CN1072212C

CN1072212C - Oxadiazines pesticides

Info

Publication number: CN1072212C
Application number: CN95197855A
Authority: CN
Inventors: M·A·凯基瑟; P·T·麦克多纳德
Original assignee: Uniroyal Chemical Co Inc
Current assignee: Uniroyal Chemical Co Inc
Priority date: 1995-05-17
Filing date: 1995-05-17
Publication date: 2001-10-03
Anticipated expiration: 2015-05-17
Also published as: CN1185150A

Abstract

The present invention relates to a compound which has the following chemical formula (Ia) or salt of the compound, which is acceptable on physiology. In the formula, Z is (a); in the formula, x is an integral number which is from 0 to 4, n is an integral number which is from 0 to 5, the definition of R is as follows, or Z is (b); in the formula, n is an integral number from 0 to 5, and the definition of R is as follows. R is selected from the following base groups: hydrogen, C1 to C4 alkyl, C1 to C4 alkoxyl, halogen, nitryl, phenyl, cyano, phenoxy, benzyloxy, phenyl, C1 to C4 dialkylamino, C1 to C4 alkylthio, C1 to C4 haloalkoxy, or C1 to C4 haloalkyl. R1 is C1 to C4 haloalkyl except chloroalkyl, or a compound of the following formula (IIa). In the formula, R<4> is hydrogen, halogen, C1 to C4 haloalkyl or C1 to C4 haloalkoxy. A prerequisite is that when x is equal to 0, R<1> is not C1 to C4 haloalkyl. The compounds have the activity for killing insects and mites.

Description

Desinsection De oxadiazine

Invention field

The present invention relates to replace the De oxadiazine, this compound unexpectedly has the activity of desirable sterilant, (comprising as sterilant, miticide).On the other hand, the present invention relates to contain the insect-killing composition of such compound, and use such compound and/method of composition Pest Control.

Background of invention

The harm that acarid and insect are caused has brought a series of problems to agricultural.The field crops of many kinds comprises cash crop such as soybean, corn, peanut, cotton, clover and tobacco, need prevent to be subjected to the harm of acarid and/or insect.In addition, vegetables such as tomato, potato, pea, beet, Radix Dauci Sativae etc., and fruit, nut, ornamental plant and seedbed plant such as apple, peach, citrus, almond and grape also all need to prevent to be subjected to the harm of these insects.

Ismail etc., sterilant biological chemistry physiology 47,1-7 (1993) have described some Er Qing oxadiazine and as acaricidal application.Dekeyser etc., J.Econ.Entomol.86 (5): 1339-1343 (1993) have described some Er Qing oxadiazine and as the application of sterilant.Dekeyser etc., sterilant science 38:309-314 (1993) have described the design of some Er Qing oxadiazine and have synthesized.Dekeyser etc., agricultural food product The Chemicals 41:1329-1331 (1993) have described the synthetic of some Er Qing oxadiazine and have killed mite and parasiticidal activity.The pharmaceutical chemistry magazine, 1966,753-758 has described the different 4H-1 that has the active 2-of anticonvulsive agent position to replace to muroid that it is said, 3,4-oxadiazine.United States Patent (USP) 3,420,826 relate to the 4H-1 of some 2,4,6 replacement, and 3, the 4-oxadiazines it is said the same effective as tranquilizer, anticonvulsive agent and sterilant, particularly all the more so to nematode, plant and fungi.United States Patent (USP) 3,420,825 relate to the method for some compounds like this of producing.WO-A-9211249 has narrated Mou Xie oxadiazine base, sulfo-triazinyl and triazinyl carbanilide, and they are applicable to the control arthropods.

Brief summary of the invention

The present invention relates to have the compound and the physiologically acceptable salt thereof of following chemical formula:

In the formula, Z is

a)

X is from 0 to 4 integer in the formula, and n is from 0 to 5 integer, and R is defined as follows; Perhaps

b)

N is from 0 to 5 integer in the formula, and R is defined as follows;

R is selected from following radicals: hydrogen; C ₁-C ₄Alkyl; C ₁-C ₄Alkoxyl group; Halogen; Nitro; Phenyl; Cyano group; Phenoxy group; Benzyloxy; Benzyl; C ₁-C ₄Dialkyl amido; C ₁-C ₄Alkylthio; C ₁-C ₄Halogenated alkoxy; Perhaps C ₁-C ₄Haloalkyl;

R ¹Be a following formula group:

R in the formula ⁴Be hydrogen, halogen, C ₁-C ₄Haloalkyl or C ₁-C ₄Halogenated alkoxy, preferably a following formula group:

R in the formula ⁴Be halogen, C ₁-C ₄Fluoro-alkyl or C ₁-C ₄Fluoroalkyl is more preferably-Cl-CF ₃Perhaps-OCF ₃

Composition of the present invention by (A) one or more have the compound of above-mentioned chemical formula I structure and (B) a kind of appropriate carriers form.This appropriate carriers can be actually solid or liquid.Compound of the present invention and composition have the activity of sterilant, the activity of particularly anti-insect and acarid.

