DE2341554A1 - SCHAEDLING INHIBITOR - Google Patents

Description

Scheid 1 ing sbekämpf ung sira tte 1

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

wherein R and R,., which can be the same or different, are hydrogen or an optionally branched alkyl group having 1 to 5 carbon atoms, or together with the nitrogen atom, optionally, under

Inclusion of another nitrogen or oxygen atom can form a ring, R is hydrogen or an optionally branched alkyl radical with 1 to 5 Means carbon atoms, and Q means a residue

SO S

U U Il

-C-SR ₄ , -SCOR ₅ or a radical -SCOR, in which R

an optionally branched alkyl radical with 1 to 5 carbon atoms, R ₅ and R an optionally branched alkyl radical with 1 to 8 carbon atoms or a cycloalkyl radical with up to 7 ring carbon atoms

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means, with the proviso that if Q is a remainder

-SCOR ,. and R, and R ₀ simultaneously stand for hydrogen or for an optionally branched alkyl radical with 1 to 5 carbon atoms, R_ should stand for an optionally branched alkyl radical with 1 to 5 carbon atoms, as well as the acid addition salts derived therefrom which are suitable for pest control, as well as processes for the production of these compounds,

The compounds of the general formula I or their salts can be prepared by the following reactions:

a) Compounds of the general formula I in which R, R and R have the meanings given above and

ti

Q for a residue -C-SR. stands, where. R the. referred to above Has meanings which are referred to below as compounds of the general formula Ia by reacting a compound of the general formula II

wherein R ₁ , R and R have the meanings given above and M stands for sodium or potassium, with

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at least two equivalents of a compound of the general formula III

Il

M SCSR III,

in which R. has the meaning given above and M is alkali, - preferably potassium, or

b) Compounds of the general formula I in which R- / R and R have the meanings given above and

• 3

Q stands for a radical -SCOR .., where R ,. the above

5 5

Has signed meanings which are referred to below as compounds of the general formula Ib by reacting a compound of the general formula IV

IV

wherein R, R and R have the meanings given above and M is sodium or potassium, with at least two equivalents of a compound of general formula V

0
ii
X ¹ SCOR V,

wherein R _{5 has} the meaning indicated above and

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X ^{1 represents} chlorine or bromine, or

c) Compounds of the general formula I, in which R, R " and R_ have the meanings given above and

Il

Q stands for a radical -SCOR, in which R stands for the abovementioned Has meanings which are referred to below as compounds of the general formula Ic are, by reacting a compound of the general formula VI

N <- * ■> VI,

where R., ¹ R and R have the meanings given above and Y is a group which can be exchanged by xanthate, such as, for example, the toluenesulfonyl group, benzenesulfonyl group, with a compound of the general formula VII ■

M ₄ SCOR ₆ VII

where Rg has the meaning given above and M _{4 is} an alkali metal,

and optionally subsequent reaction with an acid to form the acid addition salt of the compound of the general Formula I.

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The preparation of the compounds of the general formula. I according to process variant a) can be as follows be performed:

The compounds of general formula II is in one suitable solvent such as water, preferably in the presence of another, not with water miscible solvents such as chloroform, preferably at room temperature and with stirring during a certain period of time, for example 1 to 5 hours, with at least two equivalents, preferably a certain excess of the compound of general formula III. The work-up takes place in the usual way, for example by extraction from the aqueous phase.

The preparation of the compounds of general formula I according to process variant b) can be carried out as follows will:

The compound of the formula IV is advantageously prepared immediately before the further reaction, for example from the compound of the general formula VIII

R ,. ^ CH ₂ SC-CH ₃

i-CR ₃ VIII,

R ₀ ^ - CH_SC-CH

* · ^Λ w

in which R, R and R have the meaning given above, by solvolysis with sodium or potassium alcohol

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holat in a suitable alcohol such as methanol or ethanol, preferably with heating z.3. to reflux temperature and using an acidic substance-free protective gas, such as nitrogen, forth, distilled in the presence of the protective gas from the excess solvent and the acetic acid ester formed transferred to a suitable inert solvent such as anhydrous acetonitrile, chloroform etc., and add the sulfenyl halide with stirring, for example at room temperature of the general formula V, preferably in a suitable solvent, such as anhydrous acetonitrile, Chloroform etc., and stir for a certain period of time, e.g. 16 hours. After filtering off the The alkali halide formed is worked up in the usual manner.

The preparation of the compounds of the general formula I according to process variant c) can be carried out as follows be performed:

The alkali metal oxanthate of formula VII is added in portions to the compound of general formula VI in a suitable solvent, such as, for example, ethanol, acetonitrile or, preferably, methanol, optionally in suspension. After further stirring at room temperature, if necessary, the mixture is preferably heated to 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

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as lightly colored oils, which in the usual organic Solvents are soluble.

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

The compounds of the general formulas II, III, IV, V, - VII and VIII are known or can be carried out according to known processes or in analogy to processes known per se getting produced.

The compounds of the Formula VI can be prepared in a known manner, for example by reacting a compound of the general formula IX

H
R ₁ (CHX ") _m

"^ N-C-R x IX

R ₅ (CHX ")
¹

wherein R., R and R_ have the meaning given above and x "stands for halogen and m and η for 1 or 0, with the proviso that m + η = 1, with a compound of the general formula X

MeSY X

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wherein Y has the meaning given above and Me is a metal or ammonium cation, preferably sodium, means, in a suitable solvent, such as ethanol, isopropanol, methanol, are obtained.

The compounds of the general formulas IX and X can be prepared according to literature processes. If the preparation of the starting compounds is not described, these are known or per se known processes or can be produced analogously to those described here or analogously to processes known per se.

