtained, yield 88%. Molecular weight 375. Brown oil. 'H-NMR /CDCI3/: CHN=8.30 ppm.

Example 21

21/ To 15 g /0.05 mole/ of [/2-chloro-4-trifluoromethyl/-phenoxy]-benzaldehyde 8.1 g /0.05 mole/ of 3-trifluoromethyl-aniline are added dropwise. The yellow emulsion-type reaction mixture is heated on a water-bath /65-70[deg]C/ for 2 hours. The mixture is cooled and the product is crystallized from methanol. Thus 14.2 g of the desired compound are obtained, yield 64%. Molecular weight 443. The light cream-coloured product melts at 94-86[deg]C. Characteristic fragments of the mass spectrum:

283/ 150/ =F3CC6H3/CI/OC6H4C 172/ 520/ =CHNC6H4CF3 145/ 850/ =C6H4CF3 'H-NMR /CDCI3/: CH-N=8,63 ppm.

Example 22 i3-[/2-chloro-4-trifluoromethyl/-phenoxy]-benzylidene}-2-chloro-5-trifluoromethyl-aniline /Compound No. 22/ One proceeds according to Example 21 except that 3-trifluoromethyl-aniline is replaced by 9.8 g /0.05 mole/ of 2-chloro-5-trifluoromethyl-aniline and the product is crystallized from petrolether /40-70/. Thus 16.6 g of the desired compound are obtained, yield 70%. Molecular weight 478. The white crystals melt at 85-90[deg]C. Characteristic fragments of the mass spectrum:

Example 23

442/ 240/ =F3CC6H3/CI/OC6H4CHNC6H3CF3

206/ 440/ =CHN/Cl/C6H3CF3 179/ 300/ =CIC6H3CF3 {3-[/2-chloro-4-trifluoromethyl/-phenoxy]-benzylidene}-3,4-dichloro aniline (Compound No. 23) To 6.0 g (0.02 mole) 3-[/2-chloro-4-trifluoromethyl/-phenoxy]-benzaldehyde 4.5 g (0.028 mole) 3,4-dichloro-aniline are added. The reaction mixture is stirred for 3 hours over water bath at a temperature of 80-85 C. grad and after cooling it is diluted with ether. The yellow parcitipation is filtered and the filtrate is dried over magnesium sulphate and the solvent is removed by suction. Thus 8.2 g of the desired compound are obtained. Yield: 92 0/0 Molecular Weight: 443. Colour and Form: Brown, thick oil 'H-NMe (CDCI3/: JCH=N=8.25 ppm.

Example 24

One proceeds according to Example 18 except that isopropyl amine is replaced by 1.2 g /0.02 mole/ of ethylene diamine. Thus 6.0 g of the desired compound are obtained, yield 96%. Molecular weight 624. Yellow liquid.

In the following Examples A-D the preparation of the reference compounds used in the comparative herbicidal tests is described. The said compounds fall under the scope of European patent No. 0 034 012 but have not been specifically disclosed therein.

Example A 5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitrobenzaldehyde-ethyl imine /reference compound A/ 6.9 g /0.02 mole/ of 5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitro-benzaldehyde are dissolved in 15 ml of anhydrous ethanol and ethyl amine is bubbled through the solution for half an hour. During the introduction of ethyl amine the temperature rises to 60[deg]C. The reaction mixture is stirred for a further period of two hours and cooled. The desired product precipitates in the form of crystals. Thus 6.6 g of the desired compound are obtained, yield 88%. Molecular weight 372. The light brown crystals melt at 61-63[deg]C. Characteristic fragments of the mass spectrum:

CH2=3,60 ppm /q, J=7Hz/.

Example B

B/

To 6.9 g /0.02 mole/ of 5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitro-benzaldehyde 1.18 g /0.02 mole/ of propyl amine are added. The reaction mixture is heated on a hot water-bath for an hour. After cooling the oily residue is crystallized from 10 ml of ethanol. Thus 6.4 g of the desired compound are obtained, yield 83%. Molecular weight 386. The pale yellow crystals melt at 60-63[deg]C. Characteristic fragments of the mass spectrum:

297/ 310/ =F3C/Cl/C6H3OC6H3O 'H-NMR /CDCI3/: 8CH=8,68, CH3=0,90 /tr, J=7Hz/, CH2=1,68 /sext., J=7Hz/, NCH2=3,57 ppm /tr, J=7Hz/.

