AP150A

AP150A - Novel imidate insecticides.

Info

Publication number: AP150A
Application number: APAP/P/1988/000108A
Authority: AP
Inventors: Michael David Broadhurst; Thomas Houston Cromartie; Karl Joseph Fisher; William George Haag; David Braun Kanne; Michael Robert Leadbetter
Original assignee: Ici America Inc
Priority date: 1987-11-17
Filing date: 1988-11-17
Publication date: 1991-10-31
Also published as: PL275832A1; MY104112A; EP0317265B1; DK640788D0; GB2212495A; GB8826675D0; DE3889861D1; HUT49575A; AP8800108A0; KR900006275A; JPH02149A; AU2562388A; CN1033798A; JP2809280B2; IL88393A0; US5189060A; DK640788A; EG18713A; EP0317265A2; ATE106393T1

Abstract

A series of novel imidate insecticides

Description

NOVEL ΙΜΙΡΑΊΈ INSECTICIDES

This invention relates to a series of novel imidate insecticides distinguished by the general formula (I) in which

R-j is an optionally substituted aryl group in which the substituents are halo, Cj-C₄ alkyl, (J-C4 haloalkoxy, <j-C₄ alkoxy, C^-C₄ haloalkylthio, Οβ-Όθ cycloalkyl, nitro, C-|-C₄ haloalkyl, C2-C5 carboalkoxy, Ci~C₄ alkylthio, cyano, C-,-C₄ alkylsulfonyl, C]-C₄ haloalkyl sulfonyl,

C2-C5 alkylcarbony1, C2-C4 alkyleneoxy, C-|-C₄ alkylenedioxy, C1-C3 halosubstituted alkylenedioxy, phenyl, mono-substituted phenyl, pyridyloxy, C2-C4 alkylene, C2-C4 alkenyl, and/or amido;

R2 is C;-C7 alkyl, C^-Cg haloalkyl, cyclopropyl, cyclobutyl, mono- or poly- halo- or methyl-substituted cyclopropyl, cyano, C2-C4 alkoxyalkyl, C2~Cg haloalkenyl or C2~Cg alkenyl; and

R3 is (a) an optionally substituted 3-phenoxyphenalkyl,

3-phenoxypyridylalky1, 3-(pyridyloxyJphenalkyl, 3-phenylaminophenalky1,

3- benzylphenalkyl or benzyloxyphenalkyl moiety; (b) a benzyl fur any Ime thy 1 moiety; (c) a 3- or 4-substituted benzyl or tetrafluorobenzyl moiety; (d)

4- phenoxy-2-butyn-2-yl; (e) 2-methy1-3-phenylbenzy1; or (f) 4-(4-trifluoromethyl-2-pyridyloxy) benzyl.

Conpounds of this invention demonstrate activity in controlling various types of insects, including lepidoptera, hemiptera and coleoptera, particularly in foliar application.

Another aspect of this invention involves insecticidal conpositions conprising an insecticidally effective amount of a conpound of the invention with an insecticidally suitable diluent or carrier.

AP000150

PR-7713/7874/7924/8029/8443A

In another aspect, this invention involves a method for controlling insects by administration of an insecticidally effective amount of a conpound or composition of this invention to a locus where control is desired.

The term insects as used herein refers to the broad and commonly understood usage rather than to those creatures which in the strict biological sense are classified as insects. In addition to those belonging to the class Insecta, this term includes some classes of acarids such as mites and the like.

More particularly, the compounds of formula (I) are those in which:

Ri is naphthyl, optionally substituted by up to 2 halogens; or 15 phenyl, optionally substituted by one or more of the following: C2-C5 carboalkoxy, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C2-C5 alkylcarbonyl, C2-C4 alkenyl, Cj-C4 haloalkylthio, Cj-Cg cycloalkyl, phenyl, monosubstituted phenyl, pyridyloxy, C2-C4 alkyleneoxy, C1-C4 alkylenedioxy, C-j—C3 haloalkylenedioxy, C2-C4 alkylene, amido, nitro, cyano, up to two C1-C4 alkylthio groups, up to three C1-C4 alkoxy groups, up to three C1-C4 haloalkoxy groups, up to three C1-C4 alkyl groups, up to three C1-C4 haloalkyl groups, or up to five halogens;

R2 is methyl; ethyl; n-propyl; C3-C7 branched alkyl; Cj-C$ haloalkyl, cyclopropyl optionally substituted by up to 4 methyl groups or up to 2 halogens, cyclobutyl, cyano, C2-C4 alkoxyalkyl, C₂-Cg alkenyl or C₂-Cg haloalkenyl; and

R3 is (a)

-CH-(CH2)

in vtfiich ra is 0 or 1;

A, B and C are each carbon or nitrogen, provided that A, B and C are not all nitrogen and if two of A, B and C are nitrogen, then A and C are nitrogen;

PR-7713/7874/7924/8029/8443A

R4 is hydrogen, monohalo or dihalo;

Rg is hydrogen, methyl, fluoro or ethynyl; and R7 is (i) ^5 in which D and E are each carbon or nitrogen provided that both D and E are not nitrogen, and further provided that if any of A, B or C is nitrogen, then D and E are both carbon; and

R5 is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, trifluoromethyl, cyano, C1-C4 alkylthio, C1-C4 alkylsulfonyl, or mono- or polyhalo;

r ΪΊ

in which Rq is hydrogen or halogen; or

AP 0 0 0 1 5 0

(i) Rg is 4-fluoro, 4-methoxymethyl, or 4-propargyl, and R-|q is fluoro or (ii) Rg is 3- or 4-allyl, 3- or 4-propargyl, or 3- or 4-(monoor dihalo)allyl, and R^q is hydrogen or fluoro;

PR-7713/7874/7924/8029/8443A

(d) 4-phenoxy-2-butyn-2-yl ?

(e) 3-bromo-4-f luorobenzyl;

(f) 4-(benzyloxy)benzyl;

(g) 4-( 4-fluorobenzyloxy Jbenzyl;

(h) 4-{4-trifluromethyl-2-pyridyloxy)benzyl; or

provided that:

(i) R^ is not 2,3-dichlorophenyl, 2,6-di fluorophenyl,

2,6-di(C1-C4 alkyl)phenyl, 2,4,6-tribromophenyl or 2,4,6-tri(Cp-C4 alkoxy)phenyl;

(ii) when R2 is tertiary butyl, R1 is not phenyl,

3- methyl-phenyl, 4-{n-butyl)phenyl or 4-(t-butyl)phenyly and (iii) when R2 is a C₅ alkyl group, then is not

4- isopropylphenyl.

A more preferred class of conpounds are those in which R·, does not contain substituents at both ortho positions on the phenyl ring, i.e., in which R-, does not contain a 2,6-disubstitution, 2,3,6-trisubstitution, or a 2,4,6-trisubstitution on the phenyl ring.

An even more preferred class is that in which the phenyl ring of R·, is substituted at the 3-, 4-, and/or 5-positions, including mono-, diand tri-substituted phenyl conpounds, as well as phenyl compounds having a

3,4-alkylene, alkeneoxy, alkylenedioxy, or haloalkylenedioxy substitution. Such compounds more particularly have the formula

PR-7713/7874/7924/8029/8443A in which R2 and R3 are as defined above; R-, -, is hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, Cj-C₄ alkylthio, <^-<4 haloalkoxy, C1-C4 haloalkyl thio, C2-C5 carboalkoxy, C2-C5 alkylearbonyl, nitro or cyano; R12 is hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C^-C₄ alkylthio, nitro, cyano, C2-C5 alkylcarbonyl, C1-C4 alkylsulfonyl or C2-C5 carboalkoxy; and R₁₃ is hydrogen, halogen, C1-C4 haloalkyl or C1-C4 alkoxy, or R-jj and R₁₂ taken together are C2-C4 alkylene, C2-C4 alkyleneoxy, C-|-C₄ alkylenedioxy or halo-C^-C^ alkylenedioxy; provided that R^, Rj2 and R-,3 are not all hydrogens.

Another preferred class of compounds is that in which R·, has the formula in which R14 is halogen and R15 is hydrogen or halogen. Examples of such phenyl groups are 2,3-difluoro-, 2,4-difluoro-3-chloro-, and 2,3,4-trifluorophenyl.

Also of interest are oonpounds having a 2,5-, 2,3,4- or 2,4,5substitution pattern.

As used herein, these terms have the following meanings:

Alkyleneoxy and alkylenedioxy refer to linking groups having or 2 oxygen atoms, respectively, and at least one carbon atom (optionally substituted) in a chain. Ihe alkyleneoxy moieties have between 2 and 4 carbon atoms in this chain and include, for instance, ethyleneoxy (-O-C2H4-) and the like. Alkylenedioxy moieties include methylenedioxy (-O-CH2-O-), 1,2-ethylenedioxy (-Ο<2^Η4“θ)' mono- or di-halomethylenedioxy (a methylenedioxy group in which one or both hydrogens are replaced by a halogen) and isopropylenedioxy (-O-C(013)2-0-).

PR-7713/7874/7924/8029/8443A The term carboalkoxy refers to a group having the formula

in which R^g is an alkyl group. The carbon atom content of the carbo5 alkoxy group is meant to include the carbon atom of the carbonyl moiety in that group. Thus, C2~carboalkoxy refers to carbomethoxy, etc. Similarly, the carbon atom content of an alkylcarbonyl group includes the carbon atom in the carbonyl moiety. The sinplest member of this group is thus acetyl, CH3C (0)-.

When R·) represents a phenyl ring substituted by a second phenyl ring, the second phenyl ring may be unsubstituted or mono-substituted in which the substituent is halogen, C1-C4 alkyl, C1-C4 haloalkyl, nitro, cyano, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, or C1-C4 alkylene15 dioxy (optionally further substituted by up to 2 halogens).

Terms defining halogenated groups such as haloalkyl, haloalkoxy, haloalkenyl and the like include mono- and polyhalogenated groups of the indicated number of carbon atoms. In polyhalogenated groups the halogens may be the same or different.

Propargyl refers to the 2-propynyl group -<H2-C=CH and allyl refers to the 2-propenyl group -032-01=02.

Cyclopropyl groups for R2 may be substituted by up to 4 methyl groups or alternatively up to 2 halogen atoms.

For the various subgroups falling within the general definition of R3, preferred types are:

For R4: hydrogen and 2-, 4- or 6-monohalo, particularly monochloro or monofluoro;

For R5: 2-, 3- or 4-halo, 2,4-, 3,4- or 3,5-dihalo, particularly difluoro, pentahalo, particularly pentafluoro, 4-methyl,

4-trifluoromethyl, 4-methoxy, 4-methylthio and 4-methylsulfonyl.

PR-7713/7874/7924/8029/8443A

The following are exanples of specific embodiments of groups falling within the definition of R3. For convenience in specifying positions of substitution of conpounds of the type

the position of attachment of the group

-0H-(CH₂)mwas given the number 1 and the position of attachment of group R7, the number 3. When A, B or C was a nitrogen atom, the conpounds were designated pyrid-2-yl, pyrid-6-yl or pyrid-4-yl, respectively.