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

In addition to the already mentioned excellent action against insects and pathogenic fungi, the invention At the same time, compounds showed only low toxicity to warm-blooded animals. The new compounds can therefore be used as pesticides in inhabited rooms, in basements, Screeds, used in stables etc., as well as living beings of the plant and animal kingdom in their various Protect development stages against pests, e.g. harmful insects and fungi.

The pests are controlled by the usual methods, e.g. by treating the ones to be protected Body with the active ingredients or suitable preparations that contain these active ingredients.

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For use as a pesticide or pesticide can use the erfindungsgerr.ässen compounds e.g. in the form of liquid spraying agents, wettable powders, Dust powders, granulates, grit, pastes, aerosols and the like. Be prepared.

The liquid spray agents (emulsion concentrates) also contain suitable surface-active agents, such as wetting agents and emulsifiers, e.g. polyglycol ethers, which are obtained from higher molecular weight alcohols, mercaptans or alkylphenols by addition from alkylene oxide, and / or alkylbenzenesulfonates.

The solid preparations (dust, powder and spray powder) are mixed with the usual inert mineral carriers, such as 3. Diatomaceous earth, talc, kaolinite, attapulgite, pyrophyllite, artificial mineral fillers based on SiO " and silicates, lime, Glauber's salt and vegetable carriers, like plant bowls and others, manufactured in a known manner.

In the case of wettable powders, which are in. Let the water suspend, the preparations also contain suitable hardening and dispersing agents, e.g. sodium lauryl sulfate, Sodium dodecylbenzenesulphonate, condensation products from naphthalene sulphonate + formaldehyde, polyglycol ether, lignin derivatives (e.g. sulphite waste liquor).

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

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

The active ingredients according to the invention are known in the formulations and are present in the spray liquors in mixtures with other known active ingredients. The formulations contain in the generally between 1 and 9% by weight active ingredient, preference v / else between 5 and 50 ^. Contain the utility roar generally 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 four den, e.g .:

a) 25 places by weight of a compound of the general formula I v / earth with 25 parts by weight of isooetylphenyl decaglycol ether and 50 parts by weight of xylene are mixed, whereby a clear, well emulsifiable solution in water is obtained, The concentrate is 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 octylphonyloctaglycol ether and 45 parts by weight of a petroleum fraction with a boiling point of 210-230 ° (D ₂₀ : 0.92). The concentrate is diluted with water to the desired concentration,

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c) 50 parts by weight of a compound of the general formula I v / earth 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 with Water to be diluted to the desired concentration.

The following application examples serve to explain the excellent insecticidal and fungicidal effectiveness of the compounds according to the invention, the invention is intended but do not limit it in any way.

(Bean beetle) - Contact whirl-rustic

Petri dishes with a diameter of 7 cm contain 0.1 to 0.2 ml an O, O125% of the compound of the general formula I. containing emulsion according to formulation example a) sprayed from a spray nozzle. After about 4 hours of drying of the covering v / ground 10 Bruchidius imagines placed in each bowl and covered with a lid made of fine-meshed brass wire mesh. the Animals are kept at room temperature and are not fed. 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, O% means that none of the bean beetles have been killed.

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Tabel

Active ingredient kill rate in%

after 48 hours

2-dimethylainino-1 _/ 3 bis (secbutylthio-thiocarbonylthio) propane 100

1,3-bis- (l-sec.-butoxycarbonyl-

disulfane-2-dimethylaminopropane 100

1,3-bis ~ {l ~ see. ~ Butoxythiocarbonyldisulfane-2) -2-morpholinopropane 100

1,3-bis- (1-n-butoxythiocarbonyldisulfane-2) -2-piperidinopropane 100

Insecticides Wi £ ku ^ g__g_e2en_EDh ^ stia_Ku ^ h ^ iella (flour moth) - contact effect

Petri dishes 7 cm in diameter, each containing 10 caterpillars from IO up to 12 mm in length are 0.1 to 0.2 ml of a 0.05% active ingredient of the general formula I containing Emulsion according to formulation example a) sprayed from a spray nozzle. After that, the pods are finely meshed Brass wire mesh covered. After the egg has dried, a wafer is given as feed and renewed as required. After 5 days, the degree of destruction is determined by counting the living and dead animals in%. 100% means that all caterpillars are killed, 0% means that none of the caterpillars has been killed. The evaluation is based on the following Table.

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Tabel

Active substance kill degree in after_5_days

2-dimethylamino-1,3-bis (isopropylthio-thiocarbonylthio) propane 100

Hydrogen oxalate of 2-dimethylaminol, 3-bis (isopropylthio-thiocarbonylthio) propane 100

2-dimethylamino-1,3-bis (sec-butylthiothiocarbonylthio) propane 100

Hydrogen oxalate of 2-dimethylamino

1,3-bis (see-butylthio-thiocarbonyl-

thio) propane 100

2-dimethylamino-1,3-bis (ethylthiothiocarbonylthio) propane 100

1,3-bis- (1-ethoxycarbonyl-disulfane-2) -2-dimethylaminopropane 100

1,3-bis- (1-ethoxy-

carbonyl-disulfane-2) -2-dimethyl-

aminopropane 100

1,3-bis- (1-n-butoxycarbonyl-disulfan ^
2) -2-dimethylaminopropane ^ - 100

Hydrogen oxalate of 1,3-bis- (1-n-butoxycarbonyl-disulf an-2) -2-dimethylaminopropane 100

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Active ingredient kill rate in

after 5 days

1,3-bis- (1-sec-butoxycarbonyldisulfane-2) -2-dimethylaminopropane 100

1,3-bis- (1-isopropoxythiocarbonyldisulfane ~ 2) -2-morpholino-propane 100

1,3-bis- (1-n-pentyloxythiocarbonyldisulfan-2) -2-piperidino-propane 100

1,3-bis- {1-n-pentyloxy-thiocarbonyldisulfan-t ^ ethyl ^ -dimethylamino- ·

propane 100

1,3-bis- (1-n-butoxythiocarbonyldisulfan-2) -2-pyrrolidino-propane 100

Insecticides_Wirkun2_2e ^ en_A2his_fabae (black bean aphid) - contact effect

Broad bean plants (Vicia faba) are sprayed with a the 0.0125% 2-dimethylamino-l, 3-bis- (isopropylthio-thiocarbonylthio) -propane according to formulation example a) contains, treated dripping wet. The broad bean plants are heavily infested with the black bean aphid (aphis fabae) in all stages of development. After 2 days it will the degree of destruction is determined. The degree of destruction is given in%. 100% means that all aphids have been killed 0% means that none of the aphids have been killed. The evaluation shows that the degree of destruction 100%.

