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(11) Patent Number: KE 175
(45) Date of grant: 08/10/2008
(12) PATENT
(51) Int.Cl.7: A 01N 43/40
(21) Application Number: 2000/000152
(22) Filling Date: 19/05/2000
(30)Priority Data: 09/321737 28/05/1999 us
(87)PCT details: WO OO/72680    07/12/2000
 
(73) Owner: VALENT U.SA CORPORATION, 1333 NORTH CALIFORNIA BOULEVARD SUITE 600 WALNUT CREEK, CA 94596,
U.S.A.
(72) Inventor: KINCADE, Robert, T. and East David
(74) Agent/address for correspondence: Hamilton Harrison & Mathews, P.O. Box 30333-00100, Nairobi
 
(54) Title: INSECTICIDAL COMPOSITION AND METHOD FOR THE USE THEREOF
(57) Abstract:
An insecticidal composition includes (I) at least one compound of formula (1) wherein RI is bromine, chlorine, methyl, or ethyl, R2 is bromine, chlorine, or ethyl, R3 is hydrogen, halogen, or trifluoromethyl, Xis -0-, -S-, or -NH-, and n is 2, 3, or 4, and (2) at least one compound of formula (II) wherein R and RI independently are an alkyl, alkenyl, or alkynyl group containing up to carbon atoms, R2 ishydrogen, an alkyl group containing 1 to 18 carbon atoms, a cycloalkyl group containing 3 to 8 carbon atoms, an alkenyl group containing 2 to 18 carbon atoms, or an alkylnyl group containing 3 to 18 carbons atoms, A3 is hydrogen or an alkyl group containing 1 to 6 carbon atoms, and Y is -0- or -5-. A method for killing insects such as the tobacco budworm and other Lepidoptera pests of cotton includes applying an insecticidally effective amount of such a composition to an area to be treated.

 
 

 
INSECTICIDAL COMPOSITION AND
METHOD FOR THE USE THEREOF
                                                     FIELD OF THE INVENTION
The present invention is directed to an insecticidal composition and to a method for the use thereof. In particular, the present invention is directed to an insecticidal composition which takes advantage of the synergistic action of two particular insecticides and to a method of using the composition to kill insects such as the tobacco budworm and other Lepidopteran pests of cotton.

BACKGROUND OF THE INVENTION
The tobacco budworm and other Lepidopteran insects are IC    serious pests of cotton fruit (squares and bolls). Moderate or heavy infestations can dramatically reduce lint yields.
The tobacco budworm, Heliothis virescens and cotton bollworm, Helicoverpa zea, have developed resistance to major classes of insecticides used to control them, as discussed in Martin et al., Effects of Selected Synergists on Insecticide Toxicity in Tobacco Budworm (Lepidoptera: Noctuidae) in Laboratory and Field Studies," J. Econ. Entomol. 90(3)723-731 (1997), Kanga at al., "Tolerance to Cypermethrin and Endosulfan in Field Populations of the Bollworm (Lepidoptera: Noctuidae) from Texas," J. Econ. Entomol. 89(3)583-589 (1996), Kanga et al., "Monitoring for Resistance to Organophosphorus, Carbamate, and Cyclodiene Insecticides in Tobacco Budworm Adult (Lepidopteria: Noctuidae), J. Econ. Entomol. 88(5)1144-1149 (1995), and Elzen et al., Resistance to Pyrethroids, Carbamate, and Organophosphate Insecticides in Field Populations of Tobacco Budworms (Lepidoptera: Noctuidae) in 1990," J. Econ. Entomol.
 85(6):2064-2072 (1992).
New and better control alternatives are always needed to maintain crop production and provide alternative chemistry for rotation purposes, as discussed in Laws, Delta Agricultural Digest, Intertec Publishing (1998).
While the compositions in the art have provided some control of Lepidopteran pests of cotton, there has been a need in the art for significantly greater control.
                                  SUMMARY OF THE INVENTION
An object of the present invention is to provide significantly greater control of tobacco budworm, cotton bollworm, and other Lepidopteran pests of cotton than has been provided previously in the art.
Accordingly, the present inventors conducted extensive experimentation and, as a result, they achieved the present invention, which provides a novel and highly effective, multi-chemistry alternative that provides synergistic results for the control of Lepidopteran insects on cotton and other crops on which they might be present.
 In particular, the present invention is directed to an insecticidal composition comprising (1) at least one compound of formula (I):
 
