CA1151064A - Substituted oxadiazoles and their use as wire worm and flea beetle insecticides and grub insecticides - Google Patents
Substituted oxadiazoles and their use as wire worm and flea beetle insecticides and grub insecticidesInfo
- Publication number
- CA1151064A CA1151064A CA000374489A CA374489A CA1151064A CA 1151064 A CA1151064 A CA 1151064A CA 000374489 A CA000374489 A CA 000374489A CA 374489 A CA374489 A CA 374489A CA 1151064 A CA1151064 A CA 1151064A
- Authority
- CA
- Canada
- Prior art keywords
- insecticides
- sulfur
- compound
- wire
- grub
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 241001136249 Agriotes lineatus Species 0.000 title claims abstract description 15
- 239000002917 insecticide Substances 0.000 title abstract description 11
- 241000738498 Epitrix pubescens Species 0.000 title abstract description 7
- 150000004866 oxadiazoles Chemical class 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 239000002689 soil Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000011593 sulfur Substances 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 241000902876 Alticini Species 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- FRYPWUYDPUBMRU-UHFFFAOYSA-N 2-[(4-chlorophenoxy)methyl]-5-(2,4-dichloro-5-fluorophenyl)-1,3,4-oxadiazole Chemical class C1=C(Cl)C(F)=CC(C=2OC(COC=3C=CC(Cl)=CC=3)=NN=2)=C1Cl FRYPWUYDPUBMRU-UHFFFAOYSA-N 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 230000000749 insecticidal effect Effects 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 241000238631 Hexapoda Species 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 241000500845 Costelytra zealandica Species 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 241000254173 Coleoptera Species 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 241000238876 Acari Species 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 241001427543 Elateridae Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 241001124076 Aphididae Species 0.000 description 2
- 241001124134 Chrysomelidae Species 0.000 description 2
- 241000683561 Conoderus Species 0.000 description 2
- 241000256113 Culicidae Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000255925 Diptera Species 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- 244000017020 Ipomoea batatas Species 0.000 description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 241001608567 Phaedon cochleariae Species 0.000 description 2
- 241000254062 Scarabaeidae Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 241001611608 Systena Species 0.000 description 2
- ZWIFYHVITGYSLO-UHFFFAOYSA-N diethoxy-[(3-methyl-1,2,4-oxadiazol-5-yl)methylsulfanyl]-sulfanylidene-$l^{5}-phosphane Chemical compound CCOP(=S)(OCC)SCC1=NC(C)=NO1 ZWIFYHVITGYSLO-UHFFFAOYSA-N 0.000 description 2
- 235000021186 dishes Nutrition 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- HWJHWSBFPPPIPD-UHFFFAOYSA-N ethoxyethane;propan-2-one Chemical compound CC(C)=O.CCOCC HWJHWSBFPPPIPD-UHFFFAOYSA-N 0.000 description 2
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N gamma-hexachlorocyclohexane Natural products ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 2
- JLYXXMFPNIAWKQ-GNIYUCBRSA-N gamma-hexachlorocyclohexane Chemical compound Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@@H](Cl)[C@H](Cl)[C@H]1Cl JLYXXMFPNIAWKQ-GNIYUCBRSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000003359 percent control normalization Methods 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- LDVVMCZRFWMZSG-OLQVQODUSA-N (3ar,7as)-2-(trichloromethylsulfanyl)-3a,4,7,7a-tetrahydroisoindole-1,3-dione Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)Cl)C(=O)[C@H]21 LDVVMCZRFWMZSG-OLQVQODUSA-N 0.000 description 1
- FRUIHNKZQIULDG-UHFFFAOYSA-N 2-[5-(chloromethyl)-3-methyl-2h-1,2,4-oxadiazol-3-yl]-n'-hydroxyethanimidamide Chemical compound ON=C(N)CC1(C)NOC(CCl)=N1 FRUIHNKZQIULDG-UHFFFAOYSA-N 0.000 description 1
- SOAUOABDYBGOQY-UHFFFAOYSA-N 5-chloro-2,3-dimethyl-3h-1,2,4-oxadiazole Chemical compound CC1N=C(Cl)ON1C SOAUOABDYBGOQY-UHFFFAOYSA-N 0.000 description 1
- 241001136265 Agriotes Species 0.000 description 1
- 241000169953 Blapstinus Species 0.000 description 1
- QCHVEUFFZBSFKR-UHFFFAOYSA-N C(C)#N.C(C)(N)=NO Chemical compound C(C)#N.C(C)(N)=NO QCHVEUFFZBSFKR-UHFFFAOYSA-N 0.000 description 1
- JMVSBZNQHOZUBB-UHFFFAOYSA-N CC1=NOC(=N1)CCl.CC1=NOC(=N1)CSP(=S)(OCC)OCC Chemical compound CC1=NOC(=N1)CCl.CC1=NOC(=N1)CSP(=S)(OCC)OCC JMVSBZNQHOZUBB-UHFFFAOYSA-N 0.000 description 1
- 239000005745 Captan Substances 0.000 description 1
- 241000902406 Chaetocnema Species 0.000 description 1
- 241000500864 Costelytra Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000242268 Ctenicera Species 0.000 description 1
