IE41817B1 - Bis-(dithio)-aminoalkanes - Google Patents

Abstract

The pesticide contains as active component at least one compound of the formula I in which R1 and R2 individually are methyl or ethyl or together, along with the nitrogen atom, are pyrrolidine, piperidine or morpholine. The active ingredient can be prepared by two process variants. The pesticide has a strong insecticidal, acaricidal and fungicidal action. As an insecticide, it acts on contact and ingestion as well as systemically. The pesticide is particularly suitable for controlling pests in which a certain duration of action of the applied active ingredients is required. The pesticide is applied as a liquid spray, as a dusting powder, as granules, as a paste or as an aerosol. The formulations can contain from 1 to 90% by weight of active ingredient.

Description

The present invention relates to a 2-aminopropane derivative which possesses insecticidal and fungicidal properties.

Accordingly, the present invention provides 1,3bis-(tert.-butylaithio)-2-dimethylaminopropane, of the formula X, CH N-CH CH2-SS-C(CH3)3 CH,-SS-C(CH3)3 in free base or acid addition salt form.

The acid addition salt forms include those with inorganic acids, e.g. hydrochloric, sulphuric and phosphoric acids, and those with organic acids, e.g. oxalic, benzenesulphonic, toluenesulphonic, methanesulphonic, acetic and benzoic acids, of which those forms with hydrochloric and oxalic acids are the most preferred.

The present invention further provides a process for the production of the compound of formula I in la free base or acid addition salt form , which comprises reacting a compound of formula II, CH -S~L II CH x ch2-s-l II m which' L is a group of formula -S-R1, wherein R^ is an alkyl or aryl radical, and m is 0 or 1, or L is a group -SO^^, wherein is sodium or potassium, with a compound of formula III, (ch3)3csm2 III in which M2 is sodium or potassium, in such a proportion that both L moieties in the compound of formula II are replaced by -S-C(CH3)3 radicals from the compound of formula III.

In the compound of formula II, the alkyl radical signified by R^ is preferably one containing 1 to 3 carbon atoms, and preferred examples of the aryl radical signified by Rj. are the phenyl and toluyl radicals. Mj. and are preferably each, independently, sodium in the compounds of formulae II and III, respectively.

The production of the compound of formula I is preferably effected by adding the compound of formula III, preferably in solution in a suitable solvent, e.g. water, an alcohol suoh as methanol, ethanol or propanol, a nitrile suoh as acetonitrile, a ketone such as acetone, butan-2- one or cyclohexanone, an ether such as dioxan or tetrahydrofuran, or an amide such as dimethyl10 formamide, and preferably with stirring, to the compound of formula II in solution or suspension in a suitable solvent or diluent, preferably the same medium as that used for the solvent of the compound of formula III.

The preferred solvents or diluents are water and methanol. When L in formula II is a -SO^M^ group, the addition is effected at a temperature below room temperature, preferebly within the range 0-10°C. Generally the addition is effected over a period from 20 minutes to 2 hours, and a further period of time during which the reaction mixture is stirred and kept cool, or, when Using a starting material of formula II in which L is 0 a -S-R. group, warmed, e.g. to 50°C, is often required (6) -1 m to complete the reaction. Such additional reaction time is generally between and 1 4/2 hours.

The compounds of formulae II and III used as starting materials are either known compounds or can be produced by or analogously to known methods.

The free base form of the compound of formula I can be converted into an acid addition salt form, and vice versa, by conventional techniques.

It has been found that the compound of the present invention, i.e. the compound of formula I in free base or acid addition salt form, exhibits unexpected stability, e.g. against light, humidity or heat. This is indicated by a virtual lack of tendency to decompose when distilled under high vacuum or when stored or used under conditions in which it would be expected to be affected by the prevailing light, humidity or heat conditions.

Furthermore, the compound of the invention may be produced in good yields and purity, particularly when using a compound of formula II in which L is a -SO^M^ group.

The compound of the invention possesses insec4 fcicidal activity and is therefore indicated for use as an insecticide. By the term insect as used in this specification are included not only members of the class insecta but also members of related classes of animal organisms e.g. Acaridae such as spider mites.

The terms insecticide, insecticidal and the like are to be construed accordingly.

