SU888801A3 - Insecticide composition - Google Patents

Abstract

1425763 2 - (Nitromethylene) - piperidines SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ BV 2 May 1973 [4 May 1972 (2) 9 Feb 1973 (2)] 20819/73 Heading C2C [Also in Division A5] Novel compounds of Formula I: wherein n is 0, 1 or 2; X is alkyl, alkenyl, alkynyl, aryl, aralkyl, halogen, -CN, -C(O)-OH, -C(O)-O-alkyl, -C(O)-O- aryl, -C(O)-O-aralkyl, -O-C(O)-alkyl, -O-C(O)-aryl, -OH, -O-alkyl, -O- aryl, -O-alkoxyalkyl, -O-alkenyl, -O- aralkyl, -S-alkyl, -SO-alkyl, -SO 2 -alkyl, -NH 2 , -NH(alkyl), -N(alkyl) 2 , -C(O)NH 2 , -C(O)NH(alkyl), -C(O)N(alkyl) 2 , -NO 2 , = O (involving a ring carbon, -C(O)-H, -C(O)-alkyl, (mono- or polyhalo)alkyl, -SCN, -NHOH, -NH-O- (alkyl), hydrazino, or dialkylhydrazino; Y is hydrogen, alkyl, alkenyl, aryl, halogen, -CN, -C(O)NH 2 , -C(O)NH(alkyl), -C(O)N(alkyl) 2 , -NO 2 , -C(O)-H, -C(O)-alkyl or -C(O)- O-alkyl; and R is hydrogen, alkyl, alkenyl, aryl, aralkyl, alkynyl, (mono- or polyhalo)- alkyl, -C(O)-alkyl, -C(O)-aryl, -C(O)- O-alkyl, -C(O)NH 2 , -C(O)NH(alkyl), -C(O)N(alkyl) 2 , -O-alkyl, -NO 2 , -SCN, -halogen, alkoxyalkyl, cyanoalkyl, carboalkoxyalkyl, -(CH 2 ) m O-C(O)-alkyl, -CH 2 )- m C(O)-O-alkyl, -(CH 2 )- m C(O)NH 2 , -(CH 2 )- m C(O)NH(alkyl), or -(CH 2 )- m C(O)N(alkyl) 2 , m being 1 or 2; and if Y is hydrogen, R is hydrogen and n is 0, the equimolecular complex of an alkanesulphonic acid therewith, are prepared by reacting the corresponding valerolactam (2-piperidone) with a dialkyl sulphate or a trialkyloxonium fluoroborate, followed by base or an alkoxide to yield the corresponding 2-alkoxy-3,4,5,6-tetrahydropyridine or lactam acetal respectively, which is then reacted with nitromethane, a substituted nitromethane, or another 1-nitroalkane, the 2- (nitromethylene)-piperidine product being reacted further, if required, to introduce additional substituents. The examples describe the preparation of many piperidine derivatives of Formula I and their use as insecticides.

Description

The invention relates to chemical plant protection products, in particular, to an insecticidal composition based on an active substance. A commercial drug is known - dursban (O, 0-diethyl-0-3,5,6-trichloropyril dithiophosphate), which is used as an insecticide 1. An insecticide is known, the beginning of which is 2- (nitromethylene) pyrrolidine 2. However, the known Compounds are not active enough. The purpose of the invention is to find a new insecticidal composition having a good insecticidal activity. The goal is achieved by using an insecticidal composition, the active substance of which is 2- (nitromethylene) -p-peridin of the general formula where n is 0,1,2; X - fluorine, chlorine, bromine, iodine, methyl, methylthio, ethylthio, pro Piltio, methylsulfinyl, methylsulfonyl. Y is hydrogen; chlorine, bromine, nitro, R — C —C — alkyl, allyl, methoxymethyl, hydrogen or its complex compound with methanesulfonic or ethanesulfonic acid, where is hydrogen, p-0. The content of the active substance in the composition is O, 000150 wt.%, The rest is additive. Compounds of formula 1, where R is hydrogen, are prepared analogously to the preparation of 2- (nitromethylene) -pyrrolidones L2J f; however, valerolactams (2-piperidones) are used as starting materials, Compounds of formula 1, where R has a different meaning, or hydrogen are also derived from valerolactomas (2 Piperidones): Lachts (2-piperidone) are treated with dialkyl sulfate or trialkyl-oxonium-fluoroborate, then treated with alkoxide to obtain the corresponding lactam acetal (1-alkyl-2, 2-di -. (RO) piperidine, 2-RO- 3,4,5,6-tetrahydropyridine, which is then processed nitromethane or 1-nitroalkane are prepared. Thus, the following compounds of formula I are obtained

Xfl

l J C-H02

The use of compositions is usual: solutions, dispersions, dusts, aerosols. They are prepared by methods common in the manufacture of preparative forms of pesticides.

Example. Determination of insecticidal activity.