- 241000721035 Diaprepes Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241001105160 Eleodes Species 0.000 description 1
- 241000551596 Eleodes hispilabris Species 0.000 description 1
- 241000510032 Ellipsaria lineolata Species 0.000 description 1
- 241000303278 Epitrix Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241001227244 Heteronychus Species 0.000 description 1
- 241001260426 Horistonotus Species 0.000 description 1
- 241000683448 Limonius Species 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 241000257226 Muscidae Species 0.000 description 1
- 241000077345 Mycetophylax auritus Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000488583 Panonychus ulmi Species 0.000 description 1
- 241001325166 Phacelia congesta Species 0.000 description 1
- 241001640279 Phyllophaga Species 0.000 description 1
- 241000255969 Pieris brassicae Species 0.000 description 1
- 241000500437 Plutella xylostella Species 0.000 description 1
- 241000254103 Popillia Species 0.000 description 1
- 235000005805 Prunus cerasus Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 241001454295 Tetranychidae Species 0.000 description 1
- 241000344246 Tetranychus cinnabarinus Species 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- HFRHTRKMBOQLLL-UHFFFAOYSA-N azane;diethoxy-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound [NH4+].CCOP([S-])(=S)OCC HFRHTRKMBOQLLL-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229940117949 captan Drugs 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000013058 crude material Substances 0.000 description 1
- NZRHZQGDTLNQFM-UHFFFAOYSA-N diethoxy-[(3-methyl-1,2-oxazol-5-yl)methylsulfanyl]-sulfanylidene-$l^{5}-phosphane Chemical compound CCOP(=S)(OCC)SCC1=CC(C)=NO1 NZRHZQGDTLNQFM-UHFFFAOYSA-N 0.000 description 1
- IFNMAVHRIJFMJW-UHFFFAOYSA-N diethoxy-[(5-methyl-1,2,4-oxadiazol-3-yl)methylsulfanyl]-sulfanylidene-$l^{5}-phosphane Chemical compound CCOP(=S)(OCC)SCC1=NOC(C)=N1 IFNMAVHRIJFMJW-UHFFFAOYSA-N 0.000 description 1
- -1 e.g. Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZKQFHRVKCYFVCN-UHFFFAOYSA-N ethoxyethane;hexane Chemical compound CCOCC.CCCCCC ZKQFHRVKCYFVCN-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229960002809 lindane Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AEXITZJSLGALNH-UHFFFAOYSA-N n'-hydroxyethanimidamide Chemical compound CC(N)=NO AEXITZJSLGALNH-UHFFFAOYSA-N 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000000699 topical effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
- C07F9/653—Five-membered rings
- C07F9/65306—Five-membered rings containing two nitrogen atoms
- C07F9/65318—Five-membered rings containing two nitrogen atoms having the two nitrogen atoms in positions 1 and 3
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Dentistry (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
"SUBSTITUTED OXADIAZOLES AND THEIR USE AS
WIRE WORM AND FLEA BEETLE INSECTICIDES AND
GRUB INSECTICIDES"
A method for killing wire worms and flea beetles and grubs which comprises applying to the soil habitat of the wire worms and flea beetles and grubs an insecticidally effective amount of a compound of the formula
"SUBSTITUTED OXADIAZOLES AND THEIR USE AS
WIRE WORM AND FLEA BEETLE INSECTICIDES AND
GRUB INSECTICIDES"
A method for killing wire worms and flea beetles and grubs which comprises applying to the soil habitat of the wire worms and flea beetles and grubs an insecticidally effective amount of a compound of the formula
Description
llSlV64 AS WIRE WORM AND FLEA BEETLE INSECTICIDES
AND GRUB INSECTICIDES
BACRGROUND OF THE INVENTION
The present invention relates to certain oxadiazole derivatives and their use as wire worm and flea beetle insecticides and grub insecticides.
British Patent 1,213,707 discloses insecticidal compounds of the general formula R10 Xl ~P--X2--A--~-R3 wherein Xl and X2, which may be the same or different, each represents an oxygen or sulfur atom; A represents an alkylene group; Rl represents an alkyl group, R2 repre-sents an alkyl or alkoxy group; and R3 represents a hydrogen atom or an optionally substituted carbamoyl or amino group. A particular species disclosed in the British Patent at Table 2, 9th compound from the top, is 3-(diethoxyphosphinothioylthiomethyl)-5-methyl-1,2,4-oxadiazole.
The examples of the British Patent show testing of certain of the compounds for insecticidal activity on adult houseflies; mosquito larvae, diamond back moth larvae, aphids and adult mustard beetles; red spider mites; and white butterfly larvae. None of these tests involved application and use of the insecticide in the soil habitat of the insects.