Xn its use as an insecticide, the compound of the invention displays a contact effect, a systemic effect and/or an effect through intake by feeding. Owing to its stability, it exhibits a prolonged effect. As well as for the combat of biting insects, e.g. Lepidoptera and Coleoptera, the compound is notably suitable for combat of sucking insects. The compound, especially in free base form, is particularly effective against Lepidoptera, e.g. Egyptian cotton stainers (Spodoptera littoralis), flour moths (Anagasta kuehniella), rice stem borers (Chilo suppresalis), as well as Coleoptera, e.g. potato beetles (Leptinotarsa decemlineata), rice and confused flour beetles (Tribolium eastaneum and Tribolium confusum), been weevils (Bruchidius obtectus) and corn chafers - 5 41817 aria), and Hemiptera, e.g. cotton bugs (Dysderous fasciatus). Moreover, it is also effective against Aphids and Diptera.

The compound of the invention also possesses fungicidal activity and is therefore indicated for use as a fungicide, e.g. against Uromyces phaseoli.

In addition, the compound of formula I in free base or agriculturally-acceptable acid addition salt form advantageously exhibits low mammalian and fish toxicity and phytotoxity. Agriculturally-acceptable aoid addition salt forms are defined as those forms having the same low order of mammalian and fish toxicity and phytotoxicity as the free base form.

The compound of the invention in free base or agriculturally-acceptable acid addition salt form is particularly useful in combatting insects in potato and rice cultures.

The compound of the invention in free base or agriculturally-acceptable acid addition salt form may be applied to insects or fungi in conventional manner, either by direct application of the compound or by application of the compound in association with an insecticide or fungicide carrier, diluent and/or adjuvant as a formulation. For plant protection the compound may be applied, for example, in the form of liquid or powder sprays, dusting powders, granulates, strewing powders, pastes and aerosols. granulates, strewing powders, pastes and aerosols.

The liquid sprays, which are emulsion-concentrates to be diluted with water before use, contain suitable surface-active agents, such as binding .and emulsifying agents, e.g. polyglycol ethers produced from addition of alkylene oxides to higher molecular weight alcohols, mercaptans or alkylphenols, and alkyl benzenesulphonates.

The solid formulations, e.g. dusting, strewing and spraying powders, are produced with conventional inert mineral carriers such as diatomaceous earth, talc, Lg kaolinite, attapulgite, pyrophyllite, artificial fillers based on silica and silicates, limestone, Glauberfe salt, .fn flip t'Aflp of Rpiaylng pnwilpi s {wellahl fKiwdpfs) which are biispendable in water, the rurmulattens uuntalii suitable binding and dispersing agents, e.g. sodium lauryl sulphate, sodium dodecyl benzenesulphate, condensation products of naphthalene sulphonate and formaldehyde, polyglycol ethers and lignin derivatives such as sulphite lye extract.

Granulates may be produced by coating or 5 impregnation of granular carriers such as pumice, limestone, attapulgite, kaolinite and plant carrier material with the active agent or a solution or other formulation thereof.

In addition to the previously mentioned carrier 10 and surface-active materials, formulations of the compound of the invention may also contain further additives with special purposes e.g. stabilizers, deactivators (for solid formulations on carriers with an active surface), agents for improving the adhesion to plants, corrosion inhibitors, anti-foaming agents and pigments.

Moreover, further insecticides and/or fungicides may be present in the formulations.

In general, the concentrate forms of formulation, which are also provided by the present invention, contain between 1 and 90% by weight of a compound of the present invention, preferably betvzeen 5 and 50% by weight. The liquors ready for use contain in general between 0.02 and 90% by weight of active agent, preferably between 0.1 and 20% by weight.

The amount of compound of the invention when used as an insecticide or fungicide applied to a locus to be treated will naturally depend upon the particular form of the compound of formula I employed, the particular environment zambient conditions and the species of insect or fungus to be combatted. However for plant protection satisfactory results are generally obtained when the compound is applied to a plant locus in an amount between 0.5 and 4 kg/hectare, the application being repeated as required.