 

 
wherein R1, is bromine, chlorine, methyl, or ethyl, R2 is bromine, chlorine, or ethyl, R3 is hydrogen, halogen, or trifluoromethyl, X is -0-, -S-, or -NH-, and n is 2, 3, or 4, and (2) at least one compound of formula (II):
 

 wherein R and R1 independently are an alkyl, alkenyl, or alkynyl group containing up to 6 carbon atoms, R2 is hydrogen, an alkyl group containing 1 to 18 carbon atoms, a cycloalkyt group containing 3 to 8 carbon atoms, an alkenyl group containing 2 to 18 carbon atoms, or an alkynyl group containing 3 to 18 carbon atoms, R3 is hydrogen or an alkyl group containing 1 to 6 carbon atoms, and Y is -0- or -S-.
 DETAILED DESCRIPTION OF THE INVENTION
One component of the composition of the present invention is a compound of formula (I):

 
 
wherein R1 is bromine, chlorine, methyl, or ethyl, R2 is bromine, chlorine, or ethyl, R3 is hydrogen, halogen, or trifluoromethyl, X is -0-, - S-, or -NH-, and n is 2, 3, or 4, This compound and methods for its preparation are described in detail in WO 96/11909, which is incorporated herein by reference.
A particularly preferred compound within formula (I) is one in which R, is chlorine, R2 is chlorine, R3 is hydrogen, X is -0-, and n is 3, i.e., 2-[3-[2,6-dichloro-4-(3,3-dichloroprop-2-enyloxy)phenoxy]propoxy]- 5-(trifluoromethyl)pyridine (which has been revised from 3,5-dichloro-4- (3-(5-trifluoromethyt-2-pyridyloxy)propyloxy)-1 -(3,3-di chioro-2-
propenyloxy)benzene).

A compound of formula (I) can be prepared by the following method.
A compound of formula (a)
                            R1                                  0Cl
                                                                                                                   (a)
                 HX (CH2)n                                                                 Cl
                               O             R2
wherein R1, is bromine, chlorine, methyl, or ethyl, R2 is bromine, chlorine, or ethyl, X is -0-, -9-, or -NH-, and n is 2, 3, or 4, is reacted with a compound of formula (b)

                               F
                       F                                             R3(b)
                              F
                                                       N              L
Where R3 is hydrogen, halogen, or trifluoromethyl and L is halogen (e.g., chlorine, bromine, or iodine), mesyloxy, or tosyloxy.


The reaction is preferably effected in an inert solvent in the presence of a suitable base.
Examples of the solvent which can be used are ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethers such as 1,2-dimethoxyethane, tetrahydrofuran, dioxane and dialkyl (e.g., C1-C4) ethers (e.g., diethyl ether, diisopropyl ether); N,N-dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, sulforane, acetonitrile, nitromethane; halogenated hydrocarbons such as dichioromethane, chloroform, 1,2-dichloroethane and chlorobenzene; hydrocarbons such as toluene, benzene and xylene; and water. If necessary, a mixture of these solvents can be used.
Examples of the base which can be used are hydroxides of alkali metals or alkaline earth metals, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; carbonates of alkali metals or alkaline earth metals, such as lithium carbonate, potassium carbonate, sodium carbonate and calcium carbonate; hydrides of alkali metals or alkaline earth metals, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride; alkali metal alkoxides (e.g., C1-C4) such as sodium methoxide,sodium ethoxide and potassium tertbutOxide; and organic bases such as triethylamine and pyridine. If necessary, catalysts such as ammonium salts (e.g., triethylbenzy lammonium chloride) may be added to the reaction system at a ratio of 0.01 to 1 mole per mole of the compound of formula (a).
The reaction temperature is usually set within the range of -20°C to 150°C or the boiling point of a solvent used in the reaction, preferably -5°C to 100°C or the boiling point of a solvent used in the reaction.
The molar ratio of the starting materials and dehydrating agents to be used in the reaction can be freely determined, but it is favorable to effect the reaction at an equimolar ratio or a ratio closer thereto.
After completion of the reaction, the reaction mixture is subjected to ordinary post-treatments such as organic solvent extraction and concentration, and the desired compound of the present invention can be isolated. Further, purification can be carried out by an ordinary technique such as chromatography, distillation or recrystallation.
Another component of the composition of the present invention is a compound of formula (II):
 
