AU697128B2

AU697128B2 - Pesticidal oxadiazines

Info

Publication number: AU697128B2
Application number: AU25943/95A
Authority: AU
Inventors: Mark Achiel Kekeyser; Paul Thomas Mcdonald
Original assignee: Uniroyal Chemical Ltd; Uniroyal Chemical Co Inc
Current assignee: Lanxess Canada Co; Uniroyal Chemical Co Inc
Priority date: 1995-05-17
Filing date: 1995-05-17
Publication date: 1998-09-24
Anticipated expiration: 2015-05-17
Also published as: KR100417794B1; JP3210676B2; BR9510594A; EP0825990A1; KR19990014805A; JPH10507775A; AU2594395A; WO1996036618A1

Description

WO 96/36618 PCT/US95/0627 PESTICIDAL OXADIAZINES Field of the invention This inventicn is directed to substituted oxadiazines, which compounds exhibit unexpectedly desirable activity as pesticides, including as insecticides and acaricides. In other aspects, this invention is directed to ppeticidal compositions comprising such compounds as well as to methods of controlling pests employing such compounds and/or compositions.

Background of the Invention The destruction by acarids and insects presents a serious problem to agriculture. A wide variety of field crops are in need of protection from acarids and/or insects including such valuable crops as soybeans, corn, peanuts, cotton, alfalfa and tobacco. In addition, vegetables such as toratoes, potatoes, peas, sugarbeet, carrots and the like, as well as fruits, nuts, ornamentals and seed bed crops such as apples, peaches, citrus fruit, almonds and grapes may also require protection from the ravages of such pests.

Ismail et al, Pestic. Biochem. Physiol. 47, 1-7 (1993) describe certain dihydrooxadiazines and their use as miticides. Dekeyser et al, J. Econ. Entomol. 86(5): 1339-1343 (1993) describe certain dihydrooxadiazines and their use as insecticides. Dekeyser et al, Pestic, Sci.

38: 309-314 (1993) describe the design and synthesis of certain dihydrooxadiazines. Dekeyser et al, J. Agric.

Food Chem. 41: 1329-1331 (1993) describe the synthesis and miticidal and insecticidal activity of certain dihydrooxadiazines. J. Med. Chem, 1966, 753-758 refers to various 2-substituted 4H-1,3,4-oxadiazines said to have anticonvulsant activity in mice. U.S. Patent 3,420,826 refers to certain 2,4,6-substituted 4H-1,3,4-oxadiazines, said to have utility as sedatives, D-6195 PCT anticonvulsants, and as pesticides, specifically against nematodes, plants, and fungi. U.S. Patent 3,420,825 refers to methods for producing those compounds, WOrA- 9211249 describes certain oxadiazinyl, thiadiazinyl and triaziny. carboxanilides useful to control arthropods.

Summxary of the Invention The present invention relates to compounds having the formula: R7 wherein: Z is a) -(OH2) wherein x is an integer from 0 to 4, ni is an integer from 0 to 5 and R is defined below; or b)

*CH

2 j wherein n is an iliteger from 0 to 5 and R is defined below; R is selected from the group consisting of: hydrogen; C 1

-C

4 alkyl; alkoxy; halogen; nitro; phenyl; cyano; phenoxy; benzyloxy; benzyl; Q,-C, dialkylanino; C 1

-C

4 alkylthio; haloalkoxy; or CIC haloalkyl; and RI is a group of the formula -1- D-6195 PCT 3 R 4 -CO-NH wherein R 4 is hydrogen, halogen, C-C 4 haloalkyl or C.-C, haloalkoxy, preferably a group of the formula -CO-NH- R wherein R 4 is halogen, C,-C 4 fluoroalkyl or C.-c 4 fluroralkoxy, more preferably -Cl, -CF 3 or -OCF3; and physiologically acceptable salts thereof.

The compositions of thi' "invention are comprised of one or more compounds having the structure of formula I above, and a suitable carrier. Such suitable carriers may be solid or liquid in nature. The compounds and compositions of the present invention exhibit pesticidal activity, especially against insects and acarids, DETAILED DESCRIPTION OF THE INVENTION The compounds of this invention can be prepared by reacting a hydrazide cf formula (III) below

^CONHNH

2 where R has the meanings described above, with l-bromo-2-fluoroethane in the presence of a base. Such bases include alkali metal hydroxides. Preferred bases include sodium or potassium hydroxide.

