DE1693215C3 - Organic bis (thio) aminopropane compounds, their salts and pesticides containing these compounds - Google Patents

Description

urine acid or an acidic salt (ζ. B. the hydrochloride, Hydrobromide or a chemical equivalent) of thiourea, where the halogen atoms are replaced by amidinthio groups be replaced; a lower thiocarboxylic acid (e.g. tbioacetic acid, thiobenzoic acid, Thiofurancarboxylic acid or a chemical equivalent these acids) or a salt (e.g. sodium salt, potassium salt, ammonium salt, lead salt or their chemical Equivalents) of the abovementioned thiocarboxylic acids, the halogen atoms being replaced by lower carboxylic acid acylthio groups be replaced; a xanthogenic acid (e.g. methyl, ethyl, propyl, penlylxanthooenic acid or their chemical equivalents) or a salt (e.g. the sodium, potassium or ammonium salt or their chemical equivalents) of the above-mentioned xanthogenic acids, where the halogen atoms replaced by lower alkoxythiocarbonyhio groups; an alkali trithiocarbonate, the halogenate - never by a group of the general formula

- S-CS-S -

ei ■■. izt, and hydrogen disulfide or its salts (2 H sodium, potassium or ammonium disulfide), w. >> ei the halogen atoms through dithio groups between S ^ '-. η two molecules of the starting halogen compounds are replaced, whereby the 1,2,6,7-tetra- Üv.o .mring or the 1,2,5,6-tetrathiocane ring is formed

· ■ is iewöhnlich the thio compound or its functional derivative used in an amount, av a molar basis, is at least twice as large as the amount of the dihalo compound. If the thioves bond or its functional equivalent and the dihalo compound are used in approximately equimolar amounts, the main product is the corresponding monosubstituted thiomonohalo compound, which is repeatedly subjected to a similar reaction to replace the remaining halogen atom with the same or a different substituted thio group or with a mercapto group . This method is expediently used when products are to be produced in which the two substituted thio groups are different. The reaction is preferably carried out in a solvent. Suitable solvents are, for example, water, methanol, ethanol, propanol, acetone, methyl ethyl ketone, cyclohexanone, ether, dioxane, tetrahydrofuran, dimethylformamide, pyridine, 2-methyl-5-ethylpyridine, benzene, chloroform or mixtures of two or more of these solvents. The solvent must be selected according to the type of thio compounds used. The reaction usually proceeds smoothly at room temperature. The reaction mixture can of course be heated or cooled depending on the course of the reaction.

B. The radical A in the formulas I a and 1 b is converted into the corresponding halogen compounds of the formulas

CH ₂ -CH-CH ₂ -X SS

and

R ₁ R ₁

(purple) CH ₂ -CH-CH ₂

S S

i i

R ₂ R ₂

(HIb)

introduced, in which R ₁ and R _{2 have} the same meaning as in the formulas I a and Ib and X is a halogen atom, for. B. chlorine, bromine and iodine means. The starting halogen compound represented by one of the formulas III a and III b is reacted with a secondary amine or with a primary amine. In the latter case, a further stage follows, in which the hydrogen atom in the secondary amine formed is substituted by a halogenated hydrocarbon or a ketone or an aldehyde and formic acid according to the "Leuckart reduction (or reaction)". However, the reaction with a secondary amine is more advantageous than the reaction with a primary amine, since in the former case it is not only unnecessary to carry out the subsequent reaction, but also the possibility of the formation of a mixture of secondary and tertiary amines is lower than in the case the latter reaction Suitable secondary amines for the former reaction are, for example, dimethylamine, diethylamine, methylethylamine, dipropylamine, dibutylamine, diamylamine, sec. dibutylamine, diisobutylamine, dicyclohexylamine, diphenylamine. Monomethylaniline, monoethylaniline, monomethyltoluidine, pyrrole, pyrroline, pyrrolidine, piperidine, piperazine, morpholine, thiomorpholine, azirane (ethyleneimine) or chemical equivalents of these compounds.

The reaction of the halogen compound of the form in IHa and III b with the amine takes place in one Excess of the amine or in an organic solvent such as methanol, ethanol, propanol, Acetone. Dioxane, dimethylformamide, tetrahydrofuran, benzene or toluene Da in the course of the reaction 1 mole of hydrogen halide is formed, another mole of the amine used can be used for the neutralization of the hydrogen halide formed are consumed, if not a suitable alkali at the same time is present in the reaction mixture. If you want the consumption of the amine used for the neutralization for example, for economic reasons, can therefore avoid the procedure something to be modified, like this. that a strong alkali was gradually added to the reaction mixture which contains the starting halogen compound and the approximately equivalent amount of amine. In general the reaction is favored by heating to a temperature below 200 C. Depending on the species Of the starting materials used, there are of course also cases in which the reaction proceeds smoothly at room temperature. The reaction can be carried out under normal pressure or, if appropriate, under elevated pressure will. Usually pressures below 30 at are sufficient.

If the substituted thio group is a thiol group, which is replaced by a lower Hydrocarbon radical is substituted, another modified method for producing the desired

i 693

th connection can be applied. Here, however, an Oxovei bond is used instead of the halogen compound used as the starting compound and the reaction carried out under reducing conditions. The reducing conditions can be created by using a reducing agent includes in the reaction mixture or subjects the reaction mixture to the catalytic reduction. As reducing agents, for example, an alkali metal and a lower alcohol, iron and Hydrochloric acid, iron and acetic acid, sodium amalgam or a chemical equivalent of these substances are used will.

C. A product that has been manufactured according to methods A or B can be converted into others, also under the formulas I a or I b falling compounds can be converted by the substituted thio groups modified to other substituted thio groups. The methods of modification are described below as an example.

a) Of the compounds of formula I are those which have two thiol groups as substituted Containing thio groups, converted into compounds, the two groups of the general formula

CD'

O tx

contained, in which R 'is a lower alkyl radical. One of the dithiol compounds is made with an agent the —S - R 'groups are introduced into the thiol groups. Introductory dt «. The rest A wide variety of thiolesters can be used for S R '. For example, the Thiol esters (e.g. methyl, ethyl and benzyl esters) of thiosulfuric acid or its water-soluble salts (Buntesche salts), the thiol esters of a thiosulfonic acid (e.g. methanthiosulfonate, ethanthiosulfonate or their chemical equivalents), the thiol esters of thiosulfinic acids (e.g. methanthiosulfinate, ethanthiosulfinate or their chemical equivalents), esters of thiothiocyanate, sulfenyl halides (e.g. sulfenyl chloride, Sulfenyl bromide or sulfenyl iodide) or their chemical equivalents. The hydrocarbon residue the above-mentioned thiolester, which together with the sulfur atom to which it is bonded, into the desired Compounds is to be introduced, for example, methyl, ethyl. Propyl, isopropyl. Allyl, Be butyl, isobutyl, amyl, hexyl, heptyl or benzyl. The reaction is usually carried out in a solvent such as water, methanol, ethanol, dioxane. Tetrahydrofuran, dimethylformamide, benzene, toluene or mixtures of two or more of these solvents, carried out and runs smoothly in the medium adjusted to about pH 7.0 to 9.0 Room temperature. In some cases, however, heating the reaction mixture to a Temperature below about 100'C favorable results can be achieved.

b) The compounds of the formulas 1. which contain two thiol groups as substituted thio groups, are also converted into compounds having an acetyl group or a thiocarbonyl group as Contain S-substituting groups by using the dimercapto compounds or their mercaptides an acylating agent, e.g. B. acetic acid.

To introduce thiocarbonyl groups, thiocarbonyl halides, such as thiophosgene or thiocarbonyl bromide, can be used as a starting resource. The reaction is usually carried out in a solvent such as water, methanol, ethanol, propanol, dioxane, tetrahydrofuran, pyridine, dimethylformamide, chemical equivalents of these solvents or mixtures of two or more of these Solvent and carried out in an alkaline to neutral medium. Usually can be at room temperature be worked, but can optionally be cooled or heated.

c) Connections of the formulas la and Ib, in which R ₁ and R 2 contain two lower hydrocarbon radicals, are converted into the corresponding mercaptans.

