IL44049A - 1,1-diphenyl-2-nitropropane and-butane derivatives,their preparation and insecticidal and acaricidal compositions containing them - Google Patents

Description

l,l- iphenyl-2-nitroprop^ne and¾utf*ne derivatives, their preparation and Ineectloldal a d acaricidaL compositions containing the© ; The present invention relates to 1 , 1 -diphenyl-2-nitro-propane and -butane derivatives, to processes for their preparati and to their use in combatting insects and members of the order'i Acarina.

The said 1 , l-diphenyl-2-nitropropane and -butane derivatives have the formula wherein represents C^-C^-alkyl, R2 represents p- (C^-C^) -alkoxyphenyl , p- (C^-C^) -alkylmercaptophenyl or 3 ,4-methylenedioxyphenyl , and Z represents C^ -CH-Cl^ or 02 -CH-C2H5.

The alkyl, alkoxy or alkylmercapto groups denot by R^ to R-j can be branched-chain or straight-chain.

These groups are: methyl, raethoxy, methylmercapto , ethyl, ethoxy, ethylmercapto, propyl, propoxy, propyl mercapto, isopropyl, isopropoxy and isopropylmercapto Compounds of formula I preferred on account of their action are those wherein R^ represents C^-C^-alkyl, R2 represents p- (C^-C^) -alkoxyphenyl or p- -alkylmercaptophenyl , and Z represents C^N-CH-CH^ or 02N-CH-C2H5.

Particularly preferred compounds of formula I are those wherein represents C-^-C^-alkyl, R.2 represents p- (C^-Cg) -alkoxyphenyl, and Z represents C^N-CH-CHg or (^ -CH-^H^ The compounds of formula I can be prepared, for example, analogously to the following known methods agent agent Applicable condensation agents are inorganic acids such as sulphuric acid; organic acids such as acetic acid; Lewis acids such as aluminium chloride or boron trifluoride in the form of complexes with inorganic or organic acids, such as phosphoric acid, acetic acid, etc.. ' The reaction is performed under normal pressure, at a temperature of between -30 and 100°C, preferably between 0 and 40°C, and optionally in solvents such as, e.g. acetic acid, nitroalkanes or methylene chloride.

The starting materials of formula II are in part known, or can be prepared by methods analogous to known methods, e.g. analogous to those described in the US Patent Specification No. 2,516,186.

The compounds of formula I have a broad insecticidal and acaricidal action, and can be used for the control of various plant and animal pests.

Compared with analogous compounds, the compounds of formula I have a surprisingly better insecticidal action, particularly against stored-food pests and mosquitoes, a toxicity level suitable for application and better decomposability .

Compounds of a structure similar to that of the compound of the present invention are known from Israel Patent Specification Nos. 32636 and 37477.

It has surprisingly been found that the compounds of the present invention have a much better activity against; herbivorous insects such as Leptinotarsa dec- emlineata and Spodoptera littoralis than compounds known from the above mentioned Israel patents.

The action of the compounds according to the invention extends moreover to all development stages, such as eggs, larvae, nymphs, pupae and adults of insects of the families: Acrididae, Blattidae, Gryllidae, Gryllotal-pidae, Tettigoniidae, Cimicidae, P^yrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, Pseudococcidae, Chrysoraelidae , Coccinellidae, Bruchidae, Scarabaeidae , Dermestidae, Tenebrionidae, Curculionidae, Tineidae, Noctuidae, Lymantriidae , Pyralidae, Galleridae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Culicidae, Trypetidae and Pulicidae, as well as acarids of the families: Ixodidae, Argasidae and Dermanyssidae .

The insecticidal or acaricidal action can be appreciably widened and adapted to suit given circumstances by the addition of other insecticides and/or acaricides.

Suitable additives are, e.g. the following active substances: organic phosphorus compounds, nitrophenols and their derivatives, formamidines , ureas, carbamates and chlorinated hydrocarbons .

