DE1693185C - 1,3 bis carbamoylthio 2 aminopro pane and pesticides containing them - Google Patents

Description

in which R ₁ and R _{2 are} lower alkyl radicals with up to 6 carbon atoms or R ₁ and R ₂ together with the adjacent nitrogen atom are a piperidine, pyrrolidine, morpholine or piperazine ring, and the salts of these compounds.

2. 1,3 - bis - carbamoylthio - 2 - dimethylaminopropane.

3.1, S-bis-carbamoylthio ^ -piperidinopropane.

4.1 ^ -Bis-carbamoylthio ^ -morpholinopropane.

5. Pesticides, characterized by a content of compounds according to Claims 1 to 4.

25th

It has already been established by the notifying party that that compounds of the general formulas

R,

N - CH,

CH - SCN CH ₂ - SCN R ₁ CH ₂ SCN

N-CH

/ I

R ₂ CH ₂ SCN

(ID

in which R ₁ and R _{2 have} the meaning given below, and salts of these compounds have excellent pesticidal activity and are suitable, for example, for pest control in households, agriculture and for sanitary purposes. It has now been found that the toxicity of the compounds of the formulas II and II 'towards warm-blooded animals can be reduced considerably without impairing the pesticidal effectiveness if both - SCN groups are each replaced by a - SCONH ₂ -GrUPpC. The invention relates to 1,3-bis-carbamoylthio-2-aminopropanes of the general formula

35

40

45

CH ₂ SCONH ₂

N - CH

(D

R,

CH ₃ SCONH,

in which R _{1 and R 2 are} lower .. 'kyl radicals with up to 6 carbon atoms or R 1 and R ₂ together with the adjacent nitrogen atom form a piperidine, pyrrolidine. Mean morpholine or piperazine ring, and the salts of these compounds. Examples of lower alkyl radicals with up to 6 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, amyl and hexyl.

The compounds can form salts with various acids, for example with 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 acid and arsenic acid, and with organic Acids such as maleic acid, citric acid, tartaric acid, oxalic acid, benzenesulfonic acid, toluenesulfonic acid. Ethanesulfonic acid and picric acid. The compounds of formula I are prepared by the compounds of the general formula II with a mineral acid such as hydrochloric acid, hydrobromic acid, hydroiodic acid and sulfuric acid. The production can in particular for example be carried out using one of the following methods:

1. You blow hydrogen halide, such as hydrogen chloride, hydrogen bromide and hydrogen iodide, in the Excess in a solution or suspension of the compound of the formula II in a lower one aliphatic alcohol, such as methanol or ethanol, and then distilled, expediently after heating, the alcohol from the resulting mixture.

2. Excess hydrogen halide of the type mentioned is blown into an aqueous solution or Suspension of the compound of formula II and then holds, if appropriate after neutralization the resulting mixture with an alkali compound (e.g. sodium hydroxide, potassium hydroxide, Sodium hydrogen carbonate or sodium carbonate) at room temperature or below.

3. The compound of the formula II is added to concentrated sulfuric acid, which is about 15 to 20% (V / V) contains water, then pour the mixture into chilled water. The thus obtained Compound is a salt and can be converted into the free base in a manner known per se will. Neutralization of the above-mentioned mixture immediately results in a free Base received.

As pesticides for agricultural and sanitary purposes, the compounds generally corresponding to the intended use for ready-made preparations assembled, e.g. B. to wettable powders, solutions, emulsifiable solutions, lubricants or Aerosols.

A wide variety of auxiliary materials can be used for the production of the finished preparations. at One or more of the compounds are used as a solution, emulsifiable solution or aerosol dissolved in a suitable liquid carrier or dispersible Suitable liquid carriers are solvents, z. B. water, lower alcohols (e.g.

