BENZYLATED CIS-2,3-EPOXYCYCLOALKANOL HERBICIDES

Abstract: Benzylated cis-2,3-epoxycycloalkanols of general formula (I), in which X, Y, R<1>, R<2>, R<3> and n have the meanings given in the description, are useful as herbicides.

Description: BENZYLATED CIS-2,3-EP0XYCYCL0ALKAN0L HERBICIDES The invention relates to novel benzylated cis-2,3- epoxycycloalkanols, their production and intermediates for their production and their use as agents having a herbicidal and plant growth-regulating action. It is already known that certain benzyl ethers have herbicidal properties (e.g. EP 081 893, EP 334 120 and EP 497 453). However, the herbicidal action of the known compounds is frequently not adequate, or there are selectivity problems in agricultural main crops when the herbicidal action is suitable. It was found that benzylated cis-2,3-epoxycycloalkanols of the general formula I in which X and Y can be the same or different and stand for H, halogen, C^g-alkyl or Cι_ 6 -halogen alkyl, R 1 stands for C^g-alkyl, C 2 _6-alkenyl, C _ 6 -alkinyl, halogen-C- j _g-alkyl, halogen-C 2 _5-alkenyl or halogen C _g -alkinyl, R 2 ,R 3 can be the same or different and stand for H, ^g- alkyl, C 2 _ 6 -alkenyl, C _ 6 -alkinyl, halogen-Cι_g alkyl, halogen-C 2 _g-alkenyl, halogen C 2 _ 6 -alkinyl, optionally phenyl substituted once or repeatedly, identically or differently with halogen, C- j .g-alkyl, halogen-^_g- alkyl, nitro or cyano, cyano, C- | _g alkoxycarbonyl, C | _g -alkoxy, halogen-C-,_ 6 -alkoxy, -CH 2 -OR 4 (R 4 equals C^g- alkyl, halogen-C^_g-alkyl, allyl, benzyl or propargyl) or R 2 and R 3 together stand for -(CH ) m - (m equals 2, 3, 4 or 5), and n stands for 0 or 1 , have a superior effectiveness compared with the known compounds. Halogen is taken to mean fluorine, chlorine, bromine and iodine. The terms "alkyl", "alkenyl" and "alkinyl" are taken to mean both straight-chained and branched hydrocarbon radicals. The invention also relates to intermediates of the general formula II for the production of compounds of the formula I, in which R 1 , R 2 , R 3 and n have the meaning given under the general formula I. The compounds according to the invention of the general formula I can be produced by reacting a compound of the general formula II with a compound of the general formula III in which X and Y have the meaning given under the general formula I and Z stands for chlorine, bromine, iodine, an alkyl or arylsulphoxy group, by methods known per se in the presence of a base. The reaction is carried out in a suitable solvent such as e.g. benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dimethylformamide or 1 , -dioxan in the presence of a base such as sodium hydride or potassium-t-butylate at temperatures between 0. °C and the boiling point of the solvent in question. The compounds of the general formula II which are used as intermediate can be produced by reacting 2-cycloalkenols of the general formula IV in which R , R , R J and n have the meaning given under the general formula I, analogously to methods described in the literature (see e.g. P. Kocovksy, Tetrahedron Lett. .29 . , 2475 (1988)). The compounds of the general formula IV can be produced by reacting 2-cycloalkenones of the general formula V in which R , R , R° and n have the meaning given under the general formula I, analogously to methods described in the literature (see e.g. M. Mousseron, R. Jarquier, M. Mousseron- Lauet, R. Zagdonn, Bull. Soc. Chim. Fr. 1042 (1952)). The compounds of the general formula V are commercially available or can be produced by methods known from the literature or analogously to these (e.g.: N.W.A. Geraghty and N.M. Morris, Synthesis 1989, 603, Yanagita, Inayama, J. Org. Chem., J_9, 1732 (1954)). The compounds according to the invention produced according to the methods described above can be isolated from the reaction mixture by usual methods, for example by distilling off the solvent at normal or reduced pressure, by precipitation with water or by extraction. An increased degree of purity can as a rule be obtained by column chromatographic cleaning and by fractional distillation or crystallization. The compounds according to the invention are as a rule almost colourless and odourless liquids or crystals which are limitedly soluble in water, aliphatic hydrocarbons, such as petroleum ether, hexane, pentane and cyclohexane, well soluble in halogenated hydrocarbons, such as chloroform, methylene chloride and carbon tetrachloride, aromatic hydrocarbons, such as benzene, toluene and xylene, ethers, such as diethyl ether, tetrahydrofuran and dioxan, carboxylic acid nitriles, such as acetonitrile, alcohols, such as ethanol and methanol, carboxylic acid amides, such as dimethylformamide, sulphoxides, such