3-phenoxybenzyl,

3-phenoxy-(alpha-methyl)benzyl,

3-phenoxyphenethyl,

3-(4-pyridyloxy)benzyl,

3-(4-fluorophenoxy)benzyl,

3-(4-chlorophenoxy)benzyl,

3-(4-brcroophenoxy)benzyl,

3-( 4-iodophenoxy) benzyl,

3-(2,4-d i fluorophenoxy)benzyl,

3-(3,4-d if1uorophenoxy)benzy1,

3-(3,5-difluorophenoxy)benzyl,

3-(2,3,4,5,6-pentafluorophenoxy)benzyl,

3-(4-fluorophenoxy)-4-fluorobenzyl,

3-(4-fluorophenoxy)-4-chlorobenzyl,

3-(4-chlorophenoxy)-4-fluorobenzyl,

3-phenoxy-4-fluorobenzyl,

3-(4-fluorophenoxy)-6-chlorobenzy1,

3-(4-fluorophenoxy)-5-fluorobenzyl,

3-(4-fluorophenoxy)-4,6-d i fluorobenzyl,

3-(4-fluorophenoxy)-6-fluorobenzyl, sIOOOdV

PR-7713/7874/7924/8029/8443A

3-(4-fluorophenoxy)-2-fluorobenzyl,

3-(4-cyanophenoxy)benzyl,

3-(4-methylphenoxy)benzy1,

3-(4-methoxyphenoxy)benzyl,

3-( 3,4-di f luorophenoxy) -4-f luorobenzyl,

3-(3-fluorophenoxy)benzyl,

3-(2-fluorophenoxy)benzyl,

3-(3-chlorophenoxy)benzyl,

3-(4-trifluorome thylphenoxyJbenzyl,

3-(4-methylthiophenoxy)benzyl,

3-(4-fluorophenoxy)-(alpha-fluoro) benzyl, 3-phenoxy-pyrid-2-yl-methyl,

3-phenoxy-pyrid-4-yl-methyl,

3-phenoxy-pyr id-6-yl-methyl,

3-( 4-f luorophenoxy )pyrid-2-ylmethyl,

3-( 4-chlorophenoxy )pyr id-2-ylmethyl,

3-( 4-f luorophenoxy )pyrid-4-ylraethyl,

3-( 4-chlorophenoxy )pyr id-2-ylmethyl,

3-( 4-chlorophenoxy )pyrid-4-ylmethyl,

3-( 4-chlorophenoxy )pyrid-6-ylmethy 1,

3-( 3,4-difluorophenoxy )pyrid-2-ylmethyl, 3-( 4-methylphenoxy )pyrid-2-ylmethy 1,

3-( 4-f luorophenoxy )pyrid-6-ylmethyl, 3-(pyrid-2-yloxy )benzyl,

3- (4-chloropyrid-2-yloxy)benzyl,

2,3,4,5,6-tetrafluorobenzyl,

4- methoxymethyl-2,3,5,6-tetrafluorobenzyl,

4-propargyl-2,3,5,6-tetrafluorobenzyl, 3-allyloxybenzyl,

3-(benzyl)benzyl,

3-(benzyloxy)benzyl,

3-(4-fluorobenzyloxy)benzy1,

3-(phenylami no)benzyl,

3-(4-fluorophenylamino)benzyl,

1- (3-phenoxyphenyl)prop-2-ynyl,

3- bromo-4-fl uorobenzyl,

4- phenoxy-2-butyn-2-yl,

4-(benzyloxy)benzyl,

4-(4-fluorobenzyloxy) benzyl,

4- (4-trifluoromethyl-2-pyridyloxy )benzyl

2- methyl-3-phenylbenzyl,

5- benzyl-3-f ur any line thyl.

PR-7713/7874/7924/8029/8443A Processes for Preparation of Conpounds of This Invention

Process (A)

Compounds of this inventiion in general are prepared by reaction of an imidoyl halide (preferably chloride) with an alkali metal alkoxide according to the general reaction:

R₁-N=c-R₂ + R3OM -¥ R-|-N=C

\)R₃ in which M is an alkali metal, preferably sodium or potassium and Hal is a 10 halogen, particularly chloro or bromo.

This reaction is conducted at a temperature of from about -70*C to about +65*C, most preferably at about room tenperature, for a time which may range from about 5 minutes to about 24 hours. The reaction is conducted in the presence of a solvent, for exanple, an aromatic hydrocarbon such as benzene, toluene, xylene or naphthalene, or an ether, such as diethyl ether, diisopropyl ether, diisoamyl ether, dibutyl ether, furan, 1,2-dimethoxyethane, or tetrahydrofuran (preferably tetrahydrofuran). In some instances, apparent to those skilled in the art, it is advantageous to add the solution of the alkali metal alkoxide to a solution of the imidoyl halide or to use substantial excesses of alkoxide.

The resulting product may be recovered by conventional techniques.

The alkoxide R3CM is produced by reaction of an appropriate alcohol, such as 3-phenoxybenzyl alcohol, with an alkali metal-containing base, for instance, an alkali metal hydride (e.g., potassium or preferably sodium hydride) in the presence of a solvent such as that used in reaction of the alkali metal alkoxide with the imidoyl halide. In general, this reaction is conducted at reflux tenperature under an inert atmosphere for a time which may range up to about 2 hours.

The alcohols, if not commercially available, can be prepared according to known methods such as those described in the following references: U. S. patents 4,256,893; 4,261,920; and 4,329,518, and Volume

7 of the text Chemie der Pflanzenschutz und Schadlingsbekanpfungsmittel (phenoxybenzyl, phenoxypyridylmethyl and pyridyloxy type alcohols);

AP 0 0 0 1 5 0

PR-7713/7874/7924/8029/8443A

Elliott et al, J. Chem Soc. (C), 1971, pp. 2551-1554 (5-benzyl-2-furanylmethanol); Pesticide Science 14, 560-570 (1983) (2-methyl-3-phenylbenzyl alcohol); 0. S. patents 4,370,346 and 4,594,355; British patent 2,122,616; European patent applications 196,156 and 271,240; and J. Sci. Pood & Agriculture 18, 167 (1967) for various substituted benzyl alcohols; European patent application 211,561 for 3-phenylaminobenzyl alcohols;

Swiss patent 549,342 for 4-phenoxy-2-butyn-1-ol; and Japanese patent 49-27331 for 1-( 3-phenoxyphenyl )-2-propyn-1-ol.

The imidoyl halide may be prepared from a starting amine having the formula R-|NH2 or amide having the formula

depending on availability. “Hie amines are either generally available or may be prepared by procedures known in the art, for exanple, those described in Conpendium of Organic Synthetic Methods, Harrison et al. (Wiley-Interscience, New York, 1971).

The amides, if not available, may be produced by reaction of the amine with an appropriate acid chloride having the formula

The tenperature of this reaction ranges from about -40*C to about +80*C. Suitable solvents include hydrocarbon solvents such as toluene and chlorinated hydrocarbon solvents such as methylene chloride, chloroform, carbon tetrachloride, ethylene dichloride, tetrachloroethane and the like, preferably methylene chloride. This reaction is conducted in the presence of a base, preferably a tertiary amine. Suitable bases include triethylamine, quinoline, dimethylaniline, diethylaniline, and pyridine. Triethyl amine is the preferred base. The resulting amide is recovered and purified by conventional means.

The imidoyl halide may be prepared from the amide by reacting it with a halogenating agent such as phosphorus pentachloride or phosgene in an organic solvent such as that utilized in the amide production (preferably methylene chloride) or alternatively using phosphorus oxychloride as

PR-7713/7874/7924/8029/8443A the solvent. The reaction is carried out under an inert atmosphere for a time which may be up to 24 hours, preferably from 1 to 24 hours, at a temperature of from about 0*C to about 110*C. Before the imidoyl chloride-containing product is passed to the final step, all substances, such as phosphorus oxychloride or hydrogen chloride, which can react with the alkoxide in the final step, should be removed. This can generally be accomplished by evaporation or distillation.

Alternatively, the compounds of this invention may be prepared 10 by a two-step process indicated as follows:

Process (B)

R-:

(1) R₂CN + R3OH

HX (2)

C=NH₂'HX + RlNH₂

R]N=C

OR₃ in which HX represents a mineral acid.

APO 00 1 5

In the first step, the appropriate alcohol (for instance a phenoxybenzyl alcohol) is mixed with a nitrile having the formula R₂CN at a tenperature of from about -20*C to about +40*C. Then, a solution of a mineral acid such as hydrochloric, hydrobromic, sulfuric or phosphoric acid (preferably hydrochloric acid) dissolved in a suitable organic sol25 vent is added at temperatures from about -5 to about 40*C, preferably 0*C, then stirred at room tenperature, to produce the corresponding imidate salt. Suitable solvents for this reaction include aromatic hydrocarbons such as benzene, toluene, xylene or naphthalene and ethers such as diethyl ether, diisopropyl ether, dianyl ether, furan, tetrahydrofuran and dioxane (preferably dioxane). Time for the reaction may be up to 52 hours. The imidate salts are novel and constitute an aspect of this invention.

In the second step, the imidate salt is suspended in an organic solvent such as that utilized in the previous step, preferably benzene, and reacted with an amine having the formula R^NH₂ . The mixture is reacted, optionally with stirring, at a tenperature of between about -50

PR-7713/7874/7924/8029/8443A and +80*C, most preferably at room temperature, for a period of time necessary to conduct the reaction, which may be up to 120 hours. The final imidate product may be recovered as in process (A).

⁵ Process (Ch

A third process may be used for producing many of the conpounds of this invention, with the exception of those in which R£ is a group having no alpha-hydrogen, such as cyano, tertiary butyl, vinyl or halovinyl. This process proceeds by way of an intermediate ketenimine, which may be prepared from the amide or from the imidoyl halide. In the first case, the amide (prepared for instance, as described in process A) is reacted with an inexpensive base and a trivalent phosphorus conpound, preferably triphenylphosphine. The base is preferably a tertiary amine such as tr iethylamine. The reaction is carried out at a temperature of from about -10*C to 40*C in the presence of a halogen, preferably chlorine or bromine, and an aromatic or chlorinated hydrocarbon solvent such as benzene, toluene, xylene, methylene chloride, ethylene dichloride, chloroform, carbon tetrachloride, tetrachloroethane and the like, v preferably methylene chloride. The reaction may then be conducted under reflux tenperature of the solvent and the ketenimine recovered according to methods known in the art.

Alternatively, the ketenimine may be prepared by reaction of the imidoyl halide with a base, as just described, but no halogen or trivalent phosphorus conpound present.

In the second step of this process, the ketenimine is reacted with an alcohol having the formula R3OH in the presence of a solvent, preferably an ether solvent, such as diethyl ether, dipropyl ether, di iso30 propyl ether, dibutyl ether, tetrahydrofuran or 1,2-dimethoxyethane and an alkali metal base such as potassium or sodium hydride, preferably sodium hydride. This reaction is conducted under reflux for a time as necessary which may be up to 48 hours, preferably from about 2 to about 10 hours, at the end of which the reaction mixture is cooled and the imidate product recovered as described above.

PR-7713/7874/7924/8029/8443A

This process can be depicted by the general scheme:

fl *17 (3) R^NHCR? (CfiHq)qP \ base/halogen »17 (4) R_rW=C=C + R3OH *18 ‘18

Λ

A. ^R1-N-C, or₃ in which R·,, R2 and R3 are as previously described and R17 and R-jg are 10 independently hydrogen, C-|-C₆ alkyl, halo, CJ-C5 haloalkyl, Cj-Cg alkoxy,

C2-C5 alkenyl or C2-C5 haloalkenyl, or R17 and R^g taken together are a C2-C3 alkylene chain optionally substituted by up to 4 methyl groups or up to 2 halogens.

Z'⁷

Ketenimines R-|-N=OC>. are novel.

*18

Process (D):

This process may be used as an alternative to process (A) for 20 preparation of conpounds of this invention from alcohols (R3OH) which are sensitive to, and could be adversely affected (e.g. decomposed) by, strong bases such as the alkali metal-containing bases (e.g. alkali metal hydrides) used to prepare the alkoxides (R3CM). Alcohols which may be sensitive to such strong bases include phenoxypyridyl alkanols, alpha25 ethynyl alcohols (Rg is ethynyl) such as 1-( 3-phenoxyphenyl)-2-propyn-1-ol and tetrafluoropropargylbenzyl alcohol.

AP 0 0 0 1 5 0

Conpounds of this type may be made by direct reaction of the alcohol with the imidoyl chloride in the presence of a tertiary amine base and a reaction-promoting amount of a 4-di (lower alkyl) ami nopyridine, preferably 4-dimethylaminopyridine.

Tertiary amines which may be used in this process include trialky 1 amines such as trimethyl-, triethyl-, tri-n-butylamine and the like, including tertiary amines having mixed alkyl groups, N,N-dialkylanilines such as Ν,Ν-dimethylaniline, pyridine and various substituted pyridines.

PR-7713/7874/7924/8029/8443A

Preferred tertiary amines, primarily for economic reasons, are triethylamine, Ν,Ν-dimethylaniline, and pyridine. The tertiary amine may even be an additional amount of the promoter 4-di(lower alkyl)aminopyridine, over and above that amount needed for promoting the reaction.

The tertiary amine is preferably used in a stoichiometric amount with respect to the alcohol, but may be used in excess of that amount.

The promoter 4-di (lower alkyl Jaminopyridine may be used in an amount from about 0.05 to about 1 equivalent per equivalent of alcohol, preferably from about 0.05 to about 0.15 equivalent per equivalent, most preferably about 0.1.

This process is preferably conducted at temperatures of from about 10*C to about 50*C. Lower temperatures may be used, but the reaction rate would be much slower. The process is carried out in the presence of an inert solvent such as an aromatic hydrocarbon (for instance, benzene, toluene or xylene), a chlorinated solvent (such as methylene chloride, ethylene dichloride or chlorobenzene) or an ether (such as diethyl ether, dioxane or tetrahydrofuran).

While this process is particularly suitable for producing compounds from base-sensitive alcohols, it may be used to produce compounds of this invention in general from other alcohols as described.

Alpha-fluorophenoxybenzyl compounds are made from the alphafluorobenzyl halide (preferably bromide) rather than the alcohol by reaction with an amide, R]NHCOR2, in the presence of a halide ion binding agent such as silver oxide or a silver salt, and an inert solvent. Reaction temperatures are from about -20*C to about 100*C.

