Insecticidal substituted benzylamino heterocyclic and heteroaryl derivatives

Information

  • Patent Grant
  • 8193118
  • Patent Number
    8,193,118
  • Date Filed
    Friday, May 19, 2006
    18 years ago
  • Date Issued
    Tuesday, June 5, 2012
    12 years ago
Abstract
Certain substituted benzylamino heterocyclic and heteroaryl derivatives have provided unexpected insecticidal and acaricidal activity. These compounds are represented by formula (I): wherein R, R1, R2, R3, and R4 are fully described herein. In addition, compositions comprising an insecticidally effective amount of at least one compound of formula (I), and optionally, an effective amount of at least one of an additional compound, with at least one insecticidally compatible carrier are also disclosed; along with methods of controlling insects comprising applying said compositions to a locus where insects are present or are expected to be present.
Description
FIELD OF THE INVENTION

The present invention generally relates to pesticidal compounds and their use in controlling insects and acarids. In particular, it pertains to compositions of pesticidal substituted benzylamino heterocyclic and heteroaryl derivatives and agriculturally acceptable salts thereof, and methods for their use in controlling insects and acarids.


BACKGROUND OF THE INVENTION

It is well known that insects in general can cause significant damage, not only to crops grown in agriculture, but also, for example, to structures and turf where the damage is caused by soil-borne insects, such as termites and white grubs. Such damage may result in the loss of millions of dollars of value associated with a given crop, turf or structure. Although there are many orders of insects that can cause significant crop damage, insects, for example, of the order “Homoptera” are of major importance. The order Homoptera includes, for example, aphids, leafhoppers, cicadas, whiteflies, and mealybugs. Homoptera have piercing/sucking mouthparts, enabling them to feed by withdrawing sap from vascular plants. Insect damage from Homoptera is manifested in several different ways, other than damage caused by direct feeding. For example, many species excrete honeydew, a sticky waste product that adheres to plants upon which the insect feeds and lives. Honeydew alone causes cosmetic injury to crop plants. Sooty molds will often grow on honeydew, making food products or ornamental plants look unappealing, thereby reducing their cosmetic and economic value. Some Homoptera have toxic saliva that is injected into plants while they are feeding. The saliva can cause plant damage through disfigurement and in some instances plant death. Homoptera can also vector disease-causing pathogens. Unlike direct damage, it does not take a large number of disease-vectoring insects to cause considerable damage to crop plants.


Thus, there is a continuing demand for new insecticides, and for new acaricides that are safer, more effective, and less costly. Insecticides and acaricides are useful for controlling insects and acarids which may otherwise cause significant damage both above and below the soil level to crops such as wheat, corn, soybeans, potatoes, and cotton to name a few. For crop protection, insecticides and acaricides are desired which can control the insects and acarids without damaging the crops, and which have no deleterious effects to mammals and other living organisms.


A number of articles and patents disclose some substituted benzylamino heterocyclic and heteroaryl compounds that are reported to have pesticidal uses. For example, the Journal of Insect Science, 3:4 (available online: insectscience.org/3.4) reports the effectiveness of some octopamine agonists to suppress the calling behavior of the Indian meal moth, Plodia interpunctella. Included in the studies are compounds of the following structure:




embedded image



wherein

  • R is alkyl or two halogen atoms.


Pesticide Science, 55:119-128 (1999), describes the quantitative structure-activity studies of octopaminergic ligands against the migratory locust, Locusta migratoria and the American cockroach, Periplaneta Americana. Included in the studies are compounds of the formulae:




embedded image



in which

  • R for formula (AAT) includes benzyl, and benzyl substituted with methyl, trifluoromethyl or one to two halogen atoms, and R for formula (AAO) includes phenyl substituted with trifluoromethyl or one to two halogen atoms.


Pesticide Science, 1995, 43 311-315 describes the quantitative structure-activity studies of some octopaminergic agonists against Periplaneta Americana. Included in the studies are compounds of the formula:




embedded image



wherein

  • R is hydrogen, methyl, trifluoromethyl, methoxy or one to two halogen atoms.


Bioscience, Biotechnology, and Biochemistry (1992), 56(7), 1062-5 describes the synthesis and octopaminergic activity of 2-(substituted benzylamino)-2-thiazolines.


European Journal of Medicinal Chemistry (1980), 15(1), 41-53, describes the synthesis of new “benzyl”-thiourea derivatives and their cyclic analogs with diuretic and saluretic activity.


U.S. Pat. No. 4,195,092 discloses 2-(substituted amino)-N-(3-substituted phenyl)-2-imidazoline-1-carbothioamides, useful as insecticides, of the following formula:




embedded image



wherein

  • R1 includes phenylalkyl, containing no more than about 18 carbon atoms, in which the phenyl moiety is optionally substituted with from one to three groups selected from C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, trifluoromethyl, halo, and cyano;
  • R2, R3, R4, and R5 independently are selected from hydrogen, C1-C3 alkyl, and phenyl;
  • R6 represents halo, trifluoromethyl, cyano, or 1,1,2,2-tetrafluoroethoxy;
  • R7 represents hydrogen, C1-C3 alkyl, or halo.


International Publication Number WO 91/05473 discloses fungicidal compositions, compounds, and their production and use of the following formulae:




embedded image



wherein

  • R1 and R7 are each independently hydrogen or C1-C3 allyl, R2 is hydrogen or C1-C6 alkyl, R3 and R4 independently, and each R5 independently are hydrogen or C1-C4 alkyl, R6 is a cyclohexyl group or a monocyclic or bicyclic aromatic group, substituted with from 1 to 5 groups of the formula R8, wherein R8 is halogen, a C1-C10 alkyl group, a C1-C10 alkoxy group, a tri-C1-C4-alkylsilyl group, or a phenoxy, phenyl, phenyl-C1-C2-alkylene, or phenyl-C2-alkenyene group, each optionally substituted on the phenyl or phenoxy group with one or more of halogen atoms, C1-C6 alkyl or C1-C6 alkoxy groups, trihalomethyl groups, phenyl groups or phenoxy groups. p is 0, 1, or 2, Y is a group of the formula —C(R9R9)n—, wherein n is 2, 3, or 4, each R9 independently is hydrogen or C1-C4 alkyl and X is a suitable counter-ion, together with an agriculturally acceptable carrier or diluent.


There is no disclosure or suggestion in any of the above-referenced patents or publications of the insecticidal activity of the compounds of the present invention against members of the order “Homoptera”. In addition, there is no disclosure or suggestion in any of the above-referenced patents or publications of the structures of the novel compounds of the present invention.


SUMMARY OF THE INVENTION

The present invention generally relates to insecticidal and acaricidal compositions of substituted benzylamino heterocyclic and heteroaryl derivatives and to certain new and useful compounds, namely certain substituted benzylamino heterocyclic and heteroaryl derivatives that are surprisingly active in the control of insects and acarids when used in the insecticidal and acaricidal compositions and methods of this invention. The insecticidal and acaricidal compositions of the present invention are comprised of at least one of an insecticidally effective amount of a compound of formula I and at least one insecticidally compatible carrier therefor, wherein the compound of formula I is:




embedded image



wherein

  • R, R1, R2 and R5 are described in detail below;
  • R4 is selected from:




embedded image


  • R3 is described in detail below or is taken together with the connecting atom in R4 to form a double bond as in formula (B), formula (D) and formula (F); and


    agriculturally acceptable salts thereof.



The present invention also includes compositions containing a pesticidally effective amount of at least one compound of formula I, and optionally, an effective amount of at least one additional compound, with at least one pesticidally compatible carrier.


The present invention also includes methods of controlling insects in an area where control is desired, which comprise applying a pesticidally effective amount of the above composition to the locus of crops, buildings, soil or other areas where insects are present or are expected to be present.







DETAILED DESCRIPTION OF THE INVENTION

The present invention generally relates to insecticidal and acaricidal compositions of substituted benzylamino heterocyclic and heteroaryl derivatives and to certain new and useful compounds, namely certain substituted benzylamino heterocyclic and heteroaryl derivatives that are surprisingly active in the control of insects and acarids when used in the insecticidal and acaricidal compositions and methods of this invention. The insecticidal and acaricidal compositions of the present invention are comprised of at least one of an insecticidally effective amount of a compound of formula I and at least one insecticidally compatible carrier therefor, wherein the compound of formula I is:




embedded image



wherein

  • R, R1, R2 and R5 are described in detail below;
  • R4 is selected from:




embedded image


  • R3 is described in detail below or is taken together with the connecting atom in R to form a double bond as in formula (B), formula (D) and formula (F); and


    agriculturally acceptable salts thereof.



More specifically, preferred species of this invention are those insecticidal compositions comprised of compounds of formula IA:




embedded image



wherein

  • R is selected from 1-naphthyl, phenyl or phenyl substituted with one or two substituents selected from halogen, (C1-C2) alkyl, (C1-C2) alkoxy, (C1-C2) haloalkyl and phenyl;
  • R1 is selected from hydrogen, (C1-C2) alkyl, (C1-C2) hydroxyalkyl and (C1-C2) haloalkyl;
  • R2 is selected from hydrogen and (C1-C2) alkyl; and
  • R3 is selected from hydrogen, (C1-C2) alkyl,




embedded image



where


X is oxygen or sulfur;


R7 and R8 are (C1-C2) alkoxy;


R13 is (C1-C2) alkyl;


R14 is hydrogen;


a is 2;


R15 is (C1-C2) dialkylamino;


R16 is hydrogen, (C1-C2) alkyl or (C1-C2) alkoxy; and


R19 is (C1-C2) alkyl or (C1-C2) alkoxy;


provided that




  • when R is 1-naphthyl and R3 is hydrogen, then R1 and R2 are other than (C1-C2) alkyl.



More preferred species in this aspect of the invention are those insecticidal compositions comprised of compounds of formula Ia where

  • R is 2,3-dichlororphenyl or 2,3-dimethylphenyl;
  • R1 is hydrogen or methyl; and
  • R2 and R3 are hydrogen.