The reaction is carried out under reducing conditions and / or in the presence of a heavy metal salt. A fairly large reduction is required to remove the hydrocarbon residue attached to the sulfur atom, so that fairly strong reducing agents are needed. Suitable reducing agents are, for example, alkali metals such as metallic sodium, potassium and lithium, the alkali metals above and a lower alcohol u., Methanol, ethanol or their chemical equivalents), the alkali metals mentioned, and an acid (eg. Acetic acid or a chemical equivalent acetic acid), an amalgam of the alkali metals mentioned, an alkali amide (e.g. sodium amide, lithium amide or potassium amide), formic acid or hydrogen in the presence of a metal catalyst (e.g. Raney nickel, platinum, palladium or their chemical equivalents). The reaction is usually carried out in a solvent such as methanol, ethanol, liquid ammonia, dimethylamine, diethylamine, pyridine. 5-ethyl-2-methylpyridine, dimethylformamide, diethyl ether, tetrahydrofuran, dioxane or their chemical analogues, which are selected according to the type of reducing agent to be used.

Instead of or together with the reducing agent, a heavy metal salt can be used for the reaction used to remove the hydrocarbon residue of the substituted thio group to form the dithiol compounds to remove, which arise in the form of the mercaptide of the heavy metal used. Through the subsequent introduction of hydrogen sulfide into the suspension of the mercapdds arise free thiol compounds. Water-soluble salts, for example, are suitable as heavy metal salts for this purpose Salts of metals such as lead, mercury and zinc. The reaction is carried out in a solvent such as water, Chloroform, benzene, ether, their chemical equivalents, or mixtures of two or more this solvent carried out. In this case, the reaction rate is increased by heating increased in an advantageous manner.

Through the reactions described above, for example, the following compounds the formulas la and Ib are produced:

l, 2-dimercapto-3-dimethylaminopropane,

l ^ -DithiocyanatO-dimethylaminopropane,

1,2-bis (benzylthio) -3-dimethylaminopropane.

1,2-bis (n-propyldithio) -3-dimethylaminopropane,

l, 2-bis (acetylthio) -3-dimethylaminopropane,

1,2-bis (n-hexyldithio) -3-dimethylaminopropane, 1,2-bis (methyldithio) -3- (3-dimethylamino-

propyOpropane,

1,2-bis (n-propyldithio) -3-diethylaminopropane, 1,2-bis (benzylthio) -3-methylethylaminopropane,

1,3-bis (benzylthio) -2-dimethylaminopropane,
l, 3-bis (acetylthio) -2-dimethylaminopropane,
!, S-dithiocyanato ^ -dimethylaminopropane,
l, 3-bis (ethoxythiocarbonylthio) -2-dimethyl-

aminopropane,
l, 3-bis (amidinothio) -2-dimethylaminopropane

dihydrochloride,

l, 3-bis (ethyldithio) -2-dimethylaminopropane,
l, 3-bis (n-propyldithio) -2-dimethylaminopropane,!, S-dimercapto ^ -dimethylaminopropane,
l, 3-bis (benzylthio) -2-diethylaminopropane,
1,3-bis (ethoxythiocarbonylthio) -2-diethyl -

aminopropane,

l, 3-dimercapto-2-morpholinopropane,
5-dimethylamino-1 ^ -dithiane-i-thione.

The compounds I a and I b are relatively strong bases, due to the tertiary amino group and in some cases through the amidine group, and form stable acid addition salts. The thiol groups containing compounds I can owing to the acidic nature of the thiol group with strong alkalis Form salts, forming a mercaptide. The compounds I can be in the form of acid addition salts or mercaptides as well as in free form are produced and used. To manufacture the Acid addition salts are expediently chosen such acids that are used in the reaction with the compounds I form addition salts in the form of free bases, the anions of which are those inherent in the free bases pesticidal properties do not weaken. Such are also used for the production of the mercaptides strong alkalis used when reacting with the Thiol compounds among the compounds 1 form mercaptides, the cations of which have the pesticidal properties of the thiol compounds do not weaken. Suitable acid addition salts are, for example those made using inorganic acids such as hydrochloric acid, hydrobromic acid, hydriodic acid. Chloric acid. Bromic acid, iodic acid. Perchloric acid, perbromic acid. Periodic acid, sulfuric acid, Nitric acid, phosphoric and arsenic acid, using organic acids such as maleic acid, Citric acid, tartaric acid. Oxalic acid, benzenesulfonic acid. Toluenesulfonic acid, ethanesulfonic acids, Picric acid. as well as using alkyl halides such as methyl iodide. Ethyl iodide etc. "produced have been. Suitable mercaptides are, for example, those using strong alkalis, such as Sodium and potassium hydroxide, or salts of heavy metals such as lead, copper, zinc or the like. Manufactured.

As mentioned earlier, the new connections turned out to be effective in destroying lower animals such as insects, mites or nematodes however, only low toxicity to vertebrates, such as mammals and birds, and to plants. Due to these characteristic properties, the compounds are used as active components of Pesticides, especially insecticides, are used.

If the compounds are used as pesticides and verminkillers brought them into forms that correspond to the intended use, and for example incorporated into wettable powders, solutions, emulsifiable solutions, dusts and aerosols

A wide variety of auxiliary materials can be used for packaging. Using one or more of the compounds is dissolved or dispersed as a solution, emulsifiable solution or aerosol in a suitable liquid excipient. As liquid carrier stones that serve as solvents, For example, water, lower alcohols (e.g. methanol, ethanol, isopropanol, butanol, glycerine) are suitable or ethylene glycol), ketones (e.g. acetone, methyl ethyl ketone, cyclohexanone or cyclopentanone), Ether {z. B. dioxane, tetrahydrofuran, ethylene glycol monomethyl ether or diethylene glycol monomethyl ether), aliphatic hydrocarbons (e.g. n-hexane, Petrol, kerosene, heating oil, lubricating oil or machine oil), aromatic hydrocarbons (e.g. benzene, Toluene. Xylene, solvent benzene or methylnaphthalene I, essential oils. Terpenes, chlorinated diphenyl or Cottonseed oil. Mixtures of the The solvents mentioned above are used because the solvents not only have excellent dissolving power, but also should have low toxicity to plants and humans.

To produce dusts, one or more of the compounds are finely ground, e.g. B.

in ball mills. Pan grinders or beater mills, and the ground compounds are mixed with powdered diluents or carriers. Vegetable powders (e.g. soybean meal, Wheat flour, tobacco dust, walnut shell powder or sawdust), clay (e.g. kaolin, kaolinite, saponite, vermiculite, Beidellite, montmorrillinite, bentonite or kuller earth or attapulgite), talc. Pyrophyllite. Lime. Bitter lime. Diatomaceous earth, silicon dioxide. Hydroxyapatite. Calcium carbonate. Dolomite. Calcite. Calcium sulfate, hydrated clay, carbon black or sulfur

Other types of adjuvants are surface active agents that act as adhesives or developing agents serve. Emulsifiers or solubilizers to improve the effect or the stability of the agents. Of the commercially available surface-active agents, salts of sulfonated! Castor oil, Salts of alkylarylsulfonates or nonionic surfactants such as polyoxyethylene diaryl ether. Polyoxyethylene alkylaryl ether and polyoxyethylene sorbitan monoacylate (where the acyl group contains 10 to 18 carbon atoms) as emulsifiers and solvents Mediator for the agents according to the invention used ver.

The pesticides according to the invention can contain other pesticides, ζ. Β Benzene hexachloride (BHC), dichlorodiphenyhrichloroethane (DDT), aldrin, dieldrin, endrin, pyrethrin Rotenone, Parathion or other organic Phos

phorotoxins, acaricides, nematocides, fungicides, herbicides. insect attracting or repellent center ' They can also contain growth hormones, fertilizers or fragrances. All of these additions are al Auxiliaries for the products according to the invention

see.

It was found that the invention
Compounds I or the agents produced using them kill a wide variety of insects, mites and nematodes and destroy the pests mentioned as examples or at least significantly reduce the number of surviving animals. Examples of herbivorous sects etc. are:

693 215

Leptinotarsa decemlineata (Colorado potato beetle), Epilachna vigintioctomaculata, Epilachna sparsa orientalis,

Phyllotreta striolata,

Aulacophora femoralis, fully grown, Acrothinium gackkwitchii, fully grown, Calloso bruch us cinensis,

Blattela germanica (cockroach),

Lcrna oryzae, -

Musca domestica (Hausfiiege), Athalia rosae japonensis, larva, Chilo suppressalis, Plodenia litura,

Parnara guttata, larva,

Naranga aenescens, larva,

Barathra brassicae, larva,

Cryptothelea formosicola, larva, Cryptothelea minuscula, larva, Colias hyale poliographus, larvae, Pieris rapae, larva,

Petranychus, citri.

Aphis glydnes,

Rhapalosiphum pseudobrassicae, Tetranychus bimaculaius, etc.