The following are representative exanples of the preparation of compounds of this invention according to the processes described above.

PR-7713/7874/7924/8029/8443A

EXAMPLE 1

Preparation of

N- (3-Chloro-4-f luorophenyl) -O- (3-phenoxybenzyl) i sobutyryl imidate (Conpound 88 herein) (Process A) (a) Preparation of the Anilide

Ito a stirred solution of 3-chloro-4-fluoroaniline (10.0 g, 0.069 mol) and triethylamine (11.2 ml, 0.08 mol) in 100 ml methylene chloride was added isobutyryl chloride (7.8 ml, 0.075 mol) dropwise, with cooling, in an ice bath. After the addition, the reaction mixture was permitted to reach room temperature at which point 100 ml of water was added. The aqueous and organic layers were separated; the organic layer was dried over anhydrous sodium sulfate and the solvent evaporated to provide 15.2 g (103% of theoretical yield) of a tan solid, spectroscopically identified as 3-chloro-4-fluoroisobutyrylanilide, m.p. 114-117*0.

(b) Preparation of the Imidoyl chloride

To a solution of the anilide prepared in step (a) (2.1 g, 9.3 mmol) in 50 ml methylene chloride under an argon atmosphere there was added phosphorus pentachloride (1.93 g, 9.3 mmol). After two hours, the solvent was evaporated at 20 mmHg and the resulting brown oil was further evaporated at 40*C and less than 1 mmHg. The product, N-(1-chloro-2methylpropylidene)-3-chloro-4-fluoroaniline, was transferred to the next step without further purification.

(c) Preparation of the Sodium Alkoxide

A suspension of sodium hydride (0.26 g, 11 mmol) in tetrahydrofuran (40 ml) was prepared and stirred under an argon atmosphere. To this suspension there was added 3-phenoxybenzyl alcohol (1.75 ml, 10 mmol).

The resulting mixture was heated to reflux 0.5 hour and then cooled.

There was obtained a pale yellow solution of sodium 3-phenoxybenzylalkoxide which contained a small amount of gray solid.

(d) Preparation of the Imidate

To the alkoxide solution produced in step (c) there was added the imidoyl chloride prepared in step (b), dissolved in about 10 ml tetrahydrofuran, at room temperature with cooling over several minutes. At the end of one hour, the product mixture was poured into about 200 ml hexanes

PR-7713/7874/7924/8029/8443A and filtered through a pad of silica gel. The solvent was evaporated to produce 3.0 g (82% of theoretical yield) of a tan oil, which was further purified by chromatography over silica gel. Evaporation of the solvent from the product fraction gave 2.4 g (65% of theoretical yield) of a nearly colorless, viscous oil, identified spectroscopically as the desired product.

EXAMPLE 2 (Process B)

This example illustrates the preparation of the conpound of Example 1 by the second described process, through the intermediate imi date salt.

(a) A solution of 3-phenoxybenzyl alcohol (10 ml, 57.4 mmol) and isobutyronitrile (5.2 ml, 57.88 mmol) was cooled to 0*C. There was then added 12.5 ml of a 4.1 molar solution of anhydrous HC1 (62.5 mmol) in dioxane, dropwise, followed by stirring at 25*C for 16 hours. The product, 0-(3-phenoxybenzyl)isobutyrylimidate hydrochloride, separated out as a white solid.

(b) The imidate hydrochloride salt obtained above (0.99 g, 3.2 nmol) was suspended in 15 ml benzene and 0.60 g (4.1 mmol) 3-chloro-4fluoroaniline was added. The mixture was then stirred at 25*C for 72 hours and filtered through silica gel. The combined filtrates were concentrated at reduced pressure and purified on silica gel using 5% ethylacetate in hexanes as eluent. There was obtained 0.78 g of the desired product of 77% purity.

EXAMPLE 3 Preparation of

M-(3,4-Difluorophenyl )-O-( 4'-fluoro-3-phenoxybenzyl) isobutyryl imidate (Compound 66 herein) (Process C)

This example illustrates production of a conpound of this invention according to the third process, through an intermediate ketenimine.

PR-7713/7874/7924/8029/8443A (a) A mixture was prepared which contained 3,4-difluoroisobutyrylanilide (4.0 g, 20.1 mmol, prepared analogously to Exanple 1, step (a)), triethylamine (6 ml, 43 nmol) and triphenylphosphine (5.3 g, 20.2 mmol) and 50 ml methylene chloride. The mixture was cooled to O’C; then bromine (1.0 ml, 20 nmol) was added dropwise. The mixture was then refluxed for 2 hours, cooled to room temperature and concentrated at reduced pressure. The residue was extracted with 50 ml hexanes; the extract was filtered and concentrated at reduced pressure to yield 3.84 g of the crude ketenimine.

(b) The ketenimine thus prepared was combined with 3-(4-fluorophenoxy)benzy1 alcohol (obtained, for instance, by the method of Fuchs et al., U.S. Pat. 4,242,357) (0.80 g, 3.7 mmol) and the resulting mixture dissolved in 50 ml 1,2-dimethoxyethane. Sodium hydride (0.10 g, 4.2 mmol) was added and the mixture heated at reflux for 2 hours. The resulting mixture was allowed to cool, filtered, and concentrated. The crude product was purified by chromatography on silica gel using 5% ethyl acetate in hexanes as eluent. There was obtained 1.05 g (72% of theoretical yield) of the desired product.

EXAMPUB 4 Preparation of

M-( 4-Chlorophenyl )-O-( 3-phenoxybenzyl )cyclopropylcarboximidate (Conpound 35 herein) (Process A)

N-(4-chlorophenyl)cyclopropane carboxamide (4.0 g, 20.4 mrol), prepared from 4-chloroaniline and cyclopropane carboxylic acid chloride analogously to Example 1, step (a)) was dissolved in 50 ml methylene chloride and treated with PCI5 (4.25 g, 20.4 mmol) all at once, under an argon atmosphere. After 20 minutes, n-pentane was added and the solid was filtered. The solvents were evaporated at 50*C yielding a residual light brown oil, the desired imidoyl chloride. This was taken up in a small amount of dry tetrahydrofuran.

The imidoyl chloride thus prepared was then added to a solution of sodium 3-phenoxybenzyl alkoxide prepared using 4.1 g of 3-phenoxybenzyl alcohol and 0.5 g of sodium hydride as in Example 1, step (c). The mixture was let stand for 4 hours at room temperature then briefly heated

PR-7713/7874/7924/8029/8443A to reflux and cooled. Water and hexanes were added and the aqueous and organic phases separated. The organic layer was washed with water, dried over magnesium sulfate and evaporated. The residue was redissolved in hexanes and filtered through silica gel. Evaporation gave a colorless oil, identified spectroscopically as the desired product.

EXAMPLE 5 Preparation of

N-( 3-Trif luoromethylphenyl )-0-( 3-phenoxybenzyl )dichloroacetimidate (Conpound 72 herein) (Process A)

In a flask were combined 4.2 g (20.2 mol) phosphorus pentachloride, 3-trifluoromethyldichloroacetanilide [5.4 g, 19.8 mole, prepared analogously to Example 1, step (a)) and phosphorus oxychloride (solvent) under argon. The mixture was heated to 60*C for several hours; then hexanes were added and the resulting solution filtered. The filtrate was evaporated and the product imidoyl chloride, an oil, was taken up in a small amount of dry tetrahydrofuran.

Itie imidoyl choride thus prepared was added to a solution of “ -¼ sodium 3-phenoxybenzyl alkoxide (prepared analogously to Example 1 step (c) from 4.0 g 3-phenoxybenzyl alcohol and 0.5 g sodium hydride).

Ihe resulting mixture was stirred overnight at ambient tenperature; then water and hexanes were added, the mixture was phase separated, washed with 5% HC1 and saturated sodium bicarbonate solution, dried over magnesium sulfate and evaporated to produce an oil. This oil was then purified by chromatography over silica gel to give a pale yellow oil, identified spectroscopically as the desired product.

³⁰ EXAMPLE 6

Preparation of

N-( 3,4-Methylenedioxyphenyl )-O-( 3-phenoxybenzyl )propionimidate (Conpound 189 herein) (Process A)

This conpound was prepared analogously to Exanple 1 from 2.0 g (10.4 mmol) 3,4-methylenedioxypropionanilide (itself prepared from

PR-7713/7874/7924/8029/8443A

3,4-methylenedioxyaniline and propionyl chloride), 2.26 g 3-phenoxybenzyl alcohol and 0.29 g sodium hydride. There was obtained 1.9 g (50% of theoretical yield) of a colorless viscous oil, identified spectroscopically as the desired product.

EXAMPLE 7

Preparation of

N-( 3-chloro-4-f luorophenyl) -O- [ 1 -(3-phenoxyphenyl

2-propyn-l—yi Ji sobutyrimidate (Conpound 533 herein) (Process D) )(a) Preparation of the alcohol

A solution was prepared containing 2.4 g (24 mmol) trimethylsi lyl acetylene in 50 ml tetrahydrofuran. The tenperature was kept at -78*C with stirring. Then 10.0 ml of a 2.5 M solution of n-butyllithium in hexanes was slowly added. After further stirring for 15 minutes, 3.5 ml (4.0 g, 20 mmol) 3-phenoxybenzaldehyde was added. The solution was stirred at -78*C for 10 minutes and was allowed to warm to room tenperature over 30 minutes.

The reaction was quenched with 5% sodium bicarbonate. The tetrahydrofuran was removed in vacuo, the aqueous phase was extracted with methylene chloride and the organic layers combined and dried to produce a light oil.

A solution of the light oil in methanol was stirred with potassium carbonate, then concentrated, dissolved in water and extracted with ether. The desired alcohol, 1-(3-phenoxyphenyl)-2-propyn-1-01 (4.3 g, 96% of theoretical yield), a light yellow oil, was obtained from the ether extracts.

(b) Preparation of the imidate

To a solution of 0.7 g (3.0 mmol) of N-3-chloro-4-fluorophenyl i sobutyr imidoyl chloride (prepared as in Example 1 (a)-(b)] was added triethylamine (0.63 ml, 0.45 g, 4.5 mmol), 1-(3-phenoxyphenyl)-2-propyn-1-ol (prepared as above) (1.0 g, 4.5 mmol) and 4-dimethylaminopyridine (50 mg, 0.4 mmol). The mixture was stirred for 24 hours at room tenperature ,

AP 0 0 0 1 5 0

PR-7713/7874/7924/8029/8443A concentrated and diluted with 100 ml hexanes. The resulting slurry was filtered through alumina and concentrated to give 0.90 g {70% of theoretical yield) of the desired compound.

Tables 1 and 2 depict representative conpounds of this invention, prepared according to a method as described above. Table 1 contains conpounds in which R3 is a substituted or unsubstituted 3-phenoxybenzyl moiety. Table 2 contains conpounds in which R3 represents other moieties. Nearly all conpounds were produced as oils? all structures were confirmed by spectroscopic analysis.

For convenience, since nearly all conpounds in the tables are of the type in which Ri is a substituted or unsubstituted phenyl ring, the tables only depict the substituents (if any) on that ring, with H = unsub15 stituted phenyl, 3-C1 » 3-chlorophenyl, 3-Cl,4F ³ 3-chloro-4-fluorophenyl, and the like. Naphthyl conpounds are indicated as such.