Examples of the production of suitable formulations of the compounds of the invention are as follows: a) Granulate ι g of 1,3-bis-(tert-butyldithio)-2-dimethylaminopropane are dissolved in 5 g of an aromatic solvent preferably with a boiling point within the range of 1855 213°C. The solution is sprayed onto 90 g of crushed, thoroughly sieved pumice (grain size 0.3-1 mm) by a conventional technique. b) Emulsion Concentrate b) 25 parts by weight of 1,3-bis-(tertrbutyldithio) 10 2-dimethylaminopropane are mixed with 30 parts by weight of iso-octyl phenyl octaglyeol ether and 45. parts by weight of a petroleum fraction with a boiling range of 210-280°C (D20:0.92), The concentrate is diluted with water to the desired concentration. c) Emulsion Concentrate parts by weight of an acid addition salt of 1,3-bis-(tertrbutyldithio)-2-dimethylaminopropane are mixed with 2 parts by weight of sodium lauryl sulphate, parts by weight of sodium lignin sulphonate and 45 parts by weight of kaolinite. The concentrate can be diluted with water to the desired concentration.

The insecticidal and fungicidal activity of the compound of formula I in free base or acid addition salt form is indicated by the following tests.

() Insecticidal_Eff£ct_against_Bruchidius_obtectus lt)ean_weeyilj__E_Contact_effect Petri dishes of 7 cm diameter are sprayed with 0.1 to 0.2 ml of an emulsion produced according to formulation example c) containing 0.0125% of 1,3-bis-(tertvbutyldithio)-2-dimethylaminopropane. After about 4 hours drying of the coatings 10 Bruchidius imagines are introduced into each dish, which is then covered vzith a fine mesh brass-wire grid. The insects are maintained at room temperature without food. After 48 hours the death rate is noted, (percentage). A 100% death rate indicates that all the bean weevils have died and a 0% death rate means that none have died. The result was a 100% death rate. (ii) l£2Qi2§S4_fi2SE_^2S£i£l.2 Contact effect Petri dishes of 7 cm diameter are sprayed with 0.4 ml of an emulsion produced according to formulation example c) containing 0.0125% of 1,3-bis-(tert-rbutyl20 dithio)"2-dimethylaminopropane. After about 4 hours drying of the coatings 30 Tribolium imagines are introduced into each dish, which is then covered with a fine mesh brass-wire grid. The insects are maintained at room temperature without food. After 72 hours the death rate is noted (percentage). A 100% death rate indicates that all the beetles have died and a 0% death rate means that none have died. The result was a 100% death rate. ΐ£2Ε2-£}32Ε2Ελ_Ι_£22£22£_2ΕΕ§£Ε Petri dishes of 5.5 cm diameter are sprayed with 0.4 ml of an emulsion produced according to formulation example c) containing 0.0125% of 1,3-bis-(tertybutyldithio)-2-dimethylaminopropane hydrochloride. After about 4 hours drying of the coatings 30 Calandra-Imagines are introduced into each dish, which is then covered with a fine mesh brass-wire grid. The insects are maintained at room temperature without food. After 72 hours the death rate is noted (percentage). A 100% death rate indicates that all the corn chafers have died and a 0% death rate means that none have died. The result was a 100% death rate. (iv) Fungicidal_Effect_a2ainst_Uromyces_ghaseoli lbean_E22El-Z-§YSESSJiS__ Potted bean plants (Phaseolis vulgaris) in the second leaf stage are watered with 70 ml of an emulsion produced according to formulation example c) containing 0.05% of 1,3-bis-(tert-butyldithio)-2-dimethylaminopropane hydrogen oxalate such that the green parts of the plants remain untouched. After 24 hours the plants are infected with bean rust spores (Uromyces phaseoli), after whioh they are maintained for one day at 100% relative humidity followed by 8 days at 23° (16 hour days). The extent of plant damage is then evaluated, according to the following scale in respect of the damage preventative effect of the administered compound: = no significant effect (0.5% effect) = weak effect (5-50% effect) = middling to good effect (50-95% effect) J I = very good effect (95--100% effect) The compound displayed an effect with a rating of on the above scale. (v) Fun2icidal_Effect_a2ainst_Uromycesjohaseoli —_ Potted bean plants in the second leaf stage are sprayed twice with an emulsion according to formulation c) which contains 0.0125% of 1,3-bis-(tert-butyldithio)2-dimethylaminopropane hydrogen oxalate, while being turned on a revolving table, each plant being sprayed with about 0.7 ml of the emulsion. The plants thereby receive a thin covering of the emulsion which has no tendency to flow away. The sprayed plants are allowed to dry out.

