DE2209556A1 - Pesticides - Google Patents

Description

SANDOZ AG. '"Case 130-3 ^ 76

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Damage 1 Anti-Virus

The invention relates to new compounds of the general Formula I.

wherein R, an optionally branched alkyl group with 1 to 5 carbon atoms, Rp is hydrogen or an optionally branched alkyl group with 1 to 5 carbon

S O

H il.

atoms and Q is a radical -SC-OR ₇ or a radical -SCR ₂ , where R is an alkyl radical with 1 to 8 carbon atoms, a branched alkyl radical with 1 to 8 carbon atoms or a cyoloalkyl radical with 5 to 6 carbon atoms and R ₂ , denote an alkyl radical having 1 to 5 carbon atoms, and their salts, which are used for pest control, and a process for the preparation of these compounds.

The compounds of the general formula I can be prepared by reacting a compound of the general formula

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Formula II

II

wherein FL and R _{0 have} the meanings indicated above and Y is a group which can be replaced by a radical Q, where Q has the meaning indicated above, such as, for example, toluenesulphonyl group, benzenesulphonyl group, with a compound of the general formula III

MQ III

wherein Q has the meaning indicated above and M is an alkali metal.

The production can be carried out as follows:

To the compound of the general formula II in a suitable solvent, such as ethanol, acetonitrile or preferably methanol, is the alkali metal oxanthate or alkali thio fatty acid salt of the formula III added in portions. After further stirring at room temperature, if necessary, heated it is preferably kept at about 50 ° C. for some time while stirring. The reaction mixture is worked up in the usual way. The compounds of the general formula I are obtained as oils which are in the customary organic solvents are soluble.

The salts of the compounds of the formula I are obtained by adding a corresponding acid to the compounds of the general formula I. They can be characterized, for example, by their melting points.

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The compounds of the required as starting material for the preparation of the compounds of general formula I general formula II can, for example, by reacting a compound of general formula IV

IV

wherein R. and R ₂ have the meanings indicated above and X is a halogen, preferably chlorine, with a compound of the general formula V

MeSY V

wherein Y has the meaning indicated above and Me is a Metal or ammonium cation, preferably sodium, means in a suitable solvent such as ethanol, isopropanol, Methanol.

The compounds of the general formulas IV and V are prepared according to literature processes.

The compounds of general formula I and their salts, such as the acetates, benzoates, hydrogen oxalates, hydrochlorides, Hydrogen sulfates have strong insecticidal and fungicidal properties.

In addition to the already mentioned excellent action against insects and pathogenic fungi, the compounds according to the invention have at the same time only a low toxicity to warm blood. The new compounds can therefore act as pests

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Control agents are used in inhabited rooms, in basements, screeds, in stables, etc., as well as Living beings of the plant and animal kingdoms in their various stages of development against pests, e.g. slit harmful insects and fungi.

The control of the pests is carried out according to the usual methods made, e.g. by treating the body to be protected with the active ingredients or suitable preparations that contain these active ingredients.

For use as a pesticide or pesticide the compounds according to the invention can be used, for example, in the form of liquid sprays, wettable powders, Dust powders, granulates, grit, pastes, aerosols and the like can be prepared.

The liquid sprays can be the usual non-phytotoxic ones Contain solvents and thinners, such as, for example, glycol ethers, aliphatic and aromatic hydrocarbons, in particular xylene or alkylnaphthalenes and other petroleum distillates, also ketones, especially cyclohexanone or isophorone, etc.

Emulsifiable spray agents (emulsion concentrates) also contain suitable surface-active agents, such as wetting agents and emulsifiers, e.g. polyglycol ethers, which are made from higher molecular weight Alcohols, mercaptans or alkylphenols are formed by the addition of alkylene oxide and / or alkylbenzenesulfonates.

