MXPA97008819A - Pesticidal oxadiazines - Google Patents

Abstract

Compounds of formula (Ia) wherein Z is (a), wherein x is an integer from 0 to 4, n is an integer from 0 to 5 and R is defined below;or (b), wherein n is an integer from 0 to 5 and R is defined below;R is selected from the group consisting of:hydrogen;C1-C4 alkyl;C1-C4 alkoxy;halogen;nitro;phenyl;cyano;phenoxy;benzyloxy;benzyl;C1-C4 dialkylamino;C1-C4 alkylthio;C1-C4 haloalkoxy;or C1-C4 haloalkyl;and R<1>is a C1-C4 haloalkyl other than a chloroalkyl, or a groupp of formula (IIa), wherein R<4>is hydrogen, halogen, C1-C4 haloalkyl or C1-C4 haloalkoxy;or physiologically acceptable salts thereof, with the proviso that when x is 0, R<1>is not haloalkyl. These compounds exhibit insecticidal and acaricidal activity.

Description

PESTICIDE OXADIACINS FIELD OF THE INVENTION This invention relates to substituted oxadiazines, which are unexpectedly convenient activated exhibiting compounds such as pesticides, including activity as insecticides and acaricides. In other aspects, this invention relates to pesticidal compositions comprising said compounds as well as methods for controlling pests using said compounds and / or compositions.

BACKGROUND OF THE INVENTION The destruction of mites and insects presents a serious problem for agriculture. There is a wide variety of crops that need protection against mites and / or insects, including valuable crops such as soybeans, corn, peanuts, cotton, alfalfa and tobacco. In addition, vegetables such as tomatoes, potatoes, peas, beets, carrots and the like, as well as fruits, nuts, ornamental plants and plantation crops such as apples, peaches, citrus fruits, almonds and grapes may also need protection against havoc caused by these pests. Ismail et al., Pestic. Biochem. Physiol 47 ^ 1-7 (1993) describe some dihydrooxadiazines and their use, acaricides. Dekeyser et al., J. Econ. Entomol 86. (5): 1339-1343 (1993) describe some dihydrooxadiazines and their use as insecticides. Dekeyser et al, Pestic. Sci. 38: 309-3314 (1993) describes the design of the synthesis of some dihydrooxadiazines. Dekeyser et al, J. Agrie. Food Chem. 41: 1329-1331 (1993) describes the synthesis and acaricidal and insecticidal activity of certain dihydrooxadiazines. J. Med. Chem, 1966, 753-758 refer to several 4H-1, 2-substituted 3,4-oxadiazines that I are said to have anticonvulsant activity in mice. U.S. Patent 3420826 refers to some 2,4,6-substituted 4H-1, 3,4-oxadiazines, which have utility as sedatives, anticonvulsants, and pesticides specifically against nematodes, plants and fungi. US Patent No. 3420825 relates to methods for producing said WO-A-9211249 discloses certain oxadiacinyl, thiadiazinyl and triazinyl carboxanilides useful for the control of atropods.

COMPENDIUM OF THE INVENTION The present invention relates to compounds having the formula: where: Z is a) where x is an integer from 0 to 4, n is an integer from 0 to 5 and R is as defined below; or b) -CH, 0- ^ > where n is an integer from 0 to 5 and R is as defined below; R is selected from the group consisting of: hydrogen; C? -C4 alkyl; C4-C4 alkoxy; halogen, nitro; phenyl; silt, phenoxy; benzyloxy; benzyl; dialkylamino C? -C4; C 1 -C 4 alkylthio; haloalkoxy C? -C4; or C? -C4 haloalkyl; and R1 is a group that has the formula: where R4 is hydrogen haloalkyl C? -C or haloalkoxy C? -C4 preferably a group having the formula. wherein R4 is halogen, C1-C4 fluoralkyl or C1-C4 fluoroalkoxy more preferably -C-CF3 or -OCF3; and their physiologically acceptable salts.

The compositions of this invention are constituted by A one or more compounds having the structure of the preceding formula I and B a suitable carrier. Said suitable carriers can be solid or liquid in nature. The compounds and compositions of the present invention exhibit pesticidal activity especially in terms of insects and acarids.