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^ -SI ^ BiBi ^ (Gerstennehlenau) - systemic effect

Barley plants (10 plants per pot) in the 1-leaf stage, Leaf length 6-8 era, will be iTiit an active ingredient Broth according to formulation example a), which contains 0.05% of an active ingredient of general formula I, so watered so that the green parts of the plant remain untouched. The plants are pollinated after about 24 hours with powdery mildew conidia. Then the plants 7 days at 60 - 80% relative humidity. And held at constant exposure. After that, the

fungicidal effect on the infestation rated according to the following rating scale.

1 = no effect (0 - 5% effect) 3 - weak effect (up to 50% effect) 6 = medium to good effect (50 - 95% effect) 9 = very good effect (95 - 100% effect)

Active ingredient rating of the

fungicidal effect

1, 3-bis (1-n-butoxythiccarbonyl-

disulfan-2) -2-pyrrolidino-propane 9

1,3-bis- (1-n-propoxythiocarbonyldisulfan-2) -2-morpholino-propane 9

1,3-bis- (1-sec.butoxythiocarbonyldisulfan-2) -2-piperidino-propane 9

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2 ^e 2Sil Urom £ ces_Phaseol: L (bean rust) - systemic effect

Potted bean plants (Phaseolis vulgaris) in the 2-leaf stage are in 70 ml of a 0.05% of the compound of

general formula I

containing emulsion according to formulation example a) watered so that the green parts of the plants are untouched stay. After 24 hours, the plants become infected with spores of the bean rust (Uromyces phaseoli). Thereafter v / ground for 24 hours at 100% relative humidity and then for 16 days under normal laboratory conditions kept under artificial light, whereupon the infestation is evaluated. When evaluating the results was the following rating scale was used:

1 = no effect (0-5% effect)

3 = weak effect (up to 50% effect)

6 - medium to good effect (50-95% effect)

9 = very good effect (95-100% effect)

Tabel

Active ingredient ■ Evaluation of fungicidal

effect

Hydrogen oxalate des
2-Dimethylamino-1,3-bis (isopropylthio-thiocarbonylthio) propane q

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Active ingredient rating of the

1,3-bis (n-butoxycarbonyl-disulfan-2) hydrogen oxalate -2-dimethylaminopropane

Fungicidal effects ^ e ^ Urom ^ ces ^ ghaseoli (bean rust) - contact effect

Potted bean plants become at the 2-leaf stage on a turntable twice by means of a spray nozzle with an active ingredient broth according to formulation example a), the Contains 0.05% of the compound of general formula I, sprayed (about 0.7 ml per plant). Get the plants This creates a thin coating of the broth that does not run off. The coating is allowed to dry on. After 24 The plants are sprayed with Uromyces spore suspension for hours. After that, they will be at 100% for 24 hours relative humidity and then kept for 6 days under normal laboratory conditions, whereupon the infestation is evaluated. The evaluation is based on the scale given in the previous example.

Tabel

Active ingredient

Hydrogen oxalate of 2-dimethylamino-1,3-bis (isopropylthiothiocarbonylthio) propane

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Active ingredient fungicidal effect

1.3 ~ bis-sec.butoxycarbonyldisulfan-2) -2-dimethylaminopropane ■ 9

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

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The compounds of the general formula Ia can be prepared according to Examples 1-7.

Example 1: 2-Dimethylamino-1,3-bis (isopropylthio-thiocarbonylthio) propane

16.0 g (0.04 mol) of the disodium salt of 2-dimethylaniino-prop £ n-1,2-bis-thiosulfonate are dissolved in 50 ml of water and underlaid with 100 ml of chloroform. This is done with stirring 19.0 g (0.1 mol) of the potassium salt of Mcno-Isopropyitrithiocarbonats and let stir for one hour at room temperature. For work-up, the chloroform is separated off and the aqueous phase extracted about 6 times with 50 ml of chloroform each time. The combined chloroform extracts are washed with 40 ml of water, dried with anhydrous sodium sulphate and vacuum, finally freed of volatile constituents in a high vacuum at 25 °. The connection remains as a light yellow Ehromatographically uniform OeI.

Analysis: C ₁₃ H ₂₅ NS ₅ _ Molecular weight: 587.7

C 40.3 $> H 6.5 £ N 3.6 $ S 49.6

7Λ $ 2.9

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Example 2: !? Y ^ £! 2S ^: enoxalat_des_2-pimethylarni _: no-l_, 3 _:: bis-

j (isopropylthio-thiocarbony; lthio) -propane

The 2-dimethylamino-l, 3-bis prepared according to Example 1 (Isopropylthio-thiocarbonylthio) -propane is, in ethereal Solution mixed with an ethereal solution of oxalic acid in a slight excess. The hydrogen oxalate precipitates. To the suction is washed with a little ether and dried in vacuo at 30 ° for one hour. Shrap. 113-115 °.

Analysis: ^C ₁₃ ^H 25 ^NS 6 * ^C 2 ^H 2 ° 4 Molecular weight: ^ 77.8

calc. C 37.7 # H 5.7 $> N 2.9 $ S 40.3 £ found. 5.8.0 ^ - 5,? $ 3.0 % ^ 0.9 ^

In a manner analogous to that described in Examples 1 and 2, the following compounds of the general formula Ia or their salts are represented, in which Q is S

-C-SR owns.