PR-7713/7874/7924/8029/8443A

TABLE 1

	^Rr	^r2 -N=fc-O-CH₂_
		I	0¼ to	Ζ*5
	(Ri	* unsubstituted or substituted phenyl)
Cmpd.
No.	Phenyl	Subst.	^R2		*5
1	3-C1		chci₂	H	H
2	4-C1		1-C3H7	H	H
3	4-C1		-CC12CH3	H	H
4	2,4-Cl		CHC1₂	H	H
5	4-C1		CH₃	H	H
			CH₃
6	4-C1		-c=ch₂	H	H
7	3-C1		1-C3H7	H	H
8	4-C1			H	H
9	3,4-Cl		i-C₃H₇	H	H
10	3,5-Cl		i-C^Hg	H	H
11	4-C1		C₂«5	H	H
12	3-C1		t-C^Hg	H	H
13	2,5-Cl		i-C₃H₇	H	H
14	3,4-Cl		i-C₃H₇	H	H

AP 0 0 0 1 5 0

TABLE 1

PR-7713/7874/7924/8029/8443A

(continued)
Phenyl Subst.	«2	r₄	Rs

4-C1		H	a
3,5-Cl	i-C₃H₇	B	a
2-C1	i-C₃H₇	H	H
2,4,5-Cl	i-C₃H₇	B	a
2,4,6-Cl	i-C₃H₇	H	a
3,4,5-Cl	i-<₃H₇	H	H
4-C1	-CN	H	a
4-C1	-CH(CH₃)OCH₃	H	a
4-C1	i-C₃H₇	4-F	a
3-C1	-<	H	H
3,4-Cl	t-C^Hg	H	a
4-C1	sec-C4Hg	B	a
3,4-Cl	-chcich₃	H	H
2,3-Cl	c₂h₅	a	a
4-C1	chci₂	H	a
4-C1	t-C₄H₉	a	a
4-Cl	CH2C1	a	a
4—Cl	X]	H	H
4-C1	-chcich₃	a	H
2-Cl	chci₂	a	a
4-Cl	cf₃	H	H
3,4-Cl	C2H5	H	H
3,4-Cl	i-C₃H7	a	4-F
3,4-Cl	n-C₃H7	a	a
3,4-Cl	^sec~^c4^H9	a	H

TABLE 1

PR-7713/7874/7924/8029/8443A

(continued)
Phenyl Subst.	^R2	R*	*5
3,4-Cl	X-C3H7	H	3-F
H	CHC1₂	H	H
H	ch₃	H	H
H	i-OjH?	H	H
4-F	CHC1₂	H	H
4-F	-<	H	H
4-F	^i_c3^H7	H	H
3-F	1-C3H7	H	H
4-F	t-G^Hg	H	H
4-F	-OCC1₂ Cl	H	H
4-F	chf₂	H	H
2,3,4,5,6-F	X-C3H7	H	H
2,4-F	^i-c3^H7	H	H
4-F	i-C^H?	4-F	H
3,4-F	i-C₃ ^H7	H	H
3,5-F	1-C3H7	H	H
2,5-F	i-C₃H₇	H	H
2,3,5,6-F	X-C3H7	H	H
2,4,5-F	^i_c3^H7	H	H
2,4-F	c₂h₅	H	H
3,4-F	^i_c3^H7	H	4-F
4-CF₃	CHC1₂	H	H
4-CF3	-<	H	H
4-OCF3		H	H
4-OCF3	CHC1₂	H	H
2-Cl,4-CF3	-<	H	H

AP 0 0 0 1 5 o

PR-7713/7874/7924/8029/8443A

TABLE 1 (continued)

Phenyl Subst.		Rd	Rs
3-CF₃	chci₂	H	H
3-CF₃	^i_c3^H7	H	H
4-CF₃	i-C₃H₇	H	H
2,5-OCH₃	ί<₃Η₇	H	H
4-OCF₃	i-C₃H₇	H	H
3-CF₃,4-Cl	1-C3H7	H	H
2-CF₃	1-C3H7	H	H
2-CH₃,3-F	1-C3H7	H	H
2-CH₃,5-F	ΐ-<3^Η7	H	H
3-F,4-CH₃	^i-C3^H7	H	H
3-OCH₃,5-CF₃	i-C₃ ^H7	H	H
3-CF₃,5-F	^i-c3^H7	H	H
3,5-CF₃	i-C₃H₇	H	H
2-F,4-Br	^i-c3^H7	H	H
3-CF₃	i-C₃ ^H7	4-F	H
3-Cl,4-F	ί-<3Η7	H	H
3-Cl,4-F	i-C₃H₇	4-F	H
3-Cl,4-CF₃	X-C3H7	H	H
2-F,5-CF₃	^i-c3^B7	H	H
3-Cl,4-F	C2H5	H	H
3-CF3		H	H
3-CH₃,4-F	i<3H₇	H	H
3-CF3	t-C₄H9	H	H
3-Cl,4-F	X-C3H7	H	4-F
3-Cl,4-CH₃	X-C3H7	H	H
3,5-Cl,4-OCH₃	X-C3H7	H	H
2,6-Cl,4-NO₂	ⁱ“^c3^H7	H	H
2-Cl,5-CH₃	^i-c3^H7	H	H
2-Cl,4-CH₃	i-C₃H7	H	H

PR-7713/7874/7924/8029/8443A

TABLE 1 (continued)

Cnpd.

No.	Phenyl Subst.	«2	R_d	Rs
95	3-Cl,4-OCH₃	i-C₃ ^H7	H	H
96	2-CH₃,4-Cl	i-C₃H₇	H	H
97	2-CH₃,3-Cl	chci₂	H	H
98	(4-chloro-alphanaphthyl)	chci₂	H	H
99	2,5-OCH₃,4-Cl	i-C₃H₇	H	H
100	2-Cl,3,6-OCH₃	^i_c3^H7	H	H
101	3,5-Cl,4-CH₃ n	^i-C3^H7	H	H
102	π 3-O0C₂H₅,4-Cl	i<₃H₇	H	H
103	3-Cl,4-SC₂H₅ o	1-C3H7	H	H
104	it 3-Cl,4-COC₂H₅	1-C3H7	H	H
105	3-N32/4-<l	t-C₄H₉	H	H
106	3-Cl,4-Br	t-C₄H₉	H	H
107	3-Cl,4-CH₃	t-C₄Hg	H	H
108	3-C1,4-CN	-C(CH₃ )7(21	H	H
109	2-CH₃,4-Cl	t-C₄H₉	H	H
110	3-Cl,4-OCH₃	i-C₃H₇	H	4-F
111	(4-chloro-alphanaphthyl)	-CiCH^TCl	H	H
112	3-Cl,4-SO2C₂H₅	I-C3H7	H	H
			H	H
113	3-Cl,4-F	<3	H	H
114	3-(pyrid-2-yloxy)	1-C3H7	H	H
115	3-Cl,4-F	^C2^h5	H	4-F
116	3-Cl,4F	-<	H	4-F
117	3-Cl,4-F	C2F5	H	H
118	3-Cl,4-F	CHBrCH₃	H	H

APO00150

TABLE 1

PR-7713/7874/7924/8029/8443A (continued)

Phenyl Subst.	R2	R4	R5
3-Cl,4-F	i-C₃H₇	H	2-F
3-CF₃,4-F	i-C₃H₇	H	4-F
3-Cl,4-F	n-C₄H₉	H	H
3-Cl,4-P	sec-C₄H₉	H	H
3-Cl,4-F	n-C₃H₇	H	H
3-Cl,4-F	X	H	H
3-Cl,4-F	i<₃H₇	H	3-F
3-CN	i-C₃H₇	H	H
3-CH₃,4-Br	^i_C3^H7	H	H
3-Br	i-C₃H₇	H	H
2,4-F,6-Br	^i_c3^H7	H	H
2,6-Br,4-F	i-C₃H₇	H	H
4-Br	i-C₃H₇	H	H
2-Br	i-C₃H₇	H	H
2—CH₃,4-Br	I-C3H7	H	H
3-Br	t-C₄Hg	H	H
4-Br	t-C₄H₉	H	H
3-1	i-C₃H₇	H	H
4-1	i-C₃ ^H7	H	H
4-OC₂H₅	CHC1₂	H	H
4-CH₃	chci₂	H	H
4-(t-C₄H₉)	chci₂	H	H
4-SCH₃	chci₂	H	H
4-SCH₃	i-C₃H₇	H	H
3-OCH₃	^i_c3^H7	H	H
4-(i-C₃H₇)	i-C₃H₇	H	H
2-OCH₃	i-C₃H₇	H	H
2,4-OCH₃ 4-S-CH₃	i-C₃H₇	H	H
i-C₃H₇	H	H

PR-7713/7874/7924/8029/8443A

TABLE 1 (continued)

Phenyl Subst.	R?	Rd	r₅
2,3-CH₃	1-C3H7	H	H
2-013,4-0013	I-C3H7	H	H
2-0013,5-013	i-C₃ ^H7	H	H
4-80013	1-O3H7	H	H
4-(n-C₄H₉)	i-C₃H₇	H	H
4-{t-C₄H₉)	I-O3H7	H	H
^3-C2^h5	1-C3H7	H	H
3-013	I-C3H7	H	H
4-Ol₃	1-C3H7	H	H
^4-c2^h5	c₂H₅	H	H
3,4-013	i-C₃H₇	H	H
4-C₂H₅	ΐ-Ο₃Η₇	H	4-F
4-OCH3	i-C₃H₇	H	H
4-O₂H₅	i-C₃ ^H7	H	H
3-C₂H₅	t-C₄H₉	H	H
4-C₂H₅	t-C₄H₉	H	H
4-OC₂H₅	t-O₄H₉	H	H
4-(i-C₃H₇)	t-C₄H₉	H	H
3-3313	i-C₃H₇	H	H
3,4-013 0	t-C₄H₉	H	H
P 3-OOC₂H₅	t-C₄H₉	H	H
3,4-0013 Q	i-C₃H₇	H	H
3-0-013	I-C3H7	H	H
3-OC₂H₅	1-O3H7	H	H
4-ON	1-C3H7	H	H
4-NO2	chci₂	H	H
3-N02	chci₂	H	H
3-NO2	t-C₄H₉	H	H
3,4-(-0CH₂O-)	1-C3H7	H	4-F

AP 0 0 0 1 5 0

	28 TABLE 1 (continued)	PR-7713/7874/7924/8029/8443A
Phenyl Subst.	*2	r₄
3,4-(-OCH2O-)		H	H
3,4-(-OCH2O-)	c₂h₅	H	H
3,4-{OC₂H4°-)	^i-c3^H7	H	H
3,4-(-OCH2O-)	i-C₃H₇	H	H
3,4-(-OCH2O-)	1-C3H7	4-F	H
3,4-[-OC(CH3)2O-]	^i-c3^H7	H	H
3,4-(OCH2O-)	i-C₃H₇	H	2-F
4-OCH₃	n-C₃H7	H	H
3,4-(OCH2O-)	^Sec-C4^H9	H	H
4-C₆ ^h5	i-C₃H7	H	H
3,4-(-0^2^2^-)	i-C₃H₇	H	H
3-4-(-0020-)	n-C₃H₇	H	H
4-C1	i-C₃H₇	H	4-F
3,4-(-0020-)	^i-c3^H7	H	2-F
3-Cl,4-F	I-C3H7	H	2,4-F
3-CF3	^i_c3^H7	H	3-F
3-CF₃,4-Cl	i-C₃ ^H7	H	4-F
3-0	i-C₃H₇	H	4-F
3-CF₃,4-Cl	^i-c3^H7	H	3-F
3-Cl,4-F	^i-c3^H7	H	4-0
4-F	i-O₃H₇	H	4-F
2,3,4,5,6-F	ΐ-<:₃Η7	H	4-F
3,5-F	i-C₃H₇	H	4-F
3-F	^i_c3^H7	H	4-F
3-OCH₃	i-C₃H₇	H	4-F
3-CF₃	^i-C3^H7	H	4-F
3-Cl,4-F	i-C₃H₇	H	3-C1
3-Cl,4-F	t-C₄H₉	H	4-F
4-F	i-C₃H₇	H	3-C1
4-F	^i_c3^H7	H	2,4-F

TABLE 1

PR-7713/7874/7924/8029/8443A (continued)

Phenyl Subst.	«2	R4	Rs
3,4-Cl	I-C3H7	H	3-C1
4-CN	i-C₃H₇	H	3-C1
2,4-F	i-C₃B₇	H	4-F
3-Cl,4-F	sec-C₄H₉	H	4-F
3,4-Cl	sec-C4H₉	H	4-F
3,4-F	i-C₃H₇	H	4-CN
3,4-Cl	i-C₃ ^H7	H	2,4-F
3,4-F	i-C₃H7	H	2,4-F
3-Cl,4-F	i-C₃H?	H	3,5-F
3-Cl,4-F	i-C₃H₇	4-F	4-F
3-Cl,4-F	i-C₃H₇	H	3,4-F
3,4-Cl	t-C₃B₇	H	3,4-F
3-4-[-OC(CH₃)2<>]	i-C₃ ^H7	H	4-F
4-F	i-C₃H₇	H	4-OCH₃
3-Cl,4-F	i-C₃H₇	H	4-OCH3
3-F,4-CN	i-C₃H₇	H	4-F
3,4-Cl	i^₃H?	H	4-OCH3
3-Cl,4-F	-C(CH₃)₂C1	H	4-F
3-Cl,4-F	i-C-jH?	H	4-CH₃
4-Br	i-C₃ ^H7	R	4-F
4-CN	i-C₃ ^H7	H	4-F
4-(i-C₃H₇)	1-C3H7	H	4-F
3-Br	i-C₃H₇	H	4-F
3-Cl,4-F	1-C3H7	6-F	4-F
4-F	i-C₃H₇	H	4-CH₃
2,3,4,5,6-F	i-C₃ ^H7	H	2,4-F
3-F,4-CN	i-C₃H₇	H	H
4-1	i-C₃ ^H7	H	4-F
4-(t-C₄H₉)	i-C₃ ^H7	H	4-F
3-CH₃,4-F	i-C₃ ^H7	H	4-F
4-C1	i-C₃H₇	H	4-Br