The compositions of the present invention may be prepared by formulating one or more compounds of the opstoso h peetivninmyb WO 96136618 PCT/US95/06270 4 present invention with a suitable carrier, such as a liquid or solid carrier.

Suitable liquid carriers may be comprised of water, alcohols, ketones, phenols, toluene and xylenes, In such formulations, additives conventionally employed in the art may be utilized, such as one or more surface active agents and/or inert diluents, to facilitate handling and application of the resulting pesticide composition.

Alternatively, the pesticidal compounds may be applied in liquid or sprays when utilized in a liquid carrier, such as in a solution comprising a compatible solvent such as acetone, benzene, toluene or kerosene, or as dispersed in a suitable non-solvent medium such as water.

The pesticidal compositions may alternatively comprise solid carriers taking the form of dusts, granules, wettable powders, pastes, aerosols, emulsions, emulsifiable concentratest and water-soluble solids. For example, the pesticidal compounds of this invention may be applied as dusts when admixed with or absorbed onto powdered solid carriers, such as mineral silicates, e.g., mica, talc, pyrophyllite and clays, together with a surface-active dispersing agent so that a wettable powder is obtained which then is applied directly to the loci to be treated. Alternatively, the powdered solid carrier containing the compound admixed therewith may be dispersed in water to form a suspension for application in such form.

Granular formulations of the compounds are preferred for field treatment and are suitable for application by broadcasting, side dressing, soil incorporation or seed treatment, and are suitably prepared using a granular or pellitized form of carrier such as granular clays, vermiculite, charcoal or corn cobs. The pesticide is dissolved in a solvent and sprayed onto an inert mineral carrier such as attapulgite granules (10-100 mesh), and the solvent is then evaporated. Such granular WO 96/36618 PCT/US95/06270 5 compositions may contain from 2-25% pesticide based on carrier plus pesticide, with 3-15% being preferred. In addition, the pesticide may also be incorporated into a polymeric carrier such as polyethylene, polypropylene, butadiene-styrene, styrene-acryonitrile resins, polyamides, poly(vinyl acetates) and the like. When encapsulated, the pesticide may advantageously be released over an even longer time period, extending its effectiv ness further than when used in non-encapsulated form.

Another method of application to loci to be treated is aerosol treatment, for which the compound may be dissolved in an aerosol carrier which is a liquid under pressure but which is a gas at ordinary temperature 20°C) and atmospheric pressure. Aerosol formulations may also be prepared by first dissolving the compound in a less volatile solvent and then admixing the resulting solution with a highly volatile liquid aerosol carrier.

For pesticidal treatment of plants (such term including plant parts), the compounds of the invention preferably are applied in aqueous emulsions containing a surface-active dispersing agent which may be non-ionic, cationic or anionic. Suitable surface-active agents are well known in the art, and include those disclosed in U.S. Patent 2,547,724 (columns 3 and The compounds of the invention may be mixed with such surface-active dispersing agents, with or without an organic solvent, as concentrates for the subsequent addition of water to yield aqueous suspensions of the compounds at desired concentration levels.

In addition, the compounds may be employed with carriers which themselves are pesticidally active, such as insecticides, acaricides, fungicides or bactericides.

It will be understood that the amount of the pesticidally active compound in a given formulation will depend upon the specific pest to be combatted, as well as -e WO 96/36618 PCTIUS95/06270 6 upon the specific chemlcal composition and formulation of the compound being employed, the method of applying the compound/formulation and the locus of treatment so that the pesticidally effective amount of the compound may vary widely. Generally, however, concentrations of the compound as the active ingredient in pesticidally effective formulations may range from about 0.1 to about percent by weight. Sp--ay dilutions may be as low as a few parts per million, while at the opposite extreme, full strength concentrates of the compound may be usefully applied by ultra low volume techniques When plants constitute the loci of treatment, concentration per unit area may range between about 0.01 and about pounds per acre, with concentrations of between about 0.1 and about 10 pounds per acre preferably being employed for crops such as corn, tobacco, rice and the like.