wherein R and R1 independently are an alkyl, alkenyl, or alkynyl group containing up to 6 carbon atoms, R2 is hydrogen, an alkyl group containing 1 to 18 carbon atoms, a cycloalkyl group containing 3 to 8 carbon atoms, an alkenyl group containing 2 to 18 carbon atoms, or an alkynyl group containing 3 to 18 carbon atoms, R° is hydrogen or an alkyl group containing 1 to 6 carbon atoms, and Y is -0- or -S-. This compound and methods for its preparation are described in detail in U.S. Patents 3,176,600, 3,845,172, and 3,914,417, which are incorporated herein by reference.
A preferred compound within formula (II) is one in which R and R1 independently are a methyl, ethyl, ally' or alkenyl group, R2 is 10 hydrogen or an alkyl group, R3is hydrogen, and Y is -0-.

A particularly preferred compound within formula (II) is one in which R, R1 and R2 are methyl groups, R° is hydrogen, and Y is -0-. This compound is known as acephate and is commercially available, e.g., from the Chevron Chemical Company under the trade name Orthene®.
The composition of the present invention comprises a mixture of at least one compound of formula (I) and at least one compound of formula (11). A particularly preferred composition of the present invention comprises a mixture of 24342,6-dichloro-4-(3,3-dichloroprop-2-enyloxy)phenoxy]propoxy1-5-(trifluoromethyl)pyriciine    (hereinafter referred to as ''S-1812" for convenience) and acephate.
In the composition of the present invention, the ratio of the compound of formula (I): the compound of formula (II) can vary preferably from 1:3.3 to 1:127.8, more preferably from 1:3.3 to 1:64, even more preferably from 1:3.3 to 1:15, on a parts by weight basis. For example, the ratio of S-1812: acephate can vary from 1 part S-1812:5 parts acephate to 1 part S-1812:127.8 parts acephate. As an example within this range, the ratio of S-1812: acephate can vary from 1 part S-1812:16 parts acephate to 1 part 5-1812:127.8 parts acephate. As another example within this range, the ratio of S-1812: acephate can vary from 1 part S-1812:5 parts acephate to 1 part S-1812:10 parts acephate.
Other components which can be present in the invention composition include emulsifiers and solvents. For example, an emulsifiable concentrate formulation of S-1812 can be prepared using anionic-nonionic emulsifier blends such as Atlox 3454 and Atlox 3455, manufactured by Uniqema (formerly ICI Surfactants), and an aromatic hydrocarbon solvent such as Solvasso 150, manufactured by Exxon Chemical Company. When added to water, this formulation of S-1812 forms a solution containing 8-1812 which can then be added to an acephate-containing solution to form a solution of the composition of the present invention.
Once formulated, the invention composition is useful in a method for controlling Lepidopteran insects by application of the composition onto the insecticidal habitat. In general, the invention
composition can be applied onto the habitat in an amount effective to be insecticidal to the insects.
In the solution application of the present invention, the invention composition can be dissolved in from about 3 gallons to about 10 gallons of water for application per acre, such that preferably at least about 0.063 lb and 0.5 lb of active ingredient (compounds of formula (I) and formula (II), respectively), more preferably from about 0.063 lb and 0.5 lb to about 0.1 lb and 0.75 lb of active ingredient is applied per acre.
The composition of the present invention has been demonstrated in the laboratory and in the field to be highly effective against Lepidopteran insects, bollworm, beet armyworm, soybean     looper, and tarnished plant bug, providing synergistic results as compared with the performance of the individual active ingredients. As a result, the present invention provides excellent control of Lepidopteran pests of cotton and other crops on which they might occur.
The following examples illustrate specific embodiments of the present invention, but should not be construed as limiting the scope of the claims in any way. All parts, percents, ratios and the like are by weight unless otherwise indicated.
 