In another aspect of this invention, preferred species are those insecticidal compositions comprised of formula IB:




embedded image



wherein

  • R is 1-naphthyl, phenyl or phenyl substituted with one or two substituents selected from halogen or (C1-C2) alkyl;
  • R1 is selected from hydrogen, (C1-C4) alkyl and (C1-C2) haloalkyl;
  • R2 is hydrogen;
  • R5 is selected from cyano, (C1-C2) alkoxy(C1-C2) alkyl, 4-(C1-C2) alkoxybenzyl,




embedded image


where

    • X is oxygen or sulfur;
    • R7 and R8 are (C1-C2) alkoxy or (C1-C2) haloalkyl;
    • R10 is hydrogen;
    • R11 is (C1-C4) alkyl;
    • R13 is (C1-C2) alkyl;
    • R14 is hydrogen or (C1-C2) alkyl;
    • a is 2;
    • R15 is (C1-C2) alkyl or (C1-C2) dialkylamino;
    • R16 is (C1-C2) alkyl or (C1-C2) alkoxy; and
    • R19 is (C1-C2) alkyl or (C1-C2) alkoxy;


      provided that
  • when R is 1-naphthyl and R5 is formula (5) where X is sulfur, R13 is methyl and R14 is hydrogen, then R1 is other than (C1-C2) alkyl; and
  • when R is 3-chloro-2-methylphenyl and R1 is hydrogen, then R5 is other than formula (5) where X is oxygen, R13 is methyl and R14 is hydrogen or formula (6)


where a is 2 and R15 is methyl.


More preferred species in this aspect of the invention are those insecticidal compositions comprised of compounds of formula IB where

  • R is 2,3-dichlorophenyl, 2,3-dimethylphenyl or 3-chloro-2-methylphenyl;
  • R1 is hydrogen; and
  • R5 is cyano, formula (1), formula (5) or formula (7).


In another aspect of this invention, preferred species are those insecticidal compositions comprised of formula IC:




embedded image



where

  • R is selected from 1-naphthyl, 2-(C1-C2) alkoxyphenyl, 3-(C1-C2) alkoxyphenyl, 4-(C1-C2) alkoxyphenyl, 2,4-(C1-C2) dialkoxyphenyl, phenyl or phenyl substituted with one or two substituents selected from halogen, (C1-C2) alkyl and (C1-C2) haloalkyl;
  • R1 is selected from hydrogen, (C1-C3) alkyl, phenyl or benzyl;
  • R2 is hydrogen; and
  • R3 is selected from hydrogen, (C1-C2) alkyl,




embedded image


where

    • X is oxygen or sulfur;
    • R7 and R8 are (C1-C2) alkoxy;
    • R13 is (C1-C2) alkyl;
    • R14 is hydrogen;
    • a is 2;
    • R15 is (C1-C2) dialkylamino;
    • R16 is hydrogen, (C1-C2) alkyl or (C1-C2) alkoxy, and
    • R19 is (C1-C2) alkyl or (C1-C2) alkoxy;


      provided that
  • when R1 and R3 are hydrogen, then R is other than 2-methylphenyl, 2,4-dimethylphenyl or 2-chloro-6-methylphenyl;
  • when R is phenyl, R1 and R3 are methyl, then the compound is other than the ((1S)-1-phenylethyl)methyl-1,3-thiazolin-2-ylamine isomer;
  • when R is phenyl, R1 is methyl and R3 is hydrogen, then the compound is other than the ((1R)-1-phenylethyl)-1,3-thiazolin-2-ylamine isomer; and
  • when R is 2,3-dichlorophenyl and R1 is hydrogen, then R3 is other than formula (7) where X is oxygen and R16 is methoxy.


More preferred species in this aspect of the invention are those insecticidal compositions comprised of compounds of formula Ic where

  • R is 2,3-dichlororphenyl or 2,3-dimethylphenyl;
  • R1 is hydrogen or methyl; and
  • R3 is hydrogen or formula (7) where X is oxygen and R16 is (C1-C2) alkoxy.


In another aspect of this invention, preferred species are those insecticidal compositions comprised of formula ID:




embedded image


ID

where




  • R is phenyl optionally substituted with one or two substituents selected from halogen or (C1-C2) alkyl;

  • R1 and R2 are hydrogen; and

  • R5 is selected from





embedded image



where

    • X is oxygen or sulfur;
    • R7 and R8 are (C1-C2) alkoxy;
    • R13 is (C1-C2) alkyl;
    • R14 is hydrogen;
    • a is 2;
    • R15 is (C1-C2) dialkylamino;
    • R16 is hydrogen, (C1-C2) alkyl or (C1-C2) alkoxy; and
    • R19 is (C1-C2) alkyl or (C1-C2) alkoxy.


More preferred species in this aspect of the invention are those insecticidal compositions comprised of compounds of formula ID where

  • R is 2,3-dichlororphenyl, 2,3-dimethylphenyl;
  • R5 is formula (I) where X is sulfur or formula (7) where X is oxygen and R16 is (C1-C2) alkoxy.


In another aspect of this invention, preferred species are those insecticidal compositions comprised of formula IE:




embedded image



where

  • R is selected from 1-naphthyl, phenyl or phenyl substituted with one or two substituents selected from halogen, (C1-C2) alkyl and (C1-C2) haloalkyl;
  • R1 is selected from hydrogen, (C1-C3) alkyl, phenyl or benzyl;
  • R2 is hydrogen; and
  • R3 is selected from hydrogen, (C1-C2) alkyl,




embedded image


where

    • X is oxygen or sulfur;
    • R7 and R8 are (C1-C2) alkoxy-,
    • R13 is (C1-C2) alkyl;
    • R14 is hydrogen or (C1-C2) alkyl;
    • a is 2;
    • R15 is (C1-C2) alkyl or (C1-C2) dialkylamino;
    • R16 is hydrogen, (C1-C2) alkyl or (C1-C2) alkoxy; and
    • R19 is (C1-C2) alkyl or (C1-C2) alkoxy.


In another aspect of this invention, preferred species are those insecticidal compositions comprised of formula IF:




embedded image



where

  • R is phenyl optionally substituted with one or two substituents selected from halogen or (C1-C2) alkyl;
  • R1 and R2 are hydrogen; and
  • R5 is selected from cyano,




embedded image



where

    • X is oxygen or sulfur;
    • R7 and R8 are (C1-C2) alkoxy;
    • R13 is (C1-C2) alkyl;
    • R14 is hydrogen or (C1-C2) alkyl;
    • a is 2;
    • R15 is (C1-C2) alkyl or (C1-C2) dialkylamino;
    • R16 is hydrogen, (C1-C2) alkyl or (C1-C2) alkoxy, and
    • R19 is (C1-C2) alkyl or (C1-C2) alkoxy.


Certain of the substituted benzylamino heterocyclic and heteroaryl derivatives, useful in the compositions of the present invention, are novel compounds. Many of these compounds are represented by formula IG:




embedded image



wherein

  • R is selected from 1-naphthyl, phenyl or phenyl substituted with one or two substituents selected from halogen, (C1-C2) alkyl, (C1-C2) alkoxy, (C1-C2) haloalkyl and phenyl;
  • R1 is selected from hydrogen, (C1-C2) alkyl, (C1-C2) hydroxyalkyl and (C1-C2) haloalkyl;
  • R2 is selected from hydrogen and (C1-C2) alkyl; and
  • R3 is selected from hydrogen, (C1-C2) alkyl,




embedded image



where

    • X is oxygen or sulfur;
    • R7 and R8 are (C1-C2) alkoxy;
    • R13 is (C1-C2) alkyl;
    • R14 is hydrogen;
    • a is 2;
    • R15 is (C1-C2) dialkylamino;
    • R16 is hydrogen, (C1-C2) alkyl or (C1-C2) alkoxy; and
    • R19 is (C1-C2) alkyl or (C1-C2) alkoxy; and agriculturally acceptable salts thereof;


      provided that
  • when R1 is methyl and R2 and R3 are hydrogen, then R is other than phenyl;
  • when R is 1-naphthyl and R3 is hydrogen, then R1 and R2 are other than (C1-C2) alkyl; and
  • when R1, R2 and R3 are hydrogen, then R is other than 2-chlorophenyl, 2-fluorophenyl, 2-methylphenyl, 4-chlorophenyl, 3-trifluoromethylphenyl, 3,4-dichlorophenyl and 3,5-dichlorophenyl.


Other substituted benzylamino heterocyclic and heteroaryl derivatives, useful in the compositions of the present invention, are novel compounds. These compounds are represented by formula IH:




embedded image



wherein

  • R is 1-naphthyl, phenyl or phenyl substituted with one or two substituents selected from halogen or (C1-C2) alkyl;
  • R1 is selected from hydrogen, (C1-C4) alkyl and (C1-C2) haloalkyl;
  • R2 is hydrogen;
  • R5 is selected from cyano, (C1-C2) alkoxy(C1-C2) alkyl, 4-(C1-C2) alkoxybenzyl,




embedded image



where

    • X is oxygen or sulfur;
    • R7 and R8 are (C1-C2) alkoxy or (C1-C2) haloalkyl;
    • R10 is hydrogen;
    • R11 is (C1-C4) alkyl;
    • R13 is (C1-C2) alkyl;
    • R14 is hydrogen or (C1-C2) alkyl;
    • a is 2;
    • R15 is (C1-C2) alkyl or (C1-C2) dialkylamino;
    • R16 is (C1-C2) alkyl or (C1-C2) alkoxy;
    • R19 is (C1-C2) alkyl or (C1-C2) alkoxy; and


      agriculturally acceptable salts thereof;


      provided that
  • when R is 1-naphthyl and R5 is formula (5) where X is sulfur, R13 is methyl and R14 is hydrogen, then R1 is other than (C1-C4) alkyl; and
  • when R is 3-chloro-2-methylphenyl and R1 is hydrogen, then R5 is other than formula (5) where X is oxygen, R13 is methyl and R14 is hydrogen or formula (6) where R15 is methyl.