After 24 hours the plants are sprayed with a suspension of Uromyces spores, and then maintained for 1 day at 100% relative humidity followed by 8 days at 23nC (16 hour days). The extent of plant damage is then evaluated according to the scale given in the previous example. The compound displayed an effect with a rating of 9 on this scale. -»41817 Ά~.· » (vi) £caricidal_Effect_a2ainst_Tetranychus_telarius ISBiSSEJi'i £Sl^l_S2S£2S£^SiiS££ A formulation produced as described in formulation example c) is diluted with water to the desired concen5 tration. Bean plants (Phaseolis vulgaris) are sprayed with this emulsion containing 0.05% of l,3-bis-(tert.butyldithio)-2-dimethylaminopropane hydrochloride until thoroughly wetted. These plants are infected with spider mites in all stages of development in great abundance.

After 2 days a mortality rate in percentage is - determined through counting the numbers of living and dead mites. A 100% mortality rate means that all the spider mites have been killed and a 0% rate, that none have been killed. The mortality rate was found to be 100%.

The following examples illustrate the production of the compounds of the present invention. Temperatures are in degrees Centigrade and the melting points are uncorrected.

EXAMPLE 1 li3-Cis-^tertr-butyldithi^-2-dimethyl25!iE2EE2E222 To a solution, produced by stirring 24 g (0.6 moles) of sodium hydroxide in 600 ml of water and subsequently cooled to 0-10° are added 211 g (0.6 moles) of monosodium 2-dimethylamino-propane-l,3-bis-thiosulphonate. To the resulting solution, maintained at 0-10°, is added dropwise with stirring an aqueous solution of sodium salt of tert.-butylmercaptan over a period of 30 minutes. Tlie latter solution is produced by dissolving 48 g (1.2 moles) of sodium hydroxide in 600 ml of water and then adding 108 g (1.2 moles) of tert.-butylmecaptan dropwise within the temperature range 0-10°. After the addition of the sodium salt, the mixture is stirred for a further 30 minutes at 0-10°.

To the mixture is then added GOO ml of chloroform, after which it is stirred vigorously for a short time.

The chloroform phase is then separated, washed successively with three 200 ml amounts of water, dried with anhydrous sodium sulphate, and evaporated in vacuo at 50°. The resulting oil is warmed at 50° over a period of 30 minutes under high vacuum to free it of the more volatile constituents. On cooling, the concentrated oil crystallises to a product with melting point 45°. The product distils without decomposition at 140-145p/0.1 mm of mercury pressure. Its Rf value on thin layer chromatography with silica gel and a 9:1 benzene: ethyl acetate eluant is 0.4. AnalysisC13H29NS4 Molecular weight 327.6 Calc'd. ι : C, 47.7% ·, H, 8.9% ; N, 4.3%; S, 39.1% Found ι ί 47.8% 9.0% 4.3% 38.5% The production of acid addition salts of 1,3-bis-(tert.- butyldithio)-2-dimethylaminopropane is exemplified in the following two examples.

EXAMPLE 2 li^lhis^jttert^-butyldithio^-^diinethyl5!Bi22EE2E£2®_hYS!ro2en_oxalate To an ethereal solution of the product of Example 1 is added a slight excess of ethereal solution of oxalic acid, whereupon the hydrogen oxalate salt precipitates. After collection by filtration the salt is washed with a little diethyl ether and subsequently dried during 1 hour in vacuo at 30°, giving a product with melting point 114-115°.

Analysis C13^29H^4'C2^2°4 Molecular weight 417.7 Calc'd. : C, 43.1% ; H, 7.5% ; N, 3.4% ; S, 30.7% Found : 42.9% 7.5% 3.8% 30.6% EXAMPLE 3 ir^bis-^tert^-butyldithio^-^-dimethy 1SSi22EE°ESGS_bY§E2£bj;Oride To an ethereal solution of hydrogen chloride in • I slightly excess amount is added an ethereal solution of 5 the product of Example 1, whereupon the hydrochloride salt precipitates. After collection by filtration the salt is washed with a little diethyl ether and subsequently dried'during 1 hour in vacuo at 30°, giving a product with a melting point 158°.

