SU700040A3 - Insectoacariocidonematocide agent - Google Patents

Description

one

This invention relates to chemical plant protection products, namely insecticide-acaricide nematocidal agents based on biscarbamoyl sulfide derivatives,

The use of asymmetric N-substituted Biscarba -; oylsulfide compounds as insecticides 1 is known,

The prototype of the invention is an insecticidal agent, the active principle of which is bis- (3,4-dimethylphenyl-N-methylcarbamoyl) -sulfide 2,

However, the known compounds are not sufficiently active at low concentrations.

The aim of the invention is the search for new insecticide-acaric nematocidal agents possessing high biological activity.

This is achieved using an insecticide acaricone nematocidal agent whose active substance is a biscarbamoyl sulfide derivative of the formula

R-O-CO-NR-S-NR-OCOR i (O

where R and R is methyl,

R- (- naphthyl, dimethylphenyl, grute: mega Rj is hydrogen,

R ,,

Tyl, N methylthio, 2-methylthioisopropyl or a group where the radical A together with the carbon atom forms 1,4 - dithian, 3,5, 5-trimethylthiazolidine:.-4-OH

R2 — propargy.p, 2, 2-D methyl-2, 3 digcrobenzofuran, naphthyl, isopropylphenyl, tert.butylphenyl, nitrophenyl, 5,6,7,8-tetrahydronaphthyl, meth; lthio 3-methylphenyl, 4-methoxycarbokyl .-. Shno-3-isopropylphenyl, trimethylphenyl, 2,4-dicitro-6-sec, butylphenyl, S, N-dimethylaminophenyl, 4-formyl. amino-3-methylphenyl, 4 - (2, 7-cis) -octadienylphenyl, 2-chloro-4-isopropylphenyl, nonylphenyl, dodecylphenyl.p, diphenyl, 2-methoxy-4-allylphenyl, phenoxyphenyl, 1, 4-dithiolanephenyl, 1,4-dioxolanphenyl, tert butoxyphenyl, propargyloxyphenyl, 1,3,5-tritium & or group-N c; where Ke is hydrogen, methyl, methylthio, R4. - Phenylcarbonyl, 2-methylthioisopropyl, ethoxycarbonyl, cyanoethylthio, dimethylcarbamoyl, or the group -H-CJ f. where the radical A together with the carbon atom forms 1,4-dithian, 1, 3, 5-trithian. The content of the active substance in the agent ranges from 0.5 to 95% by weight, the remaining additive. The proposed compounds are obtained according to the scheme act, the eptor it is of FC-NSN-cr U OH -SS i ai i - -K OCN-SN-CF, 9 acceptor O U T1 O R, OC-NSN-CF-R, OHJ ii l U OC-N-5-N-CO where R, R, R, R2 are as defined above. Example 1, Preparation of N-2-methylthio-2-methylpropionaldehyde-O- (L-methylcarbs 1yl) -oxime methylthioacetaldehyde-0- (N-methylcarbamoyl-oxime-sulfide. A, Into a polypropylene reaction apparatus, 80 g , 0 mol) of hydrogen fluoride in 1800 ml of toluene is cooled to a temperature of -40 ° C, 228 g (4.0 mol) of methyl etiocyanate are added dropwise with stirring, and the reaction mixture is heated to and holding. at this temperature for 1 h. Then, 206 g (2 mol) of freshly distilled dichloride are added to it 246 g (4.4 mol) of pyridium at a temperature from -20 to n ° C. After stirring for 2 hours at -10 ° C and for 16 hours at room temperature, the reaction mixture is diluted with 500 ml of water. Next, the TIC layer is washed with 3 portions of 500 ml of water, dried and distilled to obtain 244 g (66%) of bl- (K-methyl-L-fluorocarbamilamino) sulfide, bp. 55-57 ° C / / 0.25 mm Hg, mp. 40-41 ° C Found:% C 26.19; H 3.20; N 14.79 CH FgNjOg Calculated,%: C 26.09; H 3.28; N 15.21. B. In a solution of 0.714 g of 1-methylthio acetaloxime and 1.36 g of bis- (N-substituents in the formula I R