Still other substituted benzylamino heterocyclic and heteroaryl derivatives, useful in the compositions of the present invention, are novel compounds. These compounds are represented by formula IJ:




embedded image



where

  • R is selected from 1-naphthyl, 2-(C1-C2) alkoxyphenyl, 3-(C1-C2) alkoxyphenyl, 4-(C1-C2) alkoxyphenyl, 2,4-(C1-C2) dialkoxyphenyl, phenyl or phenyl substituted with one or two substituents selected from halogen, (C1-C2) alkyl and (C1-C2) haloalkyl;
  • R1 is selected from hydrogen, (C1-C3) alkyl, phenyl or benzyl;
  • R2 is hydrogen; and
  • R3 is selected from hydrogen, (C1-C2) alkyl,




embedded image




    • where

    • X is oxygen or sulfur;

    • R7 and R8 are (C1-C2) alkoxy;

    • R13 is (C1-C2) alkyl;

    • R14 is hydrogen;

    • a is 2;

    • R15 is (C1-C2) dialkylamino;

    • R16 is hydrogen, (C1-C2) alkyl or (C1-C2) alkoxy,

    • R19 is (C1-C2) alkyl or (C1-C2) alkoxy; and


      agriculturally acceptable salts thereof;


      provided that



  • when R is other than 2,3-dimethylphenyl, then at least one of R1 or R3 is other than hydrogen;

  • when R is phenyl, R1 and R3 are methyl, then the compound is other than the ((1S)-1-phenylethyl)methyl-1,3-thiazolin-2-ylamine isomer;

  • when R is phenyl, R1 is methyl R3 is hydrogen, then the compound is other than the ((1R)-1-phenylethyl)-1,3-thiazolin-2-ylamine isomer; and

  • when R is 2,3-dichlorophenyl and R1 is hydrogen, then R3 is other than formula (7) where X is oxygen and R16 is methoxy.



Other substituted benzylamino heterocyclic and heteroaryl derivatives, useful in the compositions of the present invention, are novel compounds. These compounds are represented by formula IK:




embedded image



where

  • R is phenyl optionally substituted with one or two substituents selected from halogen or (C1-C2) alkyl;
  • R1 and R2 are hydrogen; and
  • R5 is selected from




embedded image



where

    • X is oxygen or sulfur;
    • R7 and R8 are (C1-C2) alkoxy;
    • R13 is (C1-C2) alkyl;
    • R14 is hydrogen;
    • a is 2;
    • R15 is (C1-C2) dialkylamino;
    • R16 is hydrogen, (C1-C2) alkyl or (C1-C2) alkoxy;
    • R19 is (C1-C2) alkyl or (C1-C2) alkoxy; and


      agriculturally acceptable salts thereof.


Still other substituted benzylamino heterocyclic and heteroaryl derivatives, useful in the compositions of the present invention, are novel compounds. These compounds are represented by formula IL:




embedded image



where

  • R is selected from 1-naphthyl, phenyl or phenyl substituted with one or two substituents selected from halogen, (C1-C2) alkyl and (C1-C2) haloalkyl;
  • R1 is selected from hydrogen, (C1-C3) alkyl, phenyl or benzyl;
  • R2 is hydrogen; and
  • R3 is selected from hydrogen, (C1-C2) alkyl,




embedded image


where

    • X is oxygen or sulfur;
    • R7 and R8 are (C1-C2) alkoxy;
    • R13 is (C1-C2) alkyl;
    • R14 is hydrogen or (C1-C2) alkyl;
    • a is 2;
    • R15 is (C1-C2) alkyl or (C1-C2) dialkylamino;
    • R16 is hydrogen, (C1-C2) alkyl or (C1-C2) alkoxy; and
  • R19 is (C1-C2) alkyl or (C1-C2) alkoxy; and


    agriculturally acceptable salts thereof.


Other substituted benzylamino heterocyclic and heteroaryl derivatives, useful in the compositions of the present invention, are novel compounds. These compounds are represented by formula IM:




embedded image



where

  • R is phenyl optionally substituted with one or two substituents selected from halogen or (C1-C2) alkyl;
  • R1 and R2 are hydrogen; and
  • R5 is selected from cyano,




embedded image



where

    • X is oxygen or sulfur;
    • R7 and R8 are (C1-C2) alkoxy,
    • R13 is (C1-C2) alkyl;
    • R14 is hydrogen or (C1-C2) alkyl;
    • a is 2;
    • R15 is (C1-C2) alkyl or (C1-C2) dialkylamino;
    • R16 is hydrogen, (C1-C2) alkyl or (C1-C2) alkoxy and
  • R19 is (C1-C2) alkyl or (C1-C2) alkoxy, and


    agriculturally acceptable salts thereof.


In addition, in certain cases the compounds of the present invention may possess asymmetric centers, which can give rise to optical enantiomorphs and diastereomers. The compounds may exist in two or more forms, i.e., polymorphs, which are significantly different in physical and chemical properties.


The compounds of the present invention may exist as tautomers, in which migration of a hydrogen atom within the molecule results in two or more structures, which are in equilibrium. For example, compounds of formula I wherein R4 is selected from (A) and (B), (C) and (D) or (E) and (F) may exist in tautomeric forms as shown in formulae below. Such tautomerism is well known as is described in S. Patai (The Chemistry of Functional Groups: Amidines and Imidates, Vol 2, 1991, pages 259-262). It will be understood that all such tautomeric forms are embraced by the present invention.




embedded image


This invention includes the use of such enantiomorphs, polymorphs, tautomers, salts and metal complexes. Agriculturally acceptable salts and metal complexes include, without limitation, for example, ammonium salts, the salts of organic and inorganic acids, such as hydrochloric acid, sulfonic acid, ethanesulfonic acid, trifluoroacetic acid, methylbenzenesulfonic acid, phosphoric acid, gluconic acid, pamoic acid, and other acid salts, and the alkali metal and alkaline earth metal complexes with, for example, sodium, potassium, lithium, magnesium, calcium, and other metals.


The methods of the present invention are predicated on causing an insecticidally effective amount of a compound of formula I to be present within insects in order to kill or control the insects. Preferred insecticidally effective amounts are those that are sufficient to kill the insect. It is within the scope of the present invention to cause a compound of formula I to be present within insects by contacting the insects with a derivative of that compound, which derivative is converted within the insect to a compound of formula I. This invention includes the use of such compounds, which can be referred to as pro-insecticides.


Another aspect of the present invention relates to compositions containing an insecticidally effective amount of at least one compound of formula I with at least one insecticidally compatible carrier therefor.


Another aspect of the present invention relates to compositions containing an insecticidally effective amount of at least one compound of formula I, and an effective amount of at least one additional compound, with at least one insecticidally compatible carrier therefor.


Another aspect of the present invention relates to methods of controlling insects by applying an insecticidally effective amount of a composition set forth above to a locus of crops such as, without limitation, cereals, cotton, vegetables, and fruits, or other areas where insects are present or are expected to be present.


The present invention also includes the use of the compounds and compositions set forth herein for control of non-agricultural insect species, for example, dry wood termites and subterranean termites; as well as for use as pharmaceutical agents and compositions thereof. In the field of veterinary medicine, the compounds of the present invention are expected to be effective against certain endo- and ecto-parasites, such as insects and worms, which prey on animals. Examples of such animal parasites include, without limitation, Gastrophilus spp., Stomoxys spp., Trichodectes spp., Rhodnius spp., Ctenocephalides canis, and other species.


As used in this specification and unless otherwise indicated the substituent terms “alkyl” and “alkoxy”, used alone or as part of a larger moiety, includes straight or branched chains of at least one or two carbon atoms, as appropriate to the substituent; and preferably up to 12 carbon atoms, more preferably up to ten carbon atoms, most preferably up to seven carbon atoms. The term “alkenyl” and “alkynyl” used alone or as part of a larger moiety, includes straight or branched chains of at least two carbon atoms containing at least one carbon-carbon double bond or triple bond, and preferably up to 12 carbon atoms, more preferably up to ten carbon atoms, most preferably up to seven carbon atoms. The term “heterocyclic” refers to a non-aromatic ring structure of four to eight atoms consisting of carbon and nitrogen, and may include oxygen or sulfur. Five member rings include, without limitation, for example, oxazolidine and thiazoline. Six member rings include, without limitation, for example, piperazine, piperidine, morpholine and thiomorpholine. The term “aryl” refers to an aromatic ring structure, including fused rings, having four to ten carbon atoms, for example, phenyl or naphthyl and 5,6,7,8-tetrahydronaphthyl. The term “heteroaryl” refers to an aromatic ring structure, including fused rings, in which at least one of the atoms is other than carbon, for example, without limitation, sulfur, oxygen, or nitrogen. The term “brine” refers to an aqueous saturated sodium chloride solution. The term “TEA” refers to triethylamine. The term “THF” refers to tetrahydrofuran. The term “halogen” or “halo” refers to fluorine, bromine, iodine, or chlorine. The term “ambient temperature”, for example, in reference to a chemical reaction mixture temperature refers to a temperature in the range of 20° C. to 30° C. The term “insecticidal” or “acaricidal”, “insecticide” or “acaricide” refers to a compound of the present invention, either alone or in admixture with at least one of a second compound, or with at least one compatible carrier, which causes the destruction or the inhibition of action of insects or acarids.


The compounds of the present invention were prepared by methods generally known to those skilled in the art. A number of the compounds of the present invention were prepared in the manner shown in Scheme 1.




embedded image


As depicted in Scheme 1, the reaction of an appropriately substituted benzylamine (SM1) and 2-chloroethyl isocyanate (SM2) yielded the appropriately substituted benzyl 1,3-oxazolinyl amine, for example, ((2,3-dimethylphenyl)methyl)-1,3-oxazolin-2-ylamine, a compound of formula IA described in detail in Example 1 set forth below.