DETAILED DESCRIPTION OF THE INVENTION The compounds of this invention can be prepared by reacting a hydrazine having the formula I 1 which is given below where R has the meanings described above with 1-bromo-2-fluoroethane in the presence of a base. Said bases incite alkali metal hydroxides. Preferred bases include sodium or potassium hydroxide. The compositions of the present invention can be prepared by the formulation of one or more compounds of the present invention with an appropriate carrier such as an liquid or solid carrier. The appropriate liquid carriers can be constituted by, water, alcohols, ketones, phenols, toluenes and xylenes. In such formulations, additives conventionally employed in the art such as one or more inert surfactants and / or diluents may be used to facilitate handling and application of the resulting pesticidal composition. Alternatively the pesticidal compounds may be applied in the form of liquids or as sprays when used with a liquid carrier such as in a solution comprising a compatible solvent such as acetone, benzene, toluene or kerosene, or dispersed in an appropriate non-solvent medium such as Water. The pesticidal compositions may alternatively comprise solid carriers having the form of powders, granules, wettable powders, pastes, aerosols, emulsions, emulsifiable concentrates and water soluble solids. For example, the pesticidal compounds of this invention can be applied in the form of powders when they are mixed or when they are absorbed onto powdery solid carriers such as mineral silicates, for example, mica, talc, pyrophyllite and clays, together with a surface-active dispersing agent so as to obtain a wettable powder that is then applied directly to the places you want to treat. Alternatively, the solid powder carrier containing the compound in admixture therewith can disperse in water to form a suspension for application in such a form. The granular formulations of the compounds are preferred for the treatment of the field and are suitable for the application by boleo, with the fertilizer, by incorporation to the soil or by treatment of the seeds, and are prepared appropriately using a form of granulate or in the form of carrier pills such as granular clays, dermiculite, coal or corn tricks. The pesticide is dissolved in a solvent and applied by spraying on an inert mineral carrier such as attapulgite granules (10-100 mesh), and then the solvent is evaporated. Such granular compositions can contain from 2.25% carrier-based pesticide in addition to pesticide, with 3-15% being preferred. In addition, the pesticide can also be incorporated into a polymeric carrier such as polyethylene, polypropylene, butadiene-styrene, styrene-acrylonitrile, polyamides, polyvinyl acetates and the like. When encapsulated, the pesticide can be advantageously released over an even longer period of time extending its effectiveness beyond that when used in an unencapsulated form. Another method of application to the places to be treated is aerosol treatment for which the compounds can be dissolved in an aerosol carrier which is liquid under pressure but which is a gas at ordinary temperature (for example, 20 ° C) and pressure atmospheric The aerosol formulations can then also be prepared by first dissolving the compound in a less volatile solvent and then mixing the resulting solution with a highly volatile liquid aerosol carrier. For the treatment of plants with pesticides (the term "plant parts") the compounds of the invention are preferably applied to aqueous emulsions containing a dispersed surfactant agent which may be non-ionic, cationic or anionic in nature. Suitable surfactants are well known in the art and include those disclosed in U.S. Patent No. 2 546 724 (columns 3 and 4). The compounds of the invention can be mixed with said surfactant dispersing agents with or without organic solvent, in the form of concentrates for the subsequent addition of water in order to obtain aqueous suspensions of the compounds at the desired concentration levels. In addition, the compounds can be used with carriers which by themselves are pesticidally active such as insecticides, acaricides, fungicides or bactericides. It should be understood that the amount of pesticidally active compound in a given formulation will depend on the specific pest to be combated as well as on the chemical composition and specific formulation of the compound to be used., of the method of application of the compound / formulation and of the treatment site so that the pesticidally effective amount of the compound can vary widely. In general, however, the concentrations of the compound as an active ingredient in pesticidally effective formulations can range from about 0.1 to about 95% by weight. Spray dilutions can be as low as a few parts per million, while at the opposite extreme, total strength concentrates can be applied with ultra-low volume techniques. When the plants constitute the treatment site, the concentration per unit area may vary between about 0.01 and about 50 pounds per acre, with concentrations of between about 0.1 and about 10 pounds per acre being preferred for use in crops, such as corn, tobacco, rice and the like. To combat the pests, sprays of the compounds can be applied at any suitable place such as to the pests directly and / or to the plants from which they feed or in which they have their lair. Pesticide-active formulations can also be applied to the soil or to another medium where the pests are present. Harmful insects and acarids attack a wide variety of plants including ornamental and agricultural plants, and infringe great damage by consuming roots and / or foliage, extracting vital plant juices, secreting toxins and often transmitting diseases. The compounds of the present invention can be advantageously used to minimize or prevent such damages. The specific application methods as well as the selection and concentration of these compounds will vary naturally depending on circumstances such as geographical area, climate, topography, tolerance of the plant, etc. For specific circumstances, the expert in the field will be able to easily determine the appropriate compound, concentration and method of application by routine experimentation. The compounds of the present invention are particularly useful as insecticides and as acaricides for foliar application. The compounds are particularly effective in controlling insects such as tobacco budworm and mites, such as spider mites and millet. The following examples will be merely to illustrate the scope of the present invention. It is not desired to limit the scope of the invention to the actual examples provided herein.