Methanol. Ethanol, isopropanol, butanol, glycerine or ethylene glycol), ketones (e.g. acetone, methyl vinyl ketone, Cyclohexanone or cyclopentanone), ether (e.g. dioxane, tetrahydrofuran, ethylene glycol monomethyl ether or diethyl glycol monomethyl ethyl), aliphatic hydrocarbons (e.g. n-Hcxane, Petrol, kerosene, heating oil. Lubricating oil or machine oil), aromatic hydrocarbons (e.g. benzene, toluene, xylene, solvent benzene or methylnaphthalene),

essential oils, terpenes, chlorinated biphenyl or tree wort oil. Mixtures of the above are often used Solvents used because they have not only excellent dissolving power but also low To have toxicity for plants or humans.

Dust-like extenders or are usually used for the production of dusting agents and scattering agents Support materials used. For example, one or more types of connections are in a Ball mill, a pan mill or a hammer mill finely powdered and then with the powdery Mixing extenders or carrier materials. Suitable extenders or carrier materials are, for example vegetable powder (e.g. soybean flour, wheat flour, tobacco powder, walnut shell flour or Sawdust), clay (e.g. kaolin, kaolinite, saponite, vermiculite, beidellite, montmorillonite, bentonite or fuller's earth or attapulgite), talc, pyrophyllite. Lime, magnesium lime, diatomaceous earth. Silicon dioxide. Hydroxyapatite, Calcium carbonate. Dolomite, calcite, calcium sulfate, hydrated alumina, carbon black or Sulfur.

The pesticides of the present invention can also contain surface active agents Contain that as an adhesive or developer, emulsifier or solubilizer to improve the Effectiveness or stability of the finished products are used. Of the commercially available surfactants Agents are preferably salts of sulfonated! Castor oil, salts of alkylarylsulfonates or non-ionic sulfonates surface-active agents such as polyoxyethylcndiarylether, polyoxyäthylcnalkylarylether and Polyoxyethylene sorbitan monoacylate (with 10 to 18 carbon atoms in the acyl group) as emulsifiers and solubilizers used for the products of the invention.

The compound I and the pesticides prepared using it according to the Invention are effective against a wide variety of insects. Mites and nematodes. They destroy them The pests mentioned below as examples or at least considerably reduce the number of survivors Animals. Examples of herbivorous insects, etc. are:

Colorado potato beetle (Leptinotarsa declemlineata).
Large 28-square ladybug (Epilachna

viginlioctomaculata),
28-spotted ladybird (lipilachna sparsa

orientalis).

Striped earth flea (Phyllolreta striolata).
Pumpkin leaf beetle (Aulacophora femoralis, adult), vine leaf beetle (Acrothinium gackkwitchii,

adult).

Red bean louse (Callosobruclius chincnsis),
Cockroach (Blattela gcrmanica),
Rice leaf beetle (Lema oryzac),
House fly (Musca domcstica),
Cabbage sawfly (Athalia rosac japonensis, larva), chilo supprcssalis,
Tobacco cut worm (Plodcnia litura),
Rice plant maggot (Parnara gutlata, larva),
Green rice caterpillar (Naranga aenesccns, larva),
"Cabbage armyworm" (Baralhra brassicac,

larva),
"Giant bagworm" (Cryptothclea formosicola,

larva),

"Pea bagworm" (Cryptothelea minuscula,

larvae),
"Pale clouded yellow" (Colias hyale polio-

graphus, larvae),
Larva of the great cabbage white butterfly (Pieris rapae,

larva),

Citrus red mite (Petranychus citri),
Soybean louse (Aphis glycines),
Citrus leaf miner (Phyliocnistis citrella),
Peach leaf miner (Lyonetica clerkella),

Turnip louse (Rhapalosiphum pseudobrassicae),
"Two-spitted mite" (Tetranychus bimaculatus).

Preparations for direct application to the plants can contain the compound I in amounts of 0.1 to 10 percent by weight or more. When the preparation is used as a concentrate for the manufacture of sprays or more dilute dusts are intended, the content of compound I can be between 10 and 90 percent by weight.

example

part One
Manufacture of carbamoyhhio derivatives

1. Hydrogen chloride gas for 2 hours in 12 g 1,3 - dithiocyanato - 2 - dimethylaminopropane hydrochloride passed, which is suspended in 30 ml of methanol, a reaction taking place. The melhanol is distilled off from the reaction mixture under reduced pressure. The residue is dried and recrystallized from methanol, giving 13.7 g of colorless, needle-shaped crystals of 1,3-bis-carbamoylthio - 2 - dimethylamiiiopropanhydrogenchlorid of melting point 175 ° C can be obtained.

