IL41437A - Phenyl and benzyl alkynyl ethers their production and pest-population control compositions containing them - Google Patents

Description

41437/2 ο»ι»Φ3ηι ο*ηχ*· ,α»©·»η η*ηηκ *»·» ^«· V'taar » a M pheny : a»4 benzyl ¾*fcyny£ e he s* their pro c¾ion atitil pefrfc-pOpi&a ion contrpl comppsitiqnsr eonfcaintag thcim .

C 8 The present invention relates to phenyl- or benzyl- alkynyl ethers, to their production, and to their use for the control of the population of insects and phyto- pathogenic nematodes.

The compounds correspond to the formula wherein 3 represents hydrogen, .methyl or. iodine, R2 represents hydrogen, methyl or ethyl, R^ represents hydrogen or methyl, R, represents cyciohexyl, or the group wherein Rg represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, methoxy or ethoxy, , R(- represents hydrogen, methyl or chlorine , and Z represents oxygen or the group -Cl^O-, whereby the , CH2 -group i« bound to the phenyl nucleus.' Compounds to be particularly emphasised because of their effec iveness are compounds of formula I wherein represents hydrogen, methyl or iodine, R2 represents hydrogen or methyl, Rg represents hydrogen, wherein 41437/3 Rg stands for hydrogen, _ fluorine , chlorine, methyl, ethyl or ethoxy, ' _ __ . ._...-· - R,- represents hydrogen, and Z represents oxygen or the group -Cl^O-, whereby the -group is bound to the phenyl nucleus.

The production of the compounds of formula I is effected in a manner known per se (e.g. according to Houben-Weyl, Vol. VI/3, pp. 10-40, 1965) by the following reactions: In the formulae II, III, IV and V, the symbols R^, 1*2» R.j, R^, R^, and Z have the meanings given for formula I, M stands for a cation, preferably a metal, particularly for s. metal of the first or the second main group o the periodic system, or for hydrogen, and X stands for halogen, preferably chlorine, bromine or iodine.

The compounds of formula I can be obtained by reaction of a compound of formula II with an alk n l halide of formula III in various solvents and at various reaction temperatures .

Suitable inert solvents are especially ketones, such a e.g. acetone, methyl ethyl ketone, isopropyl methyl ketone cyclohexanone, also dimethoxyethane, tetrahydrofuran, dioxane, dialkyl ether, dimethylformamide, dimethyl sulphoxide, hexameth 1phosphoric acid triamide, or hydrocarbons such as toluene, xylene or benzene.

Bases are used for the production of the alcoholate or phenolate of formula II. Suitable bases or acid acceptors are, in particular, alkali and alkaline-earth carbonates, alkali and alkaline-earth hydroxides, alkali or alkaline-earth hydrides and alkali alkoxides. With the use of alkali or alkaline-earth hydrides, alkali or alkaline-earth hydroxides or alkali alkoxides as bases, the phenol or the alcohol can firstly be converted in a suitable solvent into the alkali or alkaline-earth phenolate or alcoholate (formula II, M «=» alkali or alkaline-earth metal.),· the alkynyl halide is then allowed to act on the thus formed phenolate or alcoholate.

Alkali or alkaline-earth carbonates as acid acceptors are preferably added directly to the reaction mixture consisting of phenol II, alkynyl halide III and inert solvent. Preferred solvents with the employment of alkali and alkaline-earth carbonates as bases are ketones, e.g. acetone, methyl ethyl ketone, isopropyl methyl ketone or cyclohexanone. Particularly preferred in this group of acid acceptors is potassium carbonate.

The reaction temperatures for the ether formation are between 0° and <:a. 120°C, preferably between room temperature and 80°C, or, e.g. the boiling temperature of the applied solvent (acetone, methyl ethyl ketone, etc.) The compounds of formula I wherein Z represents the group -CH2O- can also be obtained by reaction of a halide of formula IV with an alcoholate of formula V, in the *" presence of a. solvent, at various reaction temperatures . Suitable solvents are ethers such as, e.g. tetrahydrof ran, dioxane, dialkyl echer, 1,2-dimethoxyethane, also dimethylformamide , climethyl^sulphoxide , hexamethyl- phosphoric acid triamide, or hydrocarbons such as toluene, benzene or xylene.