To combat pests, sprays of the compounds may be applied to any suitable locus, such as to the pests directly and/or to plants upon which they feed or nest.

The pesticidally active formulations may also be applied to the soil or other medium in which the pests are present. Harmful insects and acarids attack a wide variety of plants, including both ornamental and agricultural plants and inflict damage by consuming roots and/or foliage, withdrawing vital juices from the plants, secreting toxins and often by transmitting diseases. The compounds of the present invention may be advantageously utilized to minimize or prevent such damage, The specific methods of application, as well as the selection and concentration of these compounds will of course vary depending upon such circumstances as geographic area, climate, topography, plant tolerance, etc. For specific circumstances, one skilled in the art may readily determine the proper compound, concentration and method of application by routine experimentation.

The compounds of the invention are particularly useful as insecticides and acaricides for foliar D-6195 PCT 7 application. The compounds are particularly effective for controlling insects, such as tobacco budworm and mites, such as spider mites and rust mites.

The following examples are given merely to illustrate the scope of the present invention. The invention herein is not intended to be limited to the actual examples provided.

EXAMPLE 1 Preparation of 2-(4-Bromophenvl)-4H-1,3,4-Oxadiazine A solution of 2.9g (0.07 mole) sodium hydroxide dissolved in 10 ml of water -wars added dropwise at room temperature to a mixture of 6.5g (0.03 mole) 4-bromobenzoic hydrazide and 4.0g (0.03 mole) l-bromo-2-fluoroethane in 25 ml of ethanol. The resulting solution was refluxed for two and one-half hours. The mixture was cooled to room temperature, diluted with 150 ml of water and 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 grams 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-bromoohenvl)-5,6-dihvdro-N-f(4trifluoromethyl)ohenyl -4H-1,3,4-oxadiazine-4-carbamide (Compound 12) To 1 gm of 2-(4-bromophenyl)-5,6-dihydro- 4 H-l, 3 4 oxadiazine dissolved in 40ml of acetonitrile, was added, with stirring, 2 drops of triethylamine followed by 1 gm of 4-(trifluoromethyl)phenyl isocyanate and stirred for 1 R WO 96/36618 PCT/US95/06270 8 hour at room temperature. The solvent was then evaporated under reduced pressure and the resulting solid was washed with hexane and air-dried, producing 1.0 gm of 2-(4-bromophenyl)-5,6-dihydro-N-[(4-trifluoromethyl)phenyl]-4H-1,3,4-oxadiazine-4-carbamide, mp 146-148°C yield).

Additional compounds were prepared in accordance with the above 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 Formulations The remaining examples relate to the pesticidal use of the compounds of this invention. In all these examples a stock solution for the compounds were prepared at 3000 ppm by dissolving 0.3 gram of the compound to be tested in 10 ml of acetone and adding 90 ml of distilled water plus four drops of ethoxylated sorbitan monolaurate, or a simliar suitable wetting agent. For each example that follows, this stock solution was used and the specificied dilutions made.

All the tests discussed below, which involved treatment with compounds of this invention at concentrations of 3000 to 500 ppm were always repeated with controls, in which the active compound was not provided, to permit a comparison upon which the percent control was calculated.

EXAMPLE 3 Mite Adulticide and Mite Ovicide/Larvicide Tests One day before treatment, a "Figure 8" configuartion of tree tanglefoot was applied to each of two cowpea primary leaves, one from each of two plants in a pot. In WO 96/36618 PCT/US95/06270 9 each figure, the circle nearer the stem was designated for the mite ovicide/larvicide test and the circle further from the stem was designated for the mite adulticice test.

Groups of adult mites (Tetranychus urticae Koch) were transferred into ovicide circles one day before treatment and the females were allowed to deposit eggs until one hour before treatment when the adults were removed. Plants were sprayed to run off with a 1000 ppm solution diluted from the 3000 ppm stock solution.

One day following treatment, groups of approximately adult mites were transferred into the adulticide rings. Five days later these rings were examined for live mites remaining on the leaves. The percent control was estimated based on the number of mites surviving on the check plants.