EXAMPLE 1 Preparation of 2- (4-bromophenyl) 4H-1, 3,4-oxadiazine. A solution of 2.9 g (0.07 mol) of sodium hydroxide dissolved in 10 ml of water was added dropwise at room temperature to a mixture of 6.5 g (0.03 mol of 4-bromobenzoic acid hydrazide and , 0 g (0.03 mol) of 1-bromo-2-fluoroethane in 25 ml of ethanol The resulting solution was refluxed for 2.5 hours The mixture was cooled to room temperature, diluted with 150 ml of water and it was extracted several times with ether (100 ml) After separation and drying over anhydrous sodium sulfate, the solution was filtered and evaporated under reduced pressure leaving 4.6 g of an oil (63.6% yield), which was purified by distillation.The product was characterized by IR and NMR spectroscopy.

EXAMPLE 1A Preparation of 2- (4-bromophenyl) -5,6-dihydro-Nf (4-trifluoromethyl) phenin 4H-1, 3,4-oxadiacin-4-carbamide (compound 12) To 1 g of 2- (4 -bromophenyl) -5,6-dihydro-4H-1, 3,4-oxadiazine dissolved in 40 ml of acetonitrile was added with stirring 2 drops of triethylamine followed by 1 g of isocyano of 4- (trifluoromethyl) phenyl and stirred for one hour at room temperature. The solvent was then evaporated under reduced pressure and the resulting solid was washed with hexane and dried in the air to obtain 1.0 g of 2- (4-bromophenyl) -5,6-dihydro-N - [(4-trifluoromethyl) -phenyl], 4H-1,3,4-oxadiazine-4-carbamide, mp. 146-148 ° C (50% yield). Additional compounds were prepared according to the preceding procedures. These compounds and their acaricidal and insecticidal activity are summarized in Tables I and II. The NMR data for compounds 1-12 are summarized in Table III.

EXAMPLE 2 Preparation of the formulations The remaining examples relate to the pesticidal use of the compounds of this invention. In all of these examples, a loading solution for the compounds was prepared at 3000 ppm by dissolving 0.3 g of the compound to be tested in 10 ml of acetone, and adding 90 ml of distilled water in addition to 4 drops of monolaurate. ethoxylated sorbitan, or other similar suitable wetting agent. For each of the examples that follow, this loading solution was used and the specified dilutions were made. All the tests discussed above that involve treatment with the compounds of this invention at a concentration of 3000 to 500 ppm, were always repeated with the controls, in which the active compound had not been provided, in order to allow a comparison on which the control percentage was calculated.