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The solid preparations (dust, powder and spray powder) are mixed with the usual inert mineral carriers, such as diatomaceous earth, talc, kaolinite, attapulgite, pyrophyllite, artificial mineral fillers Based on SiOp and silicates, lime, Glauber's salt and vegetable carriers, such as walnut shell flour and others in produced in a known manner. In the case of wettable powders, which can be suspended in water, the preparations also contain suitable wetting and dispersing agents, 'e.g. sodium lauryl sulfate, sodium dodecylbenzenesulfonate, Condensation products from naphthalene sulfonate + formaldehyde, polyglycol ether, lignin derivatives (e.g. Sulphite liquor).

The granules are made according to processes known per se by coating or impregnating granular carrier materials, such as pumice stone, lime, attapulgite, kaolinite, plant peel material and the like., Prepared with the active ingredients or their solutions or formulations.

All preparations of the active ingredients according to the invention can in addition to the carriers and surfactants already mentioned, contain special additives, such as stabilizers, Deactivating agent (for solid preparations on carriers with an active surface), agents to improve the adhesive strength on plants, corrosion inhibitors, antifoam agents, pigments etc.

The active compounds according to the invention can be used in the formulations and in the spray liquors in mixtures with other known ones

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Active ingredients are present. The formulations generally contain between 1 and 90 percent by weight of active ingredient, preferably between 5 and 50 %. The use broths generally contain between 0.02 and 90 percent by weight of active ingredient, preferably between 0.1 and 20 %.

The active ingredient formulations can be prepared in a known manner be, e.g .:

a) 25 parts by weight of a compound of general formula I are mixed with 25 parts by weight of isooctylphenyl decaglycol ether and 50 parts by weight of xylene are mixed, resulting in a clear, easily emulsifiable in water Solution received. The concentrate can be diluted with water to the desired concentration.

b) 25 parts by weight of a compound of the general formula I are mixed with 30 parts by weight of isooctylphenyloctaglycol ether and 45 parts by weight of a petroleum fraction with a boiling point of 210-280 ° (D ₃₀ : 0.92). The concentrate can be diluted with water to the desired concentration.

c) 50 parts by weight of a compound of the general formula I are mixed with 2 parts by weight of sodium lauryl sulfate, 3 parts by weight of sodium lignosulfonate and 45 parts by weight of kaolinite. The concentrate can be diluted with water to the desired concentration.

The following application examples serve to illustrate the excellent insecticidal effectiveness of the compounds according to the invention, but are not intended to restrict the invention in any way.

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Insecticidal effect against Bruchidius obtectus (bean beetle) - contact effect

Petri dishes f cm in diameter are filled with 0.1 to 0.2 ml of an emulsion containing 0.0125 % 10-bis-Cl-sec.butoxythiocarbonyl-disulfane-2) -2-dimethylaminopropane hydrogen oxalate according to formulation example .a) sprayed with a spray nozzle. After the topping has dried for about 4 hours, 10 Bruchidius imagines are placed in each bowl and these are covered with a lid made of fine-meshed brass wire mesh. The animals are kept at room temperature and are not given any food. The degree of destruction is determined after 48 hours. The degree of destruction is given in % . 100 % means that all bean beetles have been killed, 0 % means that none of the bean beetles have been killed. The evaluation shows that the degree of destruction is 100 % . For 1,3-bis- (ln.butoxythiocarbonyl-disulfane-2) -2-dimethylaminopropane in the same test, the degree of destruction is also 100 %.

Insecticidal activity against EphestiaJCuehniella (Flour moth) - contact effect

Petri dishes 6 cm in diameter, each containing 10 caterpillars 10-12 mm in length, are mixed with 0.1 to 0.2 ml of a 0.05% 1.3-bis (l-sec.butoxythiocarbonyl-disulfan-2 ) -dimethylaminopropane-containing emulsion sprayed from a spray nozzle. Then the bowls are covered with a fine-meshed brass wire mesh. After the topping has dried, a wafer is given as feed and renewed if necessary. After 5 days, the degree of destruction is determined by counting the living and dead animals in % . 100 % means that all caterpillars have been killed, 0 % means that none

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The caterpillar was bagged. The evaluation shows that the degree of destruction is 100 % . For 1,> bis- (1-isopropoxythiocarbonyl-disulfane-2) -dimettylaminopropane-hy.drogeii-oxalate · in the same tea one obtains a degree of destruction of also £ 100.