The compounds of formula I are combined with particular advantage with substances having a synergistic or intensifying effeet . Examples of such compounds are pyrethrin synergists such as piperonyl butoxide or Z- (3 ,4-methylenedioxyphenoxy) -3 , 6, 9-trioxa-undecane (Sesoxane) .

The compounds of formula I can be used on their own or together with suitable carriers and/or additives.

Suitable carriers and additives may be solid or liquid, and they correspond to the substances common in formulation practice, such as, e.g. natural and regenerated substances, solvents, dispersing agents , .wetting agents, adhesives, thickeners, binders 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 these preparations being effected in a manner commonly known in practice. Also to be mentioned are cattle dips and spray races, in which aqueous preparations are used.

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 forms : solid preparations: dusts, scattering agents, granulates, coated granulates, impregnated granulates and homogeneous granulates; liquid preparations : a) water dispersible active-substance concentrates: vettable powders, pastes, emulsions; b) solutions.

The content of active substance in the described agents is between 0.1 and 95%; it is to be meritioned in this connection that in the case of application from an aeroplane, or by means of other suitable devices, concentrations of up to 99.5% can be employed, o even the pure active substance. .

The active substances of formula I can be prepared, for example, as follows: Dusts ; The following substances are used in the preparation of a) a 5% dust, 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 and ground with the carriers .

Granulate : The following substances are used to produce a 5% granulate : 5 parts of active substance, -.. ' ..· .. · 0.25 parts 6f epichlorhydrin, 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, • 91 parts of kaolin ( particle size 0.3 - 0.8 mm).

The active substance is mixed with epichlorhydrin and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The solution thus obtained is sprayed on to kaolin, and the acetone subsequently evaporated off in vacuo.

V?e11ab1e powder : The following constituents are used for the preparation of a) a 40%, b) and c) a 25%. and d) a 10% wettable pov.'der: a) 40 parts of active substance, 5 parts of sodium lignin sulphonate, 1 part of sodium dibutyl -naphthalene sulphonate, 54 parts of silicic acid. b) 25 parts of active substance, A.5 parts of calcium lignin sulphonate 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 1.5 parts of sodium dibutyl naphthalene sulphonate, 19.5 parts of silicic acid, ' 19.5 parts of Champagne chalk, * 28.1 parts of kaolin. c) 25 parts of active substance, 2.5 parts of isooctylphenoxy-polyoxyethylene-ethano 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 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 naphthalenesulphonic 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 rollers. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration.

-Etnulsif iable concentrates : The following substances are used to produce a) a 10% and b) a 2570 emulsifiable concentrate: a) 10 parts of active substance, . 3. parts of epoxidised vegetable oil, . 13. 4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylaryl- sulphonate 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 alcohol - polyglycol ether mixture .5 parts of dimethylformamide , 57. 5 parts of xylene.

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

Spray : The follov.'ing constituents are used to prepare a 57c. spray: 5 parts of active substance, 1 part of epichlorhydrin, 94 parts of ligroin (boiling limits 160° ~190°C) .

Example 1 A) Preparation of l-p-ethoxyphenyl-l-p-tolyl-2- nitro-propane 19.5 g of l-p-tolyl-2-nitro-l-propanol and 14.6 g of ethoxybenzene are dissolved in 80 ml of methylene chloride, and the solution added dropwise at 0°C, with vigorous stirring, to 90 g of cone, sulphuric acid and 10 ml of water. The mixture is stirred for two hours at room temperature, and then poured into 400 ml of ice water .

The product is taken up in methyl chloride, and washed with saturated sodium bicarbonate solution. After the solvent has been evaporated off, the oil remaining behind is dried in high vacuum at 60°C for 2 hours to obtain 27.2 g (= 91% of theory) of 1-p-ethoxyphenyl-l-p-tolyl-2-nitropropane in the form of a viscous, 19° dark yellow oil having a refractive index of nn = 1.5571.