U.S. Patent 4,028,377 discloses insecticidal compounds of the general formula Rl~ -CH3-S-p~
wherein Rl represents hydrogen, unsubstituted alkyl, benzyl or phenyl, R2 represents methyl or ethyl, and R3 represents unsubstituted Cl-C7 alkyl optionally inter-rupted by oxygen or represents C3-C4 alkenyl.
The examples of the 4,028,377 patent show testing of certain of the compounds for insecticidal activity on ticks in cotton wool; larvae of ticks; mites;
and on root-gall-nematodes in soil. In the latter test, the soil infested with the root-gall-nematocides was treated with the compounds to be tested and then tomato seedlings were planted either immediately after the soil preparation or after 8 days waiting.
British Patent 1,261,158 discloses compounds of the general formula Rl O~X
~P-S-A-r~-- f( Y ) n The first compound disclosed in Table I of British Patent 1,261,158 is 5-(diethoxyphosphinothioylthiomethyl)-3-methylisoxazole. The compounds of the examples of British Patent 1,261,158 were tested for insecticidal effective-ness on flies, mosquito larvae, moth larvae, mustard beetles, aphids, spider mites and butterfly larvae.
U.S. Patent 3,432,519 discloses various oxadia-zoles with phosphate groups in the 5-position on the 01 oxadiazole ring. Example 2 discloses 3-methyl-5-chloro-methyl-1,2,4-oxadiazole. U.S. Patent 3,432,519 in Example 4 discloses that the last-named compound is used to destroy green flies, red spiders and caterpillars.
05 As described in the Ortho Seed Treater Manual copyrig~ 197~, Chevron Chemical Company, page 27, wire worms/have been controlled with a formulation comprising a mixture of Lindane (gamma isomer of benzene hexachloride) and Captan (n-l(trichloromethyl)thio]-4-cyclohexene-1,2-dicarboximide ) .
SUMMARY OF THE INVENTION
According to the present invention, there is provided a method for killing wire worms and/or flea beetles which comprises applying to the soil habitat of the wire worms and/or flea beetles an insecticidally effective amount of a compound of the formula N
Rl_c ~ -CH2XP-ZR2 (I) wherein Rl, R2 and R3 are alkyl of 1 to 4 carbon atoms;
and X, Y, Z and V are sulfur or oxygen.
Preferred compounds for use in this method include those wherein R2 and R3 are ethyl and, more preferably, wherein the compound is further defined in that Y is sulfur and Z and V are oxygen. Most preferably, the compound used is one wherein the compound is still further defined in that Rl is methyl and X is sulfur.
According to another alternative embodiment of the present invention there is provided a wire worm and/or a flea beetle insecticidal composition comprising a wire worm- and/or a flea beetle-insecticidally effective amount 115~064 01 of a compound of the formula I, wherein Rl, R2 and R3 are alkyl of 1 to 4 carbon atoms; and X, Y, Z and V are sulfur or oxygen; and a biologically inert carrier. Preferably, the compound used in this embodiment of the present 05 invention is 3-methyl-5-(diethoxyphosphorothioylthio-methyl)-1,2,4-oxadiazole.
- The term "wire worm" is used herein to include the larvae of click beetles and also to include "False wire wormsn. Click beetles are in the family Ela'eridae and the following genera in the Elateridae family are particularly preferred genera for the insecticidal method of the present invention: Melantus, Ctenicera, Conoderus, Limonius, Horistonotus, and Agriotes. False wire worms are in the family Tenibrionidae. The following genera in the Tenibrionidae family are particularly preferred genera against which the insecticidal method of the present invention is used: Eleodes, Blapstinus, and Embaphion.
The term "flea beetle" is used herein to mean the larvae of flea beetles of the genera Chrysomelidae.
The following genera in the Chrysomelidae family are particularly preferred genera against which the insecti-cidal method of the present invention is used:
Chaetocnema, Epitrix, Phvllotreta, and Systena.
According to the present invention, there is also provided a method for killing grubs which comprises applying to the soil habitat of the grubs an insecti-cidally effective amount of a compound of the formula I.
Preferred compounds for use in this embodiment include those wherein R2 and R3 are ethyl and, more preferably, wherein the compound is further defined in that Y is sulfur and Z and V are oxygen. Most preferably, the compound used is one wherein the compound is still further defined in that Rl is methyl and X is sulfur.
01 According to another alternative embodiment of the present invention, there is provided a grubs insecti-cidal composition comprising a grub-insecticidally effective amount of a compound of the formula I, wherein 05 Rl, R2 and R3 are alkyl of 1 to 4 carbon atoms; and X, Y, Z and V are sulfur or oxygen; and a biologically inert carrier. Preferably, the compound used in this embodiment of the present invention is 3-methyl-5-(diethoxyphosphoro-thioylthiomethyl)-1,2,4-oxadiazole.
The term ~grub" is used herein to mean the larvae of Scarab beetles. Scarab beetles are the family Scarabeidae. The following genera in the Scarabeidae family are particularly preferred genera against which the insecticidal method of the present invention is used; `
Popillia, Lachnostera, Premnotrvpes, Costelytra, Phyllo-phaga, Heteronychus and Diaprepes.