as dimethyl sulphoxide or organic bases, such as for example pyridine. The compounds according to the invention have a good herbicidal action in the case of broad-leaved weeds and grasses. A selective use is possible in various crops, e.g. in rice, rape, beet, soybeans, cotton, maize, barley, wheat and other types of cereal. Individual compounds are also particularly suitable as selective herbicides in rice, beet, cotton, soya, maize and cereals. The compounds can also be used to control weeds in perennial crops, such as e.g. in forest, ornamental woodland, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plantations, and for selective weed control in annual crops. The compounds according to the invention can be used e.g. with the following plant species: Dicotyledonous weeds of the species such as Sinapis, Lepidium, Galium, Stellania, Matricaria, Anthemis, Galinsoga, Chenopodium, Brassica, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Sonchus, Solanum, Lamium, Veronica, Abutilon, Datura, Viola, Galeopsis, Papaver, Centaurea and Chrysanthemum; Monocotyledonous weeds of the species such as Avena, Alopecurus, Echinochloa, Setaria, Panicum, Digitaria, Poa, Eleusine, Brachiaria, Lolium, Bromus, Cyperus, Elymus, Sagittaria, Monochoria, Fimbristylis, Eleocharis, Ischaemum and Apera. The quantities used vary according to the type of application, post-sowing and post-emergence, between 0.001 and 5 kg/ha. The compounds according to the invention can be used either alone, mixed with one another or with other active ingredients. The intensity of action and speed of effect can be promoted for example by action-increasing additives such as organic solvents, wetting agents and oils. Such additives therefore optionally permit a reduction in the active ingredient dosage. The active ingredients according to the invention or their mixtures are expediently applied in the form of preparations, such as powders, products for scattering, granules, solutions, emulsions or suspensions, with addition of liquid and/or solid carriers or diluents and optionally adhesion, wetting, emulsifying and/or dispersion auxiliaries. Suitable liquid carriers are for example aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulphoxide, dimethylformamide, also mineral oil fractions and vegetable oils. Suitable as solid carriers are minerals, such as for example bentonite, silica gel, talc, kaolin, attapulgite, limestone and vegetable products, such as for example flours. Surfactants to be named include for example calcium lignine sulphonate, polyethylene alkyl phenyl ether, naphthalene sulphonic acids and their salts, phenolsulphonic acids and their salts, formaldehyde condensates, fatty alcohol sulphates as well as substituted benzene-sulphonic acids and their salts. The proportion of active ingredient(s) in the various preparations can vary within wide limits. For example, the products contain roughly 10 to 90 percent by weight active ingredient, roughly 90 to 10 percent by weight liquid or solid carriers as well as optionally up to 20 percent by weight surfactants. The products can be applied in the usual way, for example with water as carrier in spray mixture quantities of roughly 100 to 1000 litres/ha. An application of the products in the so-called low-volume and ultra-low procedures is just as possible as their application in the form of so-called microgranules. The production of these preparations can take place in a manner known per se, for example by grinding or mixing processes. If desired, preparations of the individual components can also be mixed only shortly before they are used, such as is carried out in practice for example in the so-called tank mix procedure. The following examples explain the production of the compounds according to the invention. Example 1 (1RS , 2RS, 6SR)-2-(2-chloro-6-fluorobenzylox )-1 ,5,5-trimethy1-7- oxabicyclo[4.1.0] heptane 718 mg (6.40 mmol) potassium-tert.-butylate are dissolved in 50 ml tetrahydrofuran and then reacted with 1.15 g (6.40 mmol) 2- chloro-6-fluorobenzyl chloride and 1 g (6.40 mmol) (1RS, 2RS, 6SR)-2-hydroxy-1 , 5, 5-trimethyl-7-oxabicyclo[4.1.0] heptane. The mixture is stirred overnight, then compressed at the rotary evaporator and the residue is absorbed with 50 ml acetic ester. The mixture is washed with saturated sodium chloride solution, dried over magnesium sulphate and compressed anew at the rotary evaporator. The residue is purified by column chromatography using silica gel with hexane:acetic ester = 9:1. Yield: 1.37 g (4.59 mmol & 72% of theory) colourless oil R f (acetic ester) = 0.73 n 20 / D = 1.51232 The following compounds of formula I are produced in an analogous manner : X Y R 1 R 2 R 3 Fp.rc] or n 20 /π I Cl F Me c-hexyl Me 1.3824 I (Diastereomer B) Cl F Et Me c-hexyl 1.3870 (Diastereomer A) Cl F Et c-hexyl Me 1.3855 (Diastereomer B) Me H Et c-hexyl Me 1.3668 (Diastereomer A) Me - H Et c-hexyl Me 1.3714 (Diastereomer B) Cl H Et c-hexyl Me 1.3777 (Diastereomer A) Cl H Et Me c-hexyl 1.3685 (Diastereomer B) Cl F Me Me CH 2 CH 3 R f =0.71 (Diastereomer A) Cl F Me CH 2 CH 3 Me R f =0.84 (Diastereomer B) c-hexyl = cyclohexyl ^^ /^^J The following application examples explain the usability of the compounds according to the invention. In the examples: AS = active substance CYPDI Cyperus difformis 0 no damage ECHCG Echinochloa crus-galli 1 1-24% damage GOSHI Gossypium hirsutum 2 25-74% damage MOOVA Monochoria vaginalis 3 75-89% damage ORYSA Oryza sativa,japonica Koshihikari 4 90-100% damage ORYSW Oryza sativa, indica IR&$ SAGPY Sagittaria pygmaea SCPJU Scirpus juncoides SETVI Setaria viridis Application example A The plant species listed below were treated in the glass house post-sowing with the listed compounds in an application quantity of 1.0 kg active ingredient/ha. To this end, the active ingredients were sprayed uniformly over the plants as an emulsion with 500 litres of water/ha. Three weeks after the treatment, the compounds according to the invention displayed an excellent action against the weed. Compound G s acc. to 0 E example S T no. H V I I 2 0 4 10 1 3 11 0 4 12 0 4 Untreated 0 0 Application example B In the glass house the compounds listed in the table were applied by pipetting onto a water surface of ca. 170cm 2 , the test plants being used both in the post-sowing phase and in the 1-2 leaf stage. After 2 weeks it was shown that the compounds according to the invention are very effective against important rice weeds and at the same time are selective as regards water rice. Compound 0 E S S M C acc. to water R C C A 0 Y example application Y H P G 0 P no. [kg AS/ha] s C J P V D A G U Y A I 2 0.05 0 3 3 3 4 4 10 0.05 0 4 3 3 3 3 11 0.05 0 4 3 3 4 3 12 0.5 0 4 - - 4 - Untreated 0 0 0 0 0 0 Application example C (Comparative example) In the glass house, the compound listed in the table and the comparison compound were applied by pipetting onto a water surface of ca. 170 cm 2 , the test plants being used both in the post-sowing stage and the 1-3 leaf stage. After 2 weeks it was shown that the compound according to the invention is much more effective against important rice weeds than is the comparison product. Specially at higher doses, the compatibility of the compound according to the invention is better compared with the known compound in the case of seed rice and plant rice. Compound 0 0 E s s M C acc. to water R R C C A 0 Y example application Y Y H P G 0 P no. [kg AS/ha] S S C J P V D A W G u Y A I 89 0.006 0 - 4 3 2 2 3 0.025 0 2 - - - - - Cinmethylin 0.006 0 - 3 3 1 0 2 0.025 1 4 - - - - Untreated 0 0 0 0 0 0 0

Claims: Patent claims 1. Benzylated cis-2,3-epoxycycloalkanols of the general formula I in which X and Y can be the same or different and stand for H, halogen, C^g-alkyl or C^g-halogen alkyl, R 1 stands for C^g-alkyl, C 2 _ 6 -alkenyl, C 2 _ 6 -alkinyl, halogen-C^g-alkyl, halogen-C 2 _g-alkenyl or halogen C 2 _g -alkinyl, R 2 ,R 3 can be the same or different and stand for H, Cι_ 6 - alkyl, C 2 _g-alkenyl, C 2 _g-alkinyl, halogen-Cι_g alkyl, halogen-C 2 _ 6 -alkenyl, halogen C 2 _ 6 -alkinyl, optionally phenyl substituted once or repeatedly, identically or differently with halogen, C- | _g-alkyl, halogen-Cι_g- alkyl, nitro or cyano, cyano, C 1-6 alkoxycarbonyl, C^.g -alkoxy, halogen-^_ 6 -alkoxy, -CH 2 -OR 4 (R 4 equals C j .g- alkyl, halogen-C^g-alkyl, allyl, benzyl or propargyl) or R 2 and R 3 together stand for -(CH 2 ) m - (m equals 2, 3, 4 or 5), and n stands for 0 or 1. 2. Compounds of the general formula II as intermediates for the production of compounds of the formula I, in which R , R , R° and n have the meaning given under the general formula I. 3. Products with herbicidal action characterized by a content of at least one compound according to claim 1. 4. Product with herbicidal action according to claim 3 mixed with carrier and/or auxiliary substances. 5. Use of compounds according to claim 1 for the control of monocotyledonous and dicotyledonous weeds.

Inventors: BOHNER JUERGEN, BOJACK GUIDO, HOEMBERGER GUENTHER, REES RICHARD, VAN ALMSICK ANDREAS, BOHNER, JUERGEN, BOJACK, GUIDO, HOEMBERGER, GUENTHER, REES, RICHARD, VAN ALMSICK, ANDREAS
Applicants: ALMSICK ANDREAS VAN, BOHNER JUERGEN, BOJACK GUIDO, HOECHST SCHERING AGREVO GMBH, HOEMBERGER GUENTHER, REES RICHARD, BOHNER, JUERGEN, BOJACK, GUIDO, HOEMBERGER, GUENTHER, REES, RICHARD, VAN ALMSICK, ANDREAS
Application year: 1996
Main classification: C07D303
IPC codes: A01N43, C07D303