B) Preparation of l-p-ethylmercaptophenyl-l-p-tolyl- 2-nitropropane 19.5 g of l-p-tolyl-2-nitro-l-propanol and 16.2 g of ethylmercaptobenzene are dissolved in 80 ml of methylene chloride, and the solution added dropwise at 0°C to 90 g of cone, sulphuric acid and 10 ml of water . The mixture is stirred for 2 hours at room temperature, then poured into ice water, and the product extracted with methylene chloride.

The solvent is evaporated off and the oil remaining behind dried at 60° C in high vacuum for 4 hours: the yield is 29 g of l-p-ethylmercapto-phenyl-l-p-tolyl-2-nitropropane in the form of viscous, dark yellow oil 19° having a refractive index of nD = 1.5629.

The following compounds are prepared in an analogous manner : Example 2 A) Insecticidal stomach poison action Cotton and potato plants were sprayed with a 0.1% aqueous active-substance emulsion (obtained from a 10% emulsifiable concentrate) .

After the drying of the resulting coating, Spodoptera littoralis or Heliothis virescens larvae were placed on the cotton plants, and Colorado? beetle larvae (Leptinotarsa decemlineata) on the potato plants. The test was carried out at 24°C with 60% relative humidity.

The compounds according to Example 1 exhibited in the above test a good insecticidal stomach poison action against Spodoptera littoralis , Heliothis virescens and Leptinotarsa decemlineata larvae.

B) Contact action against stored-food pests and house pests Five parts by weight of an active substance and five parts by weight of talcuni are mixed together and finely ground. A further 90 parts by weight of talcum are mixed in to obtain a 5%, dust; this can be used as a starting mixture for 1 : 1-dilutions for graduated tests of the active substances with respect to their action against stored-food pests and house pests.

The test insects, German cockroach (Phyllodromia germanica) American cockroach (Periplaneta americana) Russian cockroach (Blatta orientalis) , yellow mealworm imago (Tenebrio molitor) larvae, larder beetle imago (Dermestes frischii) larvae, pelt beetle larvae (Attagenus pellio) , European house cricket (Acheta domesticus) , and grain weevil (Sitophilus granarius) , are placed on filter paper in glass dishes, the filter paper having been treated with 2 g of the 5% formulation. 2 The amount of active substance is 100 mg of AS/m . The applied 1 : 1-dilutions then give 2.5%, 1.25%, 0.6%, 0.31% and 0.16% active-substance formulations, which correspond to active-substance amounts of 50, 25, 12.5, 6.2 and 3.1 mg 2 of AS/m when 2 g of the respective dust formulation is used for each glass dish.

Compounds according to Example 1 exhibited in the above test contact action against Phyllodromia germanica, Periplaneta americana, Blatta orientalis, Tenebrio molitor, Dermestes frischii, Attagenus pellio, Acheta domesticus and Sitophilus granarius.

C) Contact action against adults of Aedes aegypti With use of an acetone solution, amounts of 1, 0.1, 0.01 and 0.001 mg of active substance per Petri dish were applied. Each test was performed twice with 10 mosquitoes for each concentration. Both the rate of action and the applied amount, for a 100% mortality were taken into account in effecting an evaluation.

Compounds according to Example 1 exhibited in the above test a favourable action against adults of Aedes aegypti.

Example 3 Action against Chilo suppressalis Rice plants of the variety Caloro were planted, 6 plants per pot, in plastic pots having a top diameter of 17 cm, and grown to a height of ca. 60 cm. Infestation with Chilo suppressalis larvae (L^; 3-4 mm long) was carried out 2 days after application of the active substance in granular form (amount applied = 8 kg of active substance per hectare) to the paddy water . The evaluation of the insecticidal action was made 10 days after application of the granules.

Compounds according to Example 1 were effective against Chilo suppressalis in the above test.

Example 4 Action against ticks A) Rhipicephalus bursa In each case, 5 adult ticks or 50 tick larvae were placed into a small glass test tube; the test tubes were then immersed for 1 to 2 minutes in 2 ml of an aqueous emulsion from a dilution series of 100, 10, 1 and 0.1 ppm of test substance. The tubes were then sealed with a standardised cotton plug, and inverted so that the active-substance emulsion could be absorbed by the cotton wool.