The compounds of the present invention may be prepared by subjecting 3-alkyl-5-chloromethyl-1,2,4-oxadiazoles (II) to a phosphorylation reaction.
The 3-alkyl-5-chloromethyl-1,2,4-oxadiazoles tII) were prepared by condensing the appropriate alkyl-amidoximes (obtained from nitriles -- see Chem. Revs. 61 155 (1961) with chloroacetyl chloride.
N-OH O N O
Rl ~ + Cl-C-CH2-Cl- ~Rl- ~ ~ -CH2-Cl (II) The 3-alkyl-5-chloromethyl-1,2,4-oxadiazoles were phosphorylated with phosphate salts of the general formula (III) to give (I) above:
Y M=K~Na~ and NH
M~X-P-ZRl X,Y = S and O
VR3 V,Z = S, O and NH
01 This last reaction can be carried out in a number of solvents, e.g., acetone, acetonitrile, ether, methanol, benzene, etc. Preferably, equimolar amounts of reactants are employed, although a small excess of either OS may be employed. Either reactant may be added to the other reactant in the solvent; however, it is preferred to add the solid phosphate salt to a solution of the 3-alkyl-5-chloromethyloxadiazole. The addition is carried out at temperatures in the range of 15-30C. Upon completion of addition of the salt, the temperature of the reaction is raised, preferably to the reflux temperature.
The reaction is generally complete in 1-5 hours. At completion of the reaction, the product reaction mixture is filtered to remove any insoluble salts. The filtrate is then stripped of solvent under reduced pressure to give crude 3-alkyl-5-(dialkoxyphos-phorothioylthiomethyl)-1,2,4-oxadiazole. The crude material can be purified by column chromatography (silica gel) and eluting with hydrocarbons and chlorinated hydrocarbons.
Example 1 -- Preparation Methods (a) Acetamidoxime -- Acetonitrile was added to a previously stirred solution of 0.55 mol hydroxylamine hydrochloride and 0.55 mol anhydrous sodium carbonate in 750 ml of absolute ethanol. This mixture was stirred for 0.5 hour at room temperature and then refluxed at 55-70C
for 24 hours. The reaction was cooled and filtered, the solid residue slurried in warm acetone and refiltered, the filtrates were combined and concentrated to an oil under reduced pressure. The oil was again taken up in acetone-ether to rid the system of dissolved inorganic salts. The acetone-ether filtrate was concentrated under reduced pressure, the oil was then triturated with ether-hexane leaving a white solid. Infrared (IR) and nuclear magnetic 01 resonance (NMR) elemental analysis indicated the acetamidoxime (m.p. 128-133C).
(b) 3-Methyl-5-Chloromethyl-1,2,4-Oxadiazole --Acetamidoxime (14.1 g) was placed in 200 ml of benzene in 05 a 3-necked, round-bottom flas~ equipped with a mechanical stirrer, condenser and dropping funnel charged with 23 9 of chloroacetyl chloride. The benzene slurry was increased in temperature to near reflux, and the chloro-acetyl chloride was added dropwise to the refluxing mixture. A Dean-Stark trap was added and refluxing continued for 3 hours. The reaction mixture was cooled and 100 ml benzene added, washed (3x125 ml) with water, dried with anhydrous MgSO4, and solvent removed under reduced pressure, leaving the desired product as an amber liquid (confirmed by IR, NMR and elemental analysis).
(c~ 3-MethYl-5-(diethoxyphosphorothioylthio-methyl)-1,2,4-oxadiazole -- 3-methyl-5-chloromethyl-1,2,4-oxadiazole (0.04 mol) was dissolved in acetone and ammonium O,O-diethyldithiophosphate (0.04 mol) was added with stirring in several portions. The reaction was then refluxed for 3 hours, cooled and filtered. The solvent was removed under reduced pressure leaving an amber oil which was chromatographed (silica gel) and eluted with hexane: methylene chloride (80%). The phosphate was obtained as an almost colorless oil.
Example 2 -- Compound Testing Against Wire Worms and Flea Beetles Larvae A granule containing 10% by weight of 3-methyl-5-(diethoxyphosphinothioylthiomethyl)-1,2,4-oxadiazole (the test compound) was distributed in the test field by a broadcast method. The field was then disced to incorpo-rate the granules to a depth of 4 to 5 inches in the soil. Dosage was at 3, 2, and 1 pound test compound per acre.
llS10~4 01 Next Julian Sweet potatoes were transplanted , into the treated plots known tG be infested with wire worms (Conoderus vespertinus and C. auritus), and flea beetles larvae (SYstena elongata). Four months later, the 05 sweet potatoes were harvested and were graded for number of roots damaged and/or scarred by wire worms and flea beetle larvae. The results are given in Table I.