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at
game R ₁ H ₂ H ₅ -SR ₄ salt Gross formula Molge
weight Enamel
Point
R ^ value * C. Ana
H lye
about,
found
N S. ο
co 5
co
O CH ₅ CH ₅ H SC ₂ H ₅ - C ₁₁ H ₂₁ NS ₆ 559.7 OeI
R _f = 0.25 56.7
57.4 5.9
6.2 5.9
4.2 53.5 pounds
52.6 " CH ₅ CH ₅ H SC ₂ H ₅ Kydroger
oxalate ' 449.7 I74-I76 54.7
54.9 5.2
5.4 5.1 42.8
40.9 CH_ CH ₅ H O "* S wiV" Oil iii-v - C ₁₅ H ₂₉ NSg 415.8 OeI
R _f = 0.6 45.5
44.2 7.0
7.5 5.4
5.7 46.3
45.3 6th CH ₃ CH ₅ H Hydrogen -
oxalate C ₁₅ H ₂₉ NS ₆ -C ₂ H ₂ O ₄ 505.8 68-70 4o, 4
59.9 6.2
6.4. 2.8
2.9 .38.0
37.5 7th CH, CH ₅ H O vs O XJ
bn.u ^ iig - ^C 15 ^H 29 ^NS 6. 415.8 OeI
R _f «0.8 45.5
45.8 7.0
7.2 5.4
5.5 46.3
46.6

* Rp value in thin layer chromatography on Kieseicrel plates G, UV 254
in the solvent acetone / low-boiling petroleum ether (1: 4)

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The compounds of the general formula Ib can be prepared according to Examples 8-12 below.

Example 8: l _L 3 _{: i} Bi ^ jJ _: ^? _: thoxycarbonyl-digul £ an-2) _: -2- diraethylamino -propane

11.7 g (0.05 mol) of 2-dimethylamino-1,3-bis-acetylthio-propane are in 300 rnl abs. Dissolved methanol. For this purpose, a solution of 0.1 mol of sodium methanolafc {is extracted with stirring 2.3 g of sodium in 50 ml of methanol) were added dropwise. Warmed up on it 'The reaction mixture is brought to reflux and it is kept at this temperature for one hour and distilled the Methanol and the ethyl acetate formed were completely removed. It must be under dry nitrogen as a protective gas

worked v / earth. After having added the residue with 500 ml of anhydrous acetonitrile is added dropwise 15.5 g (0.11 mol) Aethoxycarbonylsulfenylchlorid in 5O ml of acetonitrile at 20-25 ⁰ C and it is stirred for 16 hours at room temperature. For work-up, the precipitated NaCl is filtered off with suction and the filtrate is evaporated in vacuo. The oily residue is taken up in 300 ml of chloroform, washed twice with 50 ml of water each time and dried. After removal of the solvent in vacuo - last high vacuum at 50 ⁰ C the product is obtained as a yellow oil in pure form.

BATH ORIGINAL

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Analysis: ^C ] 36 21 ^{1 i0} 4 ^S , i H .5 , 9 % MoIg 3 , 9 ew ber. C. 36 , 7 % 5 .3 % N 3 / 4 % found .8th % %

S 35.7% 35.5%

Example 9; Hydrogen oxalate of 1,3-bis- (l ~ ethpxycarbonyl ~ disulf an-2) -2-dimethvl, aminppr.oparis

The 1,3-bis- (1-ethoxycarbonyl · disulfan-2) -2-dimethylaiTiinopropan V7ird prepared according to Example 1 in ethereal
Solution mixed with an ethereal solution of oxalic acid in a slight excess. The hydrogen oxalate precipitates in pure form. After suctioning off, you wash with something
Ether and dry in vacuo at 30 ° C for one hour. Srr.p. 91-93 ⁰ C.

Analysis: ^c n ^H 21 ^NO 4 ^S 4 * ^C 2 ^H 2 ° 4

ber.

C 34.7 % 34.3 %

H 5.2 5.1

Molecular weight: 449.6

N 3.1% S 28.5% 3.7 % 28.0%

In a manner analogous to that described in Examples 8 and 9, the following compounds (No. 10-12) can also be used general formula Ib or its salts are shown:

BATH ORIQINAL

£ 09809/1262

CN CN C ^ CO I O

• · ¹ M & r-%
> O W. J-I H ^ ₁ + J rH a U C7>. £ j πί. r-i β O ■ • "
CQ ■ I. O) O) S. !H O <H O • P -M M. N rH «S approx O pT rH CU Ui ω

cn cn • O T CN ilT cn r>. O co to in in α υ— O ^ r-T cn cn VO CN CN O σ » η cn - = J * CO ■ <> co cn O M ** <* cn cn in CN CN CJ »υ · cn ^ j * O cn CN <* CO U O H VO VO « ^ rH CQ τ cn cn ro ri O cn cn cn cn * 3 * cn υ CN I. ro rH a ^ VO U O) m co co rH O rH m U VO "O I. in in O rH in Cj CQ CQ O cn O* p * cn ^ r cn CJ «q · CN O ca υ id cn in UJ in j ») rH CN rH U U O U xalat I. Where U O Pi OJ rH U-O O O O Oil Ui cn (J cn U CN rH

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The compounds of the general formula Ic can be prepared according to Examples 13-34 below.