Nine days following treatment the ovicide/larvicide rings were examined for hatched eggs and living immature mites. The percent control was estimated based on the number of eggs hatching and immature mites surviving on the check plants. When the treatment effect was to eggs, control was designated as ovicidal when the treatment effect was to immatures, control was designated as larvicidal Results of the mite adulticide (MI) and ovicide/larvicide (MIOVL) tests are presented in Tables I and II.

EXAMPLE 4 Rice Planthopper Foliar Test The stock solution of 3000 ppm was diluted to 1000 ppm. One pot containing approximately 20 Mars variety rice seedlings was treated with each formulation by spraying with a spray atomizer. One day after treatment plants were covered with a tubular cage and twenty adult rice delphacides, Socatodes orizicola, were transferred into each cage. Five days after transferring, counts WO 96/36618 PCT/US95/06270 10 vere made of the surviving planthoppers in each pot and percent control was estimated.

Results of the testing of rice planthoppers (RPH) are presented in Tables I and II.

EXAMPLE Tobacco Budworm Test The stock solution of 3000 ppm was used for this test. For each compound, 0.2 ml was pipetted onto the surface of each of 5 diet cells, allowed to spread over the surfaces and air dried for two hours. Then a second instar Helicoverpa virescens larva was introduced into each cell. After 14 days, the number of living larvae was determined for each treatment and percent control, corrected by Abbott's formula, was calculated.

The results of the testing of tobacco budworms (TB) are given in Tables I and II.

EXAMPLE 6 Tobacco Budworm Ovicide Test A solution of 1000 ppm was prepared by dissolving 0.015 g of the compound to be tested in 2 ml of acetone and adding 13 ml of distilled water plus 1 drop of ethoxylated sorbitan monolaurate. Cheesecloth on whicY budworms had oviposited eggs 1-2 days before treatment was cut into pieces, each containing 40-80 eggs. These pieces were immersed for 1 minute in the solution. After days, the numbers of hatched and unhatched eggs were counted and an adjusted percent control determined. The results are given in Tables I and II under the heading

TBOV.

WO 9613661$ c~IS5I67 PCT/US95/06270 11 TAB3LE I CMPO #I 2 3 4 6 7 8 9 4.C11 3 0 2,4-Ct 4.CH 3

S

O4r 4-CF3 2.ClH 6 011 2 0 2,40C x Rl ml

CONHC

8 I1 4 CI 0

COHNCOH

4 CI 0

CH

2 0 CONHCaI 5 0

CONHC

8

II

4 CI 50

CONHCOU

4 cI 0 CONHCeH 4 CI 0

CONIICOH

4 CI 0

CONHCOH

4 CI 0 CONHCOI1 4 CI 50 CONHCJI1 4 C( 0 MIOVL RPH TB TBOV 100(0) 30 0 0 70(L) 100 40 100 70(L) 100 0 56 100(0) 0 0 100 100(0) 50 60 100 100(0) 0 0 100 100(0) 0 0 6 100(0) 0 100 100 70(0) 45 32 48 0 100 0 100 WO 96136618 WO 966G~8PU.05IO6270 12 TABLE 11 ,o R3 R 2 CMPD #i n_ d2 MI MID VI RPH TB TBOV 11 4-BrCIH 4

CDNHCOH

4 -4DCF 3 0 0 0 100 12 4-BrCaH 4

CDNHCOH

4 .4.aCF, 3D a a 100 1 13 3*BrCOfI 4

CONHC

8 i 4 -4'OCF 3 a a a 1aa a 14 4.C1C 8 11 4 C0NI1COH 4 -4'OCF 3 a a a 100 a 1v 4&OCF3COH 4

CDNHCOH

4 4CF 3 a a a 100 a 16 3.13r, 4-CICOI 4 C0N11C 6 1 4 4.DCF 3 a a a iaa0 a 17 3.NDCOH 4