1151~64 Q~
~, ~
o U~
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~ ~~ o ~U~ ~ o U ~_,_, ~ o v, m U~
O a o _I
O l- O O 1`
~ ~U~~ ~ O O ~, ~ J~
c: ~ a~
m o ~
~ aJ aJ
~n ,_ aJ ~
o ~q 1~ 3 ~ ~ o ~ t`~ as E~ U . . . U
a~ ~ ~ _~ ~7 ~ o m ~_, _, ~ ,, E-l oO3 ~ 111 ~ ~ O
S~ C
O
~ ~ ~ ~ ~ o a ~
o3 o ::~ a ~ m s~
~ U~
o .q .~, h U
c~
~ C ~ ~ ~ ~ ~ ~
O O ~ ~ ~ ~ ~ ~ S
¢ ¢l ~ C
E~
O O O O 0 10 ~ O
tQ ta s~
a ~ o :5 E~ E~ æ ~
U~ O U~ O
o O ~
1~510~i4 Examples 3 -- Compound Testing Against Grubs Two tests were carried out using 3-methyl-5(diethyoxyphosphino-thioylthiomethyl)-1,2,4-oxadiazole (test compound) to determine effective-ness for the control of grass grubs. In the first test, the test compound was applied directly to the insect, whereas in the second test, soil was treated with the test compound and then the insects were introduced into that soil.
Topical Application Third Instar Grassgrubs (Costelytra zealandica) having an average weight of 100.5 mg were contacted with the indicated amount of the test com-pound and were then checked periodically for effects. The test concentration and results are given in Table II.
TABLE II
Dosage Percent Affected Micrograms/insect 2 hours 3 days 7 days l 93 79 75 0.1 7 7 7 These results show that at 10 microgram/insect there is 100% con-trol, and at 1 microgram/insect there is still a 75% control.Soil Treatment _ ~ orotin silt loam, having 32% moisture content, was treated with an insecticide, either Lindan insecticide or the test compound, to give an aver-age actice concentration of 14 ppm in the soil (on a weight to weight basis).
Next 86 mm petri dishes were each firmly packed with 85 grams of this treated soil. Then 10 freshly collected Grassgrub beetles were placed in each petri dish , .
llS1064 01 which was then covered with an inverted petri dish to prevent es¢ape.
All of the beetles buried themselves in the soil within 10 minutes. Affected beetles subsequently re-os emerged. The number remaining on top of the soil at several time intervals were recorded. After 24 hours of exposure to the treated soil, all beetles were removed and placed onto untreated soil in covered dishes. The number of beetles remaining above the soil were again recorded.
These results are given in Table III.
The results in Table III show that the test compound has high insecticidal activity against the Grassgrub.
o ~1 ~ o o ~ ~ol ~ ,o, a~
R ~ ¦ cO ~ O
E- ~t ~o ~ o .~ ~
~ ~1 _~ O O ~ O
&~ ~I cn ~_ ~ O O
C~ ~ S: ~d u~ p ~d t:: ~ ~ h V~
E~
AND GRUB INSECTICIDES
BACRGROUND OF THE INVENTION
The present invention relates to certain oxadiazole derivatives and their use as wire worm and flea beetle insecticides and grub insecticides.
British Patent 1,213,707 discloses insecticidal compounds of the general formula R10 Xl ~P--X2--A--~-R3 wherein Xl and X2, which may be the same or different, each represents an oxygen or sulfur atom; A represents an alkylene group; Rl represents an alkyl group, R2 repre-sents an alkyl or alkoxy group; and R3 represents a hydrogen atom or an optionally substituted carbamoyl or amino group. A particular species disclosed in the British Patent at Table 2, 9th compound from the top, is 3-(diethoxyphosphinothioylthiomethyl)-5-methyl-1,2,4-oxadiazole.
The examples of the British Patent show testing of certain of the compounds for insecticidal activity on adult houseflies; mosquito larvae, diamond back moth larvae, aphids and adult mustard beetles; red spider mites; and white butterfly larvae. None of these tests involved application and use of the insecticide in the soil habitat of the insects.
U.S. Patent 4,028,377 discloses insecticidal compounds of the general formula Rl~ -CH3-S-p~
wherein Rl represents hydrogen, unsubstituted alkyl, benzyl or phenyl, R2 represents methyl or ethyl, and R3 represents unsubstituted Cl-C7 alkyl optionally inter-rupted by oxygen or represents C3-C4 alkenyl.
The examples of the 4,028,377 patent show testing of certain of the compounds for insecticidal activity on ticks in cotton wool; larvae of ticks; mites;
and on root-gall-nematodes in soil. In the latter test, the soil infested with the root-gall-nematocides was treated with the compounds to be tested and then tomato seedlings were planted either immediately after the soil preparation or after 8 days waiting.
British Patent 1,261,158 discloses compounds of the general formula Rl O~X
~P-S-A-r~-- f( Y ) n The first compound disclosed in Table I of British Patent 1,261,158 is 5-(diethoxyphosphinothioylthiomethyl)-3-methylisoxazole. The compounds of the examples of British Patent 1,261,158 were tested for insecticidal effective-ness on flies, mosquito larvae, moth larvae, mustard beetles, aphids, spider mites and butterfly larvae.