The reaction temperatures are between -10° and 100°C, preferably between 0" and 70°C.

Bases used for the production of the alcoholate of formula V are, in particular, alkali alkoxides and alkali hydrides .

The preparation and isolation of compounds of formula I are effected by known techniques; e.g., by a process in which the reaction solution is filtered off from the solid substance on the bottom, the filtrate concentrated by evaporation, the residue taken up in a suitable solvent (e.g. ether, hexane), and this solution washed with dilute alkali solution and water. After the drying of the organic phase over sodium sulphate and removal of the solvent, the obtaine alkynyl ether of formula I can, if necessary, be further purified by crystallisation, high vacuum distillation, or chromatography on silica gel or aluminium oxide. The reaction mixture can, moreover, be poured on^j-o ice or into ice water and subsequently extracted with a suitable solvent (e.g. ether, methylene chloride, hexane) . The further isolation and purification of the reaction product is then as described above.

The starting materials of formulae II, III, IV and V are known compounds, or can be produced by methods analogous to known methods described in the literature.

The compounds of formula I are suitable for the control of insects and phytopathogenic nematodes . To be particularly emphasised is the larvicidal and ovicidal action of the compounds of formula I against insects, e.g. of the following orders and families: Orthoptera Acrididae Gryllidae Blattidae Isoptera Kalotermitidae Hemiptera Miridae Piesmidae Lygaeidae Pyrrhocoridae Pentatomidae Cimicidae Reduviidae Jassidae Eriosomatidae Lexaniidae Coleoptera Carabidae Elateridae Coccinellxdae Tenebrionidae Dermestidae Cucujidae Chrysomelidae Curculionidae Scolytidae Scarabaeidae Lepidoptera Pyralidae Phyticidae Pyraustidae Crambidae Tortricidae Galleriidae Lyonetiidae Yponomeutidae 41437/3 Pieridae Plutellidae • Lymantriidae Noctuidae Diptera Pulicidae Simuliidae Tipulidae In the French Patent No. 1,510,861 and in the German •Offenlegungsschriften' Nos . 2,049,391 and 2,100,325, analogous compounds are . described as synergists to known insecticides. Also Israel Patent Specification No. 26400 discloses insecticidal compositions comprising an insecticidal carbamate and, as a synergist ,, a propargyl aryl ether of the formula Aryl-Y-CH2-C=C-X wherein Y is oxygen or sulfur, X is hydrogen or halogen and "Aryl" may represent, inter alia, a phenoxy-phenyl group. However, no compound of this type, which are formally included in formula I herein, was specifically disclosed in Patent Specification No. 26400.

Surprisingly, it has now been found that the compounds of formula I have an appreciably better action against larvae and eggs of insects than that of the known compounds.

First and foremost is the action of the compounds of formula I against mosquito larvae.

The compounds of formula I can be used alone or together with suitable carriers and/or additives. Suitable carriers and additives can be solid or liquid and they correspond to substances common in formulation practice, such as, e.g. natural or regenerated substances, solvents, dispersing agents, wetting agents, adhesives, thickeners, bonding agents and/or fertilisers. For application, the compounds of formula I can be processed into the form of dusts, emulsion concentrates, granulates, dispersions, sprays or solutions, the formulation of the said preparations being effected in a manner commonly known in practice.

The agents according to the invention are produced in a manner known per se by the intimate mixing and/or grinding of active substances of formula I with suitable carriers, optionally with the addition of dispersing agents or solvents which are inert to the active substances.

The active substances can be obtained and used in the following preparation forms: Solid "forms : Dusts, scattering agents* granules, coated granules, impregnated granules and homogeneous granules.

Liquid forms : ... a) active substances which are dispersible in water: wettable powders, pastes, emulsions; b) solutions.