CONRCOH

4 4-OCF 3 a a a 100 a 18 2.CI.5*C5H3N CONHCOH 4 -4'OCF 3 a a a 100 a 19 3.ICON 4

CONHCSH

4 +4UCF 3 a a a 100 a 4-IC 8 I1 4

CDNHCSH

4 .4.aCF., a a a 100 a 21 3,4*CICSH 4

CDNHCOH

4 4OCFj 0 a0 a 100 0 22 4N0 2 COIi 4

CONHCH

4 4OCF3 a a a 10a a wo 96136618 WO 9616618 CTIUS95I06270 13 TABLE I I 01 02 03 04 06 07 08 0.9 11 12 in 4.-0; m 3. 1; mn(2) 3.0,, S 2. 5; mn(2) 3. 1; S(1) 8.7 mn(2) 3 0; m 3. 1; M, ,1 M 4.0; m 4.5; s 3,7; rn 4.2 s 8. 8; m 4; sm(3) 4.4; mn 4. 4; m 4. 4; m 4. 5; m(9)7.3-8.1; s(1)9.2 s Mn(7)7.0-7.5 M(2)3.0; Mn(2)4.4; Mn(4)7.1-.7.7 in(8) 7.0-7.7 m(2)3.0; mn(2)4.4.; Mi(7)7.0-7.5; 7.0-7.6 in (8)7.0-7.8 s(2)5.0; m(14)7.0-7.5 s(1)8.5 Mn(2)3,7-4.0; tn(2)4.4-4.7; mn(8)7,2-8.2; S(1)9.4 mn(8)7.6-8.2; s(1)9.5

Claims

1. A compound having the formula '0 ~z N 'N wherein: Z is R, wherein x is an integer from 0 to 4, n is an integer from 0 to 5 and R is defined below; or b) CH 2 0 wherein n is an integer from 0 to 5 and R is defined below; R is selected from the group consisting of: hydrogen; C 1 -C 4 alkyl; C,-C 4 alkoxy; halogen; nitro; phen Iyl; cyano; phenoxy; berizyloxy; benzyl; C,-C 4 dialkylainino; C,-C 4 alkylthio; C,-.C 4 haloalkoxy; or CI.-C 4 haloalkyl; and RI is a group of the formula D-6195 PCT R 4 wherein R 4 is hydrogen, halogen, CI -C 4 haloalkyl or C.-C 4 haloalkoxy; or physio1cgically acceptable salts thereof-

2. A compound as recited in claim I. wherein Z is option n is 1 or 2; and x is 0.

3. A compound as recited in claim 1 wherein R! -a group, of the formula R 4 N wherein W 4 is C,-C 4 haloalky. or C,-C 4 haloalkoxy.

4. A compound as recited in claim 3 wherein RI is a group of the formula -CO-bNi P wherein R' is QI-C 4 fluoroalkyl or C 1 -C 4 fluoroalkoxy. S. A compound as recited in claim 3 wherein R is hydrogen, alkyl, alkoxy, halogen, CQ-C 4 haloalkoxy, or C 1 -C 4 alkylthio.

6. A compound as recited in claim 3 wherein RI is trifluoromethyl or trifluoromethoxy, -kcal- WO 96/36618 PCT iUS95/06270

16- 7. An insecticidal or acaricidal composition comprising: an effective amount of a compound as recited in claim 1; and a suitable carrier. 8. An insecticidal or acaricidal composition comprising: an effective amount of a compound as recited in claim 3; and a suitable carrier. 9. A method for controlling insects or acarids which comprises applying to a locus to be protected an effective amount of a compound as recited in claim 1. O0. A method for controlling insects or acarids which comprises applying to a locus to be protected an effective amount of a compound as recited in claim 3. iNNW INTR3UNATIONAL~ SEARCH I'M 1010 Inter ult AppieAuio No PCI/US 95/06270 A. CLASSIFICATION OF suIIjEcT'IIAI IPC 6 C07D273/O4 XA N43/8 8 A01N47/38 According to international Patent Classificaiotn (IPC) or to both national classiication and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system followed by riassfication symbols) IPC 6 C07D Documentation searched other than mrusnum documentation to the extent that such documents are includcd int thc fields searched Electronic data base consulted during the international search (name of data base and, where practical, search terms used) C. DOCUMENTS CONSIDERED TO BE RELEVANT Category' Citation of document with indication, where appropriate, of the relevant passages Relevant to claim No. X, Y JOURNAL OF AGRICULTURAL AND FOOD 1-10 CHEMISTRY, vol. 41, no. 8, August 1993 WASHINGTON DC, US) pages 1329-31, M.A. DEKEYSER ET AL. "Synthesis and initicidal and insecticidal activitities of 4-(2-fl1uoroethyl 6-di hydro-4H-1,3,4- oxadiazines' cited in the application see the whole document Further documents are listed in the continuation of box C. Patent faily members are listed in annex. Sscil cteoris o cieddocmens:T* later document published after the international filing date whici isnotor priority date and not in conflict with the application but docuiment defining the general state of the ar hc sno iItdt understand the pninciple or theory undtilying the considered to be of pattc,!air relevance invention *E earlier document but published on or after the international *X document of particular relevance; the claimed invention filing date cannot be considered novel or cannot be considered to W document which may throw doubts on priority claim(s)eor involve an inventive step when the document is taken alone which is cited to estaiblish the. publication date of another document of particular relevan ce; the clamed inVention citation or other special. rason (as specilfied) cannot be considered to involve an Inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combintion being obvious to a person skilled document published prior to the international filing date but in the art. later than the priority date claimed W document member of the same patent faintly Date of the actsual completion of the international search Date of mailing of the intemnational search report