U.S. Patent 3,432,519 discloses various oxadia-zoles with phosphate groups in the 5-position on the 01 oxadiazole ring. Example 2 discloses 3-methyl-5-chloro-methyl-1,2,4-oxadiazole. U.S. Patent 3,432,519 in Example 4 discloses that the last-named compound is used to destroy green flies, red spiders and caterpillars.
05 As described in the Ortho Seed Treater Manual copyrig~ 197~, Chevron Chemical Company, page 27, wire worms/have been controlled with a formulation comprising a mixture of Lindane (gamma isomer of benzene hexachloride) and Captan (n-l(trichloromethyl)thio]-4-cyclohexene-1,2-dicarboximide ) .
SUMMARY OF THE INVENTION
According to the present invention, there is provided a method for killing wire worms and/or flea beetles which comprises applying to the soil habitat of the wire worms and/or flea beetles an insecticidally effective amount of a compound of the formula N
Rl_c ~ -CH2XP-ZR2 (I) wherein Rl, R2 and R3 are alkyl of 1 to 4 carbon atoms;
and X, Y, Z and V are sulfur or oxygen.
Preferred compounds for use in this method include those wherein R2 and R3 are ethyl and, more preferably, wherein the compound is further defined in that Y is sulfur and Z and V are oxygen. Most preferably, the compound used is one wherein the compound is still further defined in that Rl is methyl and X is sulfur.
According to another alternative embodiment of the present invention there is provided a wire worm and/or a flea beetle insecticidal composition comprising a wire worm- and/or a flea beetle-insecticidally effective amount 115~064 01 of a compound of the formula I, wherein Rl, R2 and R3 are alkyl of 1 to 4 carbon atoms; and X, Y, Z and V are sulfur or oxygen; and a biologically inert carrier. Preferably, the compound used in this embodiment of the present 05 invention is 3-methyl-5-(diethoxyphosphorothioylthio-methyl)-1,2,4-oxadiazole.
- The term "wire worm" is used herein to include the larvae of click beetles and also to include "False wire wormsn. Click beetles are in the family Ela'eridae and the following genera in the Elateridae family are particularly preferred genera for the insecticidal method of the present invention: Melantus, Ctenicera, Conoderus, Limonius, Horistonotus, and Agriotes. False wire worms are in the family Tenibrionidae. The following genera in the Tenibrionidae family are particularly preferred genera against which the insecticidal method of the present invention is used: Eleodes, Blapstinus, and Embaphion.
The term "flea beetle" is used herein to mean the larvae of flea beetles of the genera Chrysomelidae.
The following genera in the Chrysomelidae family are particularly preferred genera against which the insecti-cidal method of the present invention is used:
Chaetocnema, Epitrix, Phvllotreta, and Systena.
According to the present invention, there is also provided a method for killing grubs which comprises applying to the soil habitat of the grubs an insecti-cidally effective amount of a compound of the formula I.
Preferred compounds for use in this embodiment include those wherein R2 and R3 are ethyl and, more preferably, wherein the compound is further defined in that Y is sulfur and Z and V are oxygen. Most preferably, the compound used is one wherein the compound is still further defined in that Rl is methyl and X is sulfur.
01 According to another alternative embodiment of the present invention, there is provided a grubs insecti-cidal composition comprising a grub-insecticidally effective amount of a compound of the formula I, wherein 05 Rl, R2 and R3 are alkyl of 1 to 4 carbon atoms; and X, Y, Z and V are sulfur or oxygen; and a biologically inert carrier. Preferably, the compound used in this embodiment of the present invention is 3-methyl-5-(diethoxyphosphoro-thioylthiomethyl)-1,2,4-oxadiazole.
The term ~grub" is used herein to mean the larvae of Scarab beetles. Scarab beetles are the family Scarabeidae. The following genera in the Scarabeidae family are particularly preferred genera against which the insecticidal method of the present invention is used; `
Popillia, Lachnostera, Premnotrvpes, Costelytra, Phyllo-phaga, Heteronychus and Diaprepes.
The compounds of the present invention may be prepared by subjecting 3-alkyl-5-chloromethyl-1,2,4-oxadiazoles (II) to a phosphorylation reaction.
The 3-alkyl-5-chloromethyl-1,2,4-oxadiazoles tII) were prepared by condensing the appropriate alkyl-amidoximes (obtained from nitriles -- see Chem. Revs. 61 155 (1961) with chloroacetyl chloride.
N-OH O N O
Rl ~ + Cl-C-CH2-Cl- ~Rl- ~ ~ -CH2-Cl (II) The 3-alkyl-5-chloromethyl-1,2,4-oxadiazoles were phosphorylated with phosphate salts of the general formula (III) to give (I) above:
Y M=K~Na~ and NH
M~X-P-ZRl X,Y = S and O
VR3 V,Z = S, O and NH
01 This last reaction can be carried out in a number of solvents, e.g., acetone, acetonitrile, ether, methanol, benzene, etc. Preferably, equimolar amounts of reactants are employed, although a small excess of either OS may be employed. Either reactant may be added to the other reactant in the solvent; however, it is preferred to add the solid phosphate salt to a solution of the 3-alkyl-5-chloromethyloxadiazole. The addition is carried out at temperatures in the range of 15-30C. Upon completion of addition of the salt, the temperature of the reaction is raised, preferably to the reflux temperature.