Scheme 2 provides a general method for the preparation of compounds of formula I in which the R5 substituent is other than hydrogen.




embedded image


As depicted in Scheme 2, the reaction of an appropriately substituted benzyl 1,3-oxazolinyl amine (a compound of formula IA) with acetic anhydride (SM3) under basic conditions, in an appropriate solvent yielded the corresponding 3-acetyl-2-substituted methylamino-1,3-oxazolidine, for example, 3-acetyl-(1-aza-2-(2,3-dimethylphenyl)ethylidene)-1,3-oxazolidine, a compound of formula IB described in detail in Example 2 set forth below.


Scheme 3 provides method for the preparation of compounds of formula IC.




embedded image


As depicted in Scheme 3, the reaction of a substituted benzylamine (SM4) and 2-chloroethyl isothiocyanate (SM5) yielded the appropriately substituted benzyl 1,3-thiazolinyl amine hydrochloride, for example, ((2,3-dichlorophenyl)methyl)-1,3-thiazolin-2-ylamine hydrochloride, a compound of formula IC described in detail in Example 3, Step A set forth below. Treatment of the hydrochloride of a compound of formula IC with a base in an appropriate solvent produced the corresponding substituted benzyl 1,3-thiazolinyl amine, for example ((2,3-dichlorophenyl)methyl)-1,3-thiazolin-2-ylamine, a compound of formula IC described in detail in Example 3, Step B set forth below.


Scheme 4 provides method for the preparation of compounds of formula IC and formula ID.




embedded image


As depicted in Scheme 4, the reaction of a disubstituted benzylamine, for example, 2,3-dimethylbenzylamine, and 2-chloroethyl isothiocyanate (SM5) yielded the appropriately substituted benzyl 1,3-thiazolinyl amine hydrochloride, for example, ((2,3-dimethylphenyl)methyl)-1,3-thiazolin-2-ylamine hydrochloride, a compound of formula IC described in detail in Example 4, Step A set forth below. Treatment of the hydrochloride of a compound of formula IC with a base in an appropriate solvent produced the corresponding substituted benzyl 1,3-thiazolinyl amine, for example ((2,3-dimethylphenyl)methyl)-1,3-thiazolin-2-ylamine, a compound of formula IC described in detail in Example 4, Step B set forth below. The reaction of the substituted benzyl 1,3-thiazolinyl amine with, for example, methyl chloroformate, under basic conditions yielded two compounds. The first, a compound of formula IC where the R3 substituent is other than hydrogen, for example, methyl 2-(1-aza-2-(2,3-dimethylphenyl)ethylidene)-1,3-thiazolidine-3-carboxylate, and the second, a compound of formula ID where the R5 substituent is other than hydrogen, for example, N-((2,3-dimethylphenyl)methyl)methoxy-N-(1,3-thiazolin-2-yl)carboxamide, both described in detail in Example 4, Step C set forth below.


Scheme 5 provides a general method for the preparation of compounds of formula I where the R1 substituent is other than hydrogen.




embedded image


As depicted in Scheme 5, the reaction of an appropriately substituted isomer of a phenylethylamine (SM7), for example, (S)-(−)-phenylethylamine, and 2-chloroethyl isocyanate (SM2) yielded the appropriately substituted phenylethyl 1,3-oxazolinyl amine, for example, ((S)-1-phenylethyl)-1,3-oxazolin-2-ylamine, a compound of formula IA described in detail in Example 5 set forth below.


One skilled in the art will, of course, recognize that the formulation and mode of application of a toxicant may affect the activity of the material in a given application. Thus, for agricultural use the present insecticidal compounds may be formulated as granules of relatively large particle size (for example, 8/16 or 4/8 US Mesh), as water-soluble or water-dispersible granules, as powdery dusts, as wettable powders, as emulsifiable concentrates, as aqueous emulsions, as solutions, or as any of other known types of agriculturally-useful formulations, depending on the desired mode of application. It is to be understood that the amounts specified in this specification are intended to be approximate only, as if the word “about” were placed in front of the amounts specified.


These insecticidal compositions may be applied either as water-diluted sprays, or dusts, or granules to the areas in which suppression of insects is desired. These formulations may contain as little as 0.1%, 0.2% or 0.5% to as much as 95% or more by weight of active ingredient.


Dusts are free flowing admixtures of the active ingredient with finely divided solids such as talc, natural clays, kieselguhr, flours such as walnut shell and cottonseed flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant; these finely divided solids have an average particle size of less than about 50 microns. A typical dust formulation useful herein is one containing 1.0 part or less of the insecticidal compound and 99.0 parts of talc.


Wettable powders, also useful formulations for insecticides, are in the form of finely divided particles that disperse readily in water or other dispersant. The wettable powder is ultimately applied to the locus where insect control is needed either as a dry dust or as an emulsion in water or other liquid. Typical carriers for wettable powders include Fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wet inorganic diluents. Wettable powders normally are prepared to contain about 5-80% of active ingredient, depending on the absorbency of the carrier, and usually also contain a small amount of a wetting, dispersing or emulsifying agent to facilitate dispersion. For example, a useful wettable powder formulation contains 80.0 parts of the insecticidal compound, 17.9 parts of Palmetto clay, and 1.0 part of sodium lignosulfonate and 0.3 part of sulfonated aliphatic polyester as wetting agents. Additional wetting agent and/or oil will frequently be added to a tank mix to facilitate dispersion on the foliage of the plant.


Other useful formulations for insecticidal applications are emulsifiable concentrates (ECs) which are homogeneous liquid compositions dispersible in water or other dispersant, and may consist entirely of the insecticidal compound and a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isphorone, or other non-volatile organic solvents. For insecticidal application these concentrates are dispersed in water or other liquid carrier and normally applied as a spray to the area to be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises 0.5 to 95% of active ingredient by weight of the insecticidal composition.


Flowable formulations are similar to ECs, except that the active ingredient is suspended in a liquid carrier, generally water. Flowables, like ECs, may include a small amount of a surfactant, and will typically contain active ingredients in the range of 0.5 to 95%, frequently from 10 to 50%, by weight of the composition. For application, flowables may be diluted in water or other liquid vehicle, and are normally applied as a spray to the area to be treated.


Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, but are not limited to, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; alkylaryl polyether alcohols; sulfated higher alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition product of long-chain mercaptans and ethylene oxide. Many other types of useful surface-active agents are available in commerce. Surface-active agents, when used, normally comprise 1 to 15% by weight of the composition.


Other useful formulations include suspensions of the active ingredient in a relatively non-volatile solvent such as water, corn oil, kerosene, propylene glycol, or other suitable solvents.


Still other useful formulations for insecticidal applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene, or other organic solvents. Granular formulations, wherein the toxicant is carried on relative coarse particles, are of particular utility for aerial distribution or for penetration of cover crop canopy. Pressurized sprays, typically aerosols wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low-boiling dispersant solvent carrier may also be used. Water-soluble or water-dispersible granules are free flowing, non-dusty, and readily water-soluble or water-miscible. In use by the farmer on the field, the granular formulations, emulsifiable concentrates, flowable concentrates, aqueous emulsions, solutions, etc., may be diluted with water to give a concentration of active ingredient in the range of say 0.1% or 0.2% to 1.5% or 2%.


The active insecticidal and acaricidal compounds of this invention may be formulated and/or applied with at least one additional compound. Such combinations may provide certain advantages, such as, without limitation, exhibiting synergistic effects for greater control of insect pests, reducing rates of application of insecticide thereby minimizing any impact to the environment and to worker safety, controlling a broader spectrum of insect pests, safening of crop plants to phytotoxicity, and improving tolerance by non-pest species, such as mammals and fish.


Additional compounds include, without limitation, other pesticides, plant growth regulators, fertilizers, soil conditioners, or other agricultural chemicals. In applying an active compound of this invention, whether formulated alone or with other agricultural chemicals, an effective amount and concentration of the active compound is of course employed; the amount may vary in the range of, e.g. about 0.001 to about 3 kg/ha, preferably about 0.03 to about 1 kg/ha. For field use, where there are losses of insecticide, higher application rates (e.g., four times the rates mentioned above) may be employed.


When the active insecticidal compounds of the present invention are used in combination with at least one additional compound, e.g., with other pesticides such as herbicides, the herbicides include, without limitation, for example: N-(phosphonomethyl)glycine such as glyphosate; aryloxyalkanoic acids such as 2,4D, MCPA, and MCPP; ureas such as isoproturon; imidazolinones such as imazapyr, imazethapyr, and imazaquin; diphenyl ethers such as acifluorfen, bifenox, and fomasafen; hydroxybenzonitriles such as ioxynil and bromoxynil; sulfonylureas such as chlorimuron, achlorsulfuron, bensulfuron, pyrazosulfuron, thifensulfuron, and triasulfuron; 2-(4-aryloxyphenoxy)alkanoic acids such as fenoxaprop, fluazifop, quizalofop, and diclofop; benzothiadiazinones such as bentazone; 2-chloroacetanilides such as butachlor, metolachlor, acetochlor, and dimethenamide; arenecarboxylic acids such as dicamba; pyridyloxyacetic acids such as fluoroxypyr; aryl triazolinones such as sulfentrazone and carfentrazone-ethyl; isoxazolidinones such as clomazone; and other herbicides.


When the active insecticidal compounds of the present invention are used in combination with at least one additional compound, e.g., with other pesticides such as other insecticides, the other insecticides include, for example: organophosphate insecticides, such as chlorpyrifos, diazinon, dimethoate, malathion, parathion-methyl, and terbufos; pyrethroid insecticides, such as fenvalerate, deltamethrin, fenpropathrin, cyfluthrin, flucythrinate, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin bifenthrin, cypermethrin, resolved cyhalothrin, etofenprox, esfenvalerate, tralomehtrin, tefluthrin, cycloprothrin, betacyfluthrin, and acrinathrin; carbamate insecticides, such as aldecarb, carbaryl, carbofuran, and methomyl; organochlorine insecticides, such as endosulfan, endrin, heptachlor, and lindane; benzoylurea insecticides, such as diflubenuron, triflumuron, teflubenzuron, chlorfluazuron, flucycloxuron, hexaflumuron, flufenoxuron, and lufenuron; and other insecticides, such as amitraz, clofentezine, fenpyroximate, hexythiazox, spinosad, and imidacloprid.