EXAMPLE 3 Acaro Ovicide and Acaic / Larvicide Adulticide Tests One day before treatment, a sticky substance was applied in "Figure 8" to each of two primary cowpea leaves, one out of every two plants in a pot. In each figure, the circle closest to the stem was designated for the mite ovicide / larvicide test, and the circle furthest from the stem was designated for the mite adulcitide test. Groups of adult mites were transferred (Tetranychus urticae Koch) to the ovicidal circles one day before the treatment, and the females were allowed to deposit their eggs until an hour before the treatment when the adults were removed. The plants were sprayed until dripping with a solution of 1000 ppm diluted from a solution of 3000 ppm load. One day after the treatment, groups of approximately 25 adult mites were transferred to the adulticidal rings. Five days later these rings were examined to determine how many live mites remained in the leaves. Percentage control was estimated based on the number of surviving mites in the control plants. Nine days after treatment, the ovicidal / larvicidal rings were examined to determine the deposited eggs and live immature mites. Percentage control was maximized based on the number of eggs deposited and the surviving immature mites in the control plants. When the effect of the treatment fell on the eggs, the control was designated as ovicide (O); When the effect of the treatment fell on the immature control was designated as larvicide (L). The results of adulticide mite (Ml) and ovicide / larvicide (MIOVL) tests are presented in Tables I and II.

EXAMPLE 4 Leaf test of the jumping insect of the rice plants A loading solution of 3000 ppm was diluted to 1000 ppm. One of the sherds containing approximately 20 rice plants of the Mars variety was treated with each of the formulations by spraying with an atomizer. One day after the treatment, the plants were covered with a tubular box and transferred to each of the boxes of the adult fish Sogatodes orizicola. Five days after the transfer, the surviving jumping insects of each pot were counted and the percentage control was estimated. The results of the test of jumping insects of rice plants (RPH) are presented in Tables I and II.

EXAMPLE 5 Tobacco budworm test A 3000 ppm loading solution was used for this assay. For each compound, 0.2 ml was introduced into the surface of each of 5 dietary cells, allowed to disperse on the surfaces and air-dried for 2 hours. Then a larva of Helicoverpa virescens of second stage was introduced in each of the cells. After 14 days, the number of live larvae was determined for each treatment and the percentage control corrected by the Abbott formula was calculated. The results of the test of the tobacco outbreak (TB) worms are given in Tables I and II. EXAMPLE 6 Ovicidal assay of the tobacco budworm A solution of 1000 ppm was prepared by dissolving 0.015 g of the compound to be tested in 2 ml of acetone, and 13 ml of distilled water was added in addition to one drop of ethoxylated sorbitan monolaurate. The gauze fabric upon which the tobacco budworms had laid eggs 1-2 days before treatment was cut into pieces, each containing 40-80 eggs. These pieces were immersed for one minute in the solution. After 5 days, the numbers of hatched and uncocked eggs were counted, and an adjusted percentage control was determined. The results are given in Tables I and II under the heading TBOV PICTURE Ccpfuesto N ° R B MI MIOVL RPH IB Igov 1 H C0NHC, H4CI 0 100 (0) 30 0 0 2 4-CH, 0 C0HNC, H4CI 0 7oa? 100 40 100 3 2.4-CI CH, 0 C0NHC, Hs 0 70 { L) 100 0 56 4 4-CHjS C0NHC, H4CI 50 100 (01 0 0 100 4-Br C0NHC, H4CI 0 100 (01 50 60 100 6 2.4 CH, C0NHC, H CI 0 100 (01 0 0 100 7 2-CI C0NHC, H4CI 0 100 (0) 0 0 6 ß 4-CF, C0NHC, H4CI 0 100 (01 0 100 100 9 2-C, H5CH, 0 C0NHCeH4CI 50 7010.}. 45 32 48 Z4-CI C0NHC (H4CI 0 0 100 0 100 TABLE II Compound No. B? Bí M¡ MIOVL RPH li TBOV 11 4 BrC, H "C0NHC, H4-4-0CF, 0 0 0 100 5 12 4-BGC.H. CONHC. -OCFj 30 0 0 100 1 13 3 BrC, H4 C0NHC, H44-0CF3 0 0 0 100 0 14 4-CIC, H4 C0NHC, H44-0CF, 0 0 0 100 0 4 0CF, C, H4 C0NHC? -4 0CF, 0 0 0 100 0 16 3-Br, 4-CIC.H, CONHC. -OCF, 0 0 0 100 0 17 3-N02C, H, C0NHCßH4-4-OCF, 0 0 0 100 0 18 2-CI-5-C, H, N C0NHC. -0CF, 0 0 0 100 0 19 3 IC.H. C0NHC? -4-0CF, 0 0 0 100 0 41C.H. C0NHC, H4-4 0CFj 0 0 0 100 0 21 3.4 CIC (H, C0NHC, H4-4-0CFa 0 0 0 100 0 22 4-N0} C, H4 CONHCeM-OCFj 0 0 0 100 0 TABLE iii 01 (2) 4.0; m. { 2) 4.5; m (9) 7.3-8.1; s (l) 9.2 02 m (2) 3.1; s (3) 3.7; m (2) 4.3; m (8) 6.9-7.7 03 m (2) 3.0; m (2) 4.2; s (2) 4.6; m (7) 7.0-7.5 04 e (3) 2.5; e (l) 8.8; m (2) 3.0; (2) 4.4; m (4) 7.1-7.7 05 m (2) 3.1; m (2) 4.4; p? (8) 7.0-7.7 06 s (3) 2.3; s (3) 2.4; tn. { 2) 3.0; (2) 4.4; m (7) 7.0-7.5; e (l) 8.7 07 m (2) 3.0; tn (2) 4.4; m (8) 7.0-7.6 08 (2) 3.1; m (2) 4.4; m (8) 7.0-7.8 09 (2) 3.0; m (2) 4.4; s (2) 5.0; m (14) 7.0-7.5 10 tn (2) 4.0; m (2) 4.5; m (7) 7.1-7.6; s (l) 8.5 11 (2.}. 3.7- .0; T? l (2) 4.4 -4.7; m (8) 7.2-8.2; 8 (1) 9.4 12 m (2) 3.7-4.0; (2 ) 4.4 -4.7; m (8) 7.6-8.2; s (l) 9.S fifteen