2. Hydrogen chloride gas is placed in a mixture of 3.6 g of water and 23.7 g of 1,3-dithipcyanato-2-dimethylaminopropanhydrogen chloride for 9 hours geleitel, with a reaction taking place. The glassy reaction mixture is left to stand for a while at room temperature and then stirred with 99% ethanol, crystals are formed which are filtered off and purified in the manner described under 1. Here, 12 g of colorless, needle-shaped crystals of!, S-bis-carbamoylthio ^ -dimcthylaminopropane hydrochloride obtained from melting point 175 C.

Elemental analysis for ('711 ,,, N ₁ O ₂ S ₂ CI:

Calculated ... C 30.70, H 5.89, N 15.35;
found .... C 30.55, H 5.85, N 15.27.

3. Hydrogen chloride gas is mixed into a mixture for 7 hours of 1.8 g of water and 11.9 g of 1,3-dithiocyanato-2-dimethylaminopropane hydrochloride conducted, with a reaction takes place. The reaction mixture is dissolved in 20 ml of water with sodium hydrogen carbonate neutralized and cooled with ice, whereupon crystals separate out. The filtered crystals are dried and recrystallized from 99% ethanol, with 5.8 g of colorless prisms of 1,3-biscarbamoylthio - 2 - dimelhylaminopropane with a melting point of 130 to 131 ° C can be obtained.

Elemental analysis for C ₇ H ₁₅ N ₁ O ₂ S ₂ :

Calculated ... C 35.41, 116.37. N 17.70;
found .... C 35.53. H 6.18, N 17.99.

4.2 g of l ^ -dithiocyanato ^ -dimethylaminopropane are added dropwise .with stirring to 20 ml of 95% strength (V V) concentrated sulfuric acid, which through Cooling is kept at a temperature below TDC. After 30 minutes the reaction mixture wii d Poured drop by drop into ice-cold water with stirring. By working up to that described under 3 Thus, 0.6 g of l ^ -Bis-carbamoylthio ^ -dimethylaminopropane from melting point 129 to 130 ° C receive.

1.8 g of this compound and 0.7 g of anhydrous oxalic acid are heated in 100 ml of anhydrous Dissolved methanol. The methanol is distilled off under reduced pressure, giving crystals are precipitated, which are filtered off and dried, 1.6 g of colorless, needle-shaped crystals of l ^ -Bis-carbamoylthio ^ -dimethylaminopropane hydrogen oxalate from melting point 147 to 148 ° C (decomp.) can be obtained.

5. Further carbamoylthio derivatives are synthesized in the manner described under I to 4. The following Results are obtained:

Table 1

l ^ -Bis-carbamoylthio- ",

2-piperidinopropane melting point, c

hydrochloride 173 to 174 (decomp.)

1,3-bis-carbamoylthio-2-morpholinopropane hydrochloride 172 to 172.5 (Zcrs.)

35

1,3-bis-carbamoylthio-2-dipropylaminopropane hydrochloride 165 to 170 (decomp.)

1,3-bis-carbamoylthio-2-methylethylaminopropane hydrochloride .

1,3-bis-carbamoylthio-2-pyrrolidinopropane hydrochloride

Melting point, '' C
. 172 to 174 (decomp.)

1,3-bis-carbamoylthio-2-diethyiaminopropane hydrochloride

170 to 175 (decomp.)