Example 13 : 1 _Ä 3-Bi s- J [I-is ^ r ^ opoxy thiocarbony 1-di sul fa η- 2 1 - 2

To 22.2 g (0.05 mol) of 1,3-bis (benzenesulfonylthio) -2-methyl-2 ~ dimethylaminopropane in 300 ml of absolute methanol is added at room temperature with stirring to 19.2 g (0.11 mol) of potassium isopropyl xanthate in portions. After three hours of stirring at room temperature, the mixture is warmed to 50 ° C. and stirred for another approx Hour, after cooling down. Room temperature is filtered from the precipitated potassium p-toluenesulfinate 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 drying the chloroform solution with sodium sulfate is evaporated in vacuo. The remaining OeI can be made poorer by Frz / are freed from the volatile constituents at 50 ° C for half an hour in a high vacuum,

Analysis: ^C i4 ^H 27 ^NO 2 ^S 6 Molecular weight: 433.8

ber, C 38.8% H 6.3 % N 3.2% S 44.4%

found, C 38.8%. H 6.3% N 3.0% S 43.6%

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Example. 14 .: l ^ B-Bis-Jl-isogrqgoxythiocarbonvl-disulf an-2 -) _ ~ 2-

4/3 g (0.01 mol) of 1,3-BiS- (I-isopropoxythiocarbonyl-disulfane-2} ~ 2-ynethyl-2-diirethylantinopropane are dissolved in 50 ml of absolute / tether 1.0 g (0.011 mol) • anhydrous oxalic acid in 30 ml of absolute ether. The hydrogen oxalate which has precipitated is filtered off with suction ₍ re-washed with absolute ether and dried . Crystals of Srap. 134-135 ° C remain,

Analysis: ^c ₁₄ ^H 27 ^HO 2 ^S 6 ^IC 2 ^H 2 ^O 4 Molecular weight: 523.8

ber, C 36.7% H 5.6% N 2.7% S 36.7% found C 37.7% H 5.6% N 2.9% S 37.0%

In a manner analogous to that described in Examples 13 and 14, the following compounds (No. 15-18) and, as described in Examples 19-22, the following compounds (No. 23-34) can also be used of the general formula Ic or their salts are obtained

Il

den, where Q is -SC-OR ^. owns.

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4P «O CO OO O

example ^R l ^R 2 H -OR ₆ salt Gross-
fortael. Molge
weight Melting point analysis
CH 6th
6th , 3
, 9 % (her.
found.)
KS 41.7
41.7 15th CK ₃ CH ₃ CH ₃ sec.Butoxy ^C 16 ^H 31 ^M 2 ^S 6 461.8 OeI 41.6
41.5 6th
6th , 0
,1 3.0
3.2 34.9
34.6 16 CH ₃ CH ₃ CH ₃ sec.Butoxy Hydrogen
oxalst ^C 18 ^H 33 ^N ° 5 ^S 6 551.8 104 ° 39.2
39.4 7th
7th , 2
, 2 2.5
2.6 39.3
39.3 17th CH ₃ CH ₃ CH ₃ n-pentyloxy ^C 18 ^H 35 ^N0 2 ^S 6 489.9 OeI 44.1
44.6 6th
6th , 4 2.9
3.0 33.2
33.3 18th CH ₃ CH ₃ CH ₃ n-pentyloxy Hydrogen
oxalate ^C 2O ^H 37 ^K ° 6 ^S 6 579.9 75 ° 41.4
41.3 2.4
2.6

NJ CaI

28-130-3722

Example 19 : l ^^

gvrolidinogrogan

To 24.2 g (0.05 mol) of 1,3-bis (toluenesulfonylthio) -2-pyrolidinopropane 19.2 (0.11 mol) of potassium isopropyl xanthate are added to 300 ml of absolute methanol at room temperature with stirring in portions. After stirring for three hours at room temperature the mixture is heated to 50 ° C. and stirred for a further 1 hour. After cooling to room temperature, the precipitated product is filtered off Potassium p-toluenesulfinate and the solvent 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 chloroforral solution with sodium sulfate is evaporated in vacuo.

The remaining OeI- can by heating to 50 ° C during half an hour in a high vacuum from the volatile constituents freed from / to earth.

Analysis: C ₁₄ H ₂₇ NO ₂ S ₆ Molecular weight: 445.8

here. C 40.4% H 6.1% N 3.1% S 43.2% found C 41.1% H 6.1% N 3.5% S 42.6%

Example 2Q; 1, S-To ^^ l-

To 25.0 g (0.05 mol) of 1,3-bis (toluenesulfonylthio) -2-morpholinopropane 20.6 g (0.11 mol) of potassium sec.butylxanthogenate are added to 300 ml of absolute methanol at room temperature with stirring in portions. After stirring for three 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 off

409809/1262

~ 2S - 130-3722

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 Half an hour in a high vacuum to be freed from the volatile constituents.

Analysis: C ₁₇ H ₃₁ NO ₃ S Molecular weight: 489.8

calc. C 41.7% H 6.4% N 2.9% S 39.3%

found C 41.6% H 6.1% N 2.7% S 38.7%

1, 3-bis- (! "N-butoxythiocarbqnyl-disulfan ?.) -2-

To 25.0 g (0.05 mol) of 1,3-bis (p-toluenesulfonylthio) r-2-piperidinopropane 20.6 g (0.11 mol) of potassium n-butyl xanthate are added to 300 ml of absolute methanol at room temperature with stirring in portions. After stirring for three 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 p-tcluenesulfinate 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 heated to 50 ° C during Half an hour in a high vacuum to be freed from the volatile constituents.