EXAMPLES
Example 1
An S-1812-containing formulation identified as 'S-1812 0.83E0" was prepared by mixing the following components (w/v%):
 S-1812 (active ingredient)    10.3%
Atlox 3454F (emulsifier)    2.0%
Atlox 3455F (emulsifier)    8.0%
Solvesso 150 (solvent)    79.7%
Total    100.0%

As set forth above, 8-1812 0.83EC has 10.3% ai on a w/v% basis, i.e., 0.83 lb ai/gallon [(0.1 g ai/mI)(3785 m1/1gallon)(1 lb/454 g)].
0.2g of S-1812 0.83EC was added to 800 nil distilled H2O and stirred to give a 25 ppmai (parts per million active ingredients) solution. This solution was serially diluted by 300 ml stock/300 ml distilled H2O to yield solution concentrations of 12.5, 6.25 and 3.13 ppmai.
0.02g of acephate (Orthene, technical grade, 98% pure) was added to 50 ml of S-1812 6.25 ppmai stock and 50 ml of 5-1812 3.13 ppmal stock to give 400 ppmai acephate + 6.25 ppmai S-1812, and 400 ppmai acephate + 3.13 ppmai S-1812 mixtures.
The above procedure was repeated with 0.01g of acephate to yield 200 ppmai acephate + 6.25 or 3.13 ppmai S-1812 mixtures.
 
The procedure set forth in the preceding paragraph was repeated with 100 ml of S-1812 3.13 or 6.25 ppmai stock to yield 100 ppmai acephate + 6.25 or 3.13 ppmai 5-1812 mixtures.
Solutions of acephate alone of the various concentrations were prepared in a similar manner using distilled I-120.
The testing substrate was composed of 2.0 ml of prepared artificial tobacco budworm diet mix (Bio-Sere) dispensed into the bottom of a clear one ounce cup. The diet was dispensed in such a way that the surface when dry was level and smooth (no pits).
0.2 ml of the test mixture was pipetted onto the surface of the diet. The treated diet was placed under a fume hood to dry the test solution onto the diet surface (approximately one hour).
After drying, one second mater tobacco budworm larvae was placed into each cup, and the cup was seated with a tight fitting, but not airtight, lid. The cups were held at 25°C and 50% RH and evaluated after seven days. Larvae were rated as dead or alive at this point. There were 20 replicates per treatment with one cup = one replication.



The results of this testing are shown in Table 1 below.
 
TABLE 1: SYNERGISM BETWEEN ORTHENE AND S-1812
IN A LABORATORY EXPERIMENT WITH SECOND
I NSTAR TOBACCO BUDWORM LARVAE
S-1812&    Increase
Orthene    S-1812    In %
Ppm ai    Mortality of
S-1812    Orthene Additive    +    Mixture Mixture
8-1812 %    Orthene %    %    Orthene %              Over
Ppm Mortality Ppm alMortality Mortality Ppm aiMortality Additive
(Mixture)
3.135 1001015  3.13+100 35  


3.135 200 5103.13+20025
3.135 40030353.13+40075
6.2530 10010   406.25+10065

 6.2530 2005                   53        6.25+200           65

 6.25  30 400   3060         6.25+400           100

    
As can be seen from the results presented above in Table 1, the compounds of formulas (I) and (II) act synergistically together to increase the mortality rate beyond the sum of the rates for the compounds individually and thereby provide unexpectedly superior control of a Lepidopteran pest.
Example 2
Spray treatments were applied by a tractor mounted (highboy) spray boom to cotton field plots in Greenville, Mississippi that measured 40-50 ft by 13.2 ft by 13.2 ft with 3-4 replications per
treatment: Treatments were applied at 10 gallons of spray volume per acre. Tank-mixes were made by measuring both compounds independently and then adding them to the appropriate amount of water to produce the spray mixture. Treatments were applied in July/August at approximately one week intervals.
Plots were evaluated by sampling all damaged and undamaged bolls on 10 plants per plot. Cotton plots were evaluated for yield by machine picking the center two rows of each plot. The results are shown in Table 2 below.
 