To manufacture solid forms (dusts, scattering agents), the, active^substance.s_are_mixedt„with^ carriers^are , for example: kaolin, talcum, bolus, loess, chalk, limestone, attapulgite , dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potas-- sium aluminium silicates, (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materials ," fertilisers , for example ammonium" sulphate"," ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder, residues of plant extractions, activated charcoal etc. These substances can either be used singly or in admixture with one another.

Granules can be very easily manufactured by dissolving an active substance of the formula I in an organic solvent and applying the resulting solution to a granulated material, for example attapulgite, SiC^, granicalcium, bentonite etc. and then evaporating the solvent.

Polymer granules can also be manufactured by mixing the active substances of the formula I with polymerisable compounds (urea/formaldehyde; dicyandiamide/formaldehyde ; melamine/ formaldehyde or others), whereupon a mild polymerisation is carried out that does not affect the active substances and in . the process of which the granulation is carried out during the gel formation. It is more advantageous to impregnate finished, porous polymer granules (urea/formaldehyde, polyacrylonitr le , polyester or others) which have a specific surface area and a favourable predeterminable adsorption/desorption ratio, with the active substances, for example in the form of their solutions (in a low boiling solvent') and to remove the solvent. Polymer granules of this kind in the form of microgranules having a bulk density of 300 g/liter to 600 g/liter can also be manufactured with the aid of atomlGers. The dusting can be carried qut from aircraft over extensive areas of cultures of Useful plants.

It is aliso possible to obtain granules by compacting the carrier with the) aotive substance and carriers and subsequently comminuting the product.

To these mixtures can also be added additives which stabilioa the active substance and/or non-ionic, anionic and cationic surface active substances, which, for. example, improve the adhesion of the active ingredients on plants or parts of plants (adhesives and agglutinants ) and/or ensure a better* wettability (wetting agents) and dispersib lity (dispersing agents). Examples of suitable adhesives are the following: olein/chalk mixture, cellulose derivatives (methyl cellulose, carboxyrnethyl cellulose), hydroxyethyl glycol ethers of mono-alkyl and dialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl radical, lignifPsulphonic acids, their alkali metal and alkaline earth metal salts, polyethylene glycol ethers (carbov/axes ) fatty alcohol polyethylene- glycol ethers having 5 to 20 ethylene oxide radicals per molecule and 8 to l8 carbon atoms in the fatty alcohol moiety, condensation products of ethylene oxide/ propylene oxide, polyvinyl pyrrolidones, polyvinyl alcohols, conden- ■ sa ion products of urea and formaldehyde, and also latex products.

The water-dispersible concentrates of the active substance, i.e. wettable powders, pastes and emulsifiable concentrates, are agents which can be diluted "with water to. any concentration desired. They consist of active substance, carrier, · optionally additives which stabilise the active subs-tanoe, surface-active substance and anti-foam agents and, optionally, solvents.

Wettable powders and pastes are obtained by mixing and .grinding the active substances with dispersing agents and pulverulent carriers in suitable apparatus until homogeneity is attained. Suitable carriers are, for example, those mentioned for the solid forms of application. In some cases it is advantageous to use mixtures of different carriers. As dispersing agents. there can be used, for example, condensation products of sulphonated naphthalene and sulphonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfphonic acids with. phenol and formaldehyde, as well as alkali, ammonium and alkaline earth metal salts of lignin - sulphonic acid, in addition, alkyl arylsulphonates , alkali and alkaline earth metal salts of dibutylnaphtha lenesulphonic acid, fatty alcohol sulphates such as salts of sulphated hexa- decanols, heptadecanols , dctadecanols , and salts of sulphated fat alcohol glycol ethers, the sodium salt of oleoyl ethionate, the so dium salts of oleoyl methyl tauride, ditertiary acetylene glycols diaSlkylvdil'auK -.yar.mo ^ ic jailfcaJkii..anduvu alkaline earth metal salts.

Suitable anti-foam agents are silicones. · The active substances are mixed, ground, sieved and strained with the additives . cited hereinabove in such a manner that the siza of ho- solid ar icles does not exceed 0.02 to 0.θ μ in wetta le jjov;dors, and C.OjJ jj. in pastes. To produce emulsi iable concentrates and pastes, dispersing agents such as those cited above, organic solvents, and water arc used.

