WO2002098841A1 - Insecticides a base de biphenylthiohydrazides - Google Patents

Insecticides a base de biphenylthiohydrazides Download PDF

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Publication number
WO2002098841A1
WO2002098841A1 PCT/US2001/018237 US0118237W WO02098841A1 WO 2002098841 A1 WO2002098841 A1 WO 2002098841A1 US 0118237 W US0118237 W US 0118237W WO 02098841 A1 WO02098841 A1 WO 02098841A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
halogen
optionally substituted
groups
haloalkyl
Prior art date
Application number
PCT/US2001/018237
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English (en)
Inventor
Robert E. Diehl
David Allen Hunt
Susan Hensen Trotto
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to CA002450118A priority Critical patent/CA2450118A1/fr
Priority to PCT/US2001/018237 priority patent/WO2002098841A1/fr
Priority to EP01946108A priority patent/EP1406863A4/fr
Publication of WO2002098841A1 publication Critical patent/WO2002098841A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/58—Derivatives of thiocarboxylic acids, the doubly-bound oxygen atoms being replaced by nitrogen atoms, e.g. imino-thio ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/60—Thiocarboxylic acids having sulfur atoms of thiocarboxyl groups further doubly-bound to oxygen atoms

Definitions

  • Crop reduction due to said pests can range as high as 39% and 78%, respectively. Pest infestation can result in lower yields, lower crop quality, reduced consumption, increased perishability, increased risk of disease, higher processing cost, higher transportation cost and increased market prices. Therefore, new and effective insect and acarid control agents and crop protection methods are a continuing global need.
  • N- biphenylthiohydrazone derivatives which are effective agents for the control of pestiferous insects and especially, acarina.
  • the present invention provides novel N- biphenylhydrazone compounds of formula I
  • R is hydrogen, C ] _-C ] _oalkyl optionally substituted with one or more halogen,
  • (C 1 -C4haloalkyl) SOy phenyl optionally substituted with one to three halogen, C ⁇ -C 4 alkyl, C 1 -C 4 haloalkyl,
  • C ⁇ -C4alko y C -C4haloalkoxy, (C 1 -C 4 alkyl)S0 x , (C 1 -C4haloalkyl) SOy, NO2 or CN groups, or phenoxy optionally substituted with one to three halogen, C1-C4alkyl, C ⁇ -C4haloalkyl, C!-C4alko y,
  • C -C4haloalkyl C ⁇ -C4alkoxy, C ⁇ -C4haloalkoxy, (Cx-C alkyl ) SO x , (C 1 -C 4 haloalkyl)SO x , phenyl optionally substituted with one to three halogen, C2 . -C4alkyl Ci-C ⁇ haloalkyl, C ⁇ -C4alko y,
  • Rl2' C3-Cgcycloalkyl optionally substituted with one to three halogen
  • phenyl optionally substituted with one or more halogen, C 1 -C 4 alkyl, C ] _-C4haloalkyl, C ⁇ . -C4alko y, C ⁇ -C4haloalkoxy, N0 2 or CN groups, or pyridyl optionally substituted with one or more halogen, C 1 -C 4 alkyl, C ⁇ .-C4haloalkyl , C ⁇ -C4alko y,
  • R2 is hydrogen or C;j_-C4alk l ;
  • R 3 , R 4 , R5, Rg,and R7 are each independently hydrogen, halogen, CN, N0 2 , C ⁇ Cgalkyl, C]_-
  • R-13 R-14/ an -d 15 are each independently hydrogen or C]_- C 4 alkyl; X is 0, S or NR15;
  • R 16 is hydrogen, halogen or ⁇ C ⁇ alkyl; r is an integer of 0 or 1; p and q are each independently an integer of 0, 1, 2, or 3 with the proviso that only one of p, q, or r can be 0 and with the further proviso that the sum of p + q + r must be 4 , 5 or 6 ; and x is an integer of 0, 1 or 2 ; or the acid addition salts thereof.
  • these compounds can be used to advantage to combat mites of the species Tetranychus uri ticae (Koch) .
  • compounds of the present invention have been found to exhibit good activity against mite species which have developed resistance to existing commercial acaricides .
  • compounds of formula I not only possess acaricidal activity but also exhibit useful activity against insect pests including Spodoptera eridania, southern army worms; Diabrotica virgifera, western corn rootworms; Heliothis virescens , tobacco budworms; Aphis fabae, bean aphids, and Aphis gossypii , cotton aphids.
  • Preferred compounds of the invention are those compounds of formula I wherein R4 and Rg are each independently H or phenyl optionally substituted with one or more halogen, C- L -C ialoalkoxy, or C x -C 4 haloalkyl groups. More preferred compounds of the invention are those formula I compounds wherein R is C ⁇ , -Cgalkyl or C3 - Cgcycloalkyl optionally substituted with one to three halogens; R3 and R7 are each independently H or C]_- Cgalkoxy; and R4 and Rg are each independently H or phenyl optionally substituted with one or more halogen,
  • halogen denotes chlorine, fluorine, bromine or iodine.
  • haloalkyl notes an alkyl group, C n H2 n+ ⁇ which contains from one halogen atom to 2n+l halogen atoms.
  • haloalkoxy denotes a 0C n H2 n+ ⁇ group which contains from one to 2n+l halogen atoms.
  • the halogen atoms may be the same or different.
  • w acid addition salts denotes those salts formed by acids commonly known in the art such as hydrogen chloride, hydrogen bromide, hydrogen bisulfate, hemi-hydrogen sulfate and the like.
  • acids commonly known in the art such as hydrogen chloride, hydrogen bromide, hydrogen bisulfate, hemi-hydrogen sulfate and the like.
  • Those compounds of formula I wherein m is an integer of 1 or 2 may be prepared by the oxidation of the appropriate precursor using standard oxidizing reagents such as m-chloroperbenzoic acid (mcpba) , hydrogen peroxide and acetic acid, KMn0 , and the like in accordance with standard known reaction conditions, for instance, those described in U.S. 5,556,885. Typically this reaction is conducted at room temperature for periods of 1-4 days in a suitable solvent such as methylene chloride. This reaction is shown below flow diagram I .
