DE1693185B - 1,3-bis-carbamoylthio-2-aminopropane and pesticides containing them - Google Patents

Description

R ₁

CH ₂ SCONH ₂

ίο

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 represent a piperidine, pyrrolidine, morpholine or piperazine ring, as do the salts of these compounds.

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

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

4.1, S-bis-carbamoylthio ^ -morphoIinopropane.

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

25th

The applicant has already found that compounds of the general formulas

N-CH ₂

(ΙΓ)

ϊ /

CH - SCN

CH, - SCN

CH, SCN

N-CH

(II)

CH ₇ SCN

35

40

45

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 ΙΓ to warm-blooded animals can be reduced considerably without impairing the pesticidal effectiveness if both —SCN groups are replaced by a —SCONH ₂ group.

The invention relates to 1,3-bis-carbamoylthio-2-aminopropanes the general formula

CH ₂ SCONH ₂

60

N-CH

(I)

R ₂ CH ₂ SCONH ₂

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. 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, toluosulfonic 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. One blows hydrogen halide, such as hydrogen chloride, Hydrogen bromide and hydrogen iodide, in excess in a solution or suspension of the Compound of formula II in a lower aliphatic alcohol such as methanol or ethanol, and then, expediently after heating, distills off the alcohol from the mixture obtained.

2. You blow hydrogen halide of the type mentioned in excess 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 a pesticide door agricultural and sanitary purposes, the compounds are used generally corresponding to the intended use for finished preparations assembled, e.g. B. to wettable powders, solutions, emulsifiable solutions, dusts 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 dispersed. Suitable liquid carriers are solvents such. B. water, lower alcohols (e.g. Methanol, ethanol, isopropanol, butanol, glycerine or ethylene glycol), ketones (e.g. acetone, methyl ethyl ketone, Cyclohexanone or cyclopentanone), ether (e.g. 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),

essential oils, terpenes, chlorinated biphasic or Cottonseed OIL Mixtures of the solvents mentioned are often used, as these are not only have excellent dissolving power, but also low toxicity to plants or humans should.

For the production of dusts and dusts Dusty extenders or carriers are usually used. One or more types the compounds are, for example, in a ball mill, a pan mill or a hammer mill finely powdered and then mixed with the powdered extenders or carrier materials as Extenders or carrier materials are suitable, 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, pyrophyllium 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 niclitionogens surface-active agents, such as polyoxyethylene diaryl ethers, polyoxyethylene alkylaryl ethers and the like Polyoxyethylene sorbitan monoacylate (with 10 to 18 carbon atoms in the acyl group) as emulsifiers and solubilizers used for the products according to 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-spotted ladybug (Epilachna

vigintioctomaculata),
28spotted ladybird (Epilachna sparsa orientalis),

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

adult),

Red bean louse (Callosobruchus chinensis),
Cockroach (Blattela germanica),
Rice leaf beetle (Lema oryzae),
House fly (Musca domestica),
Cabbage sawfly (Athalia rosae japonensis, larva), rice stem borer (ChHo suppressalis),
Tobacco cut worm (Plodenia litura),
Rice plant maggot (Parnara guttata, larva),
Green rice caterpillar (Naranga aenescens, larva),
"Cabbage armywonn" (Barathra brassicae,

larva),
"Giant bagworm" (Cryptothelea 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),

Ciirus red mite (Petranychus ckri),
Soybean aphid (Aphis glycines),
Citrus leaf miner (Phyllocnistis dtrella),
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 carbamoylthio derivatives

1. Hydrogen chloride gas is dissolved in 12 g of 1,3 - dithiocyanato - 2 - dimethylaminopropane hydrochloride for 2 hours passed, which is suspended in 30 ml of methanol, a reaction taking place The methanol 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 - dimethylaminopropane hydrogen chloride with a melting point of 175 ° C.

2. Hydrogen chloride gas is placed in a mixture of 3.6 g of water and 23.7 g of 1,3-dithipcyanato-2-dimethylaminopropane hydrogen chloride for 9 hours passed, 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 ^ -dimethylaminopropane hydrochloride obtained from melting point 175 ° C.