When the active insecticidal compounds of the present invention are used in combination with at least one additional compound, e.g., with other pesticides such as fungicides, the fungicides include, for example: benzimidazole fungicides, such as benomyl, carbendazim, thiabendazole, and thiophanate-methyl; 1,2,4-triazole fungicides, such as epoxyconazole, cyproconazole, flusilazole, flutriafol, propiconazole, tebuconazole, triadimefon, and triadimenol; substituted anilide fungicides, such as metalaxyl, oxadixyl, procymidone, and vinclozolin; organophosphorus fungicides, such as fosetyl, iprobenfos, pyrazophos, edifenphos, and tolclofos-methyl; morpholine fungicides, such as fenpropimorph, tridemorph, and dodemorph; other systemic fungicides, such as fenarimol, imazalil, prochloraz, tricyclazole, and triforine; dithiocarbamate fungicides, such as mancozeb, maneb, propineb, zineb, and ziram; non-systemic fungicides, such as chlorothalonil, dichlofluanid, dithianon, and iprodione, captan, dinocap, dodine, fluazinam, gluazatine, PCNB, pencycuron, quintozene, tricylamide, and validamycin; inorganic fungicides, such as copper and sulphur products, and other fungicides.


When the active insecticidal compounds of the present invention are used in combination with at least one additional compound, e.g., with other pesticides such as nematicides, the nematicides include, for example: carbofuran, carbosulfan, terbufos, aldecarb, ethoprop, fenamphos, oxamyl, isazofos, cadusafos, and other nematicides.


When the active insecticidal compounds of the present invention are used in combination with at least one additional compound, e.g., with other materials such as plant growth regulators, the plant growth regulators include, for example: maleic hydrazide, chlormequat, ethephon, gibberellin, mepiquat, thidiazon, inabenfide, triaphenthenol, paclobutrazol, unaconazol, DCPA, prohexadione, trinexapac-ethyl, and other plant growth regulators.


Soil conditioners are materials which, when added to the soil, promote a variety of benefits for the efficacious growth of plants. Soil conditioners are used to reduce soil compaction, promote and increase effectiveness of drainage, improve soil permeability, promote optimum plant nutrient content in the soil, and promote better pesticide and fertilizer incorporation. When the active insecticidal compounds of the present invention are used in combination with at least one additional compound, e.g., with other materials such as soil conditioners, the soil conditioners include organic matter, such as humus, which promotes retention of cation plant nutrients in the soil; mixtures of cation nutrients, such as calcium, magnesium, potash, sodium, and hydrogen complexes; or microorganism compositions which promote conditions in the soil favorable to plant growth. Such microorganism compositions include, for example, bacillus, pseudomonas, azotobacter, azospirillum, rhizobium, and soil-borne cyanobacteria.


Fertilizers are plant food supplements, which commonly contain nitrogen, phosphorus, and potassium. When the active insecticidal compounds of the present invention are used in combination with at least one additional compound, e.g., with other materials such as fertilizers, the fertilizers include nitrogen fertilizers, such as ammonium sulfate, ammonium nitrate, and bone meal; phosphate fertilizers, such as superphosphate, triple superphosphate, ammonium sulfate, and diammonium sulfate; and potassium fertilizers, such as muriate of potash, potassium sulfate, and potassium nitrate, and other fertilizers.


The following examples further illustrate the present invention, but, of course, should not be construed as in any way limiting its scope. The examples are organized to present protocols for the synthesis of the compounds of formula I of the present invention, set forth a list of such synthesized species, and set forth certain biological data indicating the efficacy of such compounds.


The compounds of formula I can be synthesized by methods that are individually known to one skilled in the art from intermediate compounds readily available in commerce.


Example 1
This example illustrates one protocol for the preparation of ((2,3-dimethylphenyl)methyl)-1,3-oxazolin-2-ylamine (Compound A25)

A mixture of 1.0 gram (0.0074 mole) of 2,3-dimethylbenzylamine and 0.69 gram (0.0081 mole) of 2-chloroethylisocyanate in 10 mL of 1,4-dioxane was heated to reflux where it stirred for about 18 hours. The reaction mixture was allowed to cool and an aqueous solution of sodium hydroxide (4.0 mL of a 3.0 molar solution) was added. The reaction mixture was heated to reflux for about 18 hours then allowed to cool to ambient temperature. The reaction mixture was concentrated under reduced pressure to leave a viscous oil residue. The residue was suspended in 50 mL of ethyl acetate and washed with 20 mL of water. The organic phase was extracted with 20 mL of 3.0 molar aqueous hydrochloric acid. The aqueous extract was made basic by adding 3.0 molar aqueous sodium hydroxide and the basic mixture was extracted with 50 mL of ethyl acetate. The extract was dried with sodium sulfate, filtered and the filtrate concentrated under reduced pressure to yield 0.81 gram of the title compound as an oil. The NMR spectrum was consistent with the proposed structure.


Example 2
This example illustrates one protocol for the preparation of 3-acetyl-(1-aza-2-(2,3-dimethylphenyl)ethylidene)-1,3-oxazolidine (Compound B2)

Acetic anhydride (1.0 gram, 0.002 mole) was added to a stirred, cold (5° C.) mixture of 0.2 gram (0.002 mole) of ((2,3-dimethylphenyl)methyl)-1,3-oxazolin-2-ylamine (Compound A25), 0.1 gram (0.0008 mole) of magnesium sulfate and 0.4 gram (0.006 mole) of potassium carbonate in 10 mL of diethyl ether. The reaction mixture was allowed to warm to ambient temperature where it stirred for two hours. The reaction mixture was filtered, the filter cake was rinsed with diethyl ether, and the combined filtrates were concentrated under reduced pressure to leave a residue. The residue was stirred with a mixture of 1 mL of diethyl ether and 4 mL of hexanes. A precipitate formed and was collected by filtration, rinsed with hexanes and dried under reduced pressure to yield 0.16 gram of the title compound. The NMR spectrum was consistent with the proposed structure.


Example 3
This example illustrates one protocol for the preparation of ((2,3-dichlorophenyl)methyl)-1,3-thiazolin-2-ylamine hydrochloride (Compound C7) and ((2,3-dichlorophenyl)methyl)-1,3-thiazolin-2-ylamine (Compound C9)
Step A Synthesis of ((2,3-dichlorophenyl)methyl)-1,3-thiazolin-2-ylamine hydrochloride (Compound C7)

A mixture of 0.5 gram (0.0028 mole) of 2,3-dichlorobenzylamine and 0.27 gram (0.0081 mole) of 2-chloroethylisothiocyanate in 10 mL of 1,4-dioxane was placed in a sealed reaction vial. The reaction mixture was heated to 80° C. where it stirred for about 18 hours. The reaction mixture was allowed to cool and a solid precipitate that had formed was collected by filtration. The solid was rinsed with diethyl ether and was dried under reduced pressure to yield 0.68 gram of the title compound. The NMR spectrum was consistent with the proposed structure.


Step B Synthesis of ((2,3-dichlorophenyl)methyl)-1,3-thiazolin-2-ylamine (Compound C9)

A mixture of 0.36 gram (0.0012 mole) of ((2,3-dichlorophenyl)methyl)-1,3-thiazolin-2-ylamine hydrochloride (Compound C7) in one mL of water was added to a stirred, cold (ice water bath) mixture of 0.05 gram (0.0013 mole) of sodium hydroxide in 10 mL of water and 10 mL of diethyl ether. The reaction mixture was stirred for 10 minutes, poured into a separatory funnel and was extracted with two 50 mL portions of diethyl ether. The extracts were combined, dried with sodium sulfite and filtered. The filtrate was concentrated under reduced pressure to yield 0.31 gram of the title compound as a white solid. The NMR spectrum was consistent with the proposed structure.


Example 4
This example illustrates one protocol for the preparation of ((2,3-dimethylphenyl)methyl)-1,3-thiazolin-2-ylamine hydrochloride (Compound C11), ((2,3-dimethylphenyl)methyl)-1,3-thiazolin-2-ylamine (Compound C66), methyl 2-(1-aza-2-(2,3-dimethylphenyl)ethylidene)-1,3-thiazolidine-3-carboxylate (Compound C53) and N-((2,3-dimethylphenyl)methyl)methoxy-N-(1,3-thiazolin-2-yl)carboxamide (Compound D5)
Step A Synthesis of ((2,3-dimethylphenyl)methyl)-1,3-thiazolin-2-ylamine hydrochloride (Compound C11)

Under a dry nitrogen atmosphere, a stirred mixture of 5.56 grams (0.041 mole) of 2,3-dimethylbenzylamine and 5.0 grams (0.041 mole) of 2-chloroethylisothiocyanate in 100 mL of 1,4-dioxane was heated to 80° C. where it stirred for about 18 hours. The reaction mixture was allowed to cool and a solid precipitate that had formed was collected by filtration. The solid was rinsed with diethyl ether and was dried under reduced pressure to yield 8.0 grams of the title compound. The NMR spectrum was consistent with the proposed structure.


Step B Synthesis of ((2,3-dimethylphenyl)methyl)-1,3-thiazolin-2-ylamine (Compound C66)

A mixture of 1.4 grams (0.034 mole) of sodium hydroxide in 100 mL of water was added to a stirred, cold (ice water bath) mixture of 8.0 grams (0.031 mole) of ((2,3-dimethylphenyl)methyl)-1,3-thiazolin-2-ylamine hydrochloride (Compound C11) in 100 mL of diethyl ether. The reaction mixture was allowed to warm to ambient temperature where it stirred for two hours. The reaction mixture was poured into a separatory funnel and the organic phase was removed and saved. The aqueous phase was extracted with 100 mL of diethyl ether. The organic extract was combined with the saved organic phase, dried with sodium sulfite and filtered. The filtrate was concentrated under reduced pressure to yield 6.8 grams of the title compound as a white solid, melting point 110-114° C. The NMR spectrum was consistent with the proposed structure.