173 (decomp.)

example

Part II

Testing of carbamoylthio derivatives for pesticides

Effectiveness and
Toxicity to warm blooded animals

1. An emulsion is made by mixing 10 parts by weight of the compounds to be tested with 90 parts by volume of an aqueous ethanol mixture produced, the 20 parts by volume of Sorbitanlauralpolyoxyäthylenäther ("Tween 20"). The emulsion is diluted with tap water so that the concentration the test compound is adjusted to 0.05%. Young leaves of Chinese cabbage will be immersed in the emulsion produced in this way for several seconds. The wet leaves are left in the air until they are dry. The treated leaves are placed in Petri dishes. The test insects, viz striped fleas (Phyllotreta striolata, fully grown) and larvae of the great cabbage white butterfly (Pieris rapae. Larvae) are exposed on the leaves. After 24 hours the number of insects killed counted. The results are shown in Table 2 below.

table

Test connection

1,3-bis-carbamoylthio-2-dimethylaminopropane

1,3-bis-carbamoylthio-2-dimethylaminopiOpane hydrogen chloride

1,3-bis-carbamoylthio-2-diethylaminopropane

I, S-bis-carbamoylthio ^ -diethylaminopropane hydrogen oxalate

!, S-bis-carbamoylthio ^ -methylethylaminopropane

1,3-bis-carbamoylthio-2-methylethylaminopropanesulfate

1,3-bis-carbamoylthio-2-piperidinopropane

1,3-bis-carbamoylthio-2-pipcridine hydrochloride

1,3-bis-carbamoylthio-2-morpholinopropane

comparison

O.O-Diälhyl ^ -isopropyM-melhyl-o-pyrimidinylphosphorus-

Ihional (Diazinon)

control

number of insects killed exposed apae. larvae Phyllotreta striolata 10/10 10/10 10/10 10/10 10/10 10/10 0/10 10/10 10/10 10/10 10/10 10/10 9/10 9/10 9/10 9/10 10/10 9/10 6/10 4/10 0 / Ί0 0/10

2. 1 ml of acetone solution containing 0.1% (w / v) of the test compounds is placed on the bottom of a Petri dish dripped from 9 cm diameter. After removing the acetone, be sure to ventilate gently 20 red bean beetles (Callosobruchus chinensis) exposed in the petri dish. After 24 hours it will

counted the number of insects killed to calculate the mean mortality. The results are listed in Table 3 below:

Table 3

Tesl connection

!, S-bis-carbamoylthio ^ -dimelhylaminopropane

!, S-bis-carbamoylthio-Z-dimethylaminopropane hydrogen chloride

1,3-bis-carbamoylthio-2-diethylaminopropane hydrogen chloride

U-bis-carbamoylthio-1-methylethylaminopropane hydrogen oxalate

l ^ -Bis-carbamoylthio ^ -piperidinopropane

!, S-bis-carbamoylthio - ^ - pyrrolidinopropane hydrogen chloride

Test connection

Mild mortality

100 100 100 100 100 100 Test connection

comparison

O.O-Dimethyl-Z.Z-dichlorovinylphos-

phal (DDVP) '...

control

Medium
mortality

20th
0

3. An emulsion is made by mixing 10 parts by weight of test connections with 90 room dividers! an acetone solution, the 20 parts by volume Sorbitanlauratpolyoxyüthylenäther ("Tween 20"), and by diluting the emulsion with tap water to one Active ingredient concentration of 0.05Vo produced. Rice plants placed in pots are placed on a Place a turntable and add 20 ml of the aforementioned emulsion to each pot using a spray gun sprayed from a distance of 80 cm from the plants. A few days after spraying Ripe eggs of the rice stem borer (C'hilo suppressalis) are placed on the sprayed reefs. A week later, the stems are cut open to count the number of surviving larvae. the Results are given in Table 4 below.

table

1,3-bis-carbamoylthio-2-dimethylaminopropane

i ^ -Bis-carbarnoylthio ^ -dimethylaminopropane hydrogen chloride 1,3-bis-carbamoylthio-2-diethylaminopropane hydrogen chloride .... 1,3-bis-carbamoylthio-2-methylethylaminopropane hydrogen chloride