Detailed Description Of The Invention

Compound of the present invention is to be reacted in the presence of alkali by the hydrazine of following chemical formula III and 1-bromo-2-fluoroethane to make:

R has above-mentioned implication in the formula, and these alkali comprise alkali metal hydroxide.Preferred alkali comprises sodium hydroxide and potassium hydroxide.

Composition of the present invention can be made by one or more compounds of the present invention and appropriate carriers such as liquid or solid carrier.

Suitable liquid vehicle can comprise water, alcohol, ketone, phenol, toluene and dimethylbenzene.In these prescriptions, can use the additive that uses in the traditional technology, for example one or more tensio-active agents and/or inert diluent are beneficial to handle and use resulting insect-killing composition.

In addition, when Pesticidal compound uses in liquid vehicle, can use them with liquid or spray form, for example in the mixable solution that contains as U.S. of acetone, benzene, toluene or kerosene, perhaps be dispersed in the suitable non--solvent medium as water and so on and use.

Insect-killing composition can also contain solid carrier, and it can be forms such as pulvis, granule, wettable powder, paste, aerosol, emulsion, missible oil and water-soluble solid.For example, Pesticidal compound of the present invention is with a kind of surfactivity dispersion agent, mix with the atomizing solid carrier or be adsorbed on the atomizing solid carrier for example on silicate minerals such as mica, talcum, pyrophyllite and the clay time, can use with powder form, therefore obtain wettable pulvis, it is applied directly to pending place.In addition, the atomizing solid carrier that contains with its blended compound can be dispersed in the water, generates the suspension that uses with this form.

The granular preparation of this compound is applicable to the field processing, also be applicable to and sow, follow fertilising, mix soil and handle seed, also be fit to particulate state or the carrier of one-tenth ball such as the granular preparation that particulate state clay, vermiculite, charcoal or mealie core prepare this compound.This sterilant is dissolved in the solvent neutralization and sends forth on the inert mineral carrier, as attapulgite particle (10-100 order), evaporates this solvent then.Such particulate composition can contain the sterilant of 2-25%, adds sterilant meter, preferably 3-15% based on carrier.In addition, this sterilant can also join in the polymer support, in polyethylene, polypropylene, butadiene-styrene, styrene-acrylonitrile resin, polymeric amide, poly-(vinyl-acetic ester) etc.When encapsulated, this sterilant can be advantageously release in long-time, than the system of using encapsulated form not to prolonging its effect.

The another kind of method of using pending place is to handle with aerosol, can be in the aerosol carrier when this processing with this compound dissolution, this aerosol carrier is a liquid under pressure, and next at normal temperature (as 20 ℃) normal pressure be gas.Aerosol preparations also can prepare with the following method: at first with this compound dissolution in low-volatile solvent, then the solution that obtains is mixed with high evaporable liquid aersol carrier.

For biological proofing (this term comprises plant part) of plant, compound of the present invention preferably uses with the water miscible liquid that contains the surfactivity dispersion agent, and this dispersion agent can be nonionic, positively charged ion or anionic.Suitable tensio-active agent is known in the art, is included in those disclosed tensio-active agent in the U.S. patent 2547724 (third and fourth hurdle).Be with or without under the situation of organic solvent, compound of the present invention can with such some surfactivity dispersant, as enriched material, obtain the aqeous suspension of this compound of the concentration that requires when adding water afterwards.

In addition, this compound can use with the carrier that itself also has insecticidal activity, as sterilant, miticide, mycocide and sterilant.