Example C 5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitrobenzaldehyde-isopropyl imine /reference compound C/ One proceeds according to Example B except that propyl amine is replaced by isopropyl amine. The desired compound is obtained with a yield of 85%. Molecular weight 386. The yellow light-sensitive crystals melt at 44-45[deg]C. Characteristic fragments of the mass spectrum:

CH=3,57 ppm /oct., J=7Hz/.

Example D 5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitrobenzaldehyde-n-butyl imine /reference compound No. D/ One proceeds according to Example C except that isopropyl amine is replaced by n-butyl amine. The desired compound is obtained with a yield of 86%. Molecular weight 400. The yellow crystals melt at 42-43[deg]C. Characteristic fragments of the mass spectrum:

/tr, J=7Hz/.

Example 25 Water dispersible granules having an active ingredient content of 45% by weight /WG/

123 g of Compound No. 9 are admixed in a mortar with 12.5 g of Cab-O-Sil, M5 amorphous silica, 7.5 g of Atlox 4862 dispersing agent /condensation product of naphthalene sulfonate and formaldehyde/, 12.5 g of Geropon IN wetting agent /isopropyl naphthalene sulfonate/ and 80 g of China clay. The mixture is ground in a JMRS-80 type whirling current mill so that the ratio of the fraction having a particle diameter above 44 Microm should not exceed 0.5% by weight. To the ground product in a Werner-type kneading machine a binder solution prepared from 15 g of Polifon 0 and 35 g of water is added, whereupon the mixture is subjected to extrusion in an Alexander-werke-type extruder under using a pad having a circular origice of 1 mm.The ganules thus obtained are dried at 60[deg]C in an air current. The above process can be carried out by using as active ingredient an other compound of the general Formula /I/ /e.g. compound No. 21/.

Example 26 Wettable powder /WP/

240 g of Compound No. 11 /previously ground in a mill equipped with a rotating blade/ are admixed in a mortar with 2.5 g of Cab-O-Sil M5 silica carrier and 7.5 g of Dispergiermittel 1494 dispersing agent /sodium salt of the condensation product of sulfonated cresol and formaldehyde/. The powder thus obtained is ground in a whirling current mill /Alpine JMRS 80/ under an injector air pressure of 5 bar and a grinding air pressure of 4.5 bar, whereby the feeding rate amounts to 250 g/h. Although the sprayable powder thus obtained contains no separate wetting agent, it is readily wettable, has a maximal particle size of 20 Microm and shows a floatability in the form of a 10 g/l spray at 30[deg]C after 30 minutes in CIPAC standard D water 84% and in CIPAC standard A water 91%.

Example 27 The above process can be also carried out by using as active ingredient an other compound of the general Formula /I/ e.g. compound No. 22/ ULV composition

Into a water-free enamelled autoclave 7500 g of isophorone and 2500 g of 2-ethoxy-ethanol are weighed in. 6875 g of Compound No. 10 /previously ground in a hammer mill/ are added, stirring is simultaneously started, and the temperature is raised to 45-50[deg]C with the aid of jacket heating. An hour later-after the components have been dissolved-8125 g of soya oil /or sunflower oil/ are added and stirring is continued for a further period of 20 minutes while in the meantime the temperature is lowered to 20[deg]C by cooling. The ULV composition thus obtained is applied in undiluted form without the addition of water.

