IL31317A - Oxime ethers and pesticidal preparations containing them - Google Patents

Description

* «np ο·η»»3ηι o*wtn ο»-»ηκ o»oaii Hew oxime ethers and pesticidal preparations containing them CIBA-GEIGY AG 0:29589 31317/2 The present invention relates to active substances for compositions for combatting representatives of the order Acarina (mites, ticks, etc.) as well as undesirable plants in cultures of useful plants.

These active substances are compounds of formula wherein R^ denotes a lower alkyl or haloalkyl residue or a phenyl group - which may be substituted by at most three substituents selected from halogen, nitro, trifluoroimethyl, lower alkyl or lower alkoxy, or wherein R^ in the case where n=0, denotes the 4-chlorophenoxymethyl, 2,4-dichlorophenoxy-raethyl or 2-methyl-4-chlorophenoxymethyl residue; Y represents oxygen, the -HH- group or the -N(CJH^)- group; n=0 or 1; and X represents halogen; one of the substituents 2 and j denotes the MOg- group and the other optionally represents K02 or another negativising group selected from (Ag) ; or depend ently represent hydrogen, halogen, lower alkyl or the - la — and Ag independently of one another denote hydrogen or lower alkyl; together with a suitable carrier.

The present invention provides the new oxime-ether-carbamatesp carbonates and -esters of formula I.

The invention also provides pesticides which contain compounds of formula I as active substances together with suitable carriers.

Israel Patent Specification No. 25025 discloses pesticidal and herbicidal preparations whose active ingredients may be, l.a., oxime-ether-carbamates and -esters of a structure similar to formula I above, in which fl is 0 or n is 1 and "3? is a group -HH- or -H(CH_)-. No compounds of the exact structure of formula I above, were specifically disclosed in that specification and, in particular, it does not describe s pecifically any ester-derivative (n=0 in formula I above).

It has surprisingly been fljund in accordance with the present invention, that the active compounds of formula I herein, which constitute a comparatively small group of compounds out of the broad scope generically disclosed in Israel Specification No. 25 23, poEBess a signi icantly better herbicidal selectivity than the active substances known from that specification. Owing to this selectivity°¾he compounds of formula I heroin, which is manifested even at the low rates of 1kg active substance per hectare, the new compounds are especially suitable for combatting broad-leaved (dicotyledonous) weeds in monocotyledonoue cultures, such as cereals, maize and rice.

The starting products of formula which are necessary for the manufacture of the compounds of formula I can be manufactured in a simple manner, for example from 3,5-dihalogeno-4-hydroxybenzaldoxime and an appropriately substituted chlorobenzene of formula in alkaline solution.

If these compounds of formula II are to be converted to esters of general formula I then, provided the reaction is not too drastic, all usual esterification methods can be applied to the conversion of the phenolic OH group. In order to' ensure mild conditions, it is appropriate to start from the phenolate and to react v/ith appropriate carboxylic acid halides. It is also possible to produce the phenyl-este'r grouping at temperatures in the range of 0° to 160°C with carboxylic acids or carboxylic acid anhydrides, v/ith acid esters or lactones or in individual cases also v/ith ketenes.

If the starting products II are to be converted to corresponding carbonates, the free phenolic OH group, but preferably the phenolate, can here again be reacted under mild reaction conditions with an appropriate halogeno-formic acid ester R^-O-CO-X (X = halogen, especially CI).

If the starting products II are to be converted to corresponding carbamates, the phenolic OH group can be reacted according to usual methods with isocyanates of the type - NCO or with compounds which can transiently form these isocyanat or also with carbamic acid chlorides of the type - NH - C0G1 or of the type R, - N(CH5) - C0C1 It is however also possible first to manufacture the corresponding phenolchlorocarbonate from the OH group by · means of COCI2 and then to allow this, where possible, to react with an amine R^-NH2 or R^-NH-CH^. in each case has the significance given for formula I. Possible' solvents are generally acetonitrile , ether, dioxane dimethylformamide , dimethylsulphoxide and others.