Be appreciated that, the amount of the insecticidal active compound in a customization agent depends on the specific insect that is killed, the compound particular chemical that also depends on use is formed and the concrete preparation of compound used therefor, the method for using this compound/preparation and processing place, and therefore the insecticidal effective dose of this compound can alter a great deal.But usually, this compound concentrations as active ingredient can be about 0.1-95% (weight) in the effective preparation of desinsection.Spray diluent and can hang down several ppm, and under opposite extreme case, can adopt the ultra-low volume technology to use complete dense compound effectively.When plant was process object, when the cereal, tobacco, paddy rice etc. that are applied to as corn and so on, the concentration of unit surface can be every acre of 0.01-50 pound approximately, and preferred concentration is every acre of about 0.1-10 pound.

For desinsection, this compound can be sprayed in any suitable place, as directly sending forth on the insect, and/or spray that these insects are nibbled or the plant of nesting on.The insecticidal activity preparation can also be used in the soil or other media of insect existence.Deleterious insect and acarid have been encroached on a large amount of plants, comprising ornamental plant and farm crop, by consuming root and/or leaf, draw the essential juice of plant from plant, excrete poison, and often spread disease and purpose that plant is encroached on.Can reasonably use compound of the present invention, to reach minimizing or to prevent these infringements.Selecting for use and concentration of the specific application process of these compounds and these compounds should change according to the condition as geographical position, weather, landform, plant tolerance etc. and so on certainly.Under concrete situation, those skilled in the art are easy to determine suitable compound, concentration and application process by the experiment of routine.

Compound of the present invention is effective especially as the sterilant or the miticide of foliage applying.These compounds are effective especially to control as tobacco thatch worm, as the mite of tetranychid, rust mite and so on.

Following embodiment only illustrates protection scope of the present invention.The present invention is not subjected to the restriction of following embodiment.

Embodiment 1

2-(4-bromo phenyl)-4H-1,3,4, the preparation of-oxadiazine

The solution of dissolving 2.9 gram (0.07 mole) sodium hydroxide in 10 ml waters at room temperature is added drop-wise to it in the solution of mixture in 25 milliliters of ethanol of 6.5 gram (0.03 mole) 4-bromo benzoic acid hydrazides and 4.0 gram (0.03 mole) 1-bromine 2-fluoroethanes.The solution that obtains refluxed 2.5 hours.With this mixture cool to room temperature,, use ether (100 milliliters) extraction more several times with the dilution of 150 ml waters.Separate and with anhydrous magnesium sulfate drying after, its solution after filtration, vapourisation under reduced pressure again obtains the oil (productive rate is 63.6%) of 4.6 grams, this oil adopts distillation to carry out purifying.Its product characterizes with IR and NMR spectrography.

Embodiment 1A

2-(4-bromo phenyl)-5,6-dihydro-N[(4-trifluoromethyl) phenyl]-4H-1,2,3,4, the preparation of-oxadiazine-4-urea (compound 12)

Restrain 2-(4-bromo phenyl)-5 toward being dissolved in 1 in 40 milliliters of acetonitriles, 6-dihydro-4H-1,3,4, in the solution of-oxadiazine, under agitation add 2 triethylamines, then add 1 gram isocyanic acid 4-(trifluoromethyl) phenylester, at room temperature stirred then 1 hour.Under reduced pressure boil off solvent again, the solid that obtains obtains 1.0 gram 2-(4-bromo phenyl)-5,6-dihydro-N-[(4-trifluoromethyl with hexane wash and dry air) phenyl]-4H-1,3,4 ,-oxadiazine-4-urea, fusing point 146-148 ℃ (productive rate 50%).

The compound for preparing other according to top method.These compounds and acaricidal activity thereof and insecticidal activity come together in table I and the table II.The NMR data acquisition of compound 1-12 is in the table III.

Embodiment 2

The preparation of preparation

The following examples relate to the pesticidal applications of The compounds of this invention.In all these embodiment, the 3000ppm stock solution preparation method of these compounds is as follows: the compound dissolution that 0.3 gram is to be tested is in 10 milliliters of acetone, add 90 milliliters the distilled water and the mixture of four ethoxylation sorbitanic mono-laurates, perhaps similar suitable moistening temperature agent.Concerning following each embodiment, all used this stock solution and carried out specified dilution.

All experiments of discussing below repeat repeatedly together with control experiment, and these experiments are that to adopt concentration be that the The compounds of this invention of 3000-500ppm is handled, and do not adopt active compound in control experiment, so that can calculate the percentage inverse amplification factor, compare.

Embodiment 3

Kill the agent of mite adult and kill mite ovum agent/mite larva agent test extremely

Handle the day before yesterday, the myron spot circle (tree tanglefoot) of a figure of eight is applied on each blade of using two kinds of cowpea primary blades, each is all in an alms bowl in two kind of plant.In every kind 8 font, kill mite ovum agent/kill mite larva agent test from the nearer fourth finger of stem is customized, and kill mite adult agent test from stem fourth finger far away is customized.