Examples, of suitable solvents are: alcohols, benzene/ xylene, ' toluene, dimethyl sulphoxide, -and mineral oil fractions /hich bol between 120°and 350°C. The solvents must be practically odourless, not phytotoxic, and inert to ths active substances. can be applied in the form of solutions. For this purpose the active substances, or several active substances of the general formula If are dissolved in suitable organic solvents, mixtures of solvents or in water. Aliphatic and 'aromatic hydrocarbons, chlorinated derivatives thereof, alkylnaphthalenes, and mineral oils, singly or in admixture with each other, can be used as organic solvents.

The content of active substance in the above describe agents is between O.ljo to 95#* in v/hich connection it should be mentioned that, in the case of application from aircraft or some other suitable means of application, it is possible to use concentrations of up to 99*5^ or even pure active substance.

The active substances of the formula I can, for example, be formulated as follows: Dusts • The following substances are used to manufacture a) a 5# and b) a 2# dust: a) 5 parts of active substance 95 parts of talcum . ■ . b) . 2 parts of active substance 1 part of highly dispersed silicic acid 97 parts of talcum.

The active substances are mixed with the carriers and ground .

Granules .· The following substances are used to produce 5 granules: 5 parts of active substance, 0.25 parts of epichlorohydrin, Ο.25 parts of cetyl polyglycol ether, 5.50 parts of polyethylene glycol, 91 parts of kaolin (particle size O. > - 0.8 mm).

The active substance is mixed with epichlorohydrin and ' dissolved with 6 parts of acetone j. the polyethylene glycol and cetyl polyglycol ether are then added. The thus obtained solution is sprayed on kaolin, and the acetone subsequently evaporated in vacuo. ' ■· V/o1 abl pov;dc : The following constituents are used for the preparation of- a) a 40#, b) and c) a 25#, and d) a 1θ wettable powder: a) ^40 parts of active substance, . . 5 parts of sodium ligninsulphonate, 1 part of sodium dibutylnaphthalenesulphonic acid, 5 parts of silici2 acid . b) 25 parts of active substance, ^.5 parts of calcium of ligninsulphonate, 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 1.5 parts of sodium dibutylnaphthalenesulphonic acid I9.5 parts of silicic acid, I9.5 parts of Champagne chalk, .· 28.I parts of kaolin. c) 25 parts of active substance, .5 parts of isooctylpheho.xy-polyoxyethylene-ethanol 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselguhr, 46 parts of kaolin, d) 10 parts of active substance, 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates, 5 parts of n ph halenesulphonic acid/ formaldehyde^ condensate., 82 parts of kaolin* The active substances are intimately mixed, in suitable mixers, with the additives, the mixture being then ground in the appropriate mills and tollers. Wettable powders are obtained which can be diluted with water to give suspension of any desired concentra ion.

Emulsifiable concentrates: The following Hubstances are used to produce a) a 10% b) a 25% emulsifiable and c) a 50% emulsifiable concentrate: a) 10 parts of active substance, 3.4 parts of epoxidised vegetable oil, 3.4 parts of combination emulsifier consisting of fatty alcohol polyglycol ether and alkylarylsulphonate calcium salt , 40 parts of dimethylformamide, 43.2 parts of xylene, b) -25 parts of active substance, 2.5 parts of epoxidised vegetable oil, 10 parts of an alkylarylsulphonate/fatty alcoholpoly- glycol ether mixture 5 parts of dime hyIformamide , 57.5 parts of xylene, c) 50 parts of active substance, 'c . 4.2 parts of tribu ylphenol-polyglyliol ether, i 5.8 parts of calcium dodecylbenzc2 sulphona te , 20 parts of eye lohexanone , I 20 parts of xylol.

From these concentrates it is possible to produce, by dilution with water, emulsions . of any desired concentra ion.

Spra :. ...