Claims (6)

1. A compound that has the formula where: Z is a) where x is an integer from 0 to 4, n is an integer from 0 to 5 and R is as defined below; or b) where x is an integer from 0 to 5 and R is as defined below; R is selected from the group consisting of: hydrogen; C? -Calkoxy C? -C alkyl; halogen, nitro; phenyl; cyano, phenoxy; benzyloxy; benzyl; dialkylamino C? -C4; C1-C4 alkylthio; haloalkoxy C? -C4; or C1-C4 haloalkyl; and Ri is a group of the formula- wherein R 4 is hydrogen, halogen, C 1 -C 4 haloalkyl or C 1 -C 4 haloalkoxy; or their physiologically acceptable salts, with the proviso that when x is 0 then 1 is not haloalkyl.

2. A compound according to claim 1, wherein Z is option a); is not 1 or 2, and x is 0.

3. A compound according to claim 1, wherein R1 is a group having the formula wherein R 4 is C 1. C 4 haloalkyl or C 1 -C 4 haloalkoxy

4. A compound according to claim 3, wherein R 1 is a group having the formula wherein R4 is C1-C4 fluoralkyl or C? -C4 fluoroalkoxy

5. A compound according to claim 3, wherein R is hydrogen, C1-C4 alkyl, C? -C4 alkoxy, halogen, haloalkoxy d-C4 or C1-? C4

6. A compound according to claim 3, wherein R4 is chloro, trifluoromethyl, or trifluoromethoxy. An insecticidal or acaricidal composition comprising: (A) an effective amount of a compound according to claim 1; and (B) an appropriate carrier. 8. An insecticidal or acaricidal composition comprising: (A) an effective amount of a compound according to claim 3; and (B) an appropriate carrier. 9. A method for controlling insects or acarids which comprises applying to an area to be protected an effective amount of a compound according to claim 1. 10. A method for controlling insects or acarids which comprises applying to an area to be protected an effective amount of a compound according to claim 3.