The compositions for direct application to the plants can be 0.1 to 10 percent by weight or contain larger amounts of the compounds 1. When the agent is used as a concentrate for the production of injections or more dilute dusts, the content of compounds I can be between and 90 percent by weight.

The pesticidal activity of Compounds 1 is demonstrated by the experiments described below illustrated.

Comparative experiments 1. Toxicity

The LD ₅₀ is determined for test compounds when applied locally to mature larvae of the rice borer (Chilo suppressalis). The number of larvae killed is counted 48 hours after application of the test compounds. The results are given in the table below.

Table 1

connection

LD ₅₀ iMicro-

J-bis (acetylthio) -3-dimethyIaminopro-

panhydrogen oxalate

_3-bis (acetylthk)) - 2-dimethylamino-

propane hydrogen oxalate

1,3-dithiocvanate-2-dimethyl aminopropane

.S-dithiocyanate-I-dimethylaminopropane

(Hydrogen oxalate)

13-bis (ethyldithio) -2-dimethylamino-

propane hydrogen oxalate

J-Dithiocyanato-2-roorpholinopropane .. l_3-Dithiocyanato-2-pyTrolidinopropane ... l_2-Dithiocyanato-3-pyrrolidinopropane ... Ji-dithiocyanato-3-diethylaminopropane

(rose oxalate)

0.25 i.7 020 030

15 0.5 7 3

15th

connection

EPN (o-ethyl-o-p-nitrophenylphenylphosphonothioate) (for comparison) Malathion (for comparison) (S- (l, 2-dicarbäthoxyäthyD-O.O-dimethyldithiophosphat)

tD ₅ "

(Micro-

gram / g)

3.0

27

2. Pesticidal effectiveness against EPN

(o-ethyl-o-p-nitrophenylphenylphosphonothionate) on larvae of the rice borer (Chilo suppressalis)

For each experiment, 16 rice plants were used, which were grown in an area of 90 x 90 cm. Ripe rice handworm eggs were placed on the rice plants.
Aqueous solutions (about 120 cm ³ per square meter), which contained 0.05% of the test compounds were sprayed to the rice plants. One week after the point in time at which the larvae had entered the stalks, the number of larvae that survived was counted and the percentage of surviving animals was determined. The results are shown in Table 2.

Table 2 Time of application

(counted from the day

which the larvae in the stalks

entered 1

surviving animals. %

* Days! Day before, before

1,3-dithiocyanate-2-di-1

methylaminopropane!

(free) J 7.S

1,3-dilhiocyanate-2-di-

methylaminopropane

(Hydrogen oxalate) j 10.9

Control connection I

(EPN), 29.4 Z5

Control attempt (without j

Middle!) I 38.2 30.1

immidiatly after

Zl

1.3 ί 1 ,;

5.2

74.1

2 days after

The percentage of animals killed was 48 hours after topical application of various salts of 1,3-dithiocyanate-2- <iüire aylaminopropane! Larvae of the rice bite in comparison to EPN determined. The following results were obtained:

Table 3

connection

Dosage in mflcrograms / g

Maleate j 100

p-toluenesulfonate

Diethyl dithiophosphate
Free base

EPN (as a control) ...

20th S. 3.2 100 100 100 100 100 100 100 100 100 100 100 100 100 100 60

3. Efficacy against Plutella maculipensis Rdfe larvae of Plutella maculipensis were au Leaves of Chinese cabbage are set, treated with aqueous solutions of the test compounds

had been. The percentage of animals killed was determined after 24 hours. The results are listed in the following table.

Table 4

Degree of feeding

the leaves *)

1,693 2 15th 12th Table 6 animals

Conc Killed Test connection tration of
aqueous animals solution (%) 1,3-dithiocyanate-2-di- methylaminopropane (free) 0.05 100 0.025 100 1,3-dithiocyanate-2-di- methylaminopropane (Hydrogen oxalate) 0.05 100 0.025 100 Control attempt with chlorocyclohexane 0.05 85 0.025 50 Control attempt without Control agents .. 0 0

0.4 0.4

0 0.1

4.1

4.0 *) Average of eight sheets

4. Effectiveness against cabbage worms (Pieris rapae)

Young leaves of Chinese cabbage were soaked in an aqueous solution containing 0.01% of the test compounds contains, immersed and allowed to stand in the air to dry the leaf surface. To those treated in this way Leaves that have been put in pots are planted with cabbage worms (Pieris rapae, larvae). To The number of insects killed is counted for 24 hours. The result is shown in Table 5.

Table 5 connection

1 J-Dithiocyanato- ^ - morpholinopropane

1,3-dithiocyanato-2-dimethylaminopropane

1,3-bis (thiocarbamoyl) -2-dimethylaminopropane

EPN (as control) (o-Athylo-p-nitrophenylphenylphosphonothioate)

Malathion (as a control)
(S- (1,2-dicarbethoxyethyl Y
OO-dimethyldithiophosphate)

Concentration of

Test connection

0.01

0.01

Animals killed, used animals

10/10

10/10

0.01 y 10.10

0.01 J 6 10

0.01 ι 3.10 35

55

5. Efficacy against Phyllocinistis dtrella

Aqueous solutions of the test compounds were sprayed over citrus leaves obtained from (Phyllocinistis citrella). After 24 hours, the number of worms killed was again used to calculate the Percentage of animals killed is determined. The results are shown in Table 6.

5 1,3-bis (n-propyldithio-3-di- Conc Killed connection methylaminopropane (Hydro tration of
Ver animals genoxalate) binding (%) ⁰ 4,9-bis (dimethylamino) - 1,2,6,7-tetrathiecan (Hydrogen oxalate) 0.02 98.0 5-dimethylamino-1,3-dithiane 2-thione (hydrogen oxalate) ' ⁵ l ^ -Diacethylthio-S-dimethyl- 0.02 77.5 aminopropane (hydrogen oxalate) 1,2-dimercapto-3-dimethyl- 0.02 87.8 aminonroDan .. .... 20 l, 3-bis (äthyldithioi-2-dimethyl- 0.02 87.5 aminopropane (hydrogen oxalate) 1,3-dithiocyanato-2-dimethyl- 0.02 80.0 aminooroDan 0.02 79.4 ²⁵ l, 3-dithiocyanato-2-dimethyl- aminopropane (hydrogen oxalate) 0.02 100 1,3-bis (thiocarbamoyU-3-di- 0.01 SO.O methylaminopropane 30 l, 2-bis (thiocarbamoyl) -3-di- 0.02 100 methylaminopropane (Hydrogen oxalate) 0.02 100 EPN (as a control) Malathion (as a control) 0.02 100 0.02 54.3 0.02 32.7

6. Effectiveness against tobacco worms (Plodenia litura)

Leaves from the Javanese almond tree are soaked in an aqueous solution of the test compound for 10 seconds immersed for a long time and then left to stand in the air until the leaves have dried. Those treated like that Leaves are put back into pots and tobacco worms (Plodenia litura) are placed on the leaves. To The number of worms killed is determined again for 24 hours. The results are shown in Table 7.

Table 7

connection

1.3-bis (n-propyldithio) -2-dimethylaminopropane
(Hydrogen oxalate)

4.9-bisldimethylamino) -

1,2,6.7-tetrathiecan (hydrogen oxalate)

5-dimethylamino-1 J-dithiane-2-thione (Hydrogen oxalate)

1 ^ -Dimercapto ^ -dimethylaminopropane

13-dithiocyanato-2-dimethylaminopropane

13-bis (ethyidithio) -2-dimethylaminopropane (Hydrogen oxalate)

Malathion (as a control)

Concentration of

Test connection

0.02

0.02 0.02 0.02 0.02

0.02 0.02

Animals killed

100

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7. Effectiveness against nematodes

The test compounds were used in the form of aqueous solutions, each in a glass bowl (3 x 5 «m) were introduced. 50 to 100 roundworms (Rhabitoides) were placed in each of the glass vessels. given. After the vessels had been kept below 25 ° C. for 72 hours, the number of killed nematodes for the calculation of the average death rate. Every attempt was carried out three times. The results are shown in Table 8.