409809/1262

- 30 - 130-3722

Analysis: C ₁₀ H ^ ₀ NO ₀ S .. Molecular weight: 487.8

Io Jj Δ Ο

calc. C 44.3% H 6.8% N 2.9% S 39.4% found - C 44.2% H 6.7% N 3.0% S 39.0%

Example 22; Ιχ ^ -Βίε - (! "Isopropoxvthiocarbon ^ l-disulfane - ^^ -

19.0 g (0.038 mole) 1,3-bis (p-toluenesulfonylthio) -2-piperidinopropane v; slurried in 200 ml of absolute methanol and 14.6 g (0.084 mol) potassium isopropyl xanthate added. Man Stirred for 3 hours at room temperature and then for a further 1 hour at 50 ° C. The precipitated potassium toluenesulfinate is used for working up filtered off, the filtrate evaporated in vacuo, the liquid residue washed in chloroform with water and washed with Dried sodium sulfate. After chasing off the chloroform in a water jet vacuum and finally in a high vacuum at 50 ° C the desired product is obtained in pure form as Oe3., the is colored light yellow «.. - - - -.-—.

Analysis: CH NO S '. Molecular weight: 459.0

calc. C 41.8 % H 6.4 % N 3.0 % S 41.8 %

found, C 41.6 % H 6.2 % N 2.9 % S 41.6 %

In a manner analogous to that described in Examples 19-22, the following compounds (No. 23-34) can also be used general formula Ic can be obtained.

409809/1262

example

-OR,

Gross formula

Molecular weight

Physics.

Properties /
Refractive index

Analysis% ( calc.

Sef.)

CHNS

23 24 25 26 27 28 29

N-

L7-

O N-

N-

N-

O N-

n-butoxy

sec.Butoxy

n-propoxy

iso-propoxy

n-butoxy

iso-butoxy

n-pentyloxy

^C 17 ^H 3X ^N0 2 ^S 6

^C 15 ^H 27 ^NO 3 ^S 6

C ₁₅ H ₂₇ NO ₃ S ₆

^C 17 ^H 31 ^N ° 3 ^S 6

^C 19 ^H 35 ^N ° 3 ^S 6

473.8

473.8

461.7

461.7

489.8

489.8

517.9

OeI

^Oil
1.5732

• 1.5972

Oil

Oil.
■ 1.5828

Oil
Oil.

43.1 6.6 3.0 40.6

42.9 6.7 3.3 40.1

43.1 6.6 3.0 40.6

43.3 6.8 3.1 41.1

39.0 5.9 3.0 41.7

39.3 6.2 2.9 ■ 41.4

39.0 5.9 3.0 41.7

39.0 5.8 3.1 41.2

41.7 6.4 2.9 39.3

41.6 6.1 2.7 38.7

41.7 6.4 2.9 39.3

41.1 6.3 2.9 39.1

44.1 6.8 2.7 37.1

43.9 6.7 2.8 37.4

example G- * 3 -OR ₆ Gross formula Kol weight Physics.
Properties /
Refractive index A.
C. 6.8
6.7 2
3 (b he.
found.)
SS 39
39 i 4th
O 30th G- H n-butoxy ^C 18 ^H 33 ^N0 2 ^S 6 487.8 25 ^oil
njj - 1.5830 44,
44, 6.8
6.9 2
2 , 9
, 0 39
38, 4th
2
I. 31 α H sec.Butoxy 487.8 25 ° ^el
nT - 1.581? 44,
44, 6.8
6.4 CM CM O
U 39.
39 4th
7th 32 ' C- H iso-butoxy ^C 18 ^H 33 ^N0 2 ^S 6 487.8 OeI 44,
44, 6.4
6.4 • co co , 9
, 9 41,
40, 3
7th 33 G H n-propoxy ^C 16 ^H 29 ^N0 2 ^S 6 459.8 ■ 25 ^oil
nf - 1.5944 41,
42, 7.2
7.3 2
2 , 0
, 5 37! 3
4th 34 H n-pentylxy ^C 2O ^H 37 "° 2 ^S 6 515.9 25 ^oil
τζ - 1.5726 46,
46, , 7
, 6 naIysis
H 3
2 3 3
O 8th
0 6th
3

Claims (1)