AnalysisC13H2SNS4-IIC1 Molecular weight 364.1 . Calc’d. : C, 42,9% ; fl, 8.3%; Cl, 9.7%; N, 3.8%; S, 35.2% Found : 42.9% 8.4% 9.9% 3.8% 35.3% HAVING NOW PARTICULARLY DESCRIBED ANB ASCERTAINED THE NATURE OF OUR SAID INVENTION AND IN WHAT MANNER THE SAME IS TO BE PERFORMED, WE DECLARE THAT WHAT WE CLAIM IS J

Claims (5)

1. , in free base or agriculturally-acceptable acid addition salt form, in association with an Insecticide or 20 fungicide carrier, diluent and/or adjuvant. 8. A formulation according to Claim 7, in the form of a liquid spray containing a surface-active agent. 9. A formulation according to Claim 8, in which the surface active agent is a polyglycol ether produced from addition of an alkylene oxide to a higher molecular weight alcohol, mercaptan or alkylphenol, or is an 5 alkylbenzene sulphonate. X 10. A formulation according to Claim 7, in the form of a dusting, strewing or spraying powder containing an inert mineral carrier selected from diatomaceous earth, talc, kaolinite, attapulgite, pyrophyllite, an 10 artificial filler based on silica and/or silicates, an2 limestone/J Glauber 1 s salt,. ' 11. A formulation according to Claim 7, in the form of a spraying powder which is suspendable in water and containing a binding or dispersing agent selected 15 from sodium lauryl sulphate, sodium dodecyl sulphate, condensation products of naphthalene sulDhnnate and formaldehyde, polyglycol ethers and lignin derivatives. 12. A formulation according to Claim 7, in the form of granulates produced by coating or impregnation 20 of a granular carrier selected from pumice, limestone, attapulgite, kaolinite and plant carrier material with the compound of formula I. > 13. A formulation according to any one of Claims 7 to 12, comprising an additive selected from stabilizers, 25 deactivators, agents for improving adhesion to plants, corrosion inhibitors,anti-foaming agents and pigments. - 20 41817 14. A formulation according to any one of Claims 7 to 13, In which tho compound according to Claim 1 constitutes 1 to 90% by weight of the formulation . 5 15. A 'formulation according to Claim 14 in which the compound according to Claim 1 constitutes 5 to 90% by weight. 16. A formulation according to Claim 14 in a liquor form ready for application, in which the compound IQ according to Claim 1 constitutes 0.02 to 90% by weight of the formulation. 17. A formulation according to Claim 16, in which the compound according to Claim 1 constitutes 0,1 to 20% by weight of the formulation. 15 · 18. A formulation according to Claim 7, substantially as described herein with reference to any one of the Formulation Examples a) to c) and the test examples (i) to (vi) . 19. A method of combatting insects or fungi in 20 a locus which comprises applying to the locus an insecticidally- or fungicidally-effective amount of a compound of formula I, as defined in Claim 1, in free base or agriculturally-acceptable acid addition salt form. 20. A method according to Claim 19, in which the compound is applied to a potato culture. 21. A method according to Claim 19, in which the compound is applied to a rice culture. 1 to 3. 6. A compound according to Claim 1, whenever produced by a process according to either of Claims 4 15 and 5. 7. An insecticidal or fungicidal formulation comprising a compound of formula I, as defined in Claim

1. A compound of formula I, CH CH ch 2 -ss~c(ch 3 ) 3 CH 2 “SS-C(CH 3 ) in free base or acid addition salt form.

2. An acid addition salt form of a compound according to Claim 1, in which the acid is selected from hydrochloric acid, oxalic acid, benzenesulphonic acid, toluenesulphonic acid, methanesulphonic acid, sulphuric acid, phosphoric acid, acetic acid and benzoic acid.

3. A compound according to Claim 2, in which the acid is acetic acid or oxalic acid.

4. A process of producing a compound according to Claim 1, comprising reacting a compound of formula II, CH, .ch 2 -s-l ,N-CH II CH, -ch 2 -s-l in which L is a group of formula -S-R., wherein (o) A m is an alkyl or aryl radical, and m is 0 or 1, or L is a group -SC^M^, wherein is sodium or potassium, 5 with a compound of formula III, (ch 3 ) 3 csm 2 III in which M 2 is sodium or potassium, in such a proportion that both L moieties in the compound of formula II are replaced by -S-C(CH,) 3 radicals from the compound of formula III. 10 5. A process according to Claim 4, substantially as described herein with reference to any one of Examples

5. 22. A method according to Claim 19, substantially as described herein.