Table 8 Test connection

Concentration of

Test connection

(ppml

l, 3-bis (ethylthio) -2-morpholino-

propane hydrogen oxalate 1,3-dimercapto-2-dimethylamino-

propane hydrogen oxalate 1,3-bis (ethylthio) -2-pyrrolidino-

propane
1,2-bis (acetylthio) -3-dimethyl-

aminopropane
1 ^ -Dimercapto-S-dimethylamino-

propane
1,3-dithiocyanato-2-dimethylaminopropane hydrogen oxalate

1, S-dithiocyanate ^ -morpholino-

propane
1, S-dithiocyanato ^ -morpholino-

propane hydrogen oxalate 1,3-dithiocyanato-2-pyrrolidino-

propane hydrogen oxalate 1 ^ -dithiocyanato-S-pyrrolidinopropane

4,9-bis (dimethylaniino) -

1, ZoJ-tetrathiecandihydrogen-

dioxalate
1,3-bis (propyldithio) -2-dimethyl-

aminopropane hydrogen oxalate 1,3-bis (ethyldithio) -2-dimethyiaminopropane hydrogen oxalate

Control (water)

500 1000

500 1000

500 1000

500 1000

500 1000

125

500

1000

1000

500 1000

500 1000

500

1000

500

500

1000

125

500

1000

Average mortality

8.1 100

100

14.2 100

96.4 100 100 100 100 i00 100

73

100 i00

100 100

100 100 100 100

laurate polyoxyethylene ether (Tween 20) contained, dissolved and the solution diluted with tap water it was found that the concentration of the test compound was 0.2%. The numbers in Table 1 and Table 1 a are mean values of three tests carried out simultaneously.

Table 1

20th

35

-

45

Further experiments on pesticidal effectiveness: Experiment 1

Emulsions of the test compounds listed in Table 1 were applied to soybean plants obtained from Aphis glycines were infested, or kidney bean plants on which there is Tetranychus bimaculatus found sprayed. The plants were grown on a turntable. After 48 hours the Number of animals still alive determined to determine who survived. The emulsions used were prepared by adding 10 parts by weight of the test compounds in 100 parts by volume of a 50% aqueous solution Ethanol mixture containing 20 parts by volume of sorbitan

Test connection

1,3-bis (propyldithio) -2-dimethylaminopropane hydrogen oxolate

1,3-dimercapto-2-dimethylaminopropane hydrogen oxolate

4,7-bis (dimethylamino) -

1,2,6,7-tetrathiecandihydrogendioxalate

1,2-bis (benzylthio) -3-dimethylaminopropane hydrogen oxalate ..

Comparison sample (tap water)

Table 1 a Survival rate in%

Aphis
glycines Tetra
nychus
bima
culatus 0 0 0 0 0 0 33.3 112.0 81.7

Test connection

Survival rate in%

Aphis glycines

1,2-bis (n-hexyldithio) -3-dimethylairainopropane 56.7

1,2-bis (benzylthio) -3-methylethylaminopropane 83.3

1,3-bis (benzyl thio) -2-dimethylaminopropane 33.3

1,3-bis (benzylthio) -2-diethyiaminopropane 50.0

1,3-bis (ethoxythiocarbonylthio) -2-diethylaminopropane 3.3

1,3-bis (n-bxitylthio) -2-dibutylamine-iopropane 10.0

1,3-Dimercapto-2-moφholinopropane ... 0

Comparative sample (tap water) 100

Attempt 2

The test compounds were dissolved in tap water containing 0.02% of an adhesive in such amounts solved that they had the concentrations shown in Table 2. A mixture was used as the adhesive from 20% alkylphenol polyethylene glycol ether, 12% ligninsulphonic acid and 68% aqueous methanol. Young leaves of Chinese cabbage were immersed in the test solutions for a few seconds and attached to the Left to air until the surface of the leaves was dry. The leaves treated in this way were placed in containers 9 cm in diameter and 3 cm in height. Test insects (Pieris rapae, larvae and Phyllotreta stnolata, fully grown) were placed on the leaves. After 24 hours they were killed Insects counted The results are shown in Table 2 and Table 2a

39/12

Table 2

Pieris rapae Phyllotreta
striolata Killed / Test connection Conc Conc scheduled tration
the test- Killed / tration
the test connect scheduled connect manure manure 1,3-bis {propyldithio) - 9/20 2-dimethy! Aminopro- panhydrogen oxalate .. - - 0.02 4,9-bis (dimethylamino) - 1,2,6,7-tetrathiecan- dihydrogendioxalate .. 0.02 8/8 - 0.01 8/8 5-dimethylamiiio- 20/20 1,3-dithiane-2-thione hydrogen oxalate 0.02 5/8 0.02 0.01 8/8 1,2-bis (acetylthio) - 19/20 3-dimethylaminopro- 20/20 panhydrogen oxalate .. - - 0.02 0/20 methylaminopropane - 0.02 Comparative sample 0 0.8 0

The stalks were cut open to count the surviving larvae. The results are given in Table 3. _{Tab]] e3}

Conc Medium Test connection tration of
test Over
life rate connection of the larvae
(%) 1,3-bis (propyldithio) -2-dimethyl- 0.025 33.1 aminopropane hydrogen oxalate 0.05 30.0 4,9-bis (dimethylamino) - 0.025 0.0 1,2,6,7-tetrathiecandihydrogen 0.05 0.0 dioxalate Comparative sample 0 64.2

Table 2 a Test connection Conc
tration
(%) Cabbage
worms
(Pieris
rapae)
killed /
scheduled Phyllotreta
striolata
killed,
scheduled 1,2-bis (n-hexyldithio) -
3-dimethylamino
propane
1,2-bis (benzylthio) -
3-methylethylamino
propane
1,3-bis (benzylthio) -
2-dimethylamino
propane
1,3-bis (benzylthio) -
2-diethylaminopropane
1,3-bis (ethoxythiocarbo-
nylthio) -2-diethyl-
aminopropane
1,3-bis (n-butylthio) -
2-dibutylamino
propane
1,3-dimercapto-2-mor-
pholinopropane
Comparative sample 0.02
0.02
0.02
0.02
0.02
0.02
0.02
0 3/8
2/8
7/8
8/8
8/8
8/8
8/8
0/8 9/20
4/20
15/20
20/20
20/20
20/20
20/20
0/20

Attempt 4

The test compounds were dissolved in water, the sorbitan laurate polyoxyethylene ether in double Amount of test compounds contained. Radish leaves were dipped in the solutions and attached to the Left in the air when they were dry on the surface. The treated leaves were placed in glass containers placed. In each container, 20 larvae of the "daikon" leaf beetle (Phaedon brassicae) were released. After 48 hours, the insects killed were counted and the mortality rate determined. In the The numbers listed in Tables 4 and 4 a are the mean values of two experiments.

Table 4

Test connection

1,3-bis (propyldithio) -2-dimethyl-

aminopropane hydrogen oxalate
1, S-Dimercapto ^ -dimethylamino-

propane hydrogen oxalate
1 ^ -Dimercapto-S-dimethylamino-

propane hydrogen oxalate
1,3-dithiocynate-2-dimethylamino-

propane hydrogen oxalate
l, 3-bis (ethyldithio) -2-dimethyl-

aminopropane hydrogen oxalate
Comparative sample

Table 4 a

Concentration of

Test connection

0.1 0.02

0.1 0.02

0.1 0.02

0.1 0.02

0.1

0.02

Test connection

Attempt 3

The test compounds were dissolved in water containing 0.05% of the adhesive used in Experiment 2 in such amounts that they had the concentrations given in Table 3. Rice plants grown in 1/5000 Ar-Wagner pots were ^{sprayed with the solution in an amount of 10 cm 3} / pot. Ripe eggs of the chilo suppressalis were placed on the sprayed rice plants. One week after the larvae entered the 1,2-bis (n-hexyldithio) -3-dimethyl-

aminopropane

1,2-bis (benzylthio) -3-methyl-

ethylaminopropane

1,3-bis (benzylthio) -2-dimethyl-

aminopropane

l, 3-bis (benzylthio) -2-diethyl-

aminopropane

1,3-bis (ethoxythiocarbonylthio) -2-diethylaminopropane

concentration

0.1

0.1 0.1

0.1

0.1

Medium mortal wedge

81.3

77.3

100.0

100.0

100.0

81.3

95.2

74.5

100.0

100.0

Mine mortal wedge

23.3 10.0 50.0 26.7 100

613'24Ü

] 693 215

17th

continuation

Test connection

concentration

1,3-bis (n-butylthio) -2-dibutyl-

aminopropane] 0.1

1,3-dimercaptc-2-morpholino-

propane 0.1

Comparative sample.