The reaction is generally complete in 1-5 hours. At completion of the reaction, the product reaction mixture is filtered to remove any insoluble salts. The filtrate is then stripped of solvent under reduced pressure to give crude 3-alkyl-5-(dialkoxyphos-phorothioylthiomethyl)-1,2,4-oxadiazole. The crude material can be purified by column chromatography (silica gel) and eluting with hydrocarbons and chlorinated hydrocarbons.
Example 1 -- Preparation Methods (a) Acetamidoxime -- Acetonitrile was added to a previously stirred solution of 0.55 mol hydroxylamine hydrochloride and 0.55 mol anhydrous sodium carbonate in 750 ml of absolute ethanol. This mixture was stirred for 0.5 hour at room temperature and then refluxed at 55-70C
for 24 hours. The reaction was cooled and filtered, the solid residue slurried in warm acetone and refiltered, the filtrates were combined and concentrated to an oil under reduced pressure. The oil was again taken up in acetone-ether to rid the system of dissolved inorganic salts. The acetone-ether filtrate was concentrated under reduced pressure, the oil was then triturated with ether-hexane leaving a white solid. Infrared (IR) and nuclear magnetic 01 resonance (NMR) elemental analysis indicated the acetamidoxime (m.p. 128-133C).
(b) 3-Methyl-5-Chloromethyl-1,2,4-Oxadiazole --Acetamidoxime (14.1 g) was placed in 200 ml of benzene in 05 a 3-necked, round-bottom flas~ equipped with a mechanical stirrer, condenser and dropping funnel charged with 23 9 of chloroacetyl chloride. The benzene slurry was increased in temperature to near reflux, and the chloro-acetyl chloride was added dropwise to the refluxing mixture. A Dean-Stark trap was added and refluxing continued for 3 hours. The reaction mixture was cooled and 100 ml benzene added, washed (3x125 ml) with water, dried with anhydrous MgSO4, and solvent removed under reduced pressure, leaving the desired product as an amber liquid (confirmed by IR, NMR and elemental analysis).
(c~ 3-MethYl-5-(diethoxyphosphorothioylthio-methyl)-1,2,4-oxadiazole -- 3-methyl-5-chloromethyl-1,2,4-oxadiazole (0.04 mol) was dissolved in acetone and ammonium O,O-diethyldithiophosphate (0.04 mol) was added with stirring in several portions. The reaction was then refluxed for 3 hours, cooled and filtered. The solvent was removed under reduced pressure leaving an amber oil which was chromatographed (silica gel) and eluted with hexane: methylene chloride (80%). The phosphate was obtained as an almost colorless oil.
Example 2 -- Compound Testing Against Wire Worms and Flea Beetles Larvae A granule containing 10% by weight of 3-methyl-5-(diethoxyphosphinothioylthiomethyl)-1,2,4-oxadiazole (the test compound) was distributed in the test field by a broadcast method. The field was then disced to incorpo-rate the granules to a depth of 4 to 5 inches in the soil. Dosage was at 3, 2, and 1 pound test compound per acre.
llS10~4 01 Next Julian Sweet potatoes were transplanted , into the treated plots known tG be infested with wire worms (Conoderus vespertinus and C. auritus), and flea beetles larvae (SYstena elongata). Four months later, the 05 sweet potatoes were harvested and were graded for number of roots damaged and/or scarred by wire worms and flea beetle larvae. The results are given in Table I.
1151~64 Q~
~, ~
o U~
~J _,. . . . . ~
~ ~~ o ~U~ ~ o U ~_,_, ~ o v, m U~
O a o _I
O l- O O 1`
~ ~U~~ ~ O O ~, ~ J~
c: ~ a~
m o ~
~ aJ aJ
~n ,_ aJ ~
o ~q 1~ 3 ~ ~ o ~ t`~ as E~ U . . . U
a~ ~ ~ _~ ~7 ~ o m ~_, _, ~ ,, E-l oO3 ~ 111 ~ ~ O
S~ C
O
~ ~ ~ ~ ~ o a ~
o3 o ::~ a ~ m s~
~ U~
o .q .~, h U
c~
~ C ~ ~ ~ ~ ~ ~
O O ~ ~ ~ ~ ~ ~ S
¢ ¢l ~ C
E~
O O O O 0 10 ~ O
tQ ta s~
a ~ o :5 E~ E~ æ ~
U~ O U~ O
o O ~
1~510~i4 Examples 3 -- Compound Testing Against Grubs Two tests were carried out using 3-methyl-5(diethyoxyphosphino-thioylthiomethyl)-1,2,4-oxadiazole (test compound) to determine effective-ness for the control of grass grubs. In the first test, the test compound was applied directly to the insect, whereas in the second test, soil was treated with the test compound and then the insects were introduced into that soil.
