MXPA99007073A - Insecticidal oxadiazine compounds - Google Patents

Abstract

Insecticidal substituted oxadiazines having formula (I), wherein R is an optionally substituted C4-C5 heterocyclic group and R'is hydrogen, halogen, C1-C4 haloalkyl or C1-C4 haloalkoxy, insecticidal compositions containing these oxadiazines, and methods for their use.

Description

OXYDYACINE INSECTICIDE COMPOUNDS Field of the Invention This invention relates to the substituted insecticidal oxadiazine compounds, insecticidal products containing the oxadiazine compounds, and the methods for their use. Background of the Invention It has been reported that certain oxadiazin compounds are useful as pesticides and as pharmaceutical agents. For example, the patent of E. U.A. 5,536, 720 describes substituted compounds of 2-phenyl-1,3,4-oxadiazine-4-carbamide, useful as insecticides and acaricides. Trapanier and Colab. , J. Med. Chem. 9: 753-758 (1966) describe certain 2-substituted 4H-1, 3,4-oxadiazines, useful as anticonvulsants in the mouse. The patent of E. U.A. 3,420,826 describes certain 2,4,6-substituted 4H-1, 3,4-oxadiazines, useful as sedatives, anticonvulsants, and as pesticides against nematodes, plants and fungi. The patent of E. U.A. 3,420,825 describes the methods for the production of. certain 2,4,5-substituted 4H-1 compounds, 3,4-oxadiazines. It is the purpose of this invention to provide novel oxadiazine derivatives that are useful as insecticides. SUMMARY OF THE INVENTION The present invention relates to a compound having the formula: (I) wherein R is a C4-Cs heterocyclic group containing a sulfur or oxygen atom, in which the heterocyclic group can be substituted or unsubstituted with 1 to 3 halogen atoms, or with a haloalkyl group C? -C4; and R 'is hydrogen, halogen, haloalkyl C-r C or haloalkoxy C? -C4. These compounds, or the physiologically acceptable salts thereof, are useful as insecticides. The insecticidal compositions of this invention contain: (a) an effective amount of one or more compounds of the formula I, and (b) a suitable carrier. DETAILED DESCRIPTION OF THE INVENTION Preferably, the compound of this invention has the formula: Preferably, R is a heterocyclic aromatic group comprising a sulfur or oxygen atom, more preferably, a thienic, furan or pyridinyl group, optionally substituted with 1 to 3 bromine or chlorine atoms, more preferably, a bromine or a chlorine , or with trihaloalkyl dC t, more preferably, trihalomethyl, trihaloethyl, trihalomethoxy or trihaloethoxy; and R 'is trihaloalkyl C? -C4 or trihaloalkoxy d-C4, more preferably, trihalomethyl, trihaloethyl, trihalomethoxy or trihaloethoxy. Particularly preferred is the compound of the formula I wherein R is thienyl or furanyl substituted with bromine or chlorine, and R 'is trihalomethoxy or trihalomethyl. Most preferred is the compound of the formula I wherein R is 5-bromo-2-thienyl, 5-chloro-2-thienyl, or 5-bromo-2-furanyl, and R 'is trifluoromethoxy or trifluoromethyl. The compounds and compositions of this invention are useful as agents for the protection of plants against insects, and are particularly effective against cateroptera and lepidopteran insects, such as the tobacco budworm. The compounds of the present invention can be prepared by reacting an oxadiazine of formula A below, wherein R is described above, as an isocyanate of formula B below, wherein R 'is described above, and an amount catalytic triethylamine in a suitable solvent, such as acetonitrile or toluene.