The herbicidal selectivity in varieties of grain, maize and rice- on the one hand and in -leguminosae (peas, beans, soya beans, clover and lucerne) on the other, on post-emergent treatment, follows for all compounds of formula I from the field of use initially quoted, though to different extentSo. Particularly outstanding representatives are those of general formula III wherein and X have the significance given initially and Ar especially represents the following substituted phenyl groups : lkyl The acaricidal action of a series of representatives of formula I, which has "been observed against all kinds of representatives of the order Acarina such as ticks, mites, spinning mites and the like, should also be emphasised Here it is worth mentioning that the amounts used can be chosen at an order of magnitude which lies below any influence on the plants.

• Typical representatives of this are compounds of formula III wherein Ar denotes the group In the. formulae quoted, "aikyl" is intended to represent lower, including branched alkyl residues having at most 4 C atoms o The new oxime-ether-carbonates, -carbamates and -esters can "be used alone or mixed with other pesticides or "biologically stimulating or inhibiting substances or with solid carriers, solvents, diluents, thickeners, dispersing agents, wetting agents or adhesives or optionally with the addition of fertilisers.

Depending on the end use, the new substances can be used as pesticides in various ways such as form part of the state of the art and are for example described in U.S. Patent 3, 329,702 or British Patent 1,047,644 or Swiss Patent 424,359· In many cases it is- advantageous to use granules to achieve uniform release of active substances over a longer period of time. These granules can for example be manufactured by dissolving the active substance in an organic solvent, absorbing this solution by a granulated material, for example Attapulgite or S1O2, and removing the solvent.

In the ' form of one or other use such materials can also be applied by distribution over large areas (spraying, dusting and the like) by means of aircraft.

The various use forms of such materials can be more closely suited to the end uses in the usual manner by adding substances which improve the distribution, adhesion, rain resistance and possibly the penetrating power, such as for example fatty acids, resins, wetting agents, glue, caseine or alginates.

In the manufacture of he.rbicidally active materials there are furthermore numerous possible components for use in combinations, of which the most important representatives are quoted below: N-phenyl-N' , Ν' -dime hylurea, N-p-chlorophenyl-N' , Ν' -dimethylurea, N-3> -dichlorophenyl-N' , ' -dimethylurea, N—3> -dichlorophenyl-N' -methoxy-N1 -methylurea, N- -bromo-3-chlorophenyl-]!T,-methoxy-N,-methylurea, trichloracetic acid, 2 , 6-dichlorobenzonitrile , 2,3,6-trichlorobenzoic acid, 2, -D, 2, ,5-T, MCPB, MCPP, isopropyl-carbanila.te , isopropyl-3-chlorocarbanilate , N-3-chlorophenylcarbamic acid 4'-chlorobutin-2-yl-l-ester, 2,3,6-trichlorophenylacetic acid and salts, 2-chlorodiallylacetamide , 2-chloro-4, 6-bis-ethylamino-s-triazine, 2-methoxy-4, 6-bisr-ethylamino-s-triazin 2-azido- —methyl-thio-6-isopropylaminotriazine , the monomethy arsenate di-Na salt, various arsenites, Na metaborate, N chlorate and sulphamic acid.

When using the materials against ectoparasites on farm animals such .as cattle , sheep, goats and others, it is advantageous to use dipping baths in which the active substances are present alone or, as described, in an emulsified or dispersed form.

In the following text the parts denote parts by weight.

Example 1 Compound 36 120 parts of 3,5- Melting point: 1°A-195°C (decomposition).

The following compounds of the type of are obtained in an analogous manner.

Compound • Melting point °C No. - ··. [decomposition] • 1 ·. CH„- 200-201° 2 197-199° °2H5 ~ 3 n-C3H?- . 193-194° 4. . 194-197° V.

C1-CH2-CH2- 190-192° 6 193-194° The following compounds of the type of obtained in an analogous manner.

Compound Melting point °C No. [decomposition] 205-206° 27 28 ¾¾- 198-199° 29' n-C5H?- 196-197° is obtained "by reacting the Na salt of 3>5_clibromo-~ hydroxybenzaldoxime-0-21 ,4' -dinitrophenyl ether with dimethylcarbamoyl chloride.