(Grain beetle) - contact effect

Petri dishes 10 cm in diameter are sprayed on a turntable in three turns under the fixed spray nozzle with an active ingredient broth of the compound of formula I in a concentration of 500 ppm, prepared by diluting a formulation according to example a). After the spray coating has dried for four hours, 30 imagines are placed in the bowl. The dead animals are counted after 1 to 2 days. The mortality is given in % .

Active ingredient

1,3-bis- (1-isopropoxythiocarbonyldisulfane-2) -2-dimethylamino-propane

1,3-bis- (1-ieopropoxythiocarbonyldisulfane-2) -2-dimethylamino-propane hydrogen oxalate

1,3-bis- (1-n-pentoxythiocarbonyldisulfane-2) -2-dimethylamino-propane hydrogenoxa1a t

1,3-bis- (1-sec.butoxythiocarbonyl-

disulfan-2) -2-dimethylamino-propane hydrogen oxalate

Mortality time

100

100

100

100

after 1 day

after 1 day

after 1 day

after 2

Days

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» » Ft * I

<■ ς. * * φ »Jt

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% Insecticidal effect against Prodenia litura (cotton owl)

Contact and feed poison effect _{see p} .

10 Prodenia larvae each are placed in Petri dishes with a diameter of 10 mm. A *. ". ' Is displayed under the spray nozzle. . F drug broth the compound of formula I in a concen- tratlon of 5OO ppm, prepared by dilution of a formulation according to example a), sprayed AlB forage plant are treated bush beans with the same broth by the same method to "run off" and. - after drying fed to the larvae in the dishes in the course of the experiment.

When treated with

1,3-bis- (1-see.butoxythio carbonyl-disulfan-2) -2-dimethylamino-propane was found to have a mortality of 100 % after 6 days;

With 1,3-bis- (in-butoxythiocarbonyl-disulfane-2) -2-dimethylamino-propane-hydrogenoxalate, a mortality of 100 % was also determined after 6 days.

Connections such as

l, 3- [bis- (l-n-pentoxythiocarbonyl-disulfane-2)} - 2-dimethylaminopropane hydrogen oxalate,

1,3- [bis- (1-n-butoxythiocarbonyl-disulfane-2)] - 2-dimethylaminopropane hydrogen oxalate

show a good fungicidal effect (systemic and contact effect) e.g. against Erysiphe graminis (barley powdery mildew), Uromyces phaseoli (bean rust).

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The following examples serve to illustrate the preparation of the compounds of the general formula I. However, they are not intended to restrict the invention in any way. The. Temperatures are given in degrees Celsius.

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Example 1: lO-bis-il-n-pentoxythiocarbonyl ^ disulfan-

N-CH

CH,
3

CH, s "^ cHo-ss-cs-0-nc..H ,,

3 2 5 11

To 21.6 g (0.05 mol) of 1,3-bis (benzenesulfonylthio) -? .- dimethylaminopropane in 200 ml abs. Methanol is added at room temperature with stirring, 22.2 g (0.11 mol) of potassium n-pentyl xanthate in portions. After stirring for 3 hours at room temperature, the mixture is warmed to 50 ° C. and stirred for a further hour. After cooling to room temperature, the precipitated potassium benzenesulfinate is filtered off and the solvent is evaporated in a vacuum. The residue is taken up in 300 ml of chloroform and washed twice with 100 ml of water each time. After this Drying the chloroform solution with sodium sulfate is evaporated in vacuo.

The remaining oil can be freed from the volatile constituents by heating to 50 ° for ₂ hours in a high vacuum.