Elemental analysis door C ₇ H ₁₆ N ₃ O ₂ S ₂ Cl:

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 placed in a mixture of 1.8 g of water and 11.9 g of 1,3-dithiocyanato-2-dimethylaminopropane hydrogen chloride for 7 hours passed, with a reaction taking place The reaction mixture is dissolved in 20 ml of water, neutralized with sodium hydrogen carbonate and cooled with ice, whereby crystals separate out. The filtered crystals are dried and recrystallized from 99% ethanol, 5.8 g of colorless prisms of 1,3-biscarbamoylthio - 2 - dimethylaminopropane from Melting point 130 to 13 Γ C can be obtained.

Elemental analysis for C ₇ Hi ₅ N ₃ O ₂ S ₂ :

Calculated ... C35.41, H6.37, N 17.70;
Found .... C 35.53, H 6.18, N 17.99.

4. 2 g of M-DiüiJocyanato-2-dimethylainiQopropan are added dropwise with stirring to 20 ml of 95% (V / V) concentrated sulfuric acid, which is kept at a temperature below ⁰ ° C. by cooling. After 30 minutes, the reaction mixture is poured dropwise into ice-cold water with stirring. By working up in the manner described under 3, 0.6 gl ^ -Bis-carbamoylthio-2-dimethylaminopropane with a melting point of 29 to 130 ° C. are obtained.

1,845 of this compound and OJg of anhydrous oxalic acid are dissolved while warming in 100 ml of anhydrous methanol. The methanol is under distilled off under reduced pressure, crystals are precipitated, which are filtered off and dried, 1.6 g of colorless, needle-shaped crystals of!, S-bis-carbamoylthio-1-dimethylaminopropane hydrogen oxalate from melting point 147 to 148 ° C (decomp.) can be obtained.

More Carbamoylthioderivate be synthesized 5. In the manner described under I to 4 way. The following results are obtained:

Table 1 ¹ p

1,3-bis-carbamoylthio-

2-piperidinopropane melting point, »C

hydrochlprid 173 to 17 <t (decomp.)

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

35

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

1,3-bis-carbamoyl-io-2-methylethylamisopropane hydrochloride .

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

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

.. 172 to 174 (decomp.) .. 170 to 175 (decomp.) .. 173 {dec.)

Example part II

Testing of carbamoylthio derivatives for pesticides

Efficacy 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 Sorbitanlauratpolyoxyäthvlenüther ("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 prepared 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 released onto the leaves. After 24 hours, the number of insects killed is counted. The results are shown in Table 2 below listed.

table Test connection

!, S-bis-carbamoylthio ^ -dimethylaminopropane

l ^ -Bis-carbanioylthio ^ -dirnethylarninopropane hydrogen chloride

l ^ -Bis-carbamoylthio ^ -diethylatninopropane

U-bis-carbamoylthio ^ -diethylaminopropane hydrogen oxalate 1,3-Bis-carbamoyIthio-2-methylethylaminopropane

1,3-bis-carbamoyitethio-2-methylethylaminopropane sulfate

l ^ -Bis-carbamoylthio ^ -piperidinopropane

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

1,3-bis-carbamoylthio-2-morpholinopropane

comparison

O, O-diethyl-2-isopropyl-4-methyl-6-pyrimidinyl phosphorothionate (Diazinon)

control

Number of insects killed / exposed Pieris rapae, larvae Phyllotreta striolata

10/10

10/10

10/10

10/10

10/10

10/10

9/10

9/10

10/10

6/10
0/10

10/10

10/10

10/10

10/10

10/10

10/10

9/10

9/10

9/10

4/10 0/10

2. 1 ml of acetone solution containing 0.1% (w / v) of the test compounds contains, is dropped onto the bottom of a Petri dish 9 cm in diameter. After removal of the acetone by gently aerating 20 red bean beetles (Callosobruchus chinensis) in exposed to 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