The following compounds of the type of are obtained in an analogous manner to that which has been described for the manufacture of compound 36. obtained in an analogous manner The following, compounds are obtained in an analogous The following compounds of the type of are obtained in an analogous manner The .following compounds of the type of are obtained in an analogous manner , The following compounds of the are obtained in an analogous manner The following compounds of the type are obtained in an analogous manner The following compounds of the type of are obtained in a analogous manner The following compounds of the type of are obtained.-in an analogous manner o ^btai·ned, m> an ananlogous manner ,> Compound oint °C No. i Melting p si ' · ■ · [decomposition) I 118 CH¾- 181-182° 119. C1-CH2-CH2- 148-149,5 01 120 " • 165-166° . ·. 1 Example 2 NO, [compound 126] 79 parts of 3, -dibromo- -hydroxybenzaldoxime-0- [21 ,4-' - dinitro] phenyl ether in 200 parts of acetic anhydride are heated for hours under reflux, stirred for a further 6 hours at room temperature, and the product filtered, twice digested with petroleum ether (boiling point 50-70°C) and again filtered,, Melting point: 200 - 201°C (decomposition).

Example 3 [Compound 12?| 49 parts of the Na salt of 3, 5-dibromo-4-hydroxybenzaldoxi -0-21 ,4' -dinitrophenyl ether are added to 140 parts of 2,4-dichlorophenoxyacetyl chloride in 200 parts by volume of acetonitrile .and the mixture is warmed to 90°0 for 2 hours After diluting with 400 parts by volume of petroleum ether (boiling point 50-70°C) the product is filtered off, digested with water and again filtered.

Melting point: 177 - 179° The following compounds of the type- of are obtained in this manner Example 4- 68 parts of the sodium salt of 3> 5-dibromo-4--hydroxy- benzaldoxime-0-2 ' , ' -dinitrophenyl ether are added to 200 parts of chloroformic acid methyl ester in 200 parts by. volume of acetonitrile and the mixture is warmed for 2 hours to 90°C, subsequently stirred for a further 10 hours at room temperature, diluted with 300 parts by volume of a petroleum ether (boiling point 50-70°C) and filteredo After digesting with water the mixture is again filtered.

Melting point: 189-190°C [decomposition] The following compounds of the type of are obtained in an analogous manner Dusting Agents Equal parts of an active substance according to the invention and of precipitated silica are finely ground.

Dusting agents which preferably contain 1-6% of active substance can be manufactured therefrom by mixing with kaolin or talc.

Spraying Powders In order to manu acture a spraying powder the following components are for example mixed and finely ground: 50 parts of active substance according to the present invention, 20 parts of Hisil (highly adsorptive silica), parts of bolus alba (kaolin), 3· 5 parts of a reaction product of p-tert. octylphenol and ethylene oxide and 1.5 parts of sodium l-benzyl-2-stearyl-benzimidazole-6, 31-disulphonate .

Emulsion Concentrate Easily soluble active substances can also be formulated as an emulsion concentrate in accordance with the following instructions: 20 parts of active substance, 70 parts of xylene and 10 parts of a mixture of a reaction product of an alkylphenol with ethylene oxide and calcium dodecylbenzene sulphonate are mixed. On dilution with water to the desired concentration a sprayable emulsion results.

Example 5 Selective herbicidal action The compounds encompassed by formula I show a Jgood action in combatting dicotyledon plants in the post-emergent treatments.

The treatment of the experimental field with active substances according to the invention is carried out 12 da^ after sowing, when the plants have developed one to two new leaves after emerging. The amounts used are 2 , 1 and 0.5 kg of active substance per hectare 0 The results are presented in the three tables which follow. As shown by the results, the compounds mentioned are throughout suitable for combatting dicotyledon plants in varieties' of grain,. Wheat, barley, oats and maize are completely spared by almost all compounds. Some compounds are also tolerated by soya and "flax cultures. The compounds 27 , 33 , 35 , 38 , 39 , 40, 9 , 72 , 73 , 113 , 114, 116 and 118 are tolerated. by rice. The active- substances 89 . and. 91 only. affect rice. plants slightly but destroy the well-known rice weed Panicun These results are representative of all compounds listed in examples 1 to 4.

: The following ratings are applicable to the assessment in the tables: 1-2 = no action, 3-4 = slight damage, -7 = severe damage and 8-9 = plant died.