  • mcpba m-chloroperbenzoic acid
  • the appropriate N-biphenylthio- hydrazide of formula IV may be reacted with the appropriate alkyl halide in the presence of a suitable base to give the desired N-biphenylthiohydrazone compounds of formula la.
  • the base utilized can be either organic or inorganic, and typically is sodium or potassium carbonate.
  • Suitable solvents include those such as acetone, and typically the reaction is conducted at reflux temperature thereof for periods of about ⁇ to 4 hours . This reaction is illustrated below in flow diagram III .
  • Compounds of formula II may be prepared by reacting triphenylphosphine and carbon tetrachloride with the corresponding biphenyl hydrazide of formula V.
  • the formula II compound may be prepared by heating the appropriate formula V biphenyl hydrazide with phosphorus pentachloride, and treating the reaction mixture sequentially with carbon tetrachloride and phenol. These reactions are illustrated below in flow diagram V.
  • formula II compounds may be prepared using conventional literature methods such as those described by Tanaka Kiyoshi, Maeno Seiji, and Mitsuhashi Keiryo in the Journal of Heterocyclic Chemistry, 22 (1985), pp. 565- 568.
  • compounds of formula V may be readily prepared by conventional methods such as those described in WO 93/10083.
  • Growing or harvested crops may be protected from attack or infestation by insect or, particularly, acarid pests by applying to the foliage of the crops, or to the soil or water in which they are growing, a pesticidally effective amount of N-biphenylthiohydrazone derivative of formula I .
  • a pesticidally effective amount of N-biphenylthiohydrazone derivative of formula I In actual agronomic practice, generally about 10 ppm to 10,000 ppm, and preferably about 100 to 5,000 ppm, of the formula I compound is dispersed in a liquid carrier. When applied to the plants or the soil or water in which they are growing, these amounts are effective to protect the plants from insect and acarina attack and infestation.
  • compositions of the invention are generally effective at rates which provide about 0.125 kg/ha to about 250 kg/ha, preferably about 10 kg/ha to 100 kg/ha of active ingredient .
  • the rate of application may be dependent upon the prevailing environmental circumstances such as population density, degree of infestation, stage of plant growth, soil conditions, weather conditions and the like.
  • the formula I compounds may be used in conjunction with, or in combination with, other biological and chemical control agents including insecticides, nematicides, acaricides, molluscicides, and fungicides.
  • Insecticides may include nuclear polyhedrosis viruses, pyrroles, arylpyrroles, halobenzoylureas, pyrethroids, carbamates, phosphates, and similar conventional insect agents.
  • compositions suitable for the formula I N- biphenylthiohydrazone derivatives are sprays, granular compositions, flowable compositions, wettable powders, dusts, microemulsions, emulsifiable concentrates or any conventional agricultural composition. All compositions which lend themselves to soil, water and foliage application and provide effective plant protection are suitable.
  • Compositions of the invention include the I N- biphenylthiohydrazone derivative of formula I admixed with an agriculturally acceptable solid or liquid carrier. Where compositions of the invention are to be employed in combination treatments with other biological or chemical agents, the composition may be applied as an admixture of the components or may be applied sequentially to the target pest and/or crop.
  • the combination composition comprising a formula I compound and a co-pesticide may also comprise other components, for example, fertilizers, inert formulation aides such as surfactants, emulsifiers, defoamers, dyes, extenders and the like.
  • a suspension of 5-phenyl-o-anisidine (10 g, 50.0 mmol) in water and hydrochloric acid (concentrated, 180 ml) is cooled to 0° C, treated dropwise with a 0° C solution of sodium nitrite (3.45 g, 50.0 mmol) in water, stirred for one hour, treated with a -20° C solution of tin chloride (45.2 g,238 mmol) in concentrated hydrochloric acid (80 ml) , stirred for one hour at 0° C and filtered.
  • the filter cake is mixed with hot water and filtered.
  • the filtrate is cooled and filtered to obtain the title product, as beige crystals, in 64.3% yield, mp 184-186° C.
  • a suspension of (4-methoxy-3-biphenylyl) hydrazine, hydrochloride (25.07 g, 100 mmol) in methylene chloride is treated with triethylamine (21.25 g, 210 mmol).
  • a solution of trimethylacetyl chloride (12.06 g,100 mmol) in methylene chloride is added dropwise to the reaction mixture and stirred for four hours at room temperature. After pouring the reaction mixture into water, the mixture is extracted with ethyl acetate, and the extract washed with 15% hydrochloric acid, water, and a saturated aqueous solution of sodium chloride, dried over sodium sulfate and filtered.
  • Lawesson's reagent (4.14 g,103 mmol) is added to a solution of 2 , 2-dimethylthiopropionate, 2- (5-fluoro-4- methoxy-3 -biphenylyl) hydrazide (6.33 g,20 mmol) in toluene and the reaction mixture heated to 80 °C . After approximately three hours at 80° C, the reaction mixture is cooled to room temperature and filtered. The filtrate is concentrated in vacuo to give an oily residue which was purified by silica gel flash chromatography. The title product is obtained, as a white solid (4.1 g) in 61.7% yield, mp 96-97° C. Identity is confirmed by ⁇ N R, 13 CNMR, and IR.