Analysis: C ₁₇ H ₃ NO ₃ S ₆ molecular weight i 475 »6

calc. C 43.0 % HLOji N 2.9 % 3 40.4 % found . 43.2 % 6.3 #, 3.3 % 40.2 %

Example 2; 1,3-BIs- (in-pentoxythiocarbonyl-disulfane-2) -2-dimethylaminopropane hydrogen oxalate

4.0 g (0.0084 moles) 1,3-BiS- (I-n -pentoxythiocarbonyl-disulfane-2) -2-dimethylaminopropane are in 30 ml of abs. Dissolved ethanol. A solution of 1.0 g (0.011 mol) of anhydrous is added to this

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Oxalic acid in 20 ml abs. Ethanol. The precipitated hydrogen oxalate is sucked off and from abs. Recrystallized ethanol. Colorless crystals with a melting point of 88 °.

Analysis: C _ig H _7r NO ^ Sg Molecular weight:

boron. C 40.4 % H 6.2 % N 2.5 % S 34, 1 % found . 39.6 % 6.2 % 2.8 % 33.9 %

Example 3; 1,3-B j s- (l _r acetyl-disuJ fan-2) - ^ dimethyl aminopropane

CH, .CH ₀ -SS-CO-CiI,

N-CH
CH CH ₂ -SS-CO-CH

To 21.6 g (0.05 mol) of 1,3-bis (benzenesulfonylthio) -2-dimethylaminopropane in 400 ml of abs. Acetonitrile, 11 * 4 g (0.1 mol) of potassium thioacetate are added in portions at room temperature with stirring. The mixture is stirred for one hour at 5O ⁰ and allowed to cool, the reaction mixture. The precipitated salt is filtered off. After evaporation of the filtrate in vacuo at 5O ^0, the residue is taken up in 300 ml chloroform and washed twice 'with 100 ml of water. The chloroform solution is dried with sodium sulfate and evaporated in vacuo.

The oily residue is distilled in a high vacuum at 82-86 ° / 0.002 mm.

Analysis: C ₉ H ₁₇ NO ₂ S ^ Molecular Weight: 299.5

calc. C 33.7% H 5.7% N 3.6% S Found 49.1%. 33.6 % 5.8 % 4.3 % 49.6 %

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Example 4 : 1,3-bis- (l - i £ opropox.ythiocirbonyl-disulfan-2) -2-dimethylaminopropane

CH, .CH _n -SS-CS-O-CH 3 ^ ^

N-CH ^CH 3

CH ^ \ / CH

-> CH-SS-CS-O-CH ^p

To 17 g (0.37 mol) of 1,3-bis (p-toluenesulfonylthio) -2-dimethylaminopropane in 300 ml abs. Methanol is added at room temperature with stirring 13.9 S (Q, 08 mol) potassium tiopropyl xanthate in portions. After stirring for 3 hours at room temperature, the mixture is warmed to 50 ° C. and stirred for a further hour. After this Cooling to room temperature, the precipitated potassium p-toluenesulfinate is filtered off and the solvent is evaporated in the Vacuum off. The residue is taken up in 300 ml of chloroform and washed twice with 100 ml of water each time. After the chloroform solution has been dried with sodium sulfate, it is evaporated in vacuo.

The remaining oil can be heated to 50 ° C during % Hour in a high vacuum to be freed from the volatile constituents.

Analysis: ^c i3 ^H 2R ^N0 2 ^S 6 molecular weight; 419

calc. C 37.2 % H 6.0 % N 3.3 % S 45.9 % found 38.1 % 5.5 % 3.6 % 45.2 %

The corresponding hydrogen oxalate is produced analogously to Example 2.

In a manner analogous to that described in Examples 1 and 2, the following compounds of the general formula I and their salts are obtained.