The following constituents are used to prepare a) a 5% and b) a 95% spra : a) 5 parts of active substance, 1 part of epichlorohydrin, 5 parts of epichlorohydrin, Example 1 A mixture of 18.6 g of 4-hydroxy-diphenyl ether, 13.1 g of propargyl bromide and 16.6 g of anhydrous potassium carbonate in 150 ml of acetone is stirred for 16 hours at the reflux temperature. The reaction mixture is thereupon filtered off from the substance on the bottom, the acetone distilled off in vacuo, and the oily residue taken up in 200 ml of ether/hexane (1:1); this solution is washed four times with 10% potassium hydroxide solution and subsequently with water until neutral. The organic phase is finally dried over s'odium sulphate and filtration performed. After the solvent and the volatile fractions have been . completely removed in vacuo from the filtrate, there is obtained analytically 20 pure 4-propargyloxydiphenyl ether; n^ : 1.5830.

Example 2 An amount of 5.2 g of a ca. 60% suspension of sodium hydride in mineral oil is washed twice with hexane and once with tetrahydrofuran, and finally suspended in 40 ml of tetrahydrofuran* An addition is then made dropwise within half an hour, with slight cooling, of 7.4 g of propargyl alcohol, and stirring continued for a further 3 hours at room temperature. After the formation of the alcoholate, there is added dropwise, in the course of ca. one hour, the solution of 26.3 g of 4-br.omomethyl--di-pheny1-ether-in-40-ml~of-hexamethylphosphoric aci"d triamlde and 10 ml of tetrahydrofuran, and the whole further stirred overnight e.t room temperature. To effect the isolation of the product, the reaction mixture is poured into ca. 500 ml of ice water, and extraction repeatedly performed with diethyl ether. The combined ether phases are successively washed, until neutral, with water, 10% potassium hydroxide solution, and finally with sodium chloride solution. After the drying of the ether solution over sodium sulphate, the solvent and the volatile fractions are completely removed in vacuo, and the oil-like remaining behind ilica gel (eluant: diethyl ether/hexane 1:4); njj° : 1.5710.

Also the following compounds are produced in an analogous manner to that described in Examples 1 and 2.

Example 3 Inhibitory effect on larvae of Dysdercus fasciatus ' Ten larvae of Dysdercus fasciatus, which were 8 - 10 days before moulting into the adult stage, were topically treated with acetonic active-substance solutions. The larvae were then kept at 28°C with 80 - 90% relative humidity; they were fed on the shred of presoaked cottonseed. After ca. 10 days, i.e. as soon as the test insects had completed moulting, the insects were examined to determine the number of normal adults. The compounds according to Examples 1 and 2 exhibited a high degree of ef ectiveness in the above test.

Example 4 Inhibitory effect in the gas phase on the eggs of Spo optera littoralis Into one 130 ml flask with ground glass stopper were placed 40 mg of active substance, and into another of 175 ml content 100 eggs of Spodoptera littoralis. The two flasks were connected with a connecting member, and maintained at 25°C.

The evaluation of the inhibitory effect was made after .5 to 6 days .

Compounds according to Examples 1 and.2 displayed a high degree of eff ctiveness in the above test.

Example 5 Action ngainst soil nematodes In order to test the action against soil nematodes the active substance was added in a concentration of-50 ppm to soil infested with root-gall nematodes (Meioidogyne arenaria), and the whole intimately mixed. In the one test series, tomato seedlings were planted immediately afterwards in the thus prepared soil, and in the other. test series tomatoes were planted after a waiting time of 8 days .

For an assessment of the nematicidal action, the?.gall present on the roots were counted 28 days after the " planting and sowing, respectively. Compounds according to Examples 1 and 2 exhibited a good nematocidal action in. he above test.

Example .6 Into a beaker containing a solution of active substance (concentration 5 ppm) were placed about twenty 2-day-old larvae of the yellow fever mosquito (Aedes aegypti) „ The beaker was then covered with a perforated lid. After the test-insects had completed their moult into the adult stage, the insects were examined and the percentage of normal adults determined, taking as a basis the number of normal adults present in the control test.

The compounds according to Examples 1 - and 2, exhibited! · a high degree of effectiveness in the above test.