Step C Synthesis of methyl 2-(1-aza-2-(2,3-dimethylphenyl)ethylidene)-1,3-thiazolidine-3-carboxylate (Compound C53) and N-((2,3-dimethylphenyl)methyl)methoxy-N-(1,3-thiazolin-2-yl)carboxamide (Compound D5)

Under a dry nitrogen atmosphere, a solution of 0.25 gram (0.0011 mole) of ((2,3-dimethylphenyl)methyl)-1,3-thiazolin-2-ylamine dissolved in 10 mL of THF was added to a stirred suspension of 0.08 gram (0.0012 mole) of sodium hydride (60% suspension in oil). The mixture was stirred for 30 minutes, at which time a solution of 0.11 mL (0.0014 mole) of methyl chloroformate in 5 mL of THF was added slowly. The reaction mixture stirred at ambient temperature for about 18 hours. The reaction mixture was heated to 60° C. where it stirred for one hour. The reaction mixture was diluted with 25 mL of brine, then extracted with two 25 mL portions of ethyl acetate. The extracts were combined, washed with 25 mL of water, dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to leave a solid residue. Analysis of the residue by TLC indicated that two compounds were present. The residue was purified by column chromatography on silica gel, eluting with hexanes:methylene chloride (1:1). The appropriate fractions were combined and concentrated under reduced pressure to yield 0.05 gram of methyl 2-(1-aza-2-(2,3-dimethylphenyl)ethylidene)-1,3-thiazolidine-3-carboxylate (Compound C53) and 0.14 gram of N-((2,3-dimethylphenyl)methyl)methoxy-N-(1,3-thiazolin-2-yl)carboxamide (Compound D5). The NMR spectra were consistent with the proposed structures.


Example 5
This example illustrates one protocol for the preparation of ((1S)-1-phenylethyl)-1,3-oxazolin-2-ylamine (Compound A58)

A mixture of 0.5 gram (0.0041 mole) of (S)-(−)-phenylethylamine and 0.44 gram (0.0042 mole) of 2-chloroethylisocyanate in 10 mL of 1,4-dioxane was heated to reflux where it stirred for about 18 hours. The reaction mixture was allowed to cool and an aqueous solution of sodium hydroxide (1.0 mL of a 3.0 molar solution) was added. The reaction mixture was heated to reflux for three hours then allowed to cool to ambient temperature. The reaction mixture was concentrated under reduced pressure to leave a viscous oil residue. The residue was suspended in 50 mL of ethyl acetate and extracted with 10 mL of 3.0 molar aqueous hydrochloric acid. The aqueous extract was made basic by the addition of 3.0 molar aqueous sodium hydroxide. The basic mixture was extracted with two 30 mL portions of ethyl acetate. The extracts were combined, dried with sodium sulfate, filtered and the filtrate concentrated under reduced pressure to yield 0.45 gram of the title compound as a solid. The NMR spectrum was consistent with the proposed structure.


The following table sets forth some additional examples of compounds of formula I useful in the present invention:









TABLE 1







Insecticidal Substituted Benzylamino Heterocyclic Derivatives









I




embedded image












Formula I where R4 is formula (A):









IA




embedded image
















Cmpd No
R
R1
R2
R3





A1 


embedded image


H
H
H





A2 


embedded image


H
H
H





A3 


embedded image


H
H
H





A4 


embedded image


H
H
H





A5 


embedded image


H
H
H





A6 


embedded image


H
H
H





A7 


embedded image


H
H
H





A8 


embedded image


H
H
H





A9 


embedded image


H
H
H





A10


embedded image


H
H
H





A11


embedded image


H
H
H





A12


embedded image


H
H
H





A13


embedded image


H
H
H





A14


embedded image


H
H
H





A15


embedded image


H
H
H





A16


embedded image


H
H
H





A17


embedded image


H
H
H





A18


embedded image


H
H
H





A19


embedded image


H
H
H





A20


embedded image


H
H
H





A21


embedded image


H
H
H





A22


embedded image


H
H
H





A23


embedded image


H
H
H





A24


embedded image


H
H
H





A25


embedded image


H
H
H





A26


embedded image


H
H
H





A27


embedded image


H
H
H





A28


embedded image


H
H
H





A29


embedded image


H
H
H





A30


embedded image


H
H
H





A31


embedded image


H
H
H





A32


embedded image


H
H
—COCH3





A33


embedded image


H
H
—SO2N(CH3)2





A34


embedded image


H
H
—PO(OC2H5)2





A35


embedded image


H
H
—PS(OC2H5)2





A36


embedded image


H
H
—CO2CH3





A37


embedded image


H
H
—CHO





A38


embedded image


H
H
—CONHCH3





A39


embedded image


H
H
—CSNHCH3





A40


embedded image


H
H
—CH═NC2H5





A41


embedded image


H
H
—CH═NOC2H5





A42


embedded image


H
H
—COCH3





A43


embedded image


H
H
—SO2N(CH3)2





A44


embedded image


H
H
—PO(OC2H5)2





A45


embedded image


H
H
—PS(OC2H5)2





A46


embedded image


H
H
—CO2CH3





A47


embedded image


H
H
—CHO





A48


embedded image


H
H
—CONHCH3





A49


embedded image


H
H
—CSNHCH3





A50


embedded image


H
H
—CH═NC2H5





A51


embedded image


H
H
—CH═NOC2H5





A52


embedded image


—CH3
H
H





A53


embedded image


—CH3
—CH3
H





A54


embedded image


H
H
H





A55


embedded image


H
H
H





A56


embedded image


H
H
—CH3





A57


embedded image


H
H
—CH3


 A58*


embedded image


—CH3
H
H





 A59**


embedded image


—CH3
H
—CH3





 A60*


embedded image


—CH3
H
—CH3





 A61**


embedded image


—CH3
H
H





A62


embedded image


—CH3
H
H





A63


embedded image


—C2H5
H
H





A64


embedded image




embedded image


H
H





A65


embedded image


H
H
H





A66


embedded image




embedded image


H
H





A67


embedded image


H
H
H





A68


embedded image


H
H
H





A69


embedded image


—CH3
H
H





A70


embedded image


H
H
H





A71


embedded image


H
H
H





A72


embedded image


—CH3
H
H





A73


embedded image


—CH3
H
H





A74


embedded image


H
H
H





A75


embedded image


H
H
H





A76


embedded image


H
H
H





A77


embedded image


—CH3
H
H





*((1S)-1-phenylethyl) isomer


**((1R)-1-phenylethyl) isomer







Formula I where R2 is hydrogen and R4 is formula (B):









IB




embedded image















Cmpd No
R
R1
R5





B1


embedded image


H
—PS(OC2H5)2





B2


embedded image


H
—COCH3





B3


embedded image


H
—SO2CH3





B4


embedded image


H
—PS(OCH3)2





B5


embedded image


H
—CH2OCOC(CH3)3





BB6


embedded image


H
—CON(CH3)2





B7


embedded image


H
—COC2H5





B8


embedded image


H
—SO2N(CH3)2





B9


embedded image


H
—CONH(CH3)





B10


embedded image


H
—PO(OC2H5)2





B11


embedded image


H
—CO2C2H5





B12


embedded image


H
—CO2CH3





B13


embedded image


H
—PO(OCH3)2





B14


embedded image


H
—PO(N(CH3)2)2





B15


embedded image


H
—PS(OC2H5)2





B16


embedded image


H
—CH2OC2H5





B17


embedded image


H
—CHO





B18


embedded image


H
—CSNHCH3





B19


embedded image


H
—CH═NC2H5





B20


embedded image


H
—CH═NOC2H5





B21


embedded image


H
—COCH3





B22


embedded image


H
—SO2N(CH3)2





B23


embedded image


H
—PO(OC2H5)2





B24


embedded image


H
—PS(OC2H5)2





B25


embedded image


H
—CO2CH3





B26


embedded image


H
—CHO





B27


embedded image


H
—CONHCH3





B28


embedded image


H
—CSNHCH3





B29


embedded image


H
—CH═NC2H5





B30


embedded image


H
—CH═NOC2H5





B31


embedded image


H
—CN





B32


embedded image


H


embedded image







B33


embedded image


H
—PS(OC2H5)2





B34


embedded image


H
—PO[N(CH3)2]2





B35


embedded image


H
—PS(OCH3)2





B36


embedded image


H
—CN





B37


embedded image


H
—CSNHCH3





B38


embedded image


H
—COCH3





B39


embedded image


H
—COC2H5





B40


embedded image


—C(CH3)3
—CSNHCH3





B41


embedded image


—CH(CH3)2
—CSNHCH3





B42


embedded image


—CH3
—CSNHCH3





B43


embedded image


—CH3
—CSNHCH3





B44


embedded image


—CH3
—CSNHCH3





B45


embedded image


H
—CSNHCH3





 B46*


embedded image


—CH3
—CSNHCH3





B47


embedded image


H
—CSNHCH3





B48


embedded image


—CF3
—CSNHCH3





 B49*


embedded image


—CH3
—CSNHC2H5





*(2-((2R)-1-aza-2-phenylpropylidine)(1,3-oxazolidin-3-yl) isomer







Formula I where R2 is hydrogen and R4 is formula (C):