H -SCH N CH,

CH3 CH5

99-101

sn,

164-165

sn

170-171

sn. Il-N-fluorocarbamilamino) -sulfide 15 ml of dioxane is added dropwise 0.687 g of triethylamine. After removing the solution for 20 hours, it is diluted with water and extracted with ethyl acetate. The organic extract is washed with water, dried with magnesium sulfate, and concentrated in vacuo to give 1.0 g of 1-methylthioacetaldehyde-O-N-methyl-N- (N-methyl-N-fluoroformate-aminosulphenyl) -carbamoyl oxime, which is crystallized from isopropyl ether With ethyl acetate, so pl. 102-104С. Found,%: C 31.67; H 4.69; N 15.34 Calculated,%: C 31.22; H 4.49; N 15.60. C. To a solution of 2.69 g of 1-methylthioacetaldehyde-O-N-methyl-N- (N-fluoroformyl aminosulfenyl) -carbamoyl-oxime and 1.3 g of 2-methylthio-2-methylpropionalkoxime in 50 ml of dioxane with stirring 1.01 g of triethylamine. After 48 hours, the reaction mixture is diluted with water and extracted with ethyl acetate. The extract is washed with water, dried and concentrated. The resulting product, N-2-methylthio-2-methylpropionaldehyde-0- (N-meth; 1-carbomoyl) -ox-n-1-methylthioacetaldehyde-0- (N-methylcarbomoyl)-oximosulfide, is crystallized from isopropyl ether. Obtain 1.87 g of dry matter, t PL, 99-101C. found% C 37.68; H 5.72; N 14.51 C iH25LN40 S Included,%: C 37.68; N. 5.80; N 14.65. In tab. 1 shows the melting points of the compounds of the formula D, Table 1

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Baldness; ra / hennes;

nOMI-OTOi MOrO t: Oi 80 ± 5 ° F (26.67 ± 2.78 ° C) and relative humidity 0 ± 5%. The compositions of the test compounds are prepared by diluting the initial suspensions with water to obtain suspensions which contain 500 parts of the test compound per million parts by weight. finished composition. Potted bobs of standard height and age are sprayed with 100-110 ml of the composition of the test compound. Or a mixture of water-acetone-emulsifier, which does not contain the test compounds, is sprayed with De Vilbiss spray, sprayed under 0.60131 kg / cm for 25 seconds to the wailing of the liquid. After drying, the paired leaves are separated from each other and each of the leaves is placed in a Petri dish (9 cm); Packed with wet filter paper. 5 larvae are planted in each of the cups and the cups are closed. The larvae were kept at 80 i5 ° F {26.67 ± 2.77 ° C) for 3 days. Then count the number of dead larvae. Example 5. Tests on flies. As the experimental insects, the house fly Musca dom & U was aged 4 to 6 days old, grown under conditions at a temperature of 80 ± 5 ° F (26.67 t 2.77 ° C) and 5015%. The flies are individually immobilized, males and females, and placed in a cage that is equipped with a standard food mesh of approximately 127 mm in diameter, inverted above the surface covered with wrapping paper. Compositions with test compounds are prepared by diluting the initial suspension with a 10% (by weight) sugar solution, and a suspension is obtained which contains 500 hours of the test compound per million ppm. finished composition. 10 each of the composition of the test compound is applied onto a cotton swab with a cross section of 6.45 cm. This bait is inserted and placed in the center of the paper under the food mesh before being admitted by the test flies. The flies that are found in the B cage have free access to the bait for feeding for 24 hours at 80l5 ° F (26.67 ± 2.77 ° C) and relative humidity 50 Example p6. Tick Testing Adult animals of two-spotted Tetran chus urticackocti mites and insects at the larval stage of development grown on Tenderg-hun bean plants at 80 ± 5 ° F (26.67 ± 77 ° C and relative humidity 50) are used as experimental animals. ± 5%. The lost leaves are placed on the primary leaves of two bean plants 15.24–20.32 cm in height, which are grown in a clay pot of 63.5 mm in size and 150–200 mites are transferred from the cut leaves to fresh plants for 24 hours. Potted plants are sprayed with 100-110 ml while the composition is being cooked. compound or a water-acetone emulsifier mixture that does not contain the test compound. Use a de Wilbiss spray nozzle, sprayed under a pressure of 2.81 kg / cm for 25 seconds before draining. After spraying, the plants are maintained at 80 ± 5 ° F (26, 67 t2,77 ° C) and a relative humidity of 50 ± 5% for 6 days, after which the death of insects is calculated by the degree of their mobility. Then, the cucumber sprouts are removed from the pots and the soil is removed from their roots, which makes it possible to visually determine the number of growths. The results of the tests are given in table. 2. The pesticidal activity of the compounds in the indicated dosage with respect to aphids, ticks, prolongation butterflies, Mexican beetle, and xenata fly is expressed as follows: A — 70% defeat; B - defeat from 50 to 70%; C - damage less than 50%. The definition of activity against nematodes is evaluated as follows: 1 - a very large number of growths, equal to the number of growths in untreated plants; 2 - moderate number of growths; 3- a small number of growths; 4- a small number of growths; 5 absence of growths, complete destruction of nematodes. Example 7. Phytotoxicity tests. Preparing solutions in the same manner as described above, the concentration of the test compounds is 2,500 hours of the test compound per million parts by weight. finished composition. The plants are sprayed, the treated and control plants are kept for 1 hour to dry the drain, then placed in a greenhouse. After 10 days, the degree of leaf damage is determined. 1 - no noticeable damage; 5 - death of the plant; 2, 3 and 4 are the intermediate degrees of damage, the specific value of which depends on the number of damaged areas and the heat of damage to the leaves. Example 8. Toxicity tests. Some of the compounds are tested for their oral toxicity against mammals using conventional methods. Tests were carried out on rats. The test results are expressed in milligrams per kilogram of the living web (LBj-o). In tab. 2 Presentation: J test results.