Claims where R ₁ and R _? , which can be identical or different, _{t represent} hydrogen or an, optionally branched, alkyl group with 1 to 5 carbon atoms or together with the nitrogen atom, optionally including a further nitrogen or an oxygen atom, can form a ring, R is hydrogen or a, optionally branched alkyl radical with 1 to 5 carbon atoms and Q for a SO S Il Il Il Radical -C-SR ₄ , -SCOR or a radical -SCOR, where R. is an optionally branched alkyl radical with 1 to 5 carbon atoms, R _c and R one b 6 optionally branched alkyl radical with 1 to 8 carbon atoms or a cycloalkyl radical with mean up to 7 ring carbon atoms, with the proviso that, if Q is a radical S. Il -SCOR ₆ and R ₁ and R ₃ simultaneously represent hydrogen or an optionally branched alkyl radical with 1 to 5 409809/1262 - 34 - 130-3722 Are carbon atoms, R should represent an optionally branched alkyl radical with 1 to 5 carbon atoms, and the acid addition salts derived therefrom,
characterized in that one a) for the preparation of compounds of the general formula I in which R, R and R are as indicated above Have meanings and Q for a remainder S. -C-SR. stands, where R. has the meanings given above, which are hereinafter referred to as compounds of the general formula Ia, a compound of the general formula II SSO ₃ M ₁ SSO ₃ M ₁ in which R, R and R have the meanings given above and M _{1 is} sodium or potassium, with at least two equivalents of a compound of the general formula III M ₂ SCSR ₄ III , where R. has the meaning given above and M is alkali, preferably potassium ,
or 409809/1262 - 35 - 130-3722 b) for the preparation of compounds of the general formula I, in which R, R ^ and R are as indicated above Have meanings and Q for a, n O Remainder -SCOR ₁ . stands, where R has the meanings given above, which are referred to below as compounds of the general formula Ib, a compound of the general formula IV in which R_ , R and R have the meanings given above and M is sodium or potassium, with at least two equivalents of a compound of the general formula V 'SCOR ₅ V wherein R has the meanings given above and X ^{1 is} chlorine or bromine, or c) for the preparation of compounds of the general formula I in which R, R and R are as indicated above Have meanings and Q for an S. Remainder -SCOR ,. is where R ,. the above D D ten meanings which are hereinafter referred to as compounds of the general formula Ic- 409809/1262 - 36 - 130-3722 be net, a compound of formula VI VI, wherein R, R and R have the meanings given above and Y represents a group which can be exchanged by xanthate, such as, for example the toluenesulfonyl group, benzenesulfonyl group, stands, with a compound of the general formula VII M.SCOR _C VII, where Rg has the meaning given above and M. stands for an alkali cation, converts and, if appropriate, then this by reaction converted with an acid into the acid addition salt of the compound of general formula I. 2. Compounds of the general formula I, SQ SQ wherein R ₁ and R ₃ , which can be the same or different, stand for hydrogen or for an optionally branched alkyl group with 1 to 5 carbon atoms or together with the nitrogen 4 0 9 8 0 9/1262 - 37 - 130-3722 substance atom, possibly including a further nitrogen or an oxygen atom, can form a ring, R is hydrogen or a optionally branched alkyl radical with 1 to 5 carbon atoms and Q for a radical S. O or a rest S. stands, Il Il Il -C-SR, -SCOR ₅ -SCOR ..
D. where R. is an optionally branched alkyl radical having 1 to 5 carbon atoms, R _r and R. a D D optionally branched alkyl radical with 1 to 8 carbon atoms or a cycloalkyl radical with up to to 7 ring carbon atoms, with the proviso that if Q is a radical S. -SCOR ₁ , and R ₁ and R "simultaneously represent hydrogen Ό JL Δ or represent an optionally branched alkyl radical having 1 to 5 carbon atoms, R represents one optionally branched alkyl radical with 1 to 5 carbon atoms, and those derived therefrom Acid addition salts. 2-Diniethylamlno-l, ^ - t) is- (isopropylthio-thiocarbonylthio) propane and the salts derived therefrom. 4. Hydrogen oxalate of 2-dimethylamino-l,> - bis (isopropylthio-thiocarbcnylthio) propane. 409809/1262 - 38 - L30-3722 5. 2-Difflethylamino-1,3-bis (n-butylthio ~ thiocarbonyl.thio) propane and the salts derived therefrom. 6. g-Dimethylamino-l ^ -bis-Cäthylthio-thiocarbonylthio) - · propane and the salts derived therefrom. 7. Hydrogen oxalate of 2-dimethylamino-l,> - bis (ethylthiothiocarbonylthio) propane. 8. 2-Dimethylafiiino-l, j5-bis- (η-sec .butylthio-thiocarbonylthio) propane and the salts derived therefrom. 9. 1,3-bis- (1-ethoxycarbonyl-disulfane-2) -2-dimethy1-aminopropane and the salts derived therefrom. 10. 1,3-bis- (l ~ ethoxycarbonyl-disulfan-2) hydrogen oxalate -2 ~ dxmethylarainopropane. 11. 1,3-bis (1-n-butoxycarbonyl-disulfane-2) -2-dimethylarainopropane and the salts derived therefrom. 12. 1,3-bis- (1-sec-butoxycarbonyl-disulfane-2) -2-dimethylaminopropane and the salts derived therefrom. 13. 1, 3-bis (1-isopropoxythiocarbonyl-disulfane-2) -2-methyl-2-dimethylamino propane and the salts derived therefrom. 409809/1262 "- 39 - 130-3722 14. 1,3-bis- (1-sec.butoxythiocarbonyl-disulfane-2) ~ 2-methyl-2 ~ dimethylamine propane and the salts derived therefrom. 15r χ, 3-bis- (l ~ n-pentyloKythiocarbonyl-disulfan-2) -2-methyl - 2 dimethylaminopropane and the salts derived therefrom. 16 * 1,3-bis- {1-isopropoxythiocarbonyl-disulfan-2) -2-pyrrolidi no-propane and the salts derived therefrom. 17. 1,3-Bis- {1-n-butoxythiocarbonyl-disulfan-2) -2-pyrrolidino propane and the salts derived therefrom. 18. Xt 3-bis- (l * -sec.butoxythiocarbonyl-disulfan-2) -2-pyrrolidino-propane and the salts derived therefrom. 19. 1,3-BiS'- (l ~ seG.butaxythiocarbonyl-disulfarr-2) -2 "ra propane and the salts derived therefrom. 20 .. 1,3-Bi ^ - (l-n-propoxythiQcarbonyl-disulfan -? -) -2-morpholinopropane and the salts derived therefrom. 21. 1,3-bis (! "Isopropoxythiocarbonyl-disulfane-2) -2-morpholinopropane and the salts derived from it » 22. 