IC




embedded image















Cmpd No
R
R1
R3





C1 


embedded image


H
—CH3





C2 


embedded image


H
H





C3  Hydroiodide salt


embedded image


H
H





C4  Hydrochloride salt


embedded image


H
H





C5  Hydrochloride salt


embedded image


H
H





C6  Hydrochloride salt


embedded image


H
H





C7  Hydrochloride salt


embedded image


H
H





C8


embedded image


H
H





C9 


embedded image


H
H





C10 Hydrochloride salt


embedded image


H
H





C11 Hydrochloride salt


embedded image


H
H





C12 Hydrochloride salt


embedded image


H
H





C13 Hydrochloride salt


embedded image


H
H





C14


embedded image


H
H





C15 Hydrochloride salt


embedded image


H
H





C16 Hydrochloride salt


embedded image


H
H





C17 Hydrochloride salt


embedded image


H
H





C18 Hydrochloride salt


embedded image


H
H





C19 Hydrochloride salt


embedded image


H
H





C20 Hydrochloride salt


embedded image


H
H





C21 Hydrochloride salt


embedded image


H
H





C22 Hydrochloride salt


embedded image


H
H





C23 Hydrochloride salt


embedded image


H
H





C24 Hydrochloride salt


embedded image


H
H





C25


embedded image


H
H





C26


embedded image


H
H





C27


embedded image


H
H





C28


embedded image


H
H





C29


embedded image


H
—COCH3





C30


embedded image


H
—SO2N(CH3)2





C31


embedded image


H
—PO(OC2H5)2





C32


embedded image


H
—PS(OC2H5)2





C33


embedded image


H
—CO2CH3





C34


embedded image


H
—CHO





C35


embedded image


H
—CONHCH3





C36


embedded image


H
—CSNHCH3





C37


embedded image


H
—CH═NC2H5





C38


embedded image


H
—CH═NOC2H5





C39


embedded image


H
—COCH3





C40


embedded image


H
—SO2N(CH3)2





C41


embedded image


H
—PO(OC2H5)2





C42


embedded image


H
—PS(OC2H5)2





C43


embedded image


H
—CO2CH3





C44


embedded image


H
—CHO





C45


embedded image


H
—CONHCH3





C46


embedded image


H
—CSNHCH3





C47


embedded image


H
—CH═NC2H5





C48


embedded image


H
—CH═NOC2H5





C49


embedded image


—CH3
H





C50


embedded image


H
H





C51


embedded image


H
H





C52


embedded image


H
—CH3





C53


embedded image


H
—CO2CH3





 C54*


embedded image


—CH3
H





 C55**


embedded image


—CH3
—CH3





C56


embedded image


—CH3
H





C57


embedded image


—C2H5
H





C58


embedded image




embedded image


H





C59


embedded image


H
H





C60


embedded image




embedded image


H





C61


embedded image


H
H





C62


embedded image


—CH3
H





C63


embedded image


H
H





C64


embedded image


H
H





C65


embedded image


—CH(CH3)2
H





C66


embedded image


H
H





*((1S)-1-phenylethyl) isomer


**((1R)-1-phenylethyl) isomer







Formula I where R1 and R2 are hydrogen and R4 is formula (D):









ID




embedded image














Cmpd No
R
R5





D1 


embedded image


—COCH3





D2 


embedded image


—SO2N(CH3)2





D3 


embedded image


—PO(OC2H5)2





D4 


embedded image


—PS(OC2H5)2





D5 


embedded image


—CO2CH3





D6 


embedded image


—CHO





D7 


embedded image


—CONHCH3





D8 


embedded image


—CSNHCH3





D9 


embedded image


—CH═NC2H5





D10


embedded image


—CH═NOC2H5





D11


embedded image


—COCH3





D12


embedded image


—SO2N(CH3)2





D13


embedded image


—PO(OC2H5)2





D14


embedded image


—PS(OC2H5)2





D15


embedded image


—CO2CH3





D16


embedded image


—CHO





D17


embedded image


—CONHCH3





D18


embedded image


—CSNHCH3





D19


embedded image


—CH═NC2H5





D20


embedded image


—CH═NOC2H5





D21


embedded image


—PS(OCH3)2









The following table sets forth physical characterizing data for certain compounds of formula I of the present invention:









TABLE 2







Insecticidal Benzylamino Heterocyclic


Derivatives Compound Characterization











Melting Point (° C.) of Solids



Molecular Formula
Or Physical State















A1
C10H10Cl2N2O
113-115



A2
C10H11ClN2O
OIL



A3
C10H11ClN2O
OIL



A4
C10H11ClN2O
86-88



A5
C10H10Cl2N2O
OIL



A6
C10H10Cl2N2O
121-124



A7
C10H10Cl2N2O
OIL



A8
C10H10Cl2N2O
102-105



A9
C11H11F3N2O
78-79



A10
C11H11F3N2O
OIL



A11
C11H11F3N2O
114-115



A12
C11H14N2O2
OIL



A13
C12H16N2O3
OIL



A14
C12H16N2O3
OIL



A15
C12H16N2O3
SOLID



A16
C12H16N2O3
SOLID



A17
C12H16N2O3
108-112



A18
C11H14N2O2
 99-102



A19
C11H14N2O2
75-78



A20
C12H16N2O3
OIL



A21
C11H14N2O
OIL



A22
C12H16N2O
OIL



A23
C12H16N2O
OIL



A24
C11H14N2O
OIL



A25
C12H16N2O
81-83



A26
C12H16N2O
85-88



A27
C12H16N2O
OIL



A28
C10H12N2O
OIL



A29
C11H14N2O
OIL



A30
C11H13ClN2O
100-102



A52
C11H14N2O
110-112



A53
C12H16N2O
129-133



A54
C11H13ClN2O
104-108



A55
C11H13ClN2O
 98-102



A56
C11H13ClN2O
OIL



A57
C11H14N2O
OIL



A58
C11H14N2O
SOLID



A59
C12H16N2O
OIL



A60
C12H16N2O
OIL



A61
C11H14N2O
81-83



A62
C11H12Cl2N2O
100-105



A63
C12H16N2O
116-119



A64
C16H16N2O
151-153



A65
C10H10ClFN2O
42-45



A66
C17H18N2O
129-131



A67
C11H13ClN2O
130-131



A68
C11H13ClN2O
63-65



A69
C13H18N2O
149-151



A70
C12H16N2O
48-50



A71
C10H11FN2O
OIL



A72
C11H13FN2O
132-135



A73
C11H13FN2O
104-106



A74
C16H16N2O
143-148



A75
C14H14N2O
 96-100



A76
C10H11FN2O
OIL



A77
C11H11F3N2O
165-167



A78
C11H14N2O2
OIL



A79
C12H13F3N2O
139-142



B1
C16H25N2O3PS
OIL



B2
C14H18N2O2
125-126



B3
C13H18N2O3S
127-128



B4
C14H21N2O3PS
OIL



B5
C18H26N2O3
OIL



B6
C15H21N3O2
OIL



B7
C15H20N2O2
85-86



B8
C14H21N3O3S
OIL



B9
C14H19N3O2
135-136



B10
C16H25N2O4P
OIL



B11
C15H20N2O3
109-110



B12
C14H18N2O3
119-120



B13
C14H21N2O4P
OIL



B14
C16H27N4O2P
OIL



B15
C15H22N2O2
OIL



B17
C14H19N3OS
122-123



B31
C13H15N3O
125-127



B32
C20H24N2O2
OIL



B33
C15H22ClN2O3PS
OIL



B34
C15H24ClN4O2P
OIL



B35
C13H18ClN2O3PS
94-95



B36
C12H12ClN3O
126-127



B37
C13H16ClN3OS
SOLID



B38
C13H15ClN2O2
SOLID



B39
C14H17ClN2O2
SOLID



B40
C16H23N3OS
127-128



B41
C15H21N3OS
127-128



B42
C13H16FN3OS
OIL



B43
C13H16FN3OS
OIL



B44
C13H16FN3OS
OIL



B45
C18H19N3OS
123-128



B46
C13H17N3OS
109-112



B47
C16H17N3OS
136-140



B48
C13H14F3N3OS
OIL



B49
C14H19N3OS
OIL



C1
C11H14N2S
OIL



C2
C10H12N2S
82



C3
C10H13N2S•I
SOLID



C4
C10H11Cl2N2S•Cl
164-166



C5
C10H13N2S•Cl
100-102



C6
C10H12ClN2S•Cl
187-188



C7
C10H11Cl2N2S•Cl
218-220



C8
C11H14N2S
94-96



C9
C10H10Cl2N2S
119-121



C10
C11H15N2S•Cl
148-150



C11
C12H17N2S•Cl
180-182



C12
C12H17N2S•Cl
146-148



C13
C12H17N2S•Cl
170-173



C14
C12H16N2S
154-155



C15
C10H12ClN2S•Cl
148-150



C16
C10H12ClN2S•Cl
145-147



C17
C10H11Cl2N2S•Cl
163-165



C18
C10H11Cl2N2S•Cl
212-213



C19
C10H11Cl2N2S•Cl
202-204



C20
C11H12F3N2S•Cl
192-194



C21
C11H12F3N2S•Cl
147-148



C22
C11H12F3N2S•Cl
129-131



C23
C11H15N2OS•Cl
118-120



C24
C11H15N2OS•Cl
128-130



C25
C12H16N2O2S
82-85



C26
C10H11FN2S
SOLID



C27
C11H13ClN2S
124-125



C49
C11H14N2S
110-113



C50
C11H13ClN2S
118-120



C51
C11H13ClN2S
134-135



C52
C11H13ClN2S
OIL



C53
C14H18N2O2S
LIQUID



C54
C11H14N2S
84-86



C55
C12H16N2S
OIL



C56
C11H12Cl2N2S
114-116



C57
C12H16N2S
105-106



C58
C16H16N2S
124-126



C59
C10H10ClFN2S
92-94



C60
C17H18N2S
122-123



C61
C11H13ClN2S
90-95



C62
C13H18N2S
120-121



C63
C10H11FN2S
106-109



C64
C10H11FN2S
SOLID



C65
C13H18N2S
110-114



C66
C12H16N2S
110-114



D2
C14H21N3O2S2
81-84



D4
C16H25N2O2PS2
LIQUID



D5
C14H18N2O2S
129-131



D11
C12H12Cl2N2OS
137-140



D12
C12H15Cl2N3O2S2
119-120



D14
C14H19Cl2N2O2PS2
LIQUID



D15
C12H12Cl2N2O2S
105-110



D21
C12H15Cl2N2O2PS2
LIQUID










Candidate insecticides were evaluated for insecticidal activity by observing mortality in a population of treated cotton aphid (Aphis gossypii) on cotton plant leaf discs when compared to like populations of untreated cotton aphid on cotton plant leaf discs. These tests were conducted in the following manner:


Three week to one month-old cotton plants (Gossypium hirsutium) were prepared for infesting by cutting off the cotyledons and new true leaf growth, leaving the oldest two true leaves. The prepared test plant was infested with cotton aphids by translocation from cotton plants grown in a cotton aphid colony. The wells of clear 128-well trays (CD-International, Pittman, N.J.) were filled with 1 mL of a warm, aqueous 3% agar solution and allowed to cool to ambient temperature. The aphid infested cotton leaves were removed from the plants and placed bottom side up on a cutting platform. Circular discs were cut from the infested leaves and placed bottom side up onto the cooled agar gel, one disc per well. Each leaf disc was visually inspected to assure that a minimum of 10 live aphids were present. A 50 mM stock solution of the test compound was prepared by dissolving the appropriate amount of the test compound in DMSO. A solution comprising 1000 part per million (ppm) of each test compound was prepared by dissolving 10 μl of the stock solution in 140 μl of an aqueous 0.003% Kinetic® (a nonionic wetter/spreader/penetrant adjuvant, Helena Chemical Company, Collierville, Tenn.) solution. If needed, the solution of 1000 ppm of test compound was serially diluted with a solution consisting of 66 mL of DMSO and 30 μl of Kinetic® in 934 mL of water (diluting solution) to provide solutions of each test compound for lower rates of application, for example, 300 ppm, 100 ppm, 30 ppm, or 10 ppm. Each replicate infested test plant disc was sprayed with 10 μl of the test solution at about 8 psi for 1 second. For comparison purposes, a solution of a standard, such as bifenthrin, prepared in a manner analogous to that set forth above, as well as an aqueous solution of 0.003% Kinetic® containing no test compound and the diluting solution containing no test compound were also sprayed onto infested test plant discs. Upon completion of spraying the solutions of test compound, the solution of standard, and the solutions containing no test compound, the plant discs were allowed to dry. Upon completion of drying, the test trays were covered with a plastic film. Three slits were made in the film over each well to allow air into each well. The test trays were placed in a biochamber (25° C., 16 hours light, 8 hours of dark and 35-40% relative humidity) for three days. After this time, each plant disc was assessed for percent mortality caused by the test compound when compared to the population of aphids that was infested onto the test plant discs containing no test compound. A test compound was designated as possessing insecticidal activity (SA) if there was 40% to 75% mortality of cotton aphid on plant discs sprayed with that compound. If there was 75% mortality or greater of the cotton aphid, a test compound was designated as being more insecticidally active (A). If there was 40% mortality or less of the cotton aphid, the test compound was termed as inactive (I).


An assessment of the insecticidal activity at selected rates of application from this test is provided in Table 3. The test compounds of formula I are identified by numbers that correspond to those in Table 1.









TABLE 3







The Following Compounds Of The Present Invention Reduced The Population


Of Cotton Aphid By 40 to 100% When Applied At An Application Rate


Of 1000 ppm Or Less To Infested Cotton Leaf Discs
















Cmpd.
Cmpd.
Cmpd.
Cmpd.
Cmpd.
Cmpd.
Cmpd.
Cmpd.
Cmpd.
Cmpd.


No.
No.
No.
No.
No.
No.
No.
No.
No.
No.





A2
A3
A4
A5
A6
A7
A8
A10
A11
A12


A13
A14
A15
A16
A17
A18
A19
A20
A21
A22


A23
A24
A26
A27
A53
A54
A79
B3
B8
B11


B12
B13
B15
B40
B41
C1
C3
C4
C7
C8


C9
C12
C13
C14
C16
C17
C19
C20
C21
C22


C23
C24
C25
C27
C50
C52
C53
C65
C66
D2


D4
D5
D12
D14
D15









Candidate insecticides were evaluated for insecticidal activity by observing mortality in a population of cotton aphid (Aphis gossypii) on treated cotton plants when compared to like populations of cotton aphid on untreated plants. These tests were conducted in the following manner:


For each rate of application of test compound, two seven-to-ten days old cotton seedlings (Gossypium hirsutium) grown in 7.6 cm diameter pots were selected for the test. Each test plant was infested with about 120 adult cotton aphids by placing onto each test plant cuttings of leaves from cotton plants grown in a cotton aphid colony. Once infested, the test plants were maintained for up to about 12 hours to allow complete translocation of the aphids onto the test plant. A solution comprising 1000 part per million (ppm) of each test compound was prepared by dissolving 10 milligrams of the test compound in 1 mL of acetone. Each solution was then diluted with 9 mL of a solution of 0.03 mL of polyoxyethylene(10) isooctylphenyl ether in 100 mL of water. About 2.5 mL of solution of each test compound was needed to spray each replicate of test plant (5 mL total for each test compound). If needed, the solution of 1000 ppm of test compound was serially diluted with a solution of 10% acetone and 300 ppm of polyoxyethylene(10) isooctylphenyl ether in water to provide solutions of each test compound for lower rates of application, for example, 300 ppm, 100 ppm, 30 ppm, or 10 ppm. Each replicate of test plant was sprayed with the solutions of test compound until run-off on both the upper and lower surfaces of the leaves. All the test plants were sprayed using a DeVilbus Atomizer Model 152 (Sunrise Medical, Carlsbad, Calif.) at a pressure of about 0.63-0.74 kilogram per square centimeter from a distance of about 30.5 centimeters from the test plants. For comparison purposes, a solution of 10% acetone and 300 ppm of polyoxyethylene(10) isooctylphenyl ether in water containing no test compound was also sprayed onto control test plants. Upon completion of spraying the solutions of test compound and the solution containing no test compound, the plants were allowed to dry. Upon completion of drying, the test and control plants were placed in a tray containing about 2.5 centimeters of water, where they were maintained in a growth chamber for 72 hours. After this time, each plant was assessed for percent mortality caused by the test compound when compared to the population of aphids that was infested onto the test plants prior to treatment with test compound. A test compound was designated as possessing insecticidal activity (SA) if there was 40% to 75% mortality of cotton aphid on plants sprayed with that compound. If there was 75% mortality or greater of the cotton aphid, a test compound was designated as being more insecticidally active (A). If there was 40% mortality or less of the cotton aphid, the test compound was termed as inactive (I).


An assessment of the insecticidal activity at selected rates of application from this test is provided in Table 3A. The test compounds of formula I are identified by numbers that correspond to those in Table 1.









TABLE 3A







The Following Compounds Of The Present Invention Reduced The Population


Of Cotton Aphid (Aphis gossypii) Between 40% and 100% When Applied At


An Application Rate Of 1000 ppm Or Less On Infested Cotton Plants
















Cmpd.
Cmpd.
Cmpd.
Cmpd.
Cmpd.
Cmpd.
Cmpd.
Cmpd.
Cmpd.
Cmpd.


No.
No.
No.
No.
No.
No.
No.
No.
No.
No.





A1
A9
A25
A28
A29
A30
A52
A55
A56
A57


A58
A59
A60
A61
A62
A63
A64
A65
A66
A67


A68
A69
A70
A71
A72
A73
A74
A75
A76
A77


A78
B1
B2
B4
B5
B6
B7
B9
B10
B14


B17
B31
B32
B33
B34
B35
B36
B37
B38
B39


B42
B43
B44
B45
B46
B47
B48
B49
C2
C5


C6
C10
C11
C15
C18
C26
C49
C51
C54
C55


C56
C57
C58
C59
C60
C61
C62
C63
C64
D11


D21









As set forth in Tables 3 and 3A, the tested compounds of the present invention reduced the aphid population by at least 40% at an application rate of 1000 ppm or less.


While this invention has been described with an emphasis upon preferred embodiments, it will be understood by those of ordinary skill in the art that variations of the preferred embodiments may be used and that it is intended that the invention may be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications encompassed within the spirit and scope of the invention as defined by the following claims.

Claims
  • 1. An insecticidal composition comprising at least one compound of formula IA
  • 2. An insecticidal composition as claimed in claim 1 further comprising one or more additional compounds selected from the group consisting of pesticides, plant growth regulators, fertilizers and soil conditioners.
  • 3. A method of controlling insects, comprising applying a composition of claim 1 to a locus where insects are present or are expected to be present.
  • 4. An insecticidal composition comprising a compound of formula IG:
  • 5. The insecticidal composition according to claim 4, further comprising one or more additional compounds selected from the group consisting of pesticides, plant growth regulators, fertilizers and soil conditioners.
Parent Case Info

This application claims the benefit of U.S. Provisional Application No. 60/682,460 filed May 19, 2005.

PCT Information
Filing Document Filing Date Country Kind 371c Date
PCT/US2006/019365 5/19/2006 WO 00 9/10/2008
Publishing Document Publishing Date Country Kind
WO2006/127426 11/30/2006 WO A
US Referenced Citations (4)
Number Name Date Kind
4195092 Balko Mar 1980 A
4256755 Smith, Jr. Mar 1981 A
6462049 Ogura et al. Oct 2002 B1
6875768 Machiya et al. Apr 2005 B1
Foreign Referenced Citations (3)
Number Date Country
1313055 Dec 1962 FR
WO 9105473 May 1991 WO
WO2005063724 Jul 2005 WO
Related Publications (1)
Number Date Country
20090036306 A1 Feb 2009 US
Provisional Applications (1)
Number Date Country
60682460 May 2005 US