Insecticidal activity is determined using tests that enable the LC indicator to be determined (the dosage in grams of the test compound per 100 millimeters of solvent required as a solution or suspension when applied by spraying to kill 50% of experimental insects) of the compounds of the invention under consideration, in relation to different types of insects, the results are summarized in table 2. A liquid carrier, using AEMELM to make a solution or suspension, is a mixture consisting of 2 parts by volume of acetone, 8 parts by volume of water and 0.05% by weight. parts wetting means Atlox.

PRI me R 2.

The potential of test compounds for rapid motility loss was determined by observing house flies during the initial test, the results are shown in Table 2. The test compound is considered to be an agent effective in terms of rapid loss of mobility, if within 30 minutes 80% of the flies lose mobility, with coititration of 0.5% by weight (volumetric of the solution used in the molten form. Compounds 1, 5, b, 7, 11, 12, 14, 16, 17 meet these requirements.

Froze

Insecticidal activity is determined by means of tests that enable the ICjo value to be determined (the dosage in grams of the test compound per 100 ml of diluent required — if used for spraying as a solution or suspension — to kill 50% of the experimental insects) the case of compounds with respect to insect raids; The liquid carrier used to prepare the solution or suspension consisted of a mixture of 2 parts by volume of acetone, 8 parts by volume of water and 0.05 parts by weight of the wetting agent Atlox. The results are summarized in table 3.

PRI me R 4.

The potential of test compounds for rapid loss of mobility is determined by observing home flies during the initial test, the results of which are summarized in Table 3. The test compound is considered a means of ensuring rapid loss of mobility, if within 30 minutes 80% of flies lose mobility at a concentration of 0% by weight (% by volume from the solution used in a sprayed form).

Compounds 10, 19, 21, 22, 23, 24 meet these requirements.

PRI me R 5.

Compounds tested according to example 4 are tested at a dosage of 0.1 vol.% (Bulk in the composition of the solution used for spray application). Any such compound that causes a loss of mobility in 50% of the flies within 30 minutes is additionally tested, but using the same technique for determining the value of the indicator (the number of minutes required to ensure the immobility of 50% of the flies when dosing the solution used for distribution , 1 wt./about. The KTjj values found are summarized in Table 4.

PRI me R 6.

Comparative tests are carried out using as a comparison the known compounds - the commercial preparation Dursban 1 and 2 - (nitromethylene) -pyrrolidine 2.

The test objects are the cotton worm and the Tobacco Budv / o rm larva.

The toxicity index is determined and b D 50.

The results are presented in table.5.

The table shows that the proposed compound is much more toxic with respect to the insects under test.

Thus, the proposed compounds exhibit good insecticidal activity.

Table

lz tf

S

p;

about

(and

& 1 Dosage LC50 for test and indicated insects (% of true

Fly

Rice

Tl home

gorokhodolgonosik va

0.089

0.1

0,0075

0.21 0.1

0.077

0.047 0.1

0,0067

0.06 0.1

0,005

0.123 0.1

0,0042

0.5 0.1

0,0034

0.34

0.029 NOTE: approximate value - test not Compound19 Value KTjg (minutes) 0.74 Compound Index 2-nitromethylene (piperidine) j (dursban) 155 2- (nitromethylene) -pyrrolidine 89

Claims (2)

Invention Formula An insecticidal composition containing an active ingredient and an additive selected from the group consisting of a solid carrier, a solvent, a surface active agent, characterized in that, in order to enhance the insecticidal activity, it contains the 2- (nitromethylene) piperidine derivative as an active substance; formulas Chl but c-N02 KN Y Mite pau larvae Larvae of I Muddy, 2 mosquitoes per second ; 0.2 0.83 ) 0.43 ten 0.02 0.2 ,) 0.2 0.24 ,; ; 0.2 0.20 5 10 0.2 0.18 0.20, 20 0.026 , 2 10 where n - 0,1,2; X - fluorine, chlorine ,, bromine, iodine, methyl, methylthio, ethylthio, propylthio, methylsulfinyl, methylsulfonyl-, Y - hydrogen, chlorine, bromine, nitro; R — C —C — alkyl, allyl, methoxymethyl, hydrogen or its complex compound with methanesulfonic or ethanesulfonic acid, where R, Y is hydrogen, p – 0, the content of active substance in the composition is 0.0001–50 wt%, the rest is additive. Priorities by feature 04.05.72 with n - 0,1,2} X - fluorine, chlorine, bromine. Iodine methyl U - hydrogen, chlorine, bromine, nitro group) R — C — C alkyl, allyl, methoxymethyl, hydrogen. Table of toxic compounds) Table 4 21 222324 1.2 1.7 1.23.2 Table 1 of toxicity LDjo JMr / kg Tobacco Budworm 490320 95 09о02.73 with X-methylthio, ethylthio, propylthio, methylsulfinyl, methylsulfonyl R - its complex compound with methanesulfonic or ethanesulfonic acid, where R, Hydrogen, p-0. Sources of information taken into account in the examination i. Melnikov N.N. Chemistry Pesticides. M., Himi, 1968, p. 2. US Patent No. 3560523, Cl, 260-3269, 1971.