Example 28 Oily suspension concentrate /FO/

13.5 g of Sapogenat T-080emulsifier melt'at 80[deg]C ethoxylated tributyl phenol/ and 12 g of Tensiofix AS emulsifier /n-butanolic solution of calcium dodecyl benzene sulfonate and ethoxylated nonyl phenol/ previously melt at a temperature not exceeding 60[deg]C and homogenized are added to 145 g of cosmetical white oil heated to 60[deg]C in a Molinex 075 type laboratory pearl mill. To the tenside oil mixture thus obtained 30 g of ethylene glycol are added and the components are homogenized by stirring for 10 minutes. 98.1 g of compound No. 15 previously finely ground in a mortar are added to the liquid mixture, whereupon it is stirred for 5 minutes and thereafter ground for 2 hours at 1500 r.p.m. by using glass pearls having a diameter of 1 mm /350 g of grinding balls/.In the oily suspension 1.5 g of Silicon SRE /130 % emulsion of dimethyl silicon oil/ antifoam agent are distributed by stirring for 3 minutes. The above process may-also be carried out by using as active ingredient an other compound of the general Formula /I/ /e.g. Compound No. 23/.

Example 29 Emulsifiable concentrate /20 EC/

Into a 500 I enamelled autoclave equipped with a stirrer 37 g of 2-ethoxy-ethanol, 129.5 g of cyclohexanone and 91 kg of xylene are weighed in, whereupon in this solvent mixture 26 kg of Emulsogen EL 360 emulsifier /ethoxylated castor oil/ and 11.1 kg of Tensiofix CD 5 emulsifier /ethoxylated cocoa alcohol/ are added. The emulsifiers are added in melt form /60-70[deg]C/. In the last step 75.5 kg of Compound No. 12 are weighed in and stirring is continued for 2 hours. Thus a clear transparent solution is obtained. The above process may also be carried out by using as active ingredient an other compound of the general Formula /I/ /e.g. Compound No. 10 or 23/.

Example 30 Emulsifiable concentrate /35 EC/

6 of of Tensiofix CG 21 /a mixture of ethoxylated fatty alcohol, ethoxylated nonyl phenol and phosphates thereof and 24 g of Tensiofix B 7453 emulsifier /n-butanolic solution of calcium dodecyl benzene sulfonate, ethoxylated nonyl phenol and ethoxylated-propoxylated nonyl phenol/ are dissolved in a mixture of 30 g of cyclohexanone and 133 g of xylene. Finally 107 g of compound No. 11 are dissolved in the above liquid comprising the tensides. The above process may also be carried out by using as active ingredient an other compound of the general Formula /I/ /e.g. compound No. 9, 10, 13, 21, 22 or 23/.

Example 31 Dusting powder having an active ingredient content of 1 % by weight

In a 50 1 ribbon-type mixer 9510 g of China clay are admixed with 1800 g of Ultrasil VN 3 synthetic sodium aluminium silicate, whereupon to the mixture 600 g of Compound No. 21 previously ground in a hammer mill are added and stirring is continued for 30 minutes. The premix thus obtained is ground in an Ultraplex 250 type mill at a feeding rate of 20 kg/h so that the ratio of the fraction having a particle size above 44 Microm should not exceed 0.5% by weight. After grinding the premix is admixed with talc in a Loedige 300 type whirling current mixer in a ratio of 1:4 by stirring for 10 minutes. . The above process may also be carried out by using as active ingredient an other compound of the general Formula /I/.

Example 32 Granules applicable without the use of water and having an active ingredient content of 0.01% by weight

The active ingredient is dissolved in methylene chloride; the concentration of the solution is 2.0% by weight. Into a Loedige 20 type whirling current mixer 4000 g of pearl silicaeous earth carrier prepared from diatomaceous earth by calcination, having an acidic character and a particle size of 0.5-2.0 mm are placed. 20 g of the above solution /concentration 2.0% by weight/ are sprayed onto the granulated carrier through a Tee-Jet 10080 mozzle at a rate of 5 g/m, while the Loedige-type mixer is stirred at 50 r.p.m. The sorption type granules are packed. Disperl S1 1 pearl silicaeous earth is a granulated carrier having a high sorption capacity. The above process may also be carried out by using as active ingredient an other compound of the general Formula /I/.