1,3-bis- (l-n "butoxythiocarbonyl-disulfan-2) -2-mQrpholino- ' propane and the salts derived therefrom. 23. 1,3-bis- (I-isobutoxythiacarbonyl-disulfan-2) -2 ~ inorpholino- · propane and the salts derived therefrom. 24., 1,3-bis (i-n-pentyloxythiocarbonyl-disulfane - ^) -2-morpholino-propane and the salts derived therefrom. 25, l _i 3-bis (l "isopropoxythiocarbonyX-disulfan-2) -2-piperidinopropane and the salts derived therefrom, 409809/1262 - 40 - 130-3722 .26. 1,3-bis- (1-n-propoxythiocarbonyl-disulfane-2) -2-piperidinopropane and the salts derived therefrom. 27. 1,3-bis (1-sec.butoxythiocarbonyl-disulfane-2) -2-piperidinopropane and the salts derived therefrom. 28. 1,3-bis- (1-isobutoxythiocarbonyl-disulfane-2) -2-piperidinopropane and the salts derived therefrom. 29 '. 1,3-bis- (1-n-butoxythiocarbonyl-disulfane-2) -2-piperidinopropane and the salts derived therefrom. 30 I ₁ 3-bis ~ (ln-pentyloxythiocarbonyl-disulfane-2) -2-piperidino-propane and its derived salts. 31. Pesticides, characterized by a content of the compounds of general Formula I according to claim 1 and / or the acid addition salts derived therefrom as active ingredient. 32. Pesticides, characterized by a content of 2-dimethylamino ~ 1,3-bis ~ (isopropylthio-thiocarbonylthio) propane and - the salts derived therefrom as active ingredients. 33. Pesticides, characterized by Q gen;
a content of the hydrated hydroxalate of 2-dimethylamino-1,3-bis (isopropylthio-thiocarbonylthio) propane as active ingredients. 34. Pesticides, characterized by a content of 2-dimethylamine-1,3-bis (n-butylthiothiocarbonylthio) propane and the salts derived therefrom as active ingredients. 40980 971262 - 41 - 130-3722 35. Pesticides, characterized by a content of 2-dimethylamino-1,3-bis (äthylthiothiocarbonylthio) propane and the salts derived therefrom as active ingredients. 36. Pesticides, characterized by a content of the hydrogen potassiumate des 2-dimethylamino-1, 3-bis- (ethylthio-thiocarbonylthio) propane as active ingredients. 37. Pesticides, characterized by a content of 2-dimethylamino-1,3-bis (n-secbutylthio-thiocarbonylthio) propane and the salts derived therefrom as active ingredients. 38. Pesticides, characterized by a content of 1,3-bis- (1-ethoxycarbonyl-disulfane-2) -2-dimethylaminopropane and the salts derived therefrom as active ingredients. 39. Pesticides, characterized by a content of the hydrogen oxalate of 1,3-bis (l-ethoxycarbonyl-disulfane-2y ^r dimethylaminopropans as active ingredients. 40. Pesticides, characterized by a content of 1,3-bis- (1-n-butoxycarbonyl-disulfane-2) -2-dimethylaminopropane and the salts derived therefrom as active ingredients. 41. Pesticides, characterized by a content of 1,3-bis- (1-sec-butoxycarbonyldisulfan-2) -2-dimethylaminopropane and the salts derived therefrom as active ingredients. A09809 / 1262 - 42 - 130-3722 42. Pesticides, characterized by a content of 1,3-bis- (1-isopropoxythiocarbonyldisulfan-2) -2-methyl-2-dimethylaminopropane and the salts derived therefrom as active ingredients 43. Pesticides, characterized by a content of 1,3-bis (1-sec.butoxythiocarbonyl- .. disulfan-2) -2-methyl ~ 2-dimethylaminopropane and the salts derived therefrom as active ingredients. 44. Pesticides, characterized by a content of 1,3-bis- (l-n-pentyloxythiocarbonyldisulfan-2) -2-methyl-2-dimethylaininopropane and the salts derived therefrom as active ingredients. 45. Pesticides, characterized by a content of 1,3-bis- (1-isopropoxythiocarbonyldisulfan-2) -2-pyrrolidino-propane and the salts derived therefrom as active ingredients. 46. Pesticides, characterized by a content of 1,3-bis- (1-n-butoxythiocarbonyldisulfan-2) -2-pyrrolidino-propane and the salts derived therefrom as active ingredients. 47. Pesticides, characterized by a content of 1,3-bis- (1-sec.butoxythiocarbonyldisulfan-2) -2-pyrrolidino-propane and "the salts derived therefrom as active ingredients. 48. Pesticides, characterized by a content of 1,3-bis- (1-sec.butoxythiocarbonyldisulfan-2) -2-morpholino-propane and the 409809/1262 - 43 - 130-3722 conducted salts as active ingredients " 49. Pesticides, characterized by a content of 1,3-bis (1-n-propoxythiocarbonyldisulfan-2) -2-morpholino-propane and the salts derived therefrom as active ingredients » 50. Pesticides »characterized by a content of 1,3-bis-M-isopropoxythiocarbonyldisulfan-2) -2-morpholino-propane and the salts derived therefrom as active ingredients. 51. Pesticides "characterized" by a content of 1,3-bis- (1-n-butoxythiocarbonyldisulfan-2) -2-morpholino-propane and that thereof
derived salts as active ingredients. 52. Pesticides, characterized by a content of l _f 3 ~ bis (l-isobutoxythiocarbonyldisulfan-2) -2-morpholino-propane and that thereof
derived salts as active ingredients. 53. Pesticides, characterized by a content of 1,3-bis- (l-n-pentyloxythiocarbonyldisulfan-2) -2-morpholino-propane and the salts derived therefrom as active ingredients. 54. Pesticides, characterized by a content of 1,3-bis- (1-isopropoxythiocarbonyldisulfan-2) -2-piperidino-propane and the salts derived therefrom as active ingredients. 409809/1262 - 44 - 130-3722 55. Pesticides characterized by a content of 1,3-bis (1-n-prcpoxythiocarbonyldisulfan-2) -2-piperidino-propane and the salts derived therefrom as active ingredients * 56. Pesticides, characterized by a content of 1,3-bis- (1-sec.butoxythiocarbony1-disulfan-2 ) -2-piperidino-propane and the salts derived therefrom as active ingredients. 57. Pesticides, characterized by a content of 1,3-ris- (1-isobutoxythiocarbonyldisulfan ~ 2) -2-piperidino-propane and the salts derived therefrom as active ingredients. 58. Pesticides, characterized by, a content of 1,3-bis- (1-n-butoxythiocarbonyldisulfan-2) -2-piperidino-propane and the salts derived therefrom as active ingredients. 59. Pesticides, characterized by a content of 1,3-bis (1-n-pentyloxythiocarbonyldisulfan-2) -2-piperidino-propane and the salts derived therefrom as active ingredients. SANDOZ A.G. 409809/1262