Attempt 5

Medium mortality

1%)

76.7

100 0

The drops of 1 cm ^{3 of} an aqueous solution of the test compounds were placed from a pipette onto a Petri dish until the drops evenly covered the bottom of the dish. After the drops had dried by careful soaking, red bean beetles (Callosebruchus chinensis) were placed in the petri dish. After 24 hours, the insects killed were counted in order _{to determine the ideal dose (LD 50} I. The results are shown in Table and Table 5a.

Table 5

Test connection

1,3-bis (propyldithio) -2-dimethylaminopropane hydrogen oxalate

1,3-Dimercapto-2-dimethylaminopropane hydrogerjoxalate

1,3-Dimercapto-2-dimethylaminopropane sodium salt

4,9-bis (dimethylamino) -1,2,6,7-tetrathiocandihydrogendioxalate

1,2-bis (acetyltbio) -3-dimethylaminopropane hydrogen oxalate

5-dimethylamino-1,3-dithiane-2-thione

1,2-dimercapto-3-dimethylaminopropane hydrogen oxalate

1 ^ -dithiocyanate - ^ - dimethylaminopropane hydrogen oxalate

LD ₅₀ . %

0.005 to 0.01 0.001 0.05

0.025 0.002 0.005

0.0025 to 0.005, 0.000625 to 0.00125

Tesa connection

l, 3-bis (ethoxy-thiocarbonylthio) -2-dimethyl-amino-
propane hydrogen oxalate

l, 3-bis (amidinothio) -2-dimethylaminopropanhydro-
genoxalate dihydrochloride ...
1,3-bis (ethyldilhio) -2-dimethylaminopropane hydrogen oxalate

1,3-bis (acetyIthio) -2-dimethylaminopropane hydrogen oxalate

LD _5Ü ,%

0.05 to 0.1

0.05 to 0.1

0.00125 to 0.0025

0.0025 to 0.005

Table 5 a

Test connection

Lethal dose LD ₅₀ <%)

0.1

0.1

0.05 to 0.1 0.05 to 0.1 0.01 to 0.05

0.01

1,2-bis (n-hexyldithio) -3-dimethylaminopropane

1,2-bis (benzylthio) -3-methyl-

ethyl aminopropane

1,3-bis (benzylthio) -2-dimethyl-

aminopropane

l, 3-bis (benzylthio) -2-diethyl-

aminopropane

1,3-bis (ethoxythiocarbonyllhio) -

^ ⁰ 2-diethylaminopropane

1,3-bis (n-butylthio) -2-dibutyl-

aminopropane

l.S-Dimercapto ^ -morpholino- j propane j 0.0005 to 0.001

Trial 6

The test compounds were dissolved in water containing 0.1% of the same adhesive as in Experiment 2

contained. In cases where the test compounds were free bases, the aqueous solution was adjusted to pH 8.5 with a phosphoric acid buffer solution. The solutions prepared in this way were ^{sprayed on in an amount of 20 cm 3} / pot from a distance of 80 cm under a pressure of 1 atm. After 2 or 4 days, the proportion of survivors was determined. The results are shown in Table 6.

Test connection

4,9-bis (dimethylamino) -1,2,6,7-tetrathiecan

4,9-bis (dimethylamino) -1,2,6,7-tetrathiecan, dihydrogendioxalate

4-dimethylaminomethyl-1,3-dithiolane-2-thione 1,3-bis (ethyldithio) -2-dimethylaminopropane hydrogen oxalate

Comparative sample (malathion) *) Comparative sample

*) O, O'-dimethyl-S- (1 J-dicarbethoxyethyU-phosphodithioate.

Table 6

Concentration of

Test connection

0.05

0.025

0.05

0.025

0.05

0.025

0.025

survivors in%

Aphis glycines

after
2 days I 4 days

25.4
0.4

58.9

0.0

13.0

1.4
102.7
129.4

2.6

0.0
11.4

1.6
93.1

Tetranychus bimaculatus after

2 days

2.4 27.4

0.0

8.5

0.0

111.9

154.3

4 days

143.3

Trial 7

A field trial was carried out on Phyllotreta striolata on 25 to 30 radish plants that were used for each test compound was planted in a 3 x 0.6 m square. Plants with 10 to 15 leaves were made used for this attempt. The test solution of the composition shown in Table 7 was sprayed over the plants at a rate of 13 l / are. The number of insects on the radish plants was counted before and 5 days after the spraying. The calculated Percent of survivors is given in Table 7.

Table 7

Test connection

4,9-bis (diraethylamino) -J, 2,6.7-tetrathiecandihydrogen-
dioxalate

5-dimethylaminol, 3-dithiane-2-thionehydrogenoxaJate ...

control

Control (EPN) *) ...

Tough the 5 days Insects per after Radish plant to the Conc Spray tration - ■ ■ H
2.7 before the 3.3 Spray 5.0 1.2 5/10000 10.5 5/10000 4.3 0 5.4 3/10000 4.0

survivors

23.7

76.7
96.6
24.0

·) Ethyl p-nitrophenylthionobenzene phosphonate.

Trial 8

Acute toxicity test in mice (F ₁ breed) by intraperitoneal injection.

Test connection

1,2-bis (propyldithio) -2-dimethylaminopropane hydrogen oxalate

4-dimethylaminomethyl-1,3-dithiolane-2-thione

Dose I killed /
mg kg I used

1

100
200
500
100
200
500

1/3
3/3
3/3
0/3
3/3
3/3

The preparation of the compounds of formula I is illustrated by Examples 1 to 23 below. Then ready-to-use pesticides that contain the invention Containing compounds as active ingredients, described using Mixture Examples 1 to 12. It the examples are merely preferred embodiments of the invention. The temperatures »Ind uncorrected, and the quantities given relate to weight, unless otherwise stated.

example 1

In 50 cm ^{1 of} ethanol, 3.4 g of 1,3-dichloro-2-dimethylaminopropane hydrochloride were neutralized with 0.9 g of potassium hydroxide. The solution was slowly added dropwise with stirring at room temperature to a mixture of 4.9 g of sodium benzyl mercaptide ^{and 20 cm 3 of ethanol.} After the addition, the mixture was briefly warmed to separate out sodium chloride, which was then filtered off. The filtrate was concentrated under reduced pressure. What remained was an oily substance, which was extracted with ether. The ethereal solution was washed with water and dried over anhydrous sodium sulfate. An ethereal solution saturated with anhydrous oxalic acid was slowly added to the dried ethereal solution, crystals separating out, which were filtered off, decolorized and recrystallized from an ethanol-ether mixture. This gave 4.5 g of 1,3 - bis (benzylthio) - 2 - dimethylaminopropane hydrogen oxalate in the form of faffeless crystals which melted at 132 to 135.degree.

Example 2

54.4 gl ^ -Dichlor-3-diethylaminopropane hydrochloride were dissolved in a mixture of 100 cm ^{3 each of ethanol and methanol.} A mixture of 14 g of potassium hydroxide and 150 cm ^{3 of} ethanol was added to this solution while cooling with ice, whereupon potassium chloride separated out and was filtered off with suction. A mixture of 11.5 g of metallic sodium, 62.1 g of benzyl mercaptan and 100 cm ^{3 of} ethanol was added to the filtrate obtained. The mixture was refluxed for 2 hours with stirring on a water bath, during which the sodium chloride separated out, which was wiped off. The filtrate was evaporated to dryness under reduced pressure and the residue was dissolved in ether. The ethereal solution was washed with water, dried and evaporated to dryness, 67.3 gl, 2-bis (benzyIthio) -3-diethylaminopropane being obtained as a brown oil.

Example 3

4.8 g of 3-dichloro-2-dimethyl-aminopropane hydrochloride were neutralized with 1.4 g of potassium hydroxide in 150 cm ^{3 of ethanol.} 5.2 g of potassium thioacetate were slowly added to the solution at room temperature with stirring. After the addition, the mixture was briefly heated, potassium chloride separating out, which was filtered off. The filtrate was evaporated under reduced pressure to leave an oily substance, which was extracted with ether. The ether solution was washed with water, dried over anhydrous sodium sulfate and heated, the ether being distilled off and an oily substance remaining. The oily residue was dissolved in dry ether. An ethereal solution saturated with anhydrous oxalic acid was slowly added to the solution, crystals separating out and being recrystallized from a mixture of ethanol and ether. 1,3-Bis (acetylthio) -2-dimethylaminopropane hydrogen oxalate was obtained in the form of colorless crystals which melted at 91 to 94.degree.