AP 0 0 0 1 5 0

	30 TABLE 1 (continued)	PR-7713/7874/7924/8029/8443A
Phenyl Subst.		R_a
3-Cl,4-F	i-C₃H₇	H	4-Br
3-Cl,4-F	i-C₃H₇	H	4-C1
3,4-(-OCH₂°-)	i-C₃H₇	H	4-C1
3,4-[-0C(CH₃)2O-]	^i_C3^H7	H	4-C1
3,4-(-0C(CH₃)₂O-]	^i-C3^H7	4-F	H
3,4-(-0^(^0-)	i-c₃h₇	H	H
3,4-(-0CF₂O-)	^i-C3^H7	H	4-F
3,4-(-OCF₂O-)	^i_c3^H7	H	H
3,4-(-0CH2O-)	i-C₃H₇	H	4-CF₃
3-Cl,4-F	i-C₃H₇	H	4-CF₃
3,4,5-OCH₃	i-C₃H₇	H	H
2,3-CH₃	i-C#?	H	H
2,5-CH₃	i-C₃H₇	H	H
3,4-Br	i-C₃H₇	H	4-F
3,4-Br	i-C₃H₇	H	H
3-Br,4-F	i-C₃H₇	H	4-F
3-Br,4-F	ΐ-Ο₃ ^Η7	H	H
3-1	i-C₃ ^H7	H	4-F
3-Cl,4-F	i-C₃B₇	H	4-SCH₃
4-F	i-C₃H₇	H	4-SCH₃
3-Cl,4-F	c₂f₅	H	4-F
4-F	i-C₃H₇	H	4-Br
3-C1	i-€₃H₇	H	4-Br
3-Cl,4-F	sec-C4H9	4-F	H
3-Cl,4-F	ί-€₃Η₇	2-F	4-F
2-CH₃,5-Cl	i-^H?	H	H
2-OCH₃,5-Cl	^i_c3^H7	H	H
4-F	1-C3H7	H	3,4-F
3-CF₃	i^₃H₇	4-F	4-C1
3-Cl,4-F	I-C3H7	4-F	4-C1
3-CF₃	i-OjH?	4-F	4-F

TABLE 1

PR-7713/7874/7924/8029/8443A (continued)

Phenyl Subst.	R2
4-C1	i-C₃H₇	H	4-0
3-C1	i-CjH?	H	4-0
3-N02	i-OjH?	H	4-0
3-SCF₃	i-C₃H₇	H	4-F
3-Br,4-F	i-C₃ ^H7	4-F	4-F
3,4-(-OCH2<»	i-C₃H₇	6-0	4-F
3,4-F	i-C₃H₇	H	4-Br
3-Br,4-F	i-C₃H₇	H	4-Br
3-CF₃,4-F	i-€₃H₇	4-F	4-F
3,4-F	I-C3H7	4-F	4-F
3-1	i-C₃H₇	4-F	4-F
•0	i-C₃H₇	H	4-F
3-1,4-F	i-C₃H₇	4-F	4-F
3-F,4-Br	1-C3H7	4-F	4-F
3,4-[0C(CH₃)2O-]	1-C3H7	4-F	4-F
3,4-(-OCF₂O-)	i-C₃H₇	4-F	4-F
3,4-(-OCF2⁰)	i-C3H₇	4-F	H
4-OCF3	i-C₃H₇	4-F	4-F
4-CF₃	i-C₃H₇	4-F	4-F
3-OCF₂CHF₂	i-C₃ ^H7	H	4-F
3,4-Cl	^i_c3^H7	4-F	4-F
4-0	-CH(C₂H₅)₂	H	4-F
3-CF₃	-CH(C₂H5)₂	H	4-F
2,4-Cl,5-F	I-C3H7	4-F	4-F
3-^,4^	i-C₃H₇	H	H
3-CF₃	<]	H	4-F
3,4-F	1-C3H7	4-F	4-0
3,4-Cl	i-C₃ ^H7	4-F	4-0

o $ V 0 0 0 dV

TABLE 1

PR-7713/7874/7924/8029/8443A (continued)

Phenyl Subst.	R2		Rs
3-CF₃,4-F	^i_c3^H7	4-F	4-C1
3-Br,4-F	i-C₃H₇	4-F	4-C1
3-Br,4-F	^i_c3^H7	4-F	H
3-CF₃,4-F	^i-C3^H7	4-F	H
4-(t-C₄H₉)	i-C₃H₇	4-F	4-C1
3-NO2	^i_c3^H7	H	H
2-C1/5-F	i-C₃H₇	4-F	4-F
2,3,5,6-F	i-C₃H₇	H	4-F
3-C1/4-F	CHBrCHg	H	4-F
3,4-(0CH2O)	CHBrCH₃	H	H
3-CF₃,4-NO2	i-C₃H₇	H	H
3-O,4-(t-C₄H₉)	i<₃H₇	H	4-F
3-Cl,4-F	CF(CH₃)₂	H	4-F
3-Cl,4-F	CF(CH₃)₂	4-F	4-F
2,4-Cl	i-CgH?	H	H
2,4-Cl	I-C3H7	8	4-F
3,4-(-OCH2O-)	i-C₃H₇	4-F	4-C1
4-CF₃	i-C₃H₇	4-F	4-F
3-Cl,4-F	CF(CH₃)₂	H	2,4-F
3-Cl,4-F	CF(CH₃)₂	6-F	4-F
4-(i-C₃H₇)	sec-C₄H₉	H	H
3,4-F	CF(CH₃)₂	H	4-F
3-CF₃	CF(CH₃)₂	H	4-F
4-(i-C₃H₇)	c₂h₅	H	4-F
4-(i-C₃H₇)	CH(C₂H₅)₂	H	H
4-(i-C₃H₇)	t-C₄H₉	H	4-F
4-OCF₃	i-C₃H₇	4-F	4-C1
4-CF3	i-C₃H₇	4-F	4-C1
4-F	i-C₃H₇	4-F	4-C1
3-1,4-F	i-C₃H₇	4-F	4-C1

PR-7713/7874/7924/8029/8443A

TABLE 1 (continued)

Phenyl Subst.	r₂	*4	R5
3-Cl,4-F	^i_c3^H7	5-F	4-F
3-Cl,4-OCF₃	^i_<3^H7	5-F	4-F
4-(i-C₃H₇)	i-C₄H₉	H	4-F
2,4-F,3-Cl	ⁱ-^c3^H7	4-F	4-F
2,4-F,3-Cl	i-C₃H₇	H	4-C1
2,4-F,3-Cl	1-C3H7	H	H
4-Br	i-C₃H₇	4-F	4-F
3-1,4-F	i<₃H₇	4-F	H
4-1	i-C₃H₇	4-F	4-F
3,4-F	i-C₃H?	4-F	H
4-CF₃	i-C₃H₇	4-F	H
4-OCF₃	1-C3H7	4-F	H
4-(i-C₃H₇)	0	H	H
3-CF₃,4-Cl	^i_c3^H7	4-F	4-F
3-C1	i-C₃H₇	4-F	4-F
3-F	i-C3B₇	4-F	4-F
3-Cl,4-F	i-C₃H₇	4,6-F	4-F
4-(t-C₄H₉)	i-C₃ ^H7	H	4-CH₃
4-(t-C₄H₉)	^i-C3^H7	H	4-OCH₃
3-Cl,4-F	i-OjH?	4-F	3,4-F
4-CCF₃	ί-<₃ ^Η7	4-F	3,4-F
2,3,4-F	i-OjH?	H	4-F
2,3,4-F	i-C₃H₇	4-F	4-F
3-(t-C₄H₉)	^i-c3^H7	H	4-F
2-F,4-Br	ϊ-<3^Η7	H	4-F
2,4-F,3-Cl	i-C₃H?	H	4-F
4-SCH₃	^i_c3^H7	4-F	H
3-F,4-CH₃	^i-C3^H7	4-F	H
3-F,4-CH₃	1-C3H7	4-F	4-F

AP 0 0 0 1 5 o

PR-7713/7874/7924/8029/8443A

TABLE 1 (continued)

Phenyl Subst.	R2.....	r₄	Rs
3-Cl,4-CH₃	1-C3H7	4-F	H
3-Cl,4-CH₃	i-C₃ ^H7	4-F	4-F
3-CH₃,4-Br	i-C₃ ^H7	4-F	H
3-CH₃,4-Br	^i-c3^7	4-F	4-F
4-C₂H₅	^i_c3^H7	4-F	H
4-C₂H₅	1-C3H7	4-F	4-F
3-SCH₃	ΐ-<:₃Η7	4-F	H
3,4-OCH₃	i-C₃H₇	4-F	4-F
3-CF3,4-Br	i-C₃H₇	4-F	4-F
4-CF3	1-C3H7	H	4-C1
3,4-(-OCH2O-)	i-C₃H₇	4-F	4-C1
3,4-(-CCH₂O-)	^i_c3^H7	H	4-(t-C₄H₉)
3-Cl,4-OC₂H₅	i-C₃ ^H7	H	H
3-Cl,4-OC₂H₅	^i-c3^H7	4-F	4-C1
3-Cl,4-OC₂H₅	i-C₃ ^H7	4-F	H
4-OC₂H₅	^i-c3^H7	H	H
4-OC₂H₅	i^₃H₇	4-F	4-C1
4-OC₂H₅	1-C3H7	4-F	H
3-Cl,4-I	i-C₃H₇	H	4-F
3-F	i-C₃H₇	4-F	4-C1
3,4-Cl	i-C₃ ^H7	4-F	H
3-Br,4-CF₃	i-C₃H₇	4-F	4-C1
4-Br	^i_c3^H7	4-F	4-C1
3-Br,4-F	1-C3H7	4-F	4-C1
3-Cl,4-Br	1-C₃H₇	H	4-C1
3-Cl,4-Br	i-C₃H₇	4-F	4-C1
3-Cl,4-Br	i-C₃H₇	4-F	4-F
3,4-Br	i-C₃H₇	4-F	4-F
3,4-Br	i-OjH?	4-F	H
3-Cl,4-I	i^₃H₇	4-F	4-F
3-Br	1-C3H7	4-F	4-C1

PR-7713/7874/7924/8029/8443A

TABLE 1 (continued)

Phenyl Subst.	R?	R4	Rs
3-Br	1-C3H7	4-F	H
3-CF₃,4-Cl	1-C3H7	4-F	H
3-1	I-C3H7	H	4-C1
3-C1	1-C3H7	4-F	4-C1
4-Cl	1-C3H7	4-F	4-0
4-CN	X-C3H7	4-F	4-0
4-CN	I-C3H7	H	4-0
4-CN	i-C3^H7	4-F	4-F
2,4-F,3-Cl	i-C₃ ^H7	4-F	4-0
3-CH₃,4-F	i-C3fl₇	4-F	4-F
3-CH₃,4-F	i-C₃H₇	H	4-0
3-Br,4-F	i-C^?	H	4-0
3-CH₃,4-F	i-C₃H₇	4-F	4-0
3-CH₃,4-F	i-€₃H₇	4-F	H
3-CH₃	i-C₃ ^H7	4-F	4-0
3-Cl,4-CH₃	^i_c3^H7	H	4-F
3-Cl,4-CH₃	1-C3H7	H	4-0
3-Cl,4-CH₃	I-C3H7	4-F	4-0
3-CH₃	I-C3H7	H	4-F
3,4-CH₃	1-C3H7	4-F	4-0
3-CH₃,4-Br	I-C3H7	4-F	4-0
3-Cl,4-OCH₃	1-C3H7	4-F	4-F
3-Cl,4-OCH₃	i-C₃H₇	4-F	H
3-Cl,4-OCH₃	^i-c3^H7	4-F	4-0
2-C₂H₅	X-C3H7	H	4-F
4-OCH₃	^i_c3^H7	4-F	4-0
3-1,4-F	^i_c3^H7	H	4-0
4-SC>2CH₃	X-C3H7	4-F	4-F
3-Cl,4-F	-C (CH₃)=CH₂	4-F	4-C1
3-Cl,4-F	-C (CH₃)=CH₂	4-F	H
3-Cl,4-F	-c (CH₃)=CH₂	H	H

AP 0 0 0 1 5 0

TABLE 1

PR-7713/7874/7924/8029/8443A

Phenyl Subst.	(continued)
R2	-*dL-	*5
4-OCP2CHPCI	i-C₃ ^H7	H	H
4-OCF₂CHFCl	K3H7	4-F	H
3-C1,4-OCH₂CF₃	1-C3H7	H	4-F
3-Cl,4-OCH₂CF₃	^i-c3^H7	H	4-C1
4-OCH₂CF₃	^i_<:3^H7	4-F	H
4-OCH₂CF₃	i<₃H₇	H	H
3-Cl,4-OCH₂CF₃	1-C3H7	4-F	H
3-C1,4-001^3	1-C3H7	H	H
3-OC₂H₅	K3H7	4-F	4-F
2-Cl,4-CF₃	I-C3H7	H	4-F
2-Cl,4-CF₃	i-C₃H₇	4-F	H
3-F,4-OCH₂CF₃	1-C3H7	H	Cl
4-CF3	-C (CH₃)=CH₂	H	H
4-CF3	-C (CH₃)=CH₂	4-F	H
4-CF3	-C (CH₃)=CH₂	4-F	4-C1
3-Br,4-CF₃	i-C₃ ^H7	4-F	4-C1
3-Br,4-CF₃	^i_c3^H7	4-F	H
3-F,4-OCH₃	1-C3H7	4-F	H
3-OCF3	1-C3H7	4-F	4-C1
3-OCF3	i-C₃H7	4-F	H
3-Cl,4-C2H5	1-C3H7	H	4-F
3-F,4-OC2H5	1-C3H7	4-F	H
4—n-C3H7	i^₃H₇	4-F	4-F
3-F,4-Cl	I-C3H7	4-F	4-F
4-CF3	-C (CH₃)=CH₂	H	4-F
4-CF3		4-F	H
4-CF3	X]	4-F	4-C1

Cnpd. No.	Phenyl Subst.	37 TABLE 1 (continued) r₂	PR-7713/7874/7924/8029/8443A
R_d	Rr
445	2-ND2,4-CF₃	i-C₃H₇	4-F	H
446	3-Br,4-OC₂H₅	^i_c3^H7	H	4-F
447	3-Cl,4-F	i-C₃H₇	H	4-1
448	3-Cl,4-F	1-C3H7	4-C1	4-F
449	3-1,4-F	^i-c3^H7	H	4-F
450	3,4-(-OCF₂O~)	i-C₃H7	H	4-C1
451	2,4-F,3-Cl	^i_c3^H7	4-F	H
452	3-OCH₂CF₃,4-Cl	^i-c3^H7	4-F	4-C1

Q.