Claims (4)

1. 41437-2 CLAIMS: 1. Compounds of the formula wherein R^ represents hydrogen, methyl or iodine, β.2 represents hydrogen, methyl or ethyl, R-j represents hydrogen or..methyl, represents cyclohexyl, or ; the . group wherein . R- represents hydrogen, fluorine, chlorine, bromine, b methyl, ethyl, methoxy;, or ethoxy, and R,. represents hydrogen, methyl or chlorine, Z represents oxygen, or the group -CI^O-, whereby the -group is bound to the phenyl nucleus.

2. Compounds according to Claim 1, wherein R^ represents hydrogen, methyl or iodine., R2 represents hydrogen or methyl, group wherein Rg stands for hydrogen, fluorine, chlorine, methyl, ethyl or ethoxy, R,. represents hydrogen, Z represents oxygen, or the group -CH O-, whereby the 41437-2 <

3. l-Propargyloxy-4-phenoxy-benzene according to Claim 2.

4. l-Propargyloxymeth)'l-4-phenoxy-benzene according to Claim 2 5.· 3- ]-l-butine according to Claim 2. 6. 3- [4-phenoxy-phenoxy ]-l-iodo-l-propine according to Claim 2 7. Process for the production of compounds of the formula wherein represents hydrogen, methyl or iodine, '* 12 represents hydrogen, methyl or ethyl, represents hydrogen or methyl, represents cyclohexyl, or the group wherein Rg represents hydrogen, fluorine, chlorine, bromine, cmethyl, ethyl, methoxyor ethoxy, and R^ . represents hydrogen, methyl or chlorine, and Z represents oxygen, or the oup^Ci^G- , whereby the CHg- group is bound to the phenyl nucleus, the said process comprising the reaction of a compound of the formula with a compound of the formula 41437/3 wherein to R^, R,. and Z have the above given meanings, X stands for halogen, and M for a cation, preferably a metal. 8. Process for the pxoduction of compounds of the formula wherein R^ represents hydrogen, methyl..or iodine, R2 represents hydrogen, methyl or ethyl, R^ . represents hydrogen or methyl, R^ represents cyclohexyl or the — ^Z^- R^ group, whereinsiii;^ r. R represents hydrogen, fluorine, chlorine, bromine, methyl; 6 ethyl, methoxy or ebhoxy,,and represents hydrogen, methyl or chlorine, the said process comprising; the reaction of a compound of the formula with_a_.compound._of_the_formula wherein have the above given meanings, X stands for halogen and M for a cation, preferably a metal. 41437-2 wherein to R^, R,_ and Z have the above given meanings, X stands for halogen, and M for a cation, preferably a metal. 8. Process for the production of compounds of the formula wherein R^ represents hydrogen, methyloor iodine, R2 represents hydrogen, methyl or ethyl, R^ represents hydrogen or methyl, R^ represents cyclohexyl or the —^Z^" R^ group, wherein R represents hydrogen, fluoritB , chlorine, bromine, methyl, 6 ethyl, methoxy or ethoxy,,and represents hydrogen, methyl or chlorine, the said process comprising the reaction of a compound of the formula with a compound of the formula \ 2 M0-OC=R, ¾ wherein R^ to R^, and Z have the above given meanings , X stands for halogen and M for a cation, preferably a metal. 41437-2 pound of the formula wherein R^ represents hydrogen, methyl or iodine, R_2 represents hydrogen, methyl or ethyl, represents hydrogen or methyl, represents cyclohexyl, or the^^^R^ group wherein R^ represents hydrogen, fluorine, chlorine, bromine,.,methyl^ ethyl, methoxy or ethoxy, and R,. represents hydrogen, methyl or chlorine and Z represents oxygen, or the group -CH^O-, whereby the -group is bound to the phenyl nucleus, together with suitable carriers and/or other additives. 10. Agents according to Claim 9 containing as active component a compound, according to one of the Claims 2 to 6. 11. A method for the control insects and phytopathogenic nematodes which comprises applying to said pests a compound of the formula r4"°-