An evaluation in the case, of the adults was made after 2 weeks, and in the case of the larvae after 2 days. There were two repeats for each test.

B) Amblyomma hebraeum With a solution series analogous to that in Test A, tests were carried out using in each case 20 larvae.

Compounds according to Example 1 were effective in these tests against adults and larvae of Rhipicephalus bursa and against larvae of Amblyomma hebraeum.

Claims (3)

WHAT WE CLAIM IS:

1. A compound of the formula wherein represents C^-C^'-alkyl,

5. R2 represents p- (C^-C^) -alkoxyphenyl, p- (C-^-C^) -alkylmercaptophenyl" or 3,4-methylenedioxyphenyl, and Z represents 02N-CH.-CH3 or 02 -CH-C2H5.

2. A compound according to Claim 1 wherein 10 represents C^-C^-alkyl, R2 represents p- (C^-C^) -alkoxyphenyl or p- (C^-C^) -alkylmercaptophenyl, and Z represents 02N-CH-CH3 or 02N-CH-C2H5.

3. Compounds according to Claim 2 wherein 15 R^ represents C^-C^-alkyl, R2 represents p- (C^-C^) -alkoxyphenyl, and Z represents 02N-CH-CH3 or C^ -CH-C^. 44049/2

4. The 1-p- Ethoxyphenyl-l-p- tolyl-2-nitropropane according to Claim 3. '(

5. The 1-p-. Ethoxyphenyl-l-p-isopropylphenyl-2-nitro-propane according to Claim 3.

6. The 1-p-. Ei:hoxyphenyl-l-p-ethylphenyl-2-nitropro-pane according to Claim 3.

7. The l-p-Prop^^oxyphenyl-l-p- isopropylphenyl-2-nitro-butane according to Claim 3.

8. The 1-p-Ethoxyphenyl-l-p- tolyl-2-nitrobutane according to Claim 3.

9. The l-p-Prop^^oxy-l-p-tolyl-2-nitrobutane according to Claim 3.

10. The 1-p-Isoprop^ xy-l-p- tolyl-2-nitrobutane according to Claim 3.

11. The l-p-Methoxy-l-p-ethylphenyl-2-nitropropane according to Claim 3.

12. The l-p-Ethoxyphe.nyl-l-p-ethylphenyl-2-nitrobutane according to Claim 3.J~^

13. The l-p-Ethoxyphenyl-l-p-propylphenyl-2-nitropropane according to Claim 3.

14. The l-p-Methoxyphenyl-l-p-propylphenyl-2-nitro- propane according to Claim 3.

15. The l-p-Ethoxyphenyl-l-p-propylphenyl-2-nitro- butane according to Claim 3.

16. The l-p-Isopropylthiophenyl-l-p-tolyl-2-nitropro- pane according to Claim 2.

17. The Ι- ' ,41 -Dioxymethylenephenylj-l-p-tolyl-2-nitro- propane according to Claim 1.

18. The 1-^3 ' ,4' -Dioxymethylenephenyl-l-p-ethylphenyl- 2-nitropropane according to Claim 1. butane according to Claim 1.

20. The 1-3 ' -4 ' -Dioxymethylenephenyl-l-p-ethylphenyl-2-nitrobutane according to Claim 1.

21. Process for the preparation of compounds according to Claims 1 to 20, wherein a compound of the formula 44049/2 is reacted, in the presence of a condensation agent, with a compound of the formula Β,^β; or a compound of the formula Β--0Η-Ζ reacted, in the presence of a condensation agent OH with a compound of the formula wherei , Big and Z have the meanings given in Claim 1.

22. Inseotlcidal and acarlcidal compositions which contain as active ingredient a compound according to Claims 1 to 20 together with suitable carriers and/or additives. r 25· A method for the control of insects and members of the order Acarina at a locus, which method comprises applying to the locus a compound as claimed in Claim 1. .