<

TABLE 2

PR-7713/7874/7924/8029/8443A r-i-n=c ^VxOR₃ (Ri = unsubstituted or substituted phenyl)

Cnpd.

NO.	Phenyl Subst.	R2
453	4-Cl	chci₂
454	2,3-Cl	chci₂
455	4-Cl	i-C₃H₇
456	4-F	i-C₃H₇
457	4-Cl	i-C₃ ^H7
458	4-F	i-C₃H7
459	3-CF₃	^i_c3^H7
460	3-Cl,4-F	i-C₃H₇

TABLE 2

PR-7713/7874/7924/8029/8443A (continued)

Phenyl Subst.

3-Cl,4-F

3-C1/4-F

3-Cl,4-F

3,4-(-0020-)

3.4- (-0020-)

3.4- [-OC(CH₃)20-]

3-CF₃

3-Cl,4-F i-<3^H7

1-C3H7 ^i_c3^H7 ^i-C3^H7 ^i_c3^H7

1-C3H7 ^i_c3^H7 ^i_c3^H7 ^i_c3^H7 ^i_C3^H7

-02^

-O

PR-7713/7874/7924/8029/8443Α

ΤΑΒΓ£ 2 (continued)

Phenyl Subst. R?

3-0,4-1 1-C3H7

3-0,4-F 1-^3^7

3-0,4-F 1-C3H7

3-0,4-F i-C3H7

3-0,4-F 1-C3H7

3-CF3 1-0387

3-CF3 1-C3H7

4-Br 1-C3H7

3-0-4-F 1-C3H7

3-CF3

I-C3H7

-CH₂ i-OCH₂CH=CH₂

TABLE 2

PR-7713/7874/7924/8029/8443A (continued)

Phenyl Subst. R?

3.4- Cl i-C₃H₇

3- CF3 1-C3H7

3.4- (-OCH2O) 1-C3H7

4— Cl 1-C3H7

3.4- F 1-C3H7

2.4- F 1-C3H7

3-Cl,4-F i-C₃H₇

3-CF3 i-C₃H₇

3-CF 3 1-C3H7

3-Cl,4-F i-C₃H₇

1-C3H7

4-F

TABLE 2

PR-7713/7874/7924/8029/8443A (continued)

Phenyl Subst. R;

3-Cl,4-P 1-C3H7

3-CF3 i-C₃H₇

3-Cl,4-F 1-C3H7

3- CF₃ i~C₃ ^H7

4- (t-C₄H₉) i~C₃ ^H7

4-(t-C₄H₉) X-C3H7

3-Cl,4-F 1-C3H7

3-CFj 1-C3H7

2.4- F,3-Cl i”C₃ ^H7

3.4- (-OCH2O-) 1-C3H7

TABLE 2

PR-7713/7874/7924/8029/8443A (continued)

Cnpd.

No.

Phenyl Subst. R?

«a

502

3-Cl,4-F ^i-c3^H7

503

3-CF₃ i-C₃H7

504

4-CF3

1-^7

505

3-Cl,4-F

1-C3H7

506

3-CF3

1-0311-7 —CH

ς v 0 0 0 dV

507

3-CF3

1-0311-7 -CH

508

3-CF3 i-C3^H7

509

3-CF3 ^i_C3^H7

510

3-01,4-F ^i-c3^H7

PR-7713/7874/7924/8029/8443A

TABLE 2 (continued)

Cnpd.

No. Phenyl Subst.

J*2.

511 3-Cl,4-F i-C₃ ^H7 *2

-CH

512 3-Cl,4-F i-C₃ ^H7

513 3-CF₃ ^i-c3^H7

514 3,4-Cl i-C₃H₇

515 3,4-(-OCH₂O-) i-C₃ ^H7

516 3-Cl,4-F i-C₃H₇

517 3-CF3

1-C3H7

518 3-CF3

1-C3H7

519 3-CF3 i-€₃H₇

PR-7713/7874/7924/8029/8443A

TABLE 2 (continued)

Phenyl Subst.

3-Cl,4-F

2,4-F,3-Cl

2.4- F,3-Cl

3.4- Cl

3.4- F

3,4-F

3-Cl,4-F

3-CF₃

3-Cl,4-F

1-C3H7 ΐ-^Η?

ΐ-03Η₇ i-C3^H7

C₂H₅ t-C₄Hg

CH3 ^i_c3^H7

I-C3H7 ^i_c3^H7

F-γ ^F pL-V Λ-,ρ

-CH

-ch₂

-CH

“CH-CH₂

-CH

-ch₂.

ί )

AP 0 0 0 1 5 0

PR-7713/7874/7924/8029/8443A

TABLE 2 (continued)

Phenyl Subst. R?

4-CF3 I-C3H7

3-C1.4-F ^i_c3^H7

3,4-(-0020-) 1-C3H7

3-Cl,4-F 1-C3H7

3- Cl,4-F 1-C3H7

4- CF3 I-C3H7

4-(t-C₄H₉) i-C₃H₇

3- Cl,4-F 1-C3H7

4- CCF3 1-C3H7

4-NO2 1-C3H7

1-C3H7

3,4-(-0020-)

PR-7713/7874/7924/8029/8443A

Cnpd.

No.

541

542

543

544

545

546

547

548

549

TABLE 2

(continued)
Phenyl Subst.	R2	R3
3-Cl,4-F	i-C₃H₇	^ΟρΓ*²©
4-OCF₃	i-C₃H₇
4-CF₃	ΐ-Ο₃Η₇	^²ΤρΡΐρ) ^Fp~P^F
4-(t-C₄H₉)	i-C₃H₇	-^2-/0)-^20^3 F F
3-CH₃	i-C₃H₇

OJ LOLci

3-CF3	ⁱ“^c3^H7	fL P -^2-/0/^2^
3,4-(0CH₂O-)	^i-C3^H7	F-. ^-—F -€^H2-/0/-^CH2^CsCH
3-CF3	1-C3H7	-CH₂-CgC-QH₂-O^Q^>
3-Cl,4-F	1-C3H7	-CH^ O'Px

OJ TQ

PR-7713/7874/7924/8029/8443A

TABLE 2 (continued)

Cnpd.

No.

550

Phenyl Subst. R?

4-OCF3 i-C₃H₇

551

3-F,4-Br i-C₃H₇

552

4-C2H5 1-C3H-7

553

4-C1 i-<3^H7

-CH

554

4-C1 ^i-c3^H7

555

3-CF₃,4-Cl i-C₃H₇ —CH

556

3.4-OCF2O

1-C3H7

557

3-Br i-€₃H₇

PR-7713/7874/7924/8029/8443A

TABLE 2 (continued)

Cnpd.

No.

Phenyl Subst. R?

558

3-Br,4-F

X-C3H7

559

3,4-F i-€₃H₇ *3.

560

4-CF3

-C (CH3)=CH₂

0.

<

PR-7713/7874/7924/8029/8443A

Insecticidal Evaluation Tests

The conpounds in Tables 1 and 2 above were tested for insecticidal activity using the following testing procedures.

Housefly (HF) (Musca domestica):

Test conpounds were diluted in acetone and aliquots pipetted onto the bottom of aluminum dishes to provide 100^jg of the test conpound. To ensure even spreading of the chemical on the bottom of the dishes, 1 ml of acetone containing 0.01% peanut oil was also added to each dish. After all solvents had evaporated, the dishes were placed in circular cardboard cages containing 25 female houseflies, 1-2 days old. The cages were covered on the bottom with cellophane and on the top with tulle netting, and each contained a sugar-water saturated cotton plug for maintenance of the flies. Mortality was recorded after 48 hours.

Blade Bean Aphid (BBA) (Aphis fabae (Seep.)];

Nasturtium plants (Tropaeolum sp.) approximately 5 cm tall, were transplanted into sandy loam soil in small cups and infested with 25-50 black bean aphids of mixed ages. Twenty-four hours later they were sprayed to the point of runoff with 50-50 acetone-water solutions containing 0.05% of the test conpounds. Treated plants were held in the greenhouse and mortality was recorded after 48 hours.

Tobacco Budworm (Heliothis virescens (Fabricius)]:

(a) Contact; (IBW-C) Test conpounds were diluted to a concentration of 0.1% in a 50-50 acetonewater solution. Cotton (Gossypium sp.) cotyledons were immersed in the test solutions for 2-3 seconds and placed on a wire screen to dry. The dried leaves were placed in petri dishes containing a moistened piece of filter paper and infested with 5 seoond-instar tobacco budworm larvae. The dishes were placed in a high humidity chamber for 5 days, and percent mortality of the larvae recorded.

PR-7713/7874/7924/8029/8443A (b). Eggs: (TBW-E) Paper towel patches of 2-day old eggs of the tobacco budworm were dipped in acetone solutions containing 0.1% of the test oonpound and placed in petri dishes containing a portion of larval rearing medium. Treated eggs were maintained at 78’F and mortality was recorded after all control eggs had hatched and the young larvae were feeding on the media.

Cabbage Looper (CL) (Trichoplusia ni (Hubner)]:

Test compounds were diluted to a concentration of 0.1% in a

50-50 acetone-water solution. Cotyledons of hyzini squash (Calabacita abobrinha), approximately 1 x 1.5 inches, were immersed in the test solutions for 2-3 seconds and placed on a wire screen to dry. The dried leaves were placed in petri dishes containing a moistened piece of filter paper and infested with 5 second-instar cabbage looper larvae. The dishes were placed in a high humidity chamber. Mortality of the larvae was recorded 3-5 days later.

Beet Arnyworm (BAW) (Spodoptera ex igua):

Test compounds were diluted to a concentration of 0.1% in a

50-50 acetone-water solution. Young leaves of sugar beets (Beta vulgaris) were immersed in the test solutions for 2-3 seconds and placed on a wire screen to dry. The dried leaves were placed in petri dishes containing a moistened filter paper and infested with five second-instar beet arnyworm larvae. The dishes were placed in a high humidity diamber. Mortality of the larvae was recorded 3-5 days later.

Aster Leafhopper (LH) [Macrosteles fascifrens (Stal)]

Oat seedlings (Avena sp) were grown in a commercial potting soil in cups. When the plants were approximately 10 cm tall they were thinned to three plants per cup and dipped for 2-3 seconds in 50-50 acetone-water solutions of the test compounds. When the plants had dried, a clear plastic tube was placed over them and the bottom end pressed into the cup.

Ten aster leafhopper adults/nynphs were then placed in each tube and the tops of the tubes covered with white organdy cloth. Mortality counts were made after 48 hours.

AP 0 0 0 1 5 o

PR-7713/7874/7924/8029/8443A

Maize weevil (MW) [Sitophilus Zeamais (Motschulsky)l:

Test conpounds were diluted to a concentration of 0.01% in a 50:50 acetone:water solution. Pour com seeds [Zea mays (L.)] which had been immersed in test solutions for 2-3 seconds and allowed to dry were placed in containers together with 10 adult weevils. The containers were covered and kept at a tenperature of about 25*C. Mortality was recorded after 48 hours.