18.01.96 8 January 1996 Name and mailing address of the, ISA Authorized officer European Patent Office, P.B. $818 Patetitiaan 2 NL 2280 [IV Rijswijk- Tel. 31470)340-2040, Tx, 31 651 epo rdlar Fax: 3 340.3016Alad M lom PCTIISA,1210 (second sheat) (julY 1992) page 1 of 2 0 MA1WNAT1'QNA11. SJH4RCU WE-P RT Intcr iM Apphuiato No ___PC'i/US 95/06270 C.(Continuation) DOCUMENTS CO'ISIVERED TO EtE RELEVANT Catagory Citation or docWu ,fl, v*tindc~n wh appropnatc, of the relcvant pas Reltvant to daim No. Y JOURNAL OF ECONOMIC ENTOMOLOGY, 1-10 Vol. 86, no. 5, October 1993 COLLEGE PARK, MARYLAND US, pages 1339-43, M.A. DEKEYSER ET AL, 'Insecticidal, miticidal, and ovicidal activity of 6-dihydro-4H-1, 3,4-oxadiazines' cited in the application see the whole document y US,A,3 420 826 TREPANIER 7 January 1-10 1969 cited in the application see the whole document, in particular column 9, line 42 to column 10, line Y WO,A,92 11249 (EI. DU PONT DE NEMOURS AND 1-10 COMPANY) 9 July 1992 see the whole document, in particular pages 230 to 259 A CHEMICAL ABSTRACTS, vol. 55, no. 11,1 29 May 1961 Columbus, Ohio, US; abstract no. 10465c, N..ISHIDATE ET AL 'Cancerocidal substances., XXIX, 1, 1-Bis(2-chloroethyl)hydrazine and its derivatives as tumor-inhibiting agents' see abstract CHEM. PHARM. BULL., vol. 8, 1960 Ipages

543-50, Form PCT1ISAJIt3 (wantnuttion of kecond shmqt (July 19921, page 2 of 2 INT)C'RNATIONAL SEARCH 'rowr 10,r 11 AppC#tMr NO PCI/US 95/06270 Patent document PUblcto Patent fai'; ly Publicatio cited in search report daemeiber(e) date US"A-3420826 07-01-69 NONE WO-A-9211249 09-07-92 AT-T- 125801 15-08-95 AU-B- 659121 11-05-95 AU-B- 9127091 22-07-92 BG-A- 97888 27-05-94 BR-A- 9107246 14-06-94 CA-A- 2098612 22-06-92 CN-A- 1062726 15-07-92 DE-D- 69111827 07-09-95 EP-A- 0565574 20-10-93 HU-A- 65223 02-05-94 JP-T- 6504777 02-06-94 NZ-A- 241072 25-03-94 TR-A- 25739 01-09-93 US-A- 5462938 31-10-95 ZA-A- 9110002 21-06-93 Form, PCTIISA/210 (pattnt razMUY Abtx) (JaIY 1992)