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At- .
game ^R l R ₂ SCS-0C _o H _c salt Gross
formula Molge
weight Melting point
Siedep.
(mm) Analysis # (calc.
found.)
CHNS 5 CHj CHj SCS-OC ₂ H- C _n H ₂₁ NO ₂ S ₆ 391 86 ° / 0.002 33.7 5.4 3.6 49.1
33.6 5.8 4.3 49.6 6th CHj CHj SCS-O-ICH ₇ Hydrogen
oxalate ^C 13 ^H 23 ^N0 6 ^S 6 481 107 ° 32.4 4.8 2.9 39.9
32.4 4.8 3.3 39.4 7th CHj CHj SCS-0-nC ^ H Hydrogen
oxalate C ₁₅ H ₂₇ NO ₆ S ₆ 509 134 ° 35.4 5.3 2.8 37.7
35.6 5.4 2.9 37.6 8th CHj CHj SCS-0-nC ^ H C ₁₅ H ₂₉ NO ₂ S ₆ 447 - 40.3 6.5 3.1 42.9
40.3 6.5 3.6 43.2 9 CHj CH ₃ SCS-0-sec-
^C 4 ^H 9 Hydrogen
oxalate 537 99.5 ° 38.0 5.8 2.6 35.8
38.0 5.7 2.7 35.6 10 CH ₃ CH ₃ SCS-0-sec.-
^C A C ₁₅ H ₂₉ NO ₂ S ₆ 447 - 40.3 6.5 3.1 42.9
40.2 6.5 3.8 43.0 11 CH, CH ₃ SCS-0-Cyclo-
h'3xyl Hydrogen
oxalate C ₁₇ H ₃₁ NO ₆ Sg 537 115 ° 38.0 5.8 2.6 35.8
37.8 5.5 2.8 35.7 12th CH ₃ CH ₃ SCS-0-Cyclo-
hexyl ---- C ₁₉ HjJKO ₂ S ₆ 499 ---- 45.6 6.6 2.8 38.5
44.5 6.6 2.8 37.8 13th CHj CH ₃ Hydrogen
oxalate C ₂₁ Hj ₅ NO ₆ S ₆ 589 118-125 ° 42.8 5.9 2.3 32.6
42.7 6.1 2.7 32.5

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The following example can be used to prepare the starting compounds of the general formula II will:

1,3-bio- (ben3olsulfonylthio) -2-dimethylaroinopropane

«« », Yes 0, = ■

96.3 ε (0.5 mol) l-diniethylarnino - ^^ - dichlorproparihydrochlorld are dissolved in 500 ml of alcohol and mixed with a solution of 11.5 ß (0.5 mol) of sodium in 400 tnl of alcohol. After adding 196 g (1 mol) of sodium benzene thiosulfonate and The mixture is stirred for a further 500 ml of alcohol at 80 ° for 2 hours. The precipitated table salt is suctioned off while hot. the end The product crystallizes out in pure form from the filtrate. M.p. 82-83 °.

The 1,3-bis (toluenesulfonylthio) -2-dimethylaminopropane, which is also described in the literature, can be analogous to 1,3-bis (benzenesulfonylthio) -2-dimethylaminopropane by reacting l-dimethylamino-2,3-dichloropropane and sodium p-toluene sulfate produce.

The substance crystallizes from alcohol in colorless leaflets with a melting point of II5-II6 ⁰ .

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Claims (1)