Rice water weevil (FWW) (Lissorhoptrus oryzophilus (Kuschel)]:

Test conpounds were diluted in acetone. Droplets (1 ul) of test solutions were applied to the ventral abdomens of ten female adult weevils such that 2.5 >»g of test compound was applied to each weevil. The treated weevils were placed in containers with wet cotton balls and rice foliage. The containers were covered and kept at a tenperature of about

25*C. Mortality was recorded after 48 hours.

The results of these tests are shown in Table 3. Symbols in that table are as follows:

+= 50% or grater mortality at the testing level

- » less than 50% mortality at the testing level

NT test not conducted

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PR-7713/7874/7924/8029/8443A

I I I I I I I I I I I I I I + I I I I dP

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+ I + I + I I I + + I + I I + + + I +

TABLE 3 (ΙΓ5η) ω

m m m £ m m m

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AP 0 0 0 1 5 0 £ m m m m m m

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PR-7713/7874/7924/8O29/8443A

η £

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TABLE 3 (LCsn)

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T—	<N	m		in	iC	r*	00	σ>	©
in	in	in	in	m	in	in	in	m	©
in	m	in	m	in	in	in	in	in	1C

PR-7713/7874/7924/8029/8443A

The conpounds in Tables 1 and 2 were also tested for activity against the two-spotted mite (Tetranychus urticae (Koch)] and Western spotted cucumber beetle larvae [Diabrotica undecinpunctata undecinpunctata (Mannerheim)]. Initial testing levels were 0.05% (in solution) against the mite, and 25 ppm (in soil) against the beetle. Some conpounds demonstrated 50% or more mortality against one or the other insect at the initial testing level, but most did not.

Other conpounds within the scope of this invention which have been prepared and have shown 50% or greater mortality against at least one insect in tests as described above are listed below. Most of these compounds are analogous to a conpound in Table 1 or 2, that is, they have the same groups indicated for R₂ and R3 (or R4 and R=5 of Table 1), differing only in having different substituents on the phenyl ring from the indicated compound. These were:

Analogous to conpound 81 in which the substituents on the phenyl ring are: 3-Cl,4-Br; 3-CF3,4-Br; 4-SO2CH3; 2-Cl,4-CF3;

3-F,4-OCH₂CF3; 3-OCH₃,4-Br; 3-Br,4-OCH₃; 3-F,4-OCH₃; 3-Cl,4-C₂H₅;

2- Cl,5-C₂H₅; 3-F,4-OC₂H₅; 4-n-C₃H₇; 2,3,4-F; 3-Cl,4-OC₂H₅; 3-OC₂H₅,4-Br;

3- Br,4-OC₂H₅; 3-OCH₃,4-Cl; 3-OCH3,4-CF₃; 3-OC₂H₅,4-Cl; 2-NO₂,4-CF₃;

3-F,4-1; 3-Cl,4-OCHF₂; 3-Bt,4-C₂H₅; and 2,3-F;

Analogous to conpound 82 in which the substituents on the phenyl ring are: 4-CH3; 4-OCH3; 2,3-013; 2,4-013; 3,4-Ol₃; 3,4-0013; 3-C₂H₅; 3-013; 3-C1; 4-Br; 3-CF₃,4-Br; 4-1; 3-F; 3-Cl,4-Br; 3-Cl,4-I; 3-1; 4-CN; 3-OCH3; 4-SO2CH3; 3-OC₂H₅; 3-0013,4-Br; 3-Br,4-OCH₃; 3-Cl,4-C₂H₅; 3-OCH₃,4-Cl; 3-OCH₃,4-CF₃; 3-OCH₃,4-Br; 3-F,4-Cl; 3-Br,4-OC₂H₅;

3- Cl,4-OCHF₂; 3-F,4-I and 2,3-F;

Analogous to compound 89 in which the substituents on the phenyl ring are: 4-OCF₃; 3-Cl,4-Br; 3-F,4-Br; 3-NO₂,4-F; 3-CF₃; 3-F,4-CH₃;

2-Cl,5-F; 2,5-F; 3-CF₃,4-NO₂; 4-t-C₄H₉; 3-CF3,4-Br; 2-Br,4-t-C₄H₉;

2- Br,4-i-C₃H₇; 3,5-CH₃; 3-CH₃; 2,4-CH₃; 3,4-Ol₃; 3-CH3,4-Br; 2,3-CH₃;

4- OCH3; 4-SCH3; 3,4-OCH₃; 3-OC₂H₅; 3-OCH₃,4-Br; 4-OC₂H₅; 4-Cl,4-OC₂H₅;

3- Br,4-OCH₃; 3-F,4-OCH₃; 3-OCF₃; 2-Cl,5-OC₂H₅; 3-F,4-OC₂H₅; 4-n-C₃H₇;

3-OCH₃,4-Cl; 3-CCH3,4-CF₃; 3-OC₂H₅,4-Cl; 3-OCH₃,4-Br; 3-Br,4-OC₂H₅;

3-Cl,4-OCHF_2; 3-F,4-1; and 3-Br,4-C₂H₅;

PR-7713/7874/7924/8029/8443A

Analogous to conpound 191 in vhich the substituents on the phenyl ring are: 4-F; 2,3,4-F and 2,4-F,3-Cl;

Analogous to conpound 216 in which the substituents on the phenyl ring are: 3,4-(-OCH2O-); 3-Br; 4-C1; 4-F; 4-CH₃; 2,4-CH₃; 4-OCH₃;

2.3- CH₃; 3,4-CH₃; 3-C₂H₅; 3-SCH₃; 3-CH₃; 3-Cl,4-I; 3-OCH₃; 4-SCH₃;

2- Cl,4-CF₃; 3-OCH₃,4-Br; 3-F,4-OCH₃; 3-Br,4-OCH₃; 3-OCF₃; 3-Cl,4-€₂H₅;

3- F,4-OC₂H₅; 3-OCH₃,4-Cl; 3-CF₃,4-€CH₃; 3-CC₂H₅,4-Cl; 3-OC₂H₅,4-Br;

3-Br,4-OC₂H₅; 3-F,4-1 and 3-Br,4-C₂ ^H5?

Analogous to conpound 238 in which the substituents on the phenyl ring are: 3-CF₃; 3-F; 3-1; 3-F,4-CF₃; and 4-Br;

Analogous to conpound 239 in which the substituents on the phenyl ring are: 3-CF₃; 3,4-F; 3-CCH₃; 3-CH₃; 4-OC₂H5; 2-Cl; 2-CH₃;

3- NO2,4-F; 3-4-C1; 3-F,4-CF₃; 4-t-C₄H₉; 3-C1; 3-F; 3-CF₃,4-Br; 4-Br; 4-1;

4- C₂H₅; 3-F,4-Br; 3,4-Br; 3-CF₃,4-Cl; 4-OCF₃; 3-SCH₃; 4-F; 2,4-CH₃; 4-CH₃;

3.4- CH₃; 3-CH₃,4-Br; 3-Cl,4-OCH₃; 2,3-CH₃; 4-OCH₃; 4-SCH₃; 3-Cl,4-OCH₂CF₃; 2-Cl,4-CF₃; 3-OCH₃,4-Br; 3-Br,4-OCH₃; 3-OCF₃; 3-Cl,4-C₂H₅;

3-F,4-OC₂H₅; 2,3,4-F; 3-F,4-CH₃; 3-CF₃,4-OCH₃; 3-OC₂H₅,4-Cl; 3-OC₂H₅,4-Br;

3-Br,4-CC₂H₅; 3-Cl,4-OCHF₂; 3-F, 4-1 and 3-Br,4-C₂H₅;

Analogous to conpound 267 in which the substituents on the phenyl ring are: 4-1; 4-C₂H₅; 3,4-Br, 3-Cl,4-I; 3-1; 3-SCH₃; 2,4-CH₃;

2- C₂H₅; 3-OCH₃; 4-SO2CH₃; 2-Cl,4-CF₃; 3,4-OCH₃; 3-OC₂H₅; 3-OCH₃,4-Br;

3- Br,4-OCH₃; 3-F,4-OCH₃; 4-001^3,- 3-Cl,4-CCH₃; 3-F,4-CH₃; 3-OCH₃,4-Cl;

3-CF₃,4-OCH₃; 3-OC₂H₅,4-Cl; 3-OC₂H₅,4-Br; 3-F,4-Cl; 2-NO2,4-CF₃;

3-Br,4-OC₂H5; 3-F,4-1; 3-Br,4-C₂H₅ and 2,3-F;

Analogous to conpound 274 in which the substituents on the phenyl ring are 3-Cl,4-F;

Analogous to conpound 447 in which the substituent on the phenyl ring is 4-1;

Analogous to conpound 461, in which the substituent on the phenyl ring is 4-CF₃;

PR-7713/7874/7924/8029/8443A

Analogous to conpound 462 in which the substituents on the phenyl ring are: 3-Cl,4-OCHF₂; 3-Cl,4-CH3; 2,3-013; 3-CF3,4-Br;

3.4- (-00120-); 3-N0₂; 2-C1; 2-Ol₃; 3-CF₃,4-F; 3-P,4-Ol3; 3-Cl,4-OCH₃;

3.4- OCH₃; 4-Br; 4-CF₃; 2,4-F,3-Cl; 4-01; 3-F,4-Br; 4-C₂H₅; 3-013,4-F;

3-Br; 4-1; 2-Cl,4-CF₃; 3,4-F; 3-C1; 3-C₂H₅; 4-F; 4-Ol₃; 3-CH₃; 3-OCH3;

3-01,4-001; 3-F; 4-001^3; 4-OC₂H₅; 3,4-OC₂H₅; 3,4-ai₃; 3-01,4-1; 2,4-Cl and 3,4-Cl;

Analogous to conpound 510 in which the substituent on the phenyl 10 ring is 3-Cl,4-F;

Analogous to conpound 516 in which the substituents on the phenyl ring are 3,4-(-00120-) and 2,4-F,3-Cl;

Analogous to conpound 517 in which the substituent on the phenyl ring is 3,4-(-00120-);

Analogous to conpound 518 in which the substituents on the phenyl ring are 2,4-F,3-Cl;

ir>

Analogous to conpound 520 in which the substituent on the phenyl ring is 3-CF3;

And the conpounds shown below in Table 4.

TABLE 4

PR-7713/7874/7924/8029/8443A

Phenyl Subst. R?_ R4

3-Cl,4-F	CHC1₂	H	4-F
4-1-C3H7	sec.-C4H9	H	4-F
4-I-C3H7	c₂h₅	H	H
4-1-^3117	CHBrCH₃	H	4-F
4-i-C3H7	CHBrCH₃	H	H
4-CF3	-C (CH₃)=CH₂	4-F	4-F
4-F	-C (CH₃)=CH₂	H	H
4-F	-C iCH₃)=CH₂	4-F	4-C1
4-F	-C (CH₃)=CH₂	4-F	H
3,4-F	—CJ (CH₃)=CH₂	H	H
3,4-F	-C (CH₃)=CH₂	4-F	4-C1
3,4-F	-C (CH₃)=CH₂	4-F	H
3,4-( -OCH2O-)	-C (CH₃)=CH₂	H	H
3,4-(-OCH₂O-)	-C (CH₃)-CH₂	4-F	4-C1
3,4-(-OCH2O-)	-c (CH₃)=CH₂	4-F	H
4-OCF3	-C (CH₃)<H₂	H	H
4-OCF3	-C (CH₃)=CH₂	4-F	4-C1
4-OCF3	-C (CH₃)=CH₂	4-F	H

PR-7713/7874/7924/8029/8443A

For information, the following Table 5 lists a very small number of compounds within the definition of the class of this invention which did not produce 50% or greater mortality in an insecticidal evaluation test to date.

TABLE 5

J²

R]-N=C-QR₃

Phenyl Subst. _R₂

4-C1 CHC1₂ ^r3

F^_ ^F

4-OCF3 CHC1CH₂CH₂C1

-CHo OX

Wig

2,3-Cl 1-C3H7

H C(CH₃)2CH₂C1

3,5-CF3 i-<3H₇

3-C1 i-C₃H₇

3,5-Cl i-C₃H₇

2.4- Cl i-C₃H₇

3.4- Cl i-C₃H₇

Phenyl Subst.

3—Cl t—C^Hg

PR-7713/7874/7924/8029/8443A

Table 5 - continued *2

3,4-CCH₃ I-C3H7

4-0 -CH=C(CH₃)₂

The insecticidal activity, and therefore the inclusion of a canpound not mentioned specifically herein within the class of compounds of this invention, as determined by the general formula (I), may be determined by evaluating such a compound using one or more of the above-described procedures. If a test oonpound demonstrates activity against one or more of the insects mentioned, by virtue of causing 50 percent or greater mortality at the initial evaluation level, it is considered insecticidal for the purposes of this invention.