  • Methyl iodide (0.78 g, 5.5 mmol) is added slowly to a suspension of 2 , 2 -dimethylthiopropionate- , 2- (5-fluoro- 4 -methoxy-3 -biphenylyl) hydrazide (1.6 g, 5 mmol) and potassium carbonate (0.76 g, 5.5 mmol) in acetone at reflux. After three hours, the reaction mixture is cooled, poured into water, and extracted with ethyl acetate. The extract is washed with water and saturated aqueous sodium chloride solution, dried over sodium sulfate and filtered. The filtrate is concentrated in vacuo to afford the title product as a yellow oil, (1.7 g) in 98.3% yield. Identity is confirmed by X HNMR, 13 CNMR, and IR .
  • test solutions are prepared by dissolving the test compound in a 35% acetone in water mixture to give a concentration of 10,000 ppm (4,000 ppm for cotton aphids) . Subsequent dilutions are made with water as needed. Spodoptera eridania, 3rd instar larvae, southern armyworm (SAW)
  • a Sieva limabean leaf expanded to 7-8 cm in length is dipped in the test solution with agitation for 3 seconds and allowed to dry in a hood.
  • the leaf is then placed in a 100 x 10 mm petri dish containing a damp filter paper on the bottom and ten 3rd instar caterpillars. At 5 days, observations are made of mortality, reduced feeding, or any interference with normal molting.
  • WCR Diabrotic virgifera vergifera Leconte, 3rd instar western corn rootworm
  • One cc of fine talc is placed in a 30 ml wide- mouth screw-top glass jar.
  • One mL of the appropriate acetone test solution is pipetted onto the talc so as to provide 1.25 mg of active ingredient per jar.
  • the jars are set under a gentle air flow until the acetone is evaporated.
  • the dried talc is loosened, 1 cc of millet seed is added to serve as food for the insects and 25 ml of moist soil is added to each jar.
  • the jar is capped and the contents thoroughly mixed on a Vortex Mixer.
  • Cotton cotyledons are dipped in the test solution and allowed to dry in a hood. When dry, each is cut into quarters and ten sections are placed indi- vidually in 30 mL plastic medicine cups containing a 5 to 7 mm long piece of damp dental wick. One 3rd instar caterpillar is added to each cup and a cardboard lid placed on the cup. Treatments are maintained for 3 days before mortality counts and estimates of reduction in feeding damage are made.
  • Tetranychus urticae OP-resistant strain
  • TMS 2-spotted spider mite
  • Sieva limabean plants with primary leaves expanded to 7-8 cm are selected and cut back to one plant per pot.
  • a small piece is cut back to one plant per pot.
  • a small piece is cut from an infested leaf taken from the main colony and placed on each leaf of the test plants. This is done about 2 hours before treatment to allow the mites to move over to the test plant to lay eggs. The size of the cut, infested leaf is varied to obtain about 100 mites per leaf.
  • the piece of leaf used to transfer the mites is removed and discarded.
  • the newly mite-infested plants are dipped in the test solution for 3 seconds with agitiation and set in the hood to dry. After 2 days, one leaf is removed and mortality counts are made. After 5 days, another leaf is removed and observations are made of mortality of the eggs and/or newly emerged nymphs .
  • Pots containing single nasturtium plants (Tropaeolum sp . ) about 5 cm tall are infested with about 100-200 aphids one day before the test.
  • Each pot is sprayed with the test formulation for 2 revolutions of a 4 rpm turntable in a hood, using a #154 DeVilbiss atomizer.
  • the spray tip is held about 15 cm from the plant and the spray directed so as to give complete coverage of the plants and the aphids.
  • the sprayed pots are set on their sides on white enamel trays and held for 2 days, following which mortality estimates are made.
  • Aphis gossypii (cotton aphid)
  • a heavily infested leaf is placed on top of a cotton plant which had been grown to the cotyledon stage.
  • the aphids are allowed to transfer from the leaf section to the host plant overnight.
  • the resultant infested leaves of the intact plant are dipped into the test solution and then allowed to dry.
  • Aphid mortality counts are made after the test plants have been maintained under GRO-LUX ® lights (24 hour photoperiod) at 27-28° C for 5 days. Phytotoxicity to the cotton plant is also recorded at this time.
  • a heavily infested leaf is placed on top of a cotton plant which had been grown to the cotyledon stage.
  • the aphids are allowed to transfer from the leaf section to the host plant overnight.
  • the resultant infested leaves of the intact plant are dipped into the test solution and then allowed to dry.
  • Aphid mortality counts are made after the test plants have been maintained under GRO-LUX lights (24 hour photoperiod) at 27-28°C for 5 days. Phytotoxicity to the cotton plant is also recorded at this time.
  • Sieva limabean plants with primary leaves expanded to 7-8 cm are selected and cut back to one plant per pot .
  • a small piece is cut from an infested leaf taken from the main colony and placed on each leaf of the test plants. This is done about 2 hours before treatment to allow the mites to move over to the test plant to lay eggs.
  • the size of the cut, infested leaf is varied to obtain about 100 mites per leaf.
  • the piece of leaf used to transfer the mites is removed and discarded.
  • the newly mite-infested plants are dipped in the test solution for 3 seconds with agitation and set in the hood to dry. After 2 days, one leaf is removed and mortality counts are made. After 5 days, another leaf is removed and observations are made of mortality of the eggs and/or newly emerged nymphs .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