Example 4

A solution of 12.5 g of 1,2-dichloro-3-dimethylaminopropane hydrochloride in 100 cm ^{3 of} ethanol was used

neutralized with 3.6 g of potassium hydroxide, potassium chloride separated out, which was filtered off. A solution of sodium thioacetate in ethanol, which had been prepared from 9.9 g of thioacetic acid, 3 g of metallic sodium and 100 cm ^{3 of} ethanol, was added to the filtrate. The mixture was left to stand overnight and then heated on the water bath under the reflux condenser for 40 minutes during which time sodium chloride separated out, which was filtered off. The

The filtrate became dry under reduced pressure evaporated. The oily residue was dissolved in ether. The ethereal solution was washed with water and dehydrated. To the dehydrated Solution, an ethereal solution saturated with anhydrous oxalic acid was added dropwise, crystals separated out, which were filtered off. 6 g of l, 2-bis (acetylthio) -3-dimethylaminopropane hydrogen oxalate were obtained, which decomposed at around 105 to 115 ° C. The raw crystals were made out Recrystallized methanol to give pale yellow crystals which decomposed at 124-128 ° C.

Example 5

A solution of 9.6 gl ^ -DichlorO-dimethylaminopropane hydrochloride in 50 cm ^{3 of} ethanol was neutralized with 2.8 g of potassium hydroxide, with potassium chloride separating out, which was filtered off. A solution of 8.2 g of sodium ^{trithiocarbonate in 50 cm 3 of} ethanol was added to the filtrate and the mixture was heated on a water bath under the reflux condenser for 1 hour. After cooling, the separated sodium chloride was filtered off and the filtrate was concentrated under reduced pressure. 100 cm ^{3 of} water were added to the residue and the mixture was extracted ^{three times with 50 cm 3 of ether.} The ether extracts were combined and dehydrated, whereupon a solution of 7.5 g of anhydrous oxalic acid in 100 cm ^{3 of} ether was added, with 8.2 g of crude 4-dimethylaminomethyll, 3-dithiolane-2-thione hydrogen oxalate being deposited, which separated out at about 158 decomposes up to 168 ° C. The crude crystals were recrystallized from aqueous ethanol, yellow platelets being obtained which decomposed at 187 to 189 ° C.

Example 6

35

80 g of gaseous ammonia were anhydrous in 1.21 Dissolved methanol with cooling. The solution was saturated with hydrogen sulfide. To the solution were 80 g of l ^ -dibromo-S-dimethylaminopropane hydrochloride given, whereupon the mixture is kept overnight in a sealed vessel at room temperature left standing. The mixture was then boiled for 2 days while introducing hydrogen sulfide. The obtained crystals were filtered off. The filtrate was concentrated under reduced pressure, whereby an oily residue remained, which was distilled further, 6.0 g of l ^ -DimercaptoO-dimethylaminopropane obtained at 71 to 78 ° C (5 mm Hg)

boiled. ". . . _

Example 7

A solution of 7.9 g of U-dichloro ^ -dimethylaminopropane hydrochloride in 50 cm ^{3 of} anhydrous ethanol was neutralized with 2.2 g of potassium hydroxide, the free amine being formed. A solution of 6.1 g of ammonium thiocyanal in 100 cm ^{3 of} anhydrous ethanol was added to the solution and the mixture was stirred at room temperature for 2 days. After the precipitate obtained had been filtered off, the filtrate was concentrated under reduced pressure. The oily residue was dissolved in ether, the ethereal solution washed with water and dried. An anhydrous oxalic acid solution in ether was added to the dried solution, crystals separating out, which were separated off and recrystallized from an ethanol-ether mixture, 7.4 g of 1,3-dithiocyanate-2-dimethylaminopropane hydrogen oxalate being obtained, which at 123 to 124 ° C melted with decomposition.

Example 8

A solution of 7.9 g of 1 3-dichloro-2-d, methylaminopropane in 50 cm ^{3 of} anhydrous ethanol was neutralized with Λ or potassium hydroxide, the free amine being formed. The latter was added to a solution of 12 8 g of potassium ethyl xanthate in I ₃ O cm ^{3 of} anhydrous ethanol and the mixture was stirred for days at room temperature. The resulting reaction mixture was worked up in the same way as described in Example S, wöbe; 2.9 g of 1 3 - were obtained dimethylammopropanhydrogcnoxalat, the 5-116 ^C C uni ~ he melted decomposition if Π - bis (äthoxylhicarbonylthio).
Example 9

79 2 1 VDichior 2-dirnethylaminopropane hydrochloride in 50 cm ³ anhydrous ethanol were neutralized with T) η K-'iurnhvdfONvc ¹ , whereby the free amine aebildel Vurdc. which was added to a solution of 6.1 g ΤΓ !! '> ί ·. ~ "?! ·" ΓΓ j _r HVU-n ³ anhydrous ethanol wuuk \ Γλ-s mixture was stirred for 2 days at room temperature. · ¹ ^ -. Resulting reaction mixture was soften way as in the previous example auigeai PuK T!. where IXg 1.3-bis (amidincthio) -2-dim-Mhvlamin '> propanh} drug oxalate dihydrochloride with melting point: KMS up to 108 ⁰ C (decomp.) were obtained.

Example 10

«I6i! 1 ^: i-dichloro-2-dimethy | aminopropane hydrochloride in lÖOcirT 50% aqueous ethanol were neutralized with: <>·> sodium hydroxide, whereby the free Λ mi η was formed. After adding 24.8 g of sodium thiosulfate, the mixture was briefly heated and concentrated under reduced pressure, a light brown oily substance remaining.

6.2 c of ethyl mercaptan were dissolved in 50 cm ^{3 of} a 2 normal aqueous sodium hydroxide solution. The solution was saturated with sodium chloride. The oily substance obtained in the manner described at the outset was slowly added to the solution. After standing at room temperature for about 5 to 6 hours, the mixture was extracted twice with ether. The ethereal solutions were combined, washed with water and dried.

A solution of anhydrous oxalic acid in ether was added to the ethereal solution, with crystals separating out, which were separated off and recrystallized from a mixture of ethanol and ether, 2.2 g of 1,3-bis (ethyldithio) -2-dimethylaminopropane hydrogen oxalate with a melting point of 113 to 115 ⁰ C (decomp.) were obtained.

Example 11

A mixture of 24 g of sodium sulfide and 32 g of sulfur powder was heated on the water bath, a uniform, red-orange solution being formed, to which 375 cm ^{3 of} water and 15 g of anhydrous potassium carbonate were added. The mixture was cooled with a refrigerant. A solution of 15 g of 1 ^ -Dichlor ^ -dimethylaminopropane hydrochloride in 75 cm ^{3 of} water was slowly added dropwise with stirring into the cooled mixture, the temperature being kept at -2 to -3 ° C. After the addition, the reaction mixture was left to stand in a refrigerator at -2 to -3 ° C. for 2 days. Then 50 cm ^{3 became} abnormal at room temperature

693

Aqueous sodium hydroxide solution, 25 g of potassium cyanate added to the reaction mixture, which was then extracted twice with chloroform. The extract was made treated in the same way as in the previous example, using 4.2 g of 4,9-bis (dimethylamino) -l, 2,6,7-tetrathiecandihydrogendioxalat with a melting point of ISl up to 154 ° C. (decomp.).

Example 12

A mixture of 15 g of 1,3-bis (benzylthio) _{-2-chloro-! O} propane and 45 cm ³ of a 3% solution of dimethylamine in benzene! Was placed in a pressure vessel and held for 16 hours at 160 C. After cooling, the dimethylamine hydrochloride formed was filtered off and the filtrate was evaporated to dryness under reduced pressure. The residue was dissolved in a small amount of water and ^{extracted with 50 cm 3 of} ether. The ethereal solution was dried over anhydrous sodium sulfate. An ethereal solution saturated with oxalic acid was added to the ether extract until there was no longer any precipitation. The precipitates were separated off and recrystallized, 1 g of 1,3-bis (benzy! Thiol-2-dimethylaminopropane hydrogen oxalate with a melting point of 132 to 135 ° C. being obtained.

Example 13

A mixture of 7.5 g of crude 1,3-dibenzylthio-2-chloropropane and 24 cm ^{3 of} a 33% strength solution of diethylamine in benzene was placed in a pressure vessel and kept at 160 ° C. for 14 hours. After cooling, the diethylamine hydrochloride formed was filtered off and the filtrate was evaporated to dryness under reduced pressure. A small amount of water and 20 cm ^{3 of} ether and then an ethereal solution saturated with oxalic acid were added to the residue until no more precipitate formed Melting point 135 to 142 ° C were obtained.