Example 33 Test of herbicidal activity Into a cultivating pot 30 seeds are sown at a depth of 0.5 cm. After sowing the soil is watered. Pre-emergent treatment is carried out after sowing and watering; post-emergent treatment is accomplished 10 days after the emergence of the plants by using emulsifiable concentrates having an active ingredient content of 20% and applying the active ingredient in a dose series of 0.33-1-3-9 kg.ha , The surface of the soil is regularly watered every day. The preemergent treatments are evaluated 10 days after emergence and the post emergent treatments are evaluated 10 days after treatment. The results are expressed as in the percentage of the dead plants. The results of the above test are summarized in Table 2. The definition of the abbreviations used in the heading of Table 2 are as follows:

Table 2

Example 34

Toxical effects of the treatments, in %

Continuation of Table 2

Continuation of Table 2

Continuation of Table 2

Ccntinuation of Table 2

Continuation of Table 2

Testing of fungicidal activity Agar plates are prepared by pouring a potato agar nutrient medium containing 2% by weight of dextrose into Petri dishes having a diameter of 100 mm and allowing the nutrient medium to solidify. From emulsifiable concentrates /active ingredient 20% by weight/ stock solutions having an active ingredient of 0.18; 0.06; 0.0033; 0.0066; 0.0011% by weight / 1800, 600, 100, 66 and 11 ppm, respectively/ are prepared. Suspensions comprising an appropriate number of spores of the test fungi are prepared in such dilutions, that when placing one drop of the spore suspension dispersed in water on the slide of a microscope 25-30 spores should appear in the visual field at a 100-160-fold magnification, on the basis of the average of 5-10 visual fields. From the spore suspensions thus obtained 1 ml each are added with the aid of a pipette to 1 ml of each dilution series of the test compounds. Thus solutions comprising an active ingredient concentrate /concentration 0.1; 0.03; 0.01; 0.0033 and 0.0011% by weight; i.e. 900, 300, 100, 33 and 11 ppm, respectively/ and the spore suspension are obtained. The solutions are allowed to stand for 1800 seconds, whereupon the bottom of a sterile test tube is dipped into the mixture of the fungicidal test compound and the spore suspension. A strip is drawn with the aid of the bottom of the sterile test tube on the agar-plate, whereupon the culture is inoculated. When the fungi are well-developed in the control treatment, the test is evaluated by comparing the growth of the fungi in the treated cultures with that of the untreated control.The results are expressed with the aid of the following bonity scale: 1 =no growth of the colony /0% as compared to the control/ 2=weak growth of the colony /10% as compared to the control/, 3=medium growth of the colony /50% as compared to the control/, 4=strong growth of the colony /100% as compared to the control/. The intermediate values in % are e.g. as follows: 1.5=5%, 2.5=30%, 3.5=75% of colony growth as compared to 100% growth of the control. The active ingredients of the present invention are compared not only with the untreated control but also to the highly active commercial fungicide Captan. The results are disclosed in Table 3. The fungicidal activity is expressed as average % /average of 4 replicates/. The definition of the abbreviations used in the heading are as follows: St.r.=Stemphylium radicinum He.t.=Helminthosporum turcicum Bo.c.=Botritis cinerea Fu.g.=Fusarium graminearum Co.l.=Colletotrichum lindemuthiarum Tr.r.=Trichotecium roseum Di.h.=Diaporte helianthi As.n.=Aspergillus niger Al.t.=Alternaria tenuis Table

/Continuation of Table 3/

Continuation of Table 3

Continuation of Table 3

Continuation of Table 3

Claims (1)

1. Pesticidal composition comprising as active ingredient at least one new compound of the general Formula

/wherein X, stands for hydrogen or nitro; X2 stands for C1-18 alkyl (with the proviso that if X, represents nitro, X2 cannot stand for C1-6 alkyl), or C2-6 hydroxyalkyl, or C2-6 mercaptoalkyl, or C2-6 aminoalkyl, or C3-6 alkenyl, or C3-6 alkynyl, or phenyl, or substituted phenyl of the general formula

wherein X3 stands for identical or different C1-4alkyl, trifluoromethyl, hydroxy, mercapto, nitro, amino or halogen, preferably chlorine and n is an integer 1, 2 or 3; or aralkyl, C1-6 alkyl-phenyl or a group of the general Formula

wherein X, is as stated above and m is an integer 2, 3, 4, 5 or 6/.