La présente invention concerne des dérivés N-biphénylthiohydrazone représentés par la formule (I). L'invention concerne également des compositions et les procédés d'emploi correspondant, d'une part contre les insectes et acariens nuisibles, et d'autre part pour protéger les récoltes contre ces nuisibles.
PCT/US2001/018237 2001-06-05 2001-06-05 Insecticides a base de biphenylthiohydrazides WO2002098841A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA002450118A CA2450118A1 (fr) 2001-06-05 2001-06-05 Insecticides a base de biphenylthiohydrazides
PCT/US2001/018237 WO2002098841A1 (fr) 2001-06-05 2001-06-05 Insecticides a base de biphenylthiohydrazides
EP01946108A EP1406863A4 (fr) 2001-06-05 2001-06-05 Insecticides a base de biphenylthiohydrazides

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2001/018237 WO2002098841A1 (fr) 2001-06-05 2001-06-05 Insecticides a base de biphenylthiohydrazides

Publications (1)

Publication Number Publication Date
WO2002098841A1 true WO2002098841A1 (fr) 2002-12-12

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PCT/US2001/018237 WO2002098841A1 (fr) 2001-06-05 2001-06-05 Insecticides a base de biphenylthiohydrazides

Country Status (3)

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EP (1) EP1406863A4 (fr)
CA (1) CA2450118A1 (fr)
WO (1) WO2002098841A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5556885A (en) * 1994-10-27 1996-09-17 American Cyanamid Company N-aryl- and N-heteroarylhydrazones of substituted thioacids and the s-oxides thereof as insecticidal and acaricidal agents

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3930112A1 (de) * 1989-09-09 1991-03-21 Hoechst Ag N-arylhydrazone enthaltende pflanzenschuetzende mittel und neue n-arylhydrazone
US6242647B1 (en) * 1998-12-03 2001-06-05 American Cyanamid Company Insecticidal biphenylthiohydrazides

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5556885A (en) * 1994-10-27 1996-09-17 American Cyanamid Company N-aryl- and N-heteroarylhydrazones of substituted thioacids and the s-oxides thereof as insecticidal and acaricidal agents

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1406863A4 *

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EP1406863A4 (fr) 2005-06-15
CA2450118A1 (fr) 2002-12-12
EP1406863A1 (fr) 2004-04-14

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