Topical Application Third Instar Grassgrubs (Costelytra zealandica) having an average weight of 100.5 mg were contacted with the indicated amount of the test com-pound and were then checked periodically for effects. The test concentration and results are given in Table II.
TABLE II
Dosage Percent Affected Micrograms/insect 2 hours 3 days 7 days l 93 79 75 0.1 7 7 7 These results show that at 10 microgram/insect there is 100% con-trol, and at 1 microgram/insect there is still a 75% control.Soil Treatment _ ~ orotin silt loam, having 32% moisture content, was treated with an insecticide, either Lindan insecticide or the test compound, to give an aver-age actice concentration of 14 ppm in the soil (on a weight to weight basis).
Next 86 mm petri dishes were each firmly packed with 85 grams of this treated soil. Then 10 freshly collected Grassgrub beetles were placed in each petri dish , .
llS1064 01 which was then covered with an inverted petri dish to prevent es¢ape.
All of the beetles buried themselves in the soil within 10 minutes. Affected beetles subsequently re-os emerged. The number remaining on top of the soil at several time intervals were recorded. After 24 hours of exposure to the treated soil, all beetles were removed and placed onto untreated soil in covered dishes. The number of beetles remaining above the soil were again recorded.
These results are given in Table III.
The results in Table III show that the test compound has high insecticidal activity against the Grassgrub.
o ~1 ~ o o ~ ~ol ~ ,o, a~
R ~ ¦ cO ~ O
E- ~t ~o ~ o .~ ~
~ ~1 _~ O O ~ O
&~ ~I cn ~_ ~ O O
C~ ~ S: ~d u~ p ~d t:: ~ ~ h V~
E~
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method for killing wire worms or flea beetles which comprises applying to the soil habitat of the wire worms or flea beetles an insecticidally effective amount of a compound of the formula wherein R1, R2 and R3 are alkyl of 1 to 4 carbon atoms;
and X, Y, Z and V are sulfur or oxygen.
and X, Y, Z and V are sulfur or oxygen.
2. A method in accordance with Claim 1 wherein R2 and R3 are ethyl.
3. A method in accordance with Claim 2 wherein Y is sulfur and Z and V are oxygen.
4. A method in accordance with Claim 3 wherein R1 is methyl and X is sulfur.
5. A method for killing grubs which comprises applying to the soil habitat of the grubs an insectici-dally effective amount of a compound of the formula .
wherein R1, R2 and R3 are alkyl of 1 to 4 carbon atoms;
and X, Y, Z and V are sulfur or oxygen.
wherein R1, R2 and R3 are alkyl of 1 to 4 carbon atoms;
and X, Y, Z and V are sulfur or oxygen.
6. A method in accordance with Claim 5 wherein R2 and R3 are ethyl.
7. A method in accordance with Claim 6 wherein Y is sulfur and Z and V are oxygen.
8. A method in accordance with Claim 7 wherein R1 is methyl and X is sulfur.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/143,567 US4308261A (en) | 1980-04-25 | 1980-04-25 | Substituted oxadiazoles and their use as wire worm and flea beetle insecticides |
US143,566 | 1980-04-25 | ||
US143,567 | 1980-04-25 | ||
US06/143,566 US4308260A (en) | 1980-04-25 | 1980-04-25 | Substituted oxadiazoles and their use as grub insecticides |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1151064A true CA1151064A (en) | 1983-08-02 |
Family
ID=26841167
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000374489A Expired CA1151064A (en) | 1980-04-25 | 1981-04-02 | Substituted oxadiazoles and their use as wire worm and flea beetle insecticides and grub insecticides |
Country Status (5)
Country | Link |
---|---|
AU (1) | AU6952881A (en) |
CA (1) | CA1151064A (en) |
DE (1) | DE3116449A1 (en) |
FR (1) | FR2481070A1 (en) |
GB (1) | GB2074450B (en) |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1451294A (en) * | 1965-05-18 | 1966-01-07 | Rhone Poulenc Sa | New phosphoric esters, their preparation and use |
US4237121A (en) * | 1979-06-14 | 1980-12-02 | Chevron Research Company | Substituted oxadiazoles and their use as corn root worm insecticides |
-
1981
- 1981-04-02 CA CA000374489A patent/CA1151064A/en not_active Expired
- 1981-04-14 GB GB8111820A patent/GB2074450B/en not_active Expired
- 1981-04-14 AU AU69528/81A patent/AU6952881A/en not_active Abandoned
- 1981-04-23 FR FR8108100A patent/FR2481070A1/en active Pending
- 1981-04-24 DE DE19813116449 patent/DE3116449A1/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
GB2074450B (en) | 1983-04-07 |
AU6952881A (en) | 1981-10-29 |
FR2481070A1 (en) | 1981-10-30 |
DE3116449A1 (en) | 1982-01-21 |
GB2074450A (en) | 1981-11-04 |
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