Claims; Process for the preparation of compounds of the general formula I. R / -SQ N- SQ wherein R. is an optionally branched alkyl group having 1 to 5 carbon atoms, Rp is hydrogen or an optionally branched alkyl group with 1 to 5 carbon atoms and Q is a radical -SC-OR, or a radical -SC-R ₂ , where R is an alkyl radical with 1 to 8 carbon atoms, a branched alkyl radical with 1 to 8 carbon atoms or a cycloalkyl radical with 5 to 6 carbon atoms and R ^ denotes an alkyl radical having 1 to 5 carbon atoms, and salts thereof, characterized in that a compound of the general formula II SY whereR R, and R _{2 have} the meaning indicated above and Y is a group which can be replaced by a radical Q, where Q has the meaning indicated above, with a compound of the general formula III MQ III in which Q has the meaning indicated above and M is an alkali metal, and the compounds obtained are reacted of the general formula I is optionally reacted with acids to form their salts. 209839/1220 - 17 - 130-3 * 7.6 2. The method according to claim 1, characterized in that that Y in formula II is a benzenesulfonyl group stands. 3. ' Method according to claim 1, characterized in that that Y in formula II is a toluenesulfonyl group stands. 4. Compounds of the general formula I in which R is an optionally branched alkyl group having 1 to 5 carbon atoms, Rp is hydrogen or an optionally branched alkyl group having 1 to 5 carbon atoms and Q is a radical 9 0 -SC-OR, or a radical -SGR ₂ ^, where R. is an alkyl radical having 1 to 8 carbon atoms, a branched alkyl radical having 1 to 8 carbon atoms or a cycloalkyl radical having 5 to 6 carbon atoms and R _{1 is} an alkyl radical with 1 to 5 carbon atoms and their salts. 5. Compounds of the general formula I, wherein R, a optionally branched alkyl group with 1 to 5 carbon atoms, Rp is hydrogen or an optionally branched alkyl group having 1 to 5 carbon atoms and Q is a radical S.
-S-Ö-OR- denotes, where R. stands for an alkyl radical with 1 to 8 carbon atoms, a branched alkyl radical with 1 to 8 carbon atoms or a cycloalkyl radical with 5 to 6 carbon atoms and their salts. 6 · Compounds of the general formula I according to Claim 4 as hydrogen oxalates. 7 x 1 »3-bis (1-isopropoxythiocarbonyl-disulfane-2) -2-dimethylaminopropane and its salts. 209839/1220 - 18 - 130-3 * 76 8.l, 3-bis- (l-isopropoxythiocarbonyl-disulfane-2) - 2-dimethylaminopropane hydrogen oxalate. 9 l, 3-bis- (l-n.butoxythiocarbonyl-disulfan-2) - 2-dimethylaminopropane and its salts. 10. 1,33iss- (l-n-butoxythiocarbonyl-disulfane-2) -2-dimethylaminopropane-hydrogenoxalate. 11. 1,3-BJ.s- (l-n-pentoxythiocarbonyl-disulfan-2) -2-dlmethylaminopropane and its salts. 12. 1,3-bis (1-n-pentoxythiocarbonyl-disulfane-2) -2-dlmethylaminopropane hydrogen oxalate. 13. 1,3-bis- (l-sec.butoxythiocarbonyl-disulfan-2) -2-dimethylaminopropane and its salts. 14. 1,3-bis-il-sec.butoxythiocarbonyl-disulfane-2) -2-dimethylaminopropane-hydrogenoxalate. 15. Insecticidal agents, characterized by a Content of one or more compounds of the general formula I according to claim 1 and / or their salts as Active ingredient. l6. Insecticidal agents, characterized by a Content of the compounds of the formula I according to claim 5 as active ingredient. 209839/1220 - 19 - 130-3W 17 · Insecticidal agents, characterized by a
Content of the compound of the formula I according to claim 6 as an active ingredient. 18. Insecticidal agents, characterized by a
Content of the compound of the formula I according to claim 7 as an active ingredient. 19 »Insecticides, characterized by a
Content of the compound of the formula I according to claim 8 as an active ingredient. 20. Insecticidal agents, characterized by a
Content of the compound of the formula I according to claim 9 as an active ingredient. 21. Insecticidal agents, characterized by a
Content of the compound of the formula I according to claim 10 as an active ingredient. ²² · Insecticidal agents, characterized by a
Content of the compound of the formula I according to claim 11 as an active ingredient. 23. Insecticidal agents, characterized by a
Content of the compound of the formula I according to claim 12 as an active ingredient. 24. Insecticidal agents, characterized by a
Content of the compound of the formula I according to claim 13 as an active ingredient. 209839/1220 - 20 - 130-3476 25 · Insecticidal agents, designed by one Content of the compound of the formula I according to the patent claim 14 as an active ingredient. 26. Process for the manufacture of pesticides, characterized in that compounds of the general formula I according to claim 1 and / or their Salts used as active ingredients. BATH ORIGINAL 209830/1220