The compositions of the present invention can be prepared by formulating one or more compounds of the present invention with a suitable carrier. Suitable liquid carriers can include water, alcohols, phenol ketones, toluene and xylenes. In such formulations, additives conventionally employed in this field, such as one or more surfactants and / or inert diluents, may be used to facilitate handling and application of the resulting insecticidal composition. Alternatively, the compounds of this invention can be applied as a liquid or spray when used in a liquid carrier, such as a solution containing a compatible solvent., such as for example acetone, benzene, toluene or kerosene, or a dispersion containing a suitable non-solvent medium, such as water. The compositions of this invention may contain as possible alternatives solid carriers in the form of powders, granules, wettable powders, pastes, aerosols, emulsions, emulsifiable concentrates, and water-soluble solids. For example, the compounds of this invention can be applied as powders when mixed with solid powder carriers or absorbed by them, such as mineral silicates, talc, pyrophyllite and clays, together with a surfactant dispersing agent, in such a way as to obtain a wettable powder that is then applied directly to the places to be treated. Alternatively, the solid powder carrier containing the compound in the mixture may be dispersed in water to form a suspension that is applied in such a form. Granular formulations of the compounds are preferred for treatment in the field and are suitable for application by dispersion in an area, placement on the sides, incorporation into the soil or treatment of the seeds, and are properly prepared using a conveyor form in small grains suitably using a conveyor shape in small or large grains, such as granular clays, vermiculite, carbon or corn cobs. The compound of this invention is dissolved in a solvent and sprayed on an inert mineral carrier, such as attapulgite granules (10-100 mesh), and then the solvent is evaporated. Such granular compositions may contain from 2 to 25% of a compound of this invention, on a carrier basis plus the compound, preferably 3 to 15%. In addition, the compounds of this invention can also be incorporated into a polymeric carrier, such as polyethylene, polypropylene, butadiene-styrene, styrene-acrylonitrile resins, polyamide (acetates) of polyvinyl, and the like. When encapsulated, the compound of this invention can advantageously be released for an even longer period of time, extending its effectiveness beyond when used in an unencapsulated form. Another method of applying the compound of this invention to the places to be treated is by means of the aerosol treatment, for which the compound can be dissolved in an aerosol conveyor which, under pressure, is a liquid, but at ordinary temperatures (e.g. ., 20 ° C) and under atmospheric pressure is a gas. Aerosol formulations can also be prepared by first dissolving the compound in a less volatile solvent and then mixing the resulting solution with an extremely volatile liquid aerosol transporter. For the treatment of plants (said term includes parts of plants), the compounds of the invention are preferably applied in aqueous emulsions containing a surfactant dispersing agent, which may be nonionic, cationic or anionic. Suitable surfactants are well known in the art, such as those indicated in the U.S. Patent. 2, 547, 724 (columns 3 and 4). In order to produce aqueous suspensions of the compounds at the desired concentration levels, the compounds of this invention can be mixed as concentrates -for the subsequent addition of water- with such surfactant dispersing agents, with or without an organic solvent.

In addition, the compounds can be used with carriers that are themselves pesticidally active, such as insecticides, acaricides, fungicides and bactericides. It will be understood that the effective amount of a compound in a given formulation will vary, depending, for example, on the specific pest to be combated, as well as the composition and specific chemical formulation of the compound being used, the method of application of the compound / formulation and the place of treatment. However, generally the effective amount of the compound of this invention can vary from about 0.1 to 95 weight percent. The dilutions of the spray can be as low as a few parts per million, while at the opposite extreme, the 100% concentrates of the compound can be applied lately by very low volume techniques. When the plants constitute the treatment site, the concentration per unit area may vary between about 0.01 12 to 56 kilograms per hectare, preferably being used for crops such as corn, tobacco, rice and the like, concentrations of about 0.1 12 to 1 1. 2 kilograms per hectare. To combat insects, sprays of the compounds can be applied to any suitable place, such as, for example, directly to the insects themselves and / or to the plants they devour or where they make their nests. The compositions of this invention can also be applied to the soil or other medium in which the pests are present. The specific methods of application of the compounds and compositions of this invention, as well as the selection and concentration of these compounds, will vary depending on circumstances such as crops to be protected, geographical area, climate, topography, tolerance of the plants, etc. The following examples are given to illustrate the present invention. EXAMPLES Example 1 Preparation of 5,6-dihydro-N- [4-. tri fluoro me toxi) -f in II-2-.5-bromo-2-thienyl) -4H-1, 3,4-oxadiazine-4-carboxamide (Compound No. 1) To 3 g of 5,6- dihydro-2- (5-bromo-2-thienyl) -4H-1, 3,4-oxadiacin dissolved in 50 ml of acetonitrile, 2.5 g of 4- (trifluoromethoxy) phenyl isocyanate were added, followed by two drops of triethylamine. When this addition was complete, the resulting mixture was heated for 4 hours to reflux, and then evaporated under reduced pressure, leaving a solid residue. The solid residue was recrystallized from ethanol to yield 2.6 g of 5,6-dihydro-N- [4- (trifluoromethoxy) -phenyl] -2- (5-bromo-2-thienyl) -4H-1, 3.4- Oxadiazine-4-carboxamide, as an almost white solid, p. and. 139- 140 ° C.

The remaining compounds of Table 1 were prepared using essentially the same process. Each of the compounds is characterized by its NMR data. TABLE 1 Example 2 Preparation of the matrix solution The remaining examples are related to the use of the compounds of this invention as insecticides. In all these examples, a matrix solution was prepared for the compounds at 3,000 ppm, dissolving 0.24 g of each compound to be tested in 8 ml of acetone and adding 72 ml of distilled water plus 3 drops of ethoxylated sorbitan monolaurate, a wetting agent. , this matrix solution was used in the remaining examples demonstrating the insecticidal use of representative compounds of this invention. For each example that follows, this matrix solution was used and the specified dilutions were made. All the tests discussed below, which involved treatment with the compounds of this invention, were always repeated with controls, in which the active compound was included, to allow a comparison on the basis of which the percentage of control was calculated. Example 3 Southern corn worm test The 3,000 ppm matrix solution prepared in Example 2 above was diluted to 100 ppm (test solution). For each compound, 2.5 ml of the test solution was pipetted onto a filter paper (Whatman # 3) on the bottom of a 100 mm Petri dish. Two corn seedlings were soaked in the 100 ppm solution for 1 hour and then transferred to the Petri dish containing the same test solution. After 24 hours, each dish was loaded with 5 second stage larvae of southern worm of the corn root (Diabrotica undecimpunctata). After 5 days the number of live larvae was noted and the control percentage was calculated, corrected with the Abbott formula [see J. Economic Entomology 1_8: 265-267 (1 925)].