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In tab. 3 shows the results of tests on the biological activity of the proposed compounds of the formula I, where R R CHj and known compounds.

The lethal dose is expressed in mg / kg. In tab. 3 shows the results of tests on biological activity

(Suggested)

sn.

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si, 5c-9-nz-v

Sin.

NS-1

H C-C-NSCHj

(Known)

SICHaSC-with N-OH ,, S-C-C - M-l

Claims (1)

ill 3 I, h Formula of the invention The insectoacaricone matic medium containing bicar bamoyl sulfide derivatives as an active substance and an additive selected from the group of carrier, solvent, emulsifier disperser, wherein, in order to enhance the insect acaricide nematocidal activity, the fraudsters are used in the fragments in order to enhance the insect acaricide nematocidal acid, which is contained in the emulsifier; General formula RO-CO-NR-S-NR-OCOR, where R and R are methyl; R is naphthyl, dimethylphenyl, the group —N — Cvp, 3 is hydrogen, methyl, R. is methylthio, 2-methylthioisopropyl, is a silt group, where the radical A together with the carbon atom forms 1,4-dithian, 3,5,5-trimethylthiazolidine -4-OH propargyl, 2, 2-dimethyl-2, 3-dihydrobenzofuran, naphthyl, isopropylphenyl, tert-butylphenyl, nitrophenyl, 5,6,7,8-tetrahydronaphthyl, methyl thio-3-methylphenyl, 4-methoxycarbonylamino-3 -isopropylphenyl, trimethylphenyl, 2,4-dinitro-6-sec. butylphenyl, N, N-dimethylaminophenyl, 4-formylamino-3-methylphenyl, 4- (2,7-cis) -octadienylphenyl, 2-chloro-4-isopropyltrans proposed compounds of Formula 1 where R R CHj and known compounds. The lethal phase is expressed in mg / kg. Thus, the proposed compounds have good activity. Table 3 50 2.1 nineteen 50 1.1 / D 7500 ten} not tested Conilf2iyl, dodedylphenyl, diphenyl, 2-methoxy-4-all; Lphenyl, phenoxyphenyl, 1,4 dctiolanfennl; 1 4-dkoksolanfe NIL, tert.butoxyphenyl, propargyl where Rj is hydrogen / methyl, l 1 is fennlcarbonyl, 2-methylthioisopropyl, ethoxycarbonyl, cyacoethylthis, dimethylcarbamoyl, or the group - N - Cj, where the radical A is combined with the atom of the atom, N - Cj, together with the atom with the atom of the carbon atom, dimethylcarbamoyl, or N - Cj. -Ditian, 1,3 5 tritian, in an amount of from 0.5 to 95 wt.%, the rest is additive, priority on the grounds: 01.12.75 with R and R - methyl; R is a group —N — C, where Rj is hydrogen, methyl, R4 methylthio, 2-methylthioisopropyl, or the group —N — CJX, where the radical A together with the carbon atom forms 1,4-dithian, 3,5,5-trimethylthiazolidine- 4-OH; R propargyl, 2,2-dimethyl-2,3-dihydrobenzofuran, naphthyl, isopropylphenyl, tert.butylphenyl, nitrophenyl, 5,6,7,8-tetrahydronaphthyl, methyl thio-3 -metylphenyl, 4-method of rbonylamino-3 -isopropylphenyl, trimethylphenyl,. 2, 4-dinitro-6-sec. Butyl; 1: SNIL, S, S-dimethylaminophen., 4-form-mmlamino-3-methylphenyl, 4-formylamino-3-methylphenyl, 4- (2, 7-cis a) octa-dienylphenyl; Hydrogen, methyl, methylthio or group - N - with where R A -2-metshizopropil, ethoxykyrbonilr cyanoethylthio, dimethylcarbamoyl or group - N СJV, where the radical A together with the carbon atom form a 1.3.5-trn. 04 „11,76 with R - naphthyl, dimethylphenyl; R 2. 2-chloro-4-isopropylphenyl, nonylphenyl, dodecylphenyl, diphenyl, 2-methoxy-4-allylphenyl, phenoxyphenyl, 1, 4-dithiolane phenyl, 1,4-dioxolane phenyl tert, butoxyphenyl, propargyloxyphenyl or p group -N-cCn with where Cd is phenylcarbonyl. Source of information taken into account in the examination 1, US Patent No. 3920830, cl. 424-300, publ. 18L1L5. 2, US Patent No. 3794733, cl. 424.300, publ. 1974 (prototype).