1,3-bis-carbamoylthio-2-piperidinopropane

1,3-bis-carbamoylthio-2-pyrrolidinopropane hydrogen chloride

comparison

0,0-dimethyl-0- (3-methyl-4-nitrophenyl) phosphorothionate

(Sumithion)

control

OTapc

0
0
0
0
0
0

surviving larvae in%

3 days I.
after spraying

0
0
0
0
0

57.2

Tape

0
0
0
0

24.7

4. Ripe rice stem borer eggs (Chilo suppres sprayed rice plants. 4 days later the

salis) are placed on rice plants, the stems in pots cut open to determine the number of survivors

are planted . After 5 days, the _{number of} larvae under 3 should be counted. The results are shown below in

written emulsion is given in the same way on Table 5.

table

Test connection

1,3-bis-carbamoylthio-2-dimethylaminopropane

1 ^ -Bis-carbamoylthio-2-dimethylamhiopropane hydrogen chloride M-bis-carbamoylthio ^ -diethylaminopropane hydrogen chloride

!, S-bis-carbamoylthio ^ -methylethylaminopropanhydrogen- oxalate

1,3-bis-carbamoylthio-2-piperidinopropane

Concentration,% surviving larvae. % 309 615/270 0.0125
0.025 0
0 0.0125
0.025 0
0 0.0125
0.025 0.9
0 0.0125
0.025 1.0
0 0.0125
0.025 U
0

Continuation of test connection

1,3-bis-carbamoylthio-2-pipcridinopropane hydrochloride. .

1,3-bis-carbamoyllhio-2-morpholinopropane

U-bis-carbamoylthio ^ -pyrrolidinopropane hydrogen chloride.

comparison
Ο, Ο-diethyl-op-niirophenyl-phosphorothioal (parathion)

control

JO

Concentration. %

0.0125
0.025

0.0125
0.025

0.0125
0.025

0.0125
0.025

Surviving larvae. %

1.6 0

1.5 0

3.8 0

64.4

5. To determine the acute toxicity of 1,3-di- (C'F, -Slamm, male. 4 weeks every) administered, thiocyanal derivatives and l ^ -Bis-carbamoylthiodecri- 20 The LD ₅₁ , and the 95% - Safety limit will be

The following experiment was carried out against warm-blooded animals.

A gum arabic emulsion containing 10% (w / w) of each test compound is given orally to mice calculated according to the Lichficld-Wilcoxon-Methodc on the basis of the number of mice, which in the period up to 7 days received after the administration. The results are shown in Table 6 below.

table

'Leased line

1.3-bis-carbamovHhio-2-dimethylhiminopropane

1,3-bis-carbamoyllhio-2-dimethylaminopropane hydrogen chloride ....

control

(). O-diethyl-S- (2-ethylthioethyl) -phosphorothiolothionate (Disulfoton)

LD ₅₁₁ (<J5% safety level / .el in mice, mg / kg

92 (82.9 to 102.1) 165 (138.6 to 196.3)

14.1 (12.3 to 15.9)

example Part 111

Manufacture of finished preparations

1. A solid, water-soluble pesticide is prepared by adding 50 parts by weight of i.3 - bis - carbamoyllhio - 2 - dimetliylaminopropanhydrogen chloride and 50 parts by weight of lactose are mixed.

2. A pesticide in the form of a solution is prepared by adding 10 parts by weight 1,3-bis-carbamoylthio-2-dimethylaminopropane, 2 parts by weight of laurylbenzenesulfonate and 73 parts by weight Methanol can be mixed.

3. A pesticide in the form of an emulsion is prepared by adding 25 parts by weight 1.3 - bis - carbamoylthio - 2 - dimethylaminopropane, 25 parts by volume sorbitan laurate polyoxyethylene ether (»Tween 20«) and 25 parts of xylene.

4. A powder pesticide is prepared by adding 2 parts by weight of 1,3-bis-carbamoylthio - 2 - piperidinopropane hydrogen oxalate and 98 parts by weight of talc are mixed.

Claims (1)

Patent claims: 1.1,3 - bis - carbamoylthio - 2 - aminopropane der general formula R ₁ CH ₂ SCONH ₂ \ I N-CH / I
R ₂ CH ₂ SCONH, (D