8. Composition according to Claim 1 comprising as active ingredient {5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitro-benzylidene}-2-hydroxy-aniline.

9. Composition according to Claim 1 comprising as active ingredient {3-[/2-chloro-4-trifluoro-

12. Composition according to Claim 1 comprising as active ingredient 5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitro-benzaldehyde-propargyl-imine.

13. Composition according to Claim 1 comprising as active ingredient {5-[/2-chloro-4-trifluoro-

14. Process for the preparation of new compounds of the general Formula

/wherein X, stands for hydrogen or nitro; X2 stands for C1-18 alkyl (with the proviso that if X, represents nitro, X2 cannot stand for C,_6 alkyl), or C2-6 hydroxyalkyl, or C2-6 mercaptoalkyl, or C2-6 aminoalkyl, or C3-6 alkenyl, or C3-6 alkynyl, or phenyl, or substituted phenyl of the general Formula

wherein X3 stands for identical or different C, 4 alkyl, trifluoromethyl, hydroxy, mercapto, nitro, amino or halogen, preferably chlorine and n is an integer 1, 2 or 3; or aralkyl, C1-6 alkyl-phenyl or a group of the general Formula

wherein X, is as stated above and m is an integer 2, 3, 4, 5 or 6/, which comprises reacting a substituted benzaldehyde of the general Formula

/wherein X, has the same meaning as stated above/ or an acetale or acetate thereof with a primary amine of the general Formula H2N-X2 /III/ /wherein X2 is as stated above/, if desired in the presence of an inert solvent and/or a catalyst, at 6 temperature between 0[deg]C and the boiling point of the reaction mixture and thereafter isolating the new compound of the general Formula /I/ thus obtained from the reaction mixture by known methods. 15. Process according to Claim 14 which comprises reacting a substituted benzaldehyde of the general Formula /II/ /wherein X, is as stated in Claim 14/ with a primary amine of the general Formula /III/ /wherein X2 is as stated in Claim 14.

16. Process according to Claim 14 or 15 which comprises carrying out the reaction in the presence of an inert solvent.

17. Process according to any of Claims 14-16 which comprises using a mineral acid or Lewis acid as catalyst. 18. Compounds of the general Formula

/wherein X, stands for hydrogen or nitro; X2 stands for C1-18 alkyl (with the proviso that if X, represents nitro, X2 cannot stand for C1-6 alkyl), or C1-6 hydroxyalkyl, or C2-6 mercaptoalkyl, or C2-6 aminoalkyl, or C3-6 alkenyl, or C3-6 alkynyl, or phenyl, or substituted phenyl of the general Formula

wherein X3 stands for identical or different C1-4 alkyl, trifluoromethyl, hydroxy, mercapto, nitro, amino or halogen, preferably chlorine and n is an integer 1, 2 or 3; or aralkyl, C1-6 alkyl-phenyl or a group of the general Formula

wherein X, is as stated above and m is an integer 2, 3, 4, 5 or 6/

ine.

24. bis-i5-[/2-chloro-4-trifluoromethyl/-phenoxy]-2-nitro-benzylidene}-ethylene-djimine.

31. Method for combating fungal pests and/or weeds which comprises using as active ingredient a compound of the general Formula /I/ /wherein X, and X2 are as stated in Claim 1/ in a dose of 0.1-10.0 kg.ha- , preferably 0.2-5.0 kg/ha- .

32. Method according to Claim 31 which comprises using a spray, dressing agent or dusting powder containing 0.01-5.0% by weight-preferably 0.1-3.0% by weight-of a new compound of the general Formula /I/ /wherein X, and X2 are as stated in Claim 1/.

33. A pesticidal composition substantially as hereinbefore described in any one of Examples 25 to 32. - - '

34. A process for the preparation of compounds of the general formula I where X, and X2 are as defined in claim 1, which is substantially as hereinbefore described in any one of Examples 1 to 24.

35. The title compounds of any one of Examples 1 to 24 as hereinbefore described. 36. A method as claimed in claim 31, which is substantially as hereinbefore described in Example 34 or Example 35.