Example 14

A mixture of 15 g of 1,3-bis (äthoxythiocarbonylthio) -2-bromopropane and 45 cm ^{3 of} a 33% strength solution of diethylamine in benzene was heated on a water bath for 3 hours. After cooling, the inorganic salts formed were filtered off. The filtrate was evaporated to dryness under reduced pressure. The residue was dissolved in dilute acetic acid and the solution was extracted with ethyl acetate to remove the solvent-soluble impurities. The aqueous layer was adjusted to a pH of 9.0 with sodium carbonate and extracted ^{twice with 50 cm 3 of ether each time.} An ethereal solution saturated with oxalic acid was added to the ether extracts until no more precipitate settled. The precipitates were separated off and recrystallized, 1.5 g of 1,3-bis (ethoxythiocarbonylthio) -2-diethylaminopropane hydrogen oxalate being obtained.

Example 15

A mixture of 10 g of 3-bis (benzylthio) propanone-2.70 cm ^{3 of} dimethylformamide and 70 cm ^{3 of} 85% formic acid was placed in a vessel provided with a dehydration device and heated to 180 ° C. on an oil bath for 10 hours. The reaction mixture was concentrated under reduced pressure and the residue extracted with ether. The ether extract was extracted with 5% hydrochloric acid and the amine formed was separated off. The aqueous layer was made alkaline with a dilute aqueous sodium hydroxide solution and extracted with ether. The ethereal solution was washed with water, dried over sodium sulfate and evaporated to dryness to give crude 1,3-bis (benzylthio) -2-dimethylaminopropane which was dissolved in ether. The solution was shaken together with an aqueous oxalic acid solution, 1.5 g of the corresponding hydrogen oxalate melting at 132 to 135 ° C. being formed.

Example 16

A mixture of 40 cm ^{3 of} anhydrous ethanol and 80 cm ^{3 of} liquid ammonia was cooled with dry ice. A solution of 4.9 g of 1,3-bis (benzylthio) -2-dimethylaminopropane in 40 cm ^{3 of} anhydrous ethanol and 1.9 g of metallic sodium were successively added to the cooled mixture with stirring. After the addition, stirring was continued for 30 minutes. Then ammonia and ethanol were distilled off and 50 cm ^{3 of} water were added to the residue. The aqueous mixture was extracted with ether to remove the ether-soluble impurities. The aqueous layer was adjusted to pH 9.0 by adding hydrochloric acid and saturated with sodium chloride. A solution of 6 g of sodium ^{benzyl thiosulphate in 20 cm 3 of} water was added dropwise to the resulting solution with stirring, an oily substance separating out, which was extracted with ether. The ether extract was mixed with 25 cm ^{3 of} a 7% strength oxalic acid solution in water. The mixture was shaken vigorously and left to stand overnight, 2.1 g of 1,3-bis (benzylthio (-2-dimethylaminopropane hydrogen oxalate) separating out in the form of colorless crystals with a melting point of 115 to 119 ° C.

Example 17

1 "VDimercapto ^ -dimethylaminopropane. which had been prepared from 4.9 g of 1,3-bis (benzylthio) -2-dimethylaminopropane in the manner described in the previous example was dissolved in 50 cm ^{3 of} water. The aqueous solution was adjusted to a pH of 9.0 by adding hydrochloric acid and saturated with sodium chloride. A solution of 20 g of sodium propyl thiosulfate in 25 cm ^{3 of} water was added to this solution, whereupon an oily substance separated out and was ^{extracted with 80 cm 3 of} ether. The ether extract was ^{mixed with 25 cm 3 of} a 7% strength aqueous oxalic acid solution. The mixture was shaken and allowed to stand overnight to yield 1.5 g of 1.3-bis separated out (propyldithio) -2-dimethylaminopropanhy drogenoxalat in the form of colorless crystals melting point 130 mi bis'134 ⁰ C.

Example 18

A solution of 3 g of 2-dimercapto-3-dimethyl aminopropane-1,2-dithiol in 30 cm ^{3 of} water was adjusted to a pH of 9.0 with a 10% strength aqueous sodium hydroxide solution and saturated with sodium chloride a solution of 20 g of sodium propyl thiosulphate was added to 20 cm ^{3 of} water, an oily substance separating which was extracted ^{three times with 30 cm 3 of ether each time}

I 693 215

would. The ether extracts were combined and ^{mixed with 25 cm 3 of} a 7% strength aqueous oxalic acid solution. The mixture was shaken and allowed to stand overnight, during which time the desired compound crystallized out. This was filtered off and recrystallized, 1.5 g of 2-bis (propyldithio) -3-dimethylaminopropane hydrogen oxalate being obtained in the form of colorless crystals with a melting point of 128 to 132 ^° C.

Example 19

A mixture of 40 cm ^{3 of} anhydrous ethanol and 80 cm ^{3 of} liquid ammonia was cooled with dry ice. A solution of 4.6 g of 3-bis (benzylthio) -2-dimethylaminopropane in 40 cm ^{3 of} Anhydrous Ethaiu: · 'and 1.9 g of metallic sodium added with stirring After the reaction was complete, ammonia and ethanol were distilled off, the oily residue was dissolved in 50 cm ^{3 of} water and the solution was extracted with ether in order to remove the water-insoluble oily substances. After the aqueous layer had been separated off, 6.2 g of benzoyl chloride were added dropwise to it while cooling with ice and stirring.Half an hour after the addition, the oily substance which separated out was ^{extracted with 80 cm 3 of} ether. The ether extract was mixed with 25 cm ^{3 of} a 7% aqueous solution The mixture was shaken and left to stand overnight, during which the desired compound crystallized out. This was film-off and dried, yielding 2.1 g of 1,3-bis (Benzylthiol-2-dimethylaminopropane hydrogen oxalate in the form of white, lamellar crystals with melting point 154 to) 56 ° C. were obtained

Example 20

A solution of 2.7 g of 1.2-Dimercapto-3-dime! Hy! - Aminopropane and 4.2 g of sodium hydroxide in 70 cm 'of water were saturated with sodium chloride Cooling with ice and stirring, 8 g of acetic anhydride were added dripped into the solution. After adding 80 cm of ether to the mixture, this became further Stirred for 30 minutes. The ether layer was separated off, dried and mixed with that saturated with oxalic acid mixed essential solution. The mixture was shaken and allowed to stand overnight with the desired compound crystallized out. This was removed by nitration and dried, 5 g of 1,2-bis (acylthiol-3-dimethylaminopropane hydrogenoxalate in the form of white, powdery crystals with a melting point of 115 to 116 "C.

Example 21

A mixture of 40 cm ^{3 of} anhydrous ethanol and 80 cm ^{3 of} liquid ammonia was cooled with dry ice. A solution of 4.9 g of 13-bis (benzylthio) -2-dimethylaminopropane in 40 cm ^{3 of} anhydrous ethanol and then 1.9 g of metallic sodium were added to the cooled mixture. After stirring the mixture for 30 minutes, ethanol and ammonia were distilled off. 3.6 g of crude U-dimercapto-2-dimethylaminopropane remained as residue.

The crude product was dissolved in water. The solution was neutralized with hydrochloric acid, with sodium chloride saturated and extracted several times with ethyl acetate. The ethyl acetate extracts were combined dehydrated and concentrated under reduced pressure, leaving 2.3 g of purified 1,3-dimercapto-2-dimethylaminopropane were obtained.

B e i s ρ i e1 22

An aqueous mercuric chloride solution was added to a solution of 2.7 g of 2-phenyl-5-dimethylamino-1,3-dithiane hydrogen oxalate in 100 cm ^{3 of water.} The mixture was on the water bath for 10 minutes

ίο heated, whereby benzaldehyde was formed and a mercaptide separated. The precipitate was filtered off to give 4 g of crude mercaptide was obtained with melting point 100-109 ⁰ C (dec.). The crude mercaptide was ^{suspended in 100 cm 3 of} water. Hydrogen sulfide was introduced into the suspension. After filtration, the filtrate was adjusted to pH 8.0 and extracted with ether. The ether extract was dehydrated and mixed with an ethereal oxalic acid solution to give 1.8 g of 1,3-dimercapto - 2 - dimethylaminopropanhydrogenoxalat with melting point 150 ^c C (dec.) Were obtained.