The day before yesterday a few composition worm mites (two-spotted spider mite) are transferred in the circle of mite ovum agent test extremely in processing, allow female worm give birth to ovum, at this moment remove adult up to handling last hour.Use the solution that is diluted to 1000ppm by the stock solution of 3000ppm, and spray plant.

Handled back first day, and the groups of about 25 mite adults was moved on in the circle of mite adult test extremely.After five days, check on the leaf in these circles the acarid of residual work.Quantity survey (surveying) percentage inverse amplification factor according to the acarid that lives on the plant of being checked.

Handle the back the 9th day, and checked the ovum of the hatching in ovicide/larvacide test circle and the larva of survival.According to the hatching of the ovum on the plant of being checked and the quantity survey (surveying) percentage inverse amplification factor of survival larva.When the treatment effect checked ovum, the percentage inverse amplification factor is meant the effect of ovicide (O); When the treatment effect checked larva, the percentage inverse amplification factor is meant the effect of larvacide (L).

Killing the test-results of mite adult agent (MI) and the test-results of mite ovum agent extremely/mite larva agent (MIOVL) extremely lists in table I and table II.

Embodiment 4

The test of water rice hopper blade face

The stock solution of 3000ppm is diluted to 1000ppm.With every kind of preparation of atomizers spray, handle the about 20 Mars rice varieties rice shoots that are equipped with in the alms bowl.Handle one day after, cover these plants with tubular cartridge, 20 water rice hopper adult America planthoppers are transferred in each box.Shifted back five days, and counted the plant hopper that survives in each alms bowl, estimate inverse amplification factor then.

Water rice hopper (RPH) test-results is listed in table I and table II.

Embodiment 5

The test of tobacco budworm

The stock solution of 3000ppm is adopted in this test.For every kind of compound, all pipette 0.2 milliliter of stock solution and be put on each pollen sac surface of 5 edible pollen sac, make it in these surface diffusions, dry air is two hours again.Then second instar larvae Helicoverpa virescens is put in each cell.After 14 days, the survival larva number after measuring each and handling, and calculate percentage inverse amplification factor with the Abbott formula correction.

I and table II are shown in the results are shown in of tobacco budworm (TB) test.

Embodiment 6

The ovicide test of tobacco thatch worm

The compound dissolution that 0.015 gram is to be tested adds 13 ml distilled waters and 1 ethoxylation sorbitanic mono-laurate in 2 milliliters of acetone, prepare the solution of 1000ppm.1-2 days budworms lay eggs on scrim before handling, and scrim is divided into several, and every has 40-80 ovum.These sheets soaked in this solution 1 minute.After 5 days, number goes out the quantity of hatching and unhatched ovum, determines corrected inverse amplification factor.The result lists in the TBOV hurdle of table I and table II.