Test connection

1,3-bis-carbamoylthio-2-dimethylaminopropane

l ^ -Bis-carbamoylthio ^ -dimethylaminopropane hydrogen chloride

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

l ^ -Bis-carbanioylthio - ^ - niethylethylaminopropane hydrogen oxalate

1,3-bis-carbamoylthio-2-piperidinopropane

l ^ -Bis-carbanioylthio ^ -pyrrolidomopropane hydrogen chloride

comparison

O, O-dimethyl-2,2-dichlorovinyl phosphate (DDVP)

control

Medium mortality

20 0

100 100 100 100 100 100

15th

25th

3. An emulsion is made by mixing 10 parts by weight of the test compounds with 90 parts by volume an acetone solution containing 20 parts by volume of sorbitan laurate polyoxyethylene ether ("Tween 20"), and through Dilute the emulsion with tap water to an active ingredient concentration of 0.05%. In Rice plants used in pots are placed on a turntable and per pot with 20 ml of the above said emulsion with the help of a spray gun from a distance of 80 cm from the Sprayed plants. A few days after spraying, ripe rice stem borer (chilo suppressalis) placed on the sprayed rice plants. A week later the stalks are cut open, to count the number of surviving larvae. The results are given in Table 4 below.

table

Test connection

1,3-bis-carbamoylthio-2-dimethylaminopropane 0

!, B-bis-carbamoylthio ^ -dimethylaminopropane hydrogen chloride 0

!, S-bis-carbamoylthio ^ -diethylaminopropane hydrogen chloride 0

!, S-bis-carbamoylthio ^ -methylethylaminopropane hydrogen chloride 0

1,3-bis-carbamoylthio-2-piperidinopropane 0

1,3-bis-carbamoylthio-2-pyrrolidinopropanhydrogenc! i "; orid 0

comparison

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

(Sumithion)

control

4. Ripe rice stem borer eggs (Chilo suppres- rice plants are sprayed 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 50 larvae count under 3. The results are shown below in written emulsion is given in the same way on Table 5.

table

surviving larvae in%

OTage I 3 days | 5 days

after spraying

0 0 0 0 0 0 0 0 - 0 0 24.7 57.2

Test vci'biudun £

Concentration, %

surviving larvae,%

13-bis- <arbamoyltlüo-2-dimeaylaiiimopropane

l ^ -Bis-carbamoyltMo ^ -dhnethylaimnopropanhydrogencfclorid l ^ -Bis-csu-bamoyltlno-l-diethylammopTopaiihydrogenchlorid

13-bis <arbamoyltido-2-methilyiäthyla ^ ninopΓopallhydrogenoxalat

1 ^ -Bis-carbanioylthio-1-p -peridinopropane 0.0125
0.025

0.0125
0.025

0.0125
0.025

0.0125
0.025

0.0125
0.025

0 0

0 0

02 0

1.0 0

Ut 0

continuation

10

Test connection Concentration,% surviving larvae,% l ^ -Bis-carbanioylthio ^ -piperidinopropane hydrogen chloride .... 0.0125
0.025 1.6
0 1 ^ -Bi "! - carhamovlthio-2-rnoroholinoDrODan 0.0125
0.025 1.1
0 0.0125
0.025 1.5
0 l ^ -Bis-carbamoylthio ^ -pyrrolidinopropane hydrogen chloride ... comparison 0.0125
0.025 3.8
0 Ο, Ο-diethyl-O-p-nitrophenyl-phosphorothioate (parathion) - 64.4 control

5. To determine the acute toxicity of 1,3-di- (CF ₁ strain, male, 4 weeks old) administered thiocyanate derivatives and 1,3-bis-carbamoylthioderi- 20 The LD ₅₀ and the 95% safety limit are used

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 using the Lichfield-Wilcoxon method on the basis of the number of mice that lived in the period up to 7 days received after the administration. The results are shown in Table 6 below.

table Test connection

1. S-bis-carbamoylthio ^ -dimethylaminopropane

i ^ -Bis-carbamoylthio ^ -dimethylaminopropane hydrogen chloride

control

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

LD ₅₀ (95% safety limit) 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 III

Manufacture of finished preparations

1. A solid, water-soluble pesticide is prepared by adding 50 parts by weight of 1,3-bis-carbamoylthio-2-dimethylaminopropane hydrogen 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 larate polyoxyäihyicnäihcr (»Tween 20«) and 25 parts by volume of xylene are mixed.

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. l _I 3-bis-carbamoyl &io-2-atninopre> pan of the general formula R, CH ₂ SCONH ₂ N-CH (D