 UTC = untreated cotton
Curacron = profenofos
Larvin = thiodicarb
Asana XL = esfenvalerate
Karate = lambda cyhalothrin
Orthene = acephate
EC = emulsifiable concentrate
FL = flowable concentrate
SP = soluble powder
BEC has 8 lb ai/gallon
3.2FL has 3.2 lb ai/gallon .66EC has 0.66 lb al/gallon
1 .0EC has 1.0 lb ai/gallon
90SP has 90% ai on a per weight basis
.83EC has 0,83 lb ai/gallon
CV = Coefficient of Variation (a statistic for comparison of like experiments)
LSD = Fishers Least Significant Difference (a statistical method of comparing two means for significant difference by providing the smallest valid difference)
 
As can be seen from the data presented above in Table 2, a mixture of compounds of formulas (I) and (II) provides unexpectedly superior results with respect to reducing the percentage of damaged bolls, providing a higher number of bolls per plant, and providing a higher yield in pounds of seed cotton per acre as compared with the use of compounds of formulas (I) and (II) individually and as compared with the use of other insecticides.
Example 3
Additional testing was conducted against a variety of 10 Lepidopteran pests as shown-in Table 3 below.
    
Trt = treatment
UTC = untreated cotton
WP = wettable powder
SP = soluble powder
SC = soluble concentrate
35 WP has 35% al on a per weight basis
90 SP has 90% ai on a per weight basis
4 SC has 4 lb ai/gallon
FOSP = foliar spray method
GOSHJ = cotton
SPOEI = beet armyworm, Spodoptera exigua
TRINI = cabbage looper, Trichoplusia ni
LYGL1= Tarnished plant bug, Lygus lineolaris
COCCI = lady bird beetles
GEOPU = big eyed bug
CHRCA = lace wings
ARACH = spider
PDSQ = percent damaged cotton squares
NOTF = number per 10 row feet using beat cloth sampling method
NOSW = number per swing of a sweep net
NOSP = number of cotton bolls (fruits) per cotton plant
PDBO = percent damaged cotton bolls

6 DA-A = 6 days after application A
Tracer = Spinosyn A+ Spinosyn D
CV = Coefficient of Variation
LSD = Fisher's Least Significant Difference
A treatment is a particular insecticide or insecticide mixture being tested.

The number of replicates or replications is the number of times a treatment is identically repeated within the same test (for example, tested on 3-4 plots in a field test).
 
As can be seen from the results presented above in Table 3, the mixture of compounds as in the present invention again provided unexpectedly superior results as compared with the compounds individually and as compared with another insecticidal Mixture.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
 
AMENDED CLAIMS
[received by the International Bureau on 25 September 2000 (25.09.00); original claims 1-10 amended; other claims unchanged (2 pages)]
What is claimed is:
1.    An insecticidal composition comprising synergistically insecticidally effective amounts of (1) at least one compound of formula (I):
 

 wherein R, is bromine, chlorine, methyl, or ethyl, R2 is bromine, chlorine, or ethyl, R3 is .hydrogen, halogen or trifitioromethyl, X is -0-, -S-, or -NH-, and n is 2, 3, or 4, and (2) at least one compound of formula (II):
 
wherein R and R1 independently are an alkyl, alkenyl, or alkynyl group containing up to 6 carbon atoms, R2 is hydrogen, an alkyl group containing 1 to 18 carbon atoms, a cycloalkyl group containing 3 to carbon atoms, an alkenyl group containing 2 to 18 carbon atoms, or an alkynyl group containing 3 to 18 carbon atoms, A3 is hydrogen or an alkyl group containing 1 to 6 carbon atoms, and Y is -0- or -S-.
 
7. An insecticidal composition as in claim 6, wherein (A) the 2-[3-[2, 6-dichl o ro-4-(3, 3-dichloroprop-2-enyl oxy)phenoxy]propoxy1-5- (trifluoromethyl)pyridine and (B) the acephate are present in an (A):(B) ratio of 1:5 to 1:127.8 on a parts by weight basis.
8. An insecticidal composition as in claim 7, wherein (A) the 2-p-[2,6-dichloro-4-(3,3-dichloroprop-2-enyloxy)phenoxy]propoxyl-5- (trifluoromethyl)pyridine and (B) the acephate are present in an (A):(B) ratio of 1:16 to 1:127.8 on a parts by weight basis.
9. An insecticidal composition as in claim 7, wherein (A) the 2-[312,6-dichloro-4-(3,3-dichloroprop-2-enyloxy)phenoxyjpropoxy]-5- (trifluorarnethyl)pyritine and (B) the acephate are present in an (A):(B) ratio of 1:5 to 1:10 on a parts by weight basis.
10. A method for killing Lepidopteran insects, comprising applying to an area to be treated synergistically insecticidally effective amounts of a composition comprising (1) at least one compound of formula (I):

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