At sr ι el 23

1,3 - dichloro - 2 - dimethylaminopropane hydrochloride in an amount of 9.6 g with 24.8 g of sodium thiosulfate reacted in water, the disodium salt? obtained from 1.3-bis (su! fothio) -2-dimethylaminoprop.in would. The aqueous solution was poured into an aqueous solution of 7.5 g of the disodium salt of 1,3-dimercaplo-2-dimethylaminopropane dropped, the mn sodium chloride was saturated and well cooled with ice water was. The reaction mixture obtained was extracted with ether. The ether extract was washed with water and dried. An anhydrous ethereal solution of oxalic acid became the ethereal solution given, whereby crystals separate out, which are filtered off and from a mixture of ethanol and Ether were recrystallized, with 4.2 g of 4,9-bis | dimethylamino) -1.2.6.7-tetrathiecandihydrogendioxalat as small leaflets with a melting point of 154 to 156 C (decomposition) were obtained

Examples of pesticides
Mix!

1 part 1,3-bis (benzylthio) -2-diethylaminoproparate was adsorbed on 1.5 parts of diatomaceous earth and mixed with 1.5 parts of silica. The mixture was diluted with 96 parts of talc so that eir 1% dust was obtained, which zui Treatment of fruit trees is suitable.

Mixture 2

In 30 parts of methyl ethyl ketone 5 parts were < 1J-dithiocyanate-2-dimethylaminopropane dissolved. Room this solution became a solution of 10 parts of a surfactant (mainly composed of:

70% Polyoxyäthylenalkylphenylätham and 30% Na triumarylsulfonaten consists) in 55 parts of toluene ge give. A 5% emulsifiable solution was obtained, which is suitable for treating rice plants suitable

Mixture 3

45 parts of finely ground 13-dimercapto-2-d; methylaminopropane hydrogen oxalate were mixed with 5 parts of silica (its aqueous suspension sion is neutral). 48 teas were added to the mixture

ti

granular clay, as used in the paper industry, and 2 parts of sodium lignosulfonate. The mixture was finely pulverized and made into a 45% wettable powder, which is suitable for vegetables.

Mix 4

A solution of 5 parts of abietic acid polyglycol ester in 10 parts of acetone was adsorbed on 35 parts of finely powdered l ^ -Dimercapto-S-dimethylaminopropane hydrogen oxalate. The mixture was dried at a temperature below 60 ⁰ C in air. To the dried mixture were added 58 parts of finely ground clay and 2 parts of sodium lignosulfonate. The mixture was pulverized well and made into a 35% wettable powder suitable for treating fruit trees.

Mix 5

1 part of 1,3-bis (ethylthio) -2-tnorpholine propane was added to a mixture of 1 part of bentonite and 1.3 parts Diatomaceous earth adsorbed. The mixture was granulated in a granulator. There were also 10 parts Lactose wetted with a small amount of a starch paste and also dried into granules. Both Granules were mixed with 1 part of talc. The mixture became 7% tablets of 15 mm Pressed diameter that can be used as a nematocide.

Mix 6

In a mixture of 15 parts of cyclohexanone and 30 parts of methylnaphthalene, 25 parts of 4-dimethylaminomethyl-1,3-dithiolan-2-thione were dissolved. 30 parts of a surface-active agent (consisting essentially of 70% polyoxyethylene alkylphenyl ethers) were added to the solution and 30% organic sulfonates). The mixture uniformly became a 25% emulsifiable solution with stirring solved, which is suitable for use for vegetables.

Mix 7

1.5 parts of 1,3-bis (amidinothio) -2-dimethylaminopropane hydrogen oxalate dihydrochloride, 0.5 part of silica and 8 parts of talc were mixed and ground to a fine powder. The powder was with 90 parts of clay with an apparent specific gravity of about 0.5-0.6 diluted with a dusting agent which is suitable for treating fruit trees Mix 8

50 parts of 1,2-bis (äthoxythiocarbonylthio) -3-dimethylaminopropane with 15 parts of benzene, 15 parts a surface active agent (consisting mainly of polyoxyethylene diphenyl ethers) and 20 parts of another surfactant (mainly composed of polyoxyethylene alkylphenyl ethers exists) mixed. A 50% emulsifiable solution was obtained, which can be used for treatment suitable for fruit trees.

Mix 9

2 parts of 4,9-bis (dimethylamino) -l, 2,6,7-tetrathiecan were dissolved in 8 parts of methanol with heating. The solution was sprayed onto 35 parts of talc, which had been heated to about 50 to 60 ⁰ C. The mixture was passed through a ribbon blender with a heating mantle, the active ingredient being adsorbed on the talc and methanol being driven off in vapor form. The talc with the active ingredient adsorbed thereon was diluted with 63 parts of dicalite (a type of clay) to obtain a 2% dust which is suitable for treating vegetables.

Mix 10

50 parts of 1,2-bis (isopropyldithio) -3-dimethylaminopropane hydrogen oxalate were finely ground in a "fluid energy mill" and mixed with 50 parts of potassium chloride mixed. The mixture was ground again in a hammer mill, leaving a 50% wettable powder which is suitable for treating vegetables and plants.

Mix 11

10 parts of 1,3-bis (benzyldithio) -2-dimethylaminopropane hydrogen oxalate were pulverized. To the powdered compound were 2 parts of sodium lignosulfonate, 5 parts of polyoxyethylene octylphenyl ether. 3 parts of silica and 80 parts of clay are added. The Mixture was mixed thoroughly into a 10% wettable powder

Mix 12

2 parts of well-powdered 1,3-bis (ethoxythiocarbonylthio) -2-diethylaminopropane hydrogen oxalate were diluted with 98 parts of talc to give a 2% dust.

Claims (2)

Patent claims: 1. Organic bis (thio) aminopropane compounds of the general formula CH, - CH - CH, S S -A R ₁ or CH ₂
S. (Ia) [-CH ₂
S. (Ib) and salts thereof, in which A is an amino group disubstituted by lower alkyl radicals, the morpholino or pyrrolidino group, R, hydrogen, the cyano, acetyl, benzyl or a mercapto group substituted by a lower alkyl group, or both R ₁ together with ring closure are the thiocarbonyl group > C = S and either each R _{2 the} same as R ₁ or the ethoxythiocarbonyl or amidinothio group or both R ₂ together the group -S-CH ₂ -CHA-CH ₂ -S- or the thiocarbonyl group is> C = S. 2. Pesticides, characterized by a content of compounds of claim 1 as an active substance. in which A, R ₁ and R _{2 have} the meanings given in claim 1. It has been found that the compounds of the invention have a remarkable activity against Insects, mites and nematodes and are therefore valuable new pesticides. The same The salts of the compounds mentioned are effective. The invention also relates to pesticides, characterized by a content on the aforementioned organic bis (thio) aminopropane compounds as an effective substance. For use as pesticides, the compounds or their acid salts are too Appropriate mixtures are formulated which contain one or more of the active ingredients or their acidic salts contain. The compounds of the invention can be prepared by one of the methods described below will: A. The substituted thio groups are introduced into the corresponding dihalo compounds. For this purpose, dihalogen compounds of the general formula below are used CH ₂ -CH-CH ₂ -A I I χ χ (Ha) and CH ₂ -CH-CH ₂ X X ' (Hb) The invention relates to organic bis (thio) aminopropane compounds, their salts and pesticides containing these compounds. The invention accordingly relates to organic bis (thio) aminopropane compounds of the general type formula CH ₂ -CH-CH ₂ -A S S I ^K l (Ia)
A. CH ₂ -CH-CH ₂
SS R ₂ R ₂ Hb) in which A has the same meaning as in the forms in I a and 1 b and X and X 'each have a halogen atom, z. B. chlorine, bromine and iodine mean, reacted with a compound through which the halogen atom on Hydrocarbon skeleton is replaced by a mercapto group or the substituted thio group. Examples such compounds are hydrogen sulfide or its salts (e.g. sodium sulfide, potassium sulfide, Ammonium sulfide or a chemical equivalent of these salts), the halogen atoms being replaced by mercapto groups be replaced; Thiocyanic acid or its salts (e.g. sodium thiocyanate, potassium thiocyanate, Ammonium thiocyanate or their chemical equivalents), the halogen atoms being replaced by thiocyanate groups (—SCN) to be replaced; a mercaptan (e.g. methyl mercaptan, ethyl mercaptan, pro- k- pyl mercaptan, butyl mercaptan, hexyl mercaptan, Cyclohexyl mercaptan, benzyl mercaptan, thiophenol or their chemical equivalents) or a mercaptide (e.g. sodium mercaptide, potassium mercaptide, zinc mercaptide, silver mercaptide) of the above-mentioned mercaptans or a chemical equivalent of these mercaptides, the halogen atoms being replaced by two mercapto groups, both of which are substituted by a lower hydrocarbon radical; Thio