The results of the southern corn rootworm (CR) test are presented in Table 2 below. EXAMPLE 4 Foliar Test of the Rice Hemiptere The 3,000 ppm matrix solution prepared in Example 2 above was diluted to 1,000 ppm. A pot containing about 20 rice seedlings of the Mars variety was treated with each formulation, by means of a spray atomizer. One day after the treatment the plants were covered with a tubular cage and 20 adult rice delfacidas -Sogatodes orizicola were transferred to each cage. Five days after the transfer, the surviving hemipterans were counted in each pot and the percentage of control was estimated. The results of the rice hemiptera test (RPH) are presented in Table 2 below. Example 5 Tobacco budworm test For each compound, 0.2 ml of the matrix solution prepared in Example 2 above, was pipetted onto the surface of each of the 5 dietary cells, allowed to be It will spread on the surface and air dried for 2 hours. A second-stage larva of Helicoverpa virescens was then introduced into each cell. After 14 days, the number of live larvae was determined for each treatment, and the control percentage corrected with the Abbott formula was calculated.

The results of the tobacco budworm (TB) test are presented in Table 2 below. TABLE 2 PERCENTAGE OF CONTROL OF THE SUREÑO ROOT WORM HEMIPTERO CORN OF TOBACCO RICE AND WORM

Claims (19)

1. A compound that has the formula: (I) wherein R is a heterocyclic group C -Cs containing a sulfur or oxygen atom, in which the heterocyclic group can be substituted or unsubstituted with 1 to 3 halogen atoms, or a haloalkyl group C1-C4; and R 'is hydrogen, halogen, C halo-C4 haloalkyl or C?-C haloalkoxy.

2. A compound according to claim 1, having the formula: < !TO) wherein R is a C4-C5 herocyclic group containing a sulfur or oxygen atom, in which the heterocyclic group can be substituted or unsubstituted with 1 to 3 halogen atoms, or a haloalkyl group C? -C4; and R 'is haloalkyl C? -C or haloalkoxy C? -C4.

3. A compound according to claim 1, wherein R is a heterocyclic aromatic group.

4. A compound according to claim 3, wherein R is a thienyl or furanyl group.

5. A compound according to claim 4, wherein R is a thienyl or furanyl group, substituted with 1 to 3 bromine or chlorine atoms.

6. A compound according to claim 5, wherein R is a thienyl or furanyl group, substituted with 1 bromine or chlorine atom.

7. A compound of. according to claim 4, wherein R is a thienyl or furanyl group, substituted with trihaloalkyl C? -C4 or trihaloalkoxy C1-C4.

A compound according to claim 7, wherein R is a thienyl or furanyl group, substituted with trihalomethyl, trihaloethyl, trihalomethoxy or trihaloethoxy.

9. A compound according to claim 4, wherein R 'is trihaloalkyl d-C4 or trihaloalkoxy d-C4.

10. A compound according to claim 9, wherein R 'is trihalomethyl, trihaloethyl, trihalomethoxy, trihaloethoxy.

11. A compound according to claim 10, wherein R 'is trifluoromethoxy or trifluoromethyl.

12. A compound according to claim 1, which has the formula: (I A) wherein R is thienyl or furanyl, substituted with bromine or chlorine, and R 'is trihalomethoxy or trihalomethyl.

13. A compound according to claim 12, wherein R is 5-bromo-2-thienyl, 5-chloro-2-thienyl, or 5-bromo-2-furanyl, and R 'is trifluoromethoxy or trifluoromethyl.

14. An insecticidal composition containing an effective amount of a compound according to claim 1, and a suitable carrier.

15. An insecticidal composition containing an effective amount of a compound according to claim 2, and a suitable carrier.

16. An insecticidal composition containing an effective amount of a compound according to claim 12, and a suitable carrier.

17. A method for controlling insects that includes the application to a site to be protected, an effective amount of a compound according to claim 1.

18. A method for controlling insects that includes the application to a site to be protected, an effective amount of a compound according to claim 2.

19. A method for controlling insects that includes the application to a site to be protected, an effective amount of a compound according to claim 12.