T a b l e 1 Use amounts: 1 kg of active substanc a e ■ - 34 - 31317/1 Table 4 (cont'd) Example 6 In order to test the acaricidal action, phaseolus plants^ in the two-leaf stage are infested, 12 hours before the treatment, by placing pieces of leaf attacked by spinning mites on them. After 12 hours a population in all stages of development is present on the test plant.

The active substance No. 75 was sprayed in the form of an emulsion onto the plant through a fine atomiser in such a way that a uniform deposit of droplets was produced on ther__ ~" surface of the leaf. After 7 days the mortality was determined and expressed as a percentage. The following mortality values were determined for two varieties of spinning mite after 2 and 7 days: a) Tetranychus urticae b) Tetranychus telarius Concentration Adults Larvae Eggs 2 Days 7 Days 2 Days 7 Days 7 Days 800 100% 80% 100% 80% 60% 00 80% 80% 100% 80% 60% 200 60% 60% 80% 60% 60% 00 0% 0% 0% 0% 0% - 36 - 31317/2

Claims (13)

1. Pesticides for combating representatives of the order Acarina (mites, ¾icks, spinning mites and the like) and undesirable plants in cultures of useful plants, which contain, as active substances, compounds of general formula wherein denotes a lower alkyl or haloalkyl residue or a phenyl group which may be substituted by at most three substituents selected from halogen, nitro, trifluorcmethyl, lower alkyl or lower alkoxy, or wherein R^, in the case where n=0, denotes the 4-chlorophenoxymethyl, 2,4-dichlorophenoxy-methyl or 2-methyl-4-chlorophenoxymethyl residue; ¥ represents oxygen, the -13H- group or the -K(CH^)- group; n=0 or 1; and X represents halogen; one of the substituents R2 and ^ denotes the )2- group and the other optionally represents N02 or another negativising group selected from -CHO, -COOH, -COOR», -CO-R', -CON(A1)(A2) or (Ag) ; or independently represent hydrogen, halogen, lower allcyl or the -N(A^)(A2) group; where * represents lower alkyl and A1 and 2 independently of one another denote hydrogen or lower alkyl; together with a suitable carrier.

2. Pesticides according to Claim 1 which contain, as active substances, compounds of formula - 37 31317/2 wherein R^, R^, T and n have the same meaning as in Claim 1, X' denoted chlorine, bromine or iodine; and R * denotes 3 one of the groups - 02, -CHO, -SO^ ^(A≥) or -COOCH^.

3. Pesticides according to Claim 1 or 2 which contain, as active substances, compounds of formula R wherein R^' represents a lower alkyl or haloalkyl residue, an unsubstituted phenyl residue or a phenyl residue which is at most triply substituted by chlorine, bromine, -NO,,, -CH^ and or -CF^} X' denotes chlorine, bromine or iodine; R^" denote B the N02~ group or the (CH^N-SO^ group and R^' denotes hydrogen or chlorine.

4. Pesticides according to any of Claims 1 to 3 which, as the active substances, contain compounds of formula Ic - 38 - 31317/2 wherein R1" represents a lower alkyl or haloalkyl residue, an unsubstituted phenyl r> sidue or a phenyl residue which is at most triply substituted by chlorine, bromine, CH„ and/or CP„.

5. Pesticides according to any of Claims 1 to 4 which contain at least one of the following additives: carriers, solvents, diluents, thickeners, wetting agents, adhesives, emulsifiers, dispersing agents or also other pesticides*

6. A method of combating dicotyledones in cereal and maize cultures which comprises applying to said cultures a pesticidal preparation as given in any one of Claims 1 to 5.

7. A method of combating panicum in rice cultures which comprises applying to said cultures a pesticidal preparation as given in any one of Claims 1 to 5·

8. A method of combating weeds in soya cultures which comprises applying to said cultures a pesticidal preparation as given in any one of Claims 1 to 5.

9. A method for combating representatives of the order Acarina which comprises the use of a preparation given in any one of Claims 1 to 5·

10. Compounds of formula I in Claim 1.

11. Compounds of formula la in Claim ¾

12. Compounds of formula lb in Claim 3.

13. Compounds of formula Ic in Claim 4. For the Applicants DR. REIKHOLD COHU AND PARTNERS