The table I

Compound number R X R ¹MI MIOVL RPH TB TBOV

1 H - CONHC ₆H ₄Cl 0 100(O) 30 0 0

2 4-CH ₃O - COHNC ₆H ₄Cl 0 70(L) 100 40 100

3 2,4-Cl CH ₂O CONHC ₆H ₅ 0 70(L) 100 0 56

4 4-CH ₃S - CONHC ₆H ₄Cl 50 100(O) 0 0 100

5 4-Br - CONHC ₆H ₄Cl 0 100(O) 50 60 100

6 2,4-CH ₃ - CONHC ₆H ₄Cl 0 100(O) 0 0 100

7 2-Cl - CONHC ₆H ₄Cl 0 100(O) 0 0 6

8 4-CF ₃ - CONHC ₆H ₄Cl 0 100(O) 0 100 100

9 2-C ₆H ₅CH ₂O?- CONHC ₆H ₄Cl 50 70(O) 45 32 48

10 2,4-Cl - CONHC ₆H ₄Cl 0 0 100 0 100

The table II Compound number R ³R ²MI MIOVL RPH TB TBOV

11 4-BrC ₆H ₄ CONHC ₆H ₄-4-OCF ₃0 0 0 100 5

12 4-BrC ₆H ₄ CONHC ₆H ₄-4-OCF ₃30 0 0 100 1

13 3-BrC ₆H ₄ CONHC ₆H ₄-4-OCF ₃0 0 0 100 0

14 4-ClC ₆H ₄ CONHC ₆H ₄-4-OCF ₃0 0 0 100 0

15 4-OCF ₃C ₆H ₄ CONHC ₆H ₄-4-OCF ₃0 0 0 100 0

16 3-Br-4-ClC ₆H ₄CONHC ₆H ₄-4-OCF ₃0 0 0 100 0

17 3-NO ₂C ₆H ₄ CONHC ₆H ₄-4-OCF ₃0 0 0 100 0

18 2-Cl-5-C ₅H ₃N?CONHC ₆H ₄-4-OCF ₃0 0 0 100 0

19 3-IC ₆H ₄ CONHC ₆H ₄-4-OCF ₃0 0 0 100 0

20 4-IC ₆H ₄ CONHC ₆H ₄-4-OCF ₃0 0 0 100 0

21 3,4-CIC ₆H ₄ CONHC ₆H ₄-4-OCF ₃0 0 0 100 0

22 4-NO ₂C ₆H ₄ CONHC ₆H ₄-4-OCF ₃0 0 0 100 0

Table III 01 m (2) 4.0; M (2) 4.5; M (9) 7.3-8.1; S (1) 9.202 m (2) 3.1; S (3) 3.7; M (2) 4.3; M (8) 6.9-7.703 m (2) 3.0; M (2) 4.2; S (2) 4.6; M (7) 7.0-7.504 s (3) 2.5; S (1) 8.8; M (2) 3.0; M (2) 4.4; M (4) 7.1-7.705 m (2) 3.1; M (2) 4.4; M (8) 7.0-7.706 s (3) 2.3; S (3) 2.4; M (2) 3.0; M (2) 4.4; M (7) 7.0-7.5;

s(1)8.707 m(2)3.0；m(2)4.4；m(8)7.0-7.608 m(2)3.1；m(2)4.4；m(8)7.0-7.809 m(2)3.0；m(2)4.4；s(2)5.0；m(14)7.0-7.510 m(2)4.0；m(2)4.5；m(7)7.1-7.6；s(1)8.511 m(2)3.7-4.0；m(2)4.4-4.7；m(8)7.2-8.2；s(1)9.412 m(2)3.7-4.0；m(2)4.4-4.7；m(8)7.6-8.2；s(1)9.5

Claims

1. the compound of following formula or the acceptable salt of its physiology,

In the formula: Z is

a)

b)

N is from 0 to 5 integer in the formula, and R is defined as follows;

R is selected from by following radicals: hydrogen; C ₁-C ₄Alkyl; C ₁-C ₄Alkoxyl group; Halogen; Nitro; Phenyl; Cyano group; Phenoxy group; Benzyloxy; Benzyl; C ₁-C ₄Dialkyl amido; C ₁-C ₄Alkylthio; C ₁-C ₄Halogenated alkoxy; Perhaps C ₁-C ₄Haloalkyl; With

R ¹Be a following formula group:

R in the formula ⁴Be hydrogen, halogen, C ₁-C ₄Haloalkyl or C ₁-C ₄Halogenated alkoxy.

2. according to the compound of claim 1, wherein Z selects a); N is 1 or 2; X is 0.

3. according to the compound of claim 1, R wherein ¹Be a following formula group:

R in the formula ⁴Be C ₁-C ₄Haloalkyl or C ₁-C ₄Halogenated alkoxy.

4. according to the compound of claim 3, R wherein ¹Be a following formula group:

R in the formula ⁴Be C ₁-C ₄Fluoro-alkyl or C ₁-C ₄Fluoroalkyl.

5. according to the compound of claim 3, wherein R is hydrogen, C ₁-C ₄Alkyl, C ₁-C ₄Alkoxyl group, halogen, C ₁-C ₄Halogenated alkoxy or C ₁-C ₄Alkylthio.

6. according to the compound of claim 3, R wherein ⁴Be, trifluoromethyl or trifluoromethoxy.

7. desinsection or miticide composition, it comprises:

(A) compound as claimed in claim 1 of significant quantity and

(B) a kind of appropriate carriers.

8. desinsection or miticide composition, it comprises:

(A) compound as claimed in claim 3 of significant quantity and

(B) a kind of appropriate carriers.

9. method of controlling insect and acarid, this method comprise, with the compound administration as claimed in claim 1 of significant quantity to protected position.

10. method of controlling insect and acarid, this method comprise, with the compound administration as claimed in claim 3 of significant quantity to protected position.