In practice, a pure compound (active compound) can be used as an insecticide. However, in general, the compounds are first formulated with one or more inert (i.e. non-chemical ly reactive, plant compatible or herbicidally inert) carriers or diluents suitable for insecticidal use, before being applied.

The compositions or formulations, including a compound as described herein, may take any one of a number of solid or liquid forms. Examples of solid forms are dusts, granules, tablets, powders and the like. Examples of liquid forms are emulsions, solutions, suspensions, flowables, emulsifiable concentrates and pastes. Such compositions may contain, in addition to the active compound or compounds, various carriers or diluents; surface-active agents (wetting agents, dispersing agents and/ or emulsifying agents); solvents (water, or organic solvents such as aromatic solvents or chlorinated aliphatic solvents); adhesives; thickeners;

PR-7713/7874/7924/8029/8443A binders; anti-foaming agents; and other substances as mentioned herein. Solid carriers or diluents included in such oonpositions or formulations may include, for example, ground natural minerals such as kaolins, alumina, calcined diatomaceous earth, calcium carbonate, silica, kieselguhr, clays, etc.; ground synthetic minerals such as various silicates and alumino-silicates and ground vegetable products such as bark, cornmeal, sawdust, cellulose powder and the like. Conpositions containing sorptive clays will usually also contain a stabilizer, such as a glycol, to prevent or minimize degradation of the active ingredient.

To manufacture solid conpositions, the active conpounds are mixed with solid carriers or diluents such as those mentioned above and the mixture is ground to the appropriate size. Granules can be manufactured by dissolving an active compound in an organic solvent and applying the mixture, for exanple, by atomization, onto an absorptive granulated inert material, such as silica. Adhesives may be utilized to assist in the incorporation of the compound onto the solid particles.

Wettable powders and pastes are obtained by mixing and grinding an active compound with one or more dispersing agents and/or solid carriers or diluents. Also included may be wetting agents and/or dispersing agents, for exanple, lignins, methyl cellulose, naphthalenesulfonic acid derivatives, fatty alcohol sulfates and various types of alkali and alkaline earth metal salts of fatty acids.

Emulsifiable concentrates are generally obtained by dissolving the active compound in an organic solvent, for exanple, butanol, cyclohexanone, xylenes, or higher boiling aromatic hydrocarbons. To obtain suspensions or emulsions in water, wetting agents may also be added.

Flowables are prepared by mixing an active compound with one or more dispersing agents and/or solid additives, and a liquid (which may be water or an organic solvent) in which the active compound is relatively insoluble, and grinding the mixture.

ς VO 0 0 dV

PR-7713/7874/7924/8029/8443A

Both liquid and solid conpositions may be in microcapsule or encapsulated form, to permit release of the enclosed active conpound at a controlled rate over a period of time. Liquid conpositions of this type contain encapsulated droplets of approximately 1-50 microns in diameter, including the active conpound and optionally a solvent. The encapsulating material is an inert porous membrane of a polymeric material.

Solid encapsulated conpositions generally take the form of granules, in which the liquid containing the active conponent is trapped in the pores of the granular support by a porous polymeric membrane through which the active ingredient may migrate at a controlled rate, or which membrane breaks down at a controlled rate to permit escape of the active ingredient.

Typical encapsulating materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyamides, poly isocyanates, polyurethanes, mixed copolymers of the foregoing and starch xanthates.

It is possible to use highly concentrated liquid conpositions containing up to about 95% by weight of the active conpound, or even the 100% active conpound alone, when applying the conpound in the form of a finely divided liquid by use of various atomizing equipment, for exanple by airplane spraying techniques. For other purposes, however, the various types of conpositions which can be utilized for these conpounds will contain varying amounts of the conpound according to the type of conposition and the intended use.

In general, insecticidal conpositions may contain from 5 to 95% of the active conpound, more preferably from 10 to 85%. Seme typical canpositions will contain an active conpound as follows; wettable powders:

to 80% active conpound; oil suspensions, emulsions, solutions, flowables, and emulsifiable concentrates: 5 to 85% active conpound; aqueous suspensions: 20 to 50% active conpound; dusts and powders: 5 to 20% active conpound; granules and pellets: 5 to 20% active conpound.

PR-7713/7874/7924/8029/8443A

In addition to the active conpound and the various agents utilized in preparing conpositions and formulations mentioned, such oonpositions may also contain one or more other active conpounds of the type mentioned herein as well as other active pesticidal agents, such as herbicides, fungicides, insecticides, acaricides, nematocides, bactericides, and plant growth regulators. Ihe particular pesticide included in the mixture will depend upon its intended utility and the type of conplementary action required. Exanples of suitable insecticides include the following:

(a) natural pyrethrins or pyrethroids such as permethrin, fenvalerate, deltamethrin, cyhalothrin, biphenthrin, fenpropathrin, cyfluthrin, tefluthrin, enpenthrin, ethofenprox, tetramethrin, bioallethrin, fenfluthrin, prallethrin, 5-benzyl-3-furylmethyl-(E)-{1R,3S)~2,2dimethyl-3-( 2-oxothiolan-3-yli dene- methyl )cyclopropane carboxylate and pentafluorobenzyl (cis)-3-[ -2-fluoro-2-(methoxycarbonyl )e thenyl)-2,2-d imethy Icy clopropane carboxy late;

(b) organophosphates such as profenofos, sulprofos, phosmet, dichlorvos, methyl parathion, azinphos-methyl, dimeton-s-methyl, heptenophos, thiometon, fenamiphos, monocrotophos, triazophos, methamidophos, dimethoate, phosphamidon, malathion, chlorpyrifos, phosalone, fensulfothion, fonofos, phorate, phoxim, pyrimiphosmethyl, fenitrothion and diazinon;

(c) carbamates (including aryl carbamates) such as pirimicarb, cloethocarb, carbofuran, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur and oxamyl;

(d) benzoyl ureas such as triflumuron, chlorofluazuron;

(e) organic tin conpounds such as cyhexatin, fenbutatin oxide and azocyclotin;

(f) macrolides such as avermectins or milbemycins, for exanple such as abamectin, avermectin, and milbemycin;

AP 0 0 0 1 5 0

PR-7713/7874/7924/8029/8443A (g) hormones and synthetic mimics thereof such as juvenile hormone, juvabione, ecdysones, methoprene and hydroprene;

(h) pheromones; and (i) organochlorine compounds such as benzene hexachloride, DDT, chlordane or dieldrin.

In addition to the major chemical classes of insecticide listed above, other insecticides having particular targets may be employed in the mixture if appropriate for the intended utility of the mixture. For instance selective insecticides for particular crops, for example stemborer specific insecticides for use in rice such as cartap or buprofesin, can be employed. Alternatively, insecticides specific for particular insect species/stages, for exanple ovolarvicides such as clofentezine, amitraz, chlordimeform flubenzimine, hexythiazox and tetradifon, motilicides such as dicofol or propargite, adulticides such as bromopropylate, chlorobenzilate, or insect growth regulators such as hydramethylon, cyromazine, methoprene, chlorofluazuron and diflubenzuron may also be included in the compositions. Such compounds may also contain soil disinfectants or fumigants and may further contain fertilizers, thus making it possible to provide multi-purpose compositions containing one or more of the active compounds described herein as well as, optionally, other pesticides and also fertilizers, all intended and formulated for use at the same locus.

Control of insect pests is accomplished by applying a composition containing an insecticidally effective amount of an active compound as described herein to the insect, to a locus at which insecticidal control is desired, or to food sources (including seeds) on which the insects feed. For use in the last mentioned manner it is preferable to utilize a compound which is not volatile. Thus, control may be achieved by direct application of the active compounds to the insects and indirectly by application of the compounds to a locus to be protected (such as crop lands, grass ranges and forests), to a source of food for insects or to other insect habitats (for exanple, breeding or swarming areas). The rates of application of the active compound, and the concentration

PR-7713/7874/7924/8029/8443A applied, will vary according to whether the conpound or composition is being directly applied to the insect or indirectly, to a locus, food or habitat. In the latter case the rate of the application, depending on the nature of the insect or insects to be controlled, and the plant environment, will generally vary from about 0.01 to about 100 pounds per acre (about 0.011 to about 111 kg/ha).

It should be noted that the active oonpound need not be insecticidally active per se to effect insect control. The purposes of this invention are fully served if such compounds are rendered active by external influences, such as light or heat, or by some physiological action which occurs when the oonpound is ingested into the body of the insect.

Conpounds of this invention could be used to control a variety of insects such as:

Myzus persicae (aphid)

Aphis gossypii (aphid)

Aphis fabae (aphid)

Megoura viceae (aphid)

Aedes aegypti (mosquito)

Anopheles spp. (mosquitos)

Culex spp. (mosquitos)

Dysdercus fasciatus (capsid)

Musca domestica (housefly)

Pieris brassicae (white butterfly)

Plutella maculipennis (diamond back moth)

Phaedon cochlaeriae (mustard beetle)

Aonidiella spp. (scale insects)

Trialeuroides spp. (white flies)

Bemisia tabaci (white fly)

Blattella germanica (cockroach)

Periplaneta americana (cockroach)

Blatta orientalis (cockroach)

Spodoptera littoralis (cotton leafworm)

Heliothis virescens (tobacco budworm)

Chortiocetes terminifera (locust)

AP 0 0 0 1 5 0

PR-7713/7874/7924/8029/8443A

Diabrotica spp. (rootworms)

Agrotis spp. (cutworms)

Chilo supressalis (stem borer

Chilo partellus (maize stem borer)

Nilaparvata lugens (planthopper)

Nephottex virescens (leafhopper

Nephotettix cincticeps (leafhopper)

Panonychus ulmi (European red mite)

Panonychus citri (citrus red mite)

Tetranychus urticae (two-spotted spider mite)

Tetranychus cinnabarinus (carmine spider mite)

Phyllcoptruta oleivora (citrus rust mite)

Polyphagotarsonemus latus (broad mite)

Brevipalpus spp. (mites) expositions containing one or more of the active conpounds described, in an insecticidally effective amount, may be applied to the plant, locus or insect habitat in any conventional manner.

When used in connection with crop or other plant protection, application may be made in a preventive (i.e. before infestation) or eradicative manner (i.e., after infestation). Thus, powders and various liquid conpositions containing the active conpound can be applied by the use of power dusters, boom and hand sprayers and spray dusters, or applied from airplanes as dusts or sprays. When applied in the latter method they may be effective in very low dosages.

Conpositions including active conpounds may also be applied by addition to irrigation waters supplied to the field to be treated. This method of application permits penetration of the conpounds into the soil as the water is absorbed therein.

Conpositions including active conpounds may additionally be used to protect plant seeds from being attacked by soil-borne insect pests after planting and during germination, by applying the composition to the seeds as a seed dressing. This is performed generally by mixing the seeds with an active conposition in either liquid or solid form (preferably

PR-7713/7874/7924/8029/8443A liquid) in a suitable mixing apparatus. Liquid compositions for this purpose may contain an adhesive or sticking agent, such as methyl cellulose, ethyl cellulose, etc., to assist the composition in adhering to the seed. If a solid composition is utilized for this purpose, an adhesive agent may be sprayed on the seeds during or after mixing.

For use as a soil insecticide, the active conpound, or compositions containing it, may be mixed with the soil in any conventional manner, before, during or after planting of the plant seeds. Liquid compositions may be applied by spraying onto the surface or by incorporation in irrigation or sprayed water. Solid or liquid compositions containing an active conpound may be incorporated into the soil prior to or during planting by discing, plowing or other mixing operations, in order to locate the active ingredient below the surface of the soil so as to be most effective in controlling undesirable larvae.

Some examples of compositions containing the active compounds of this invention are:

Composition A: Granular Solid

Conponent

Active conpound attapulgite clay granules triethylene glycol

Weight %

APO 00 1 5 o

Total 100%

Composition B: Wettable Powder

Component

Weight %

Active conpound 80 wetting agent (sodium dialkylnaphthalene sulfonate) dispersing agent (sodium lignosulfonate) diluent (aluminum magnesium silicate) _

Total

100%

PR-7713/7874/7924/8029/8443A

Composition C: Dilute Solution

Component

Active compound solvent (xylene)

Total

Composition D: Emulsifiable Concentrate

Component

Active compound

Emulsifier (blend of metal sulfonates and polyoxyethylene ethers) solvent (xylene)

Total

Composition E; Concentrated Solution

Component

Active compound solvent (xylene)

Total

Weight %

100«

Weight %

100%

Weight %

100%

Claims

1. A compound having the formula (I) in which

R] is naphthyl, optionally substituted by up to 2 halogens; or phenyl, optionally substituted by one or more of: Cj-Cj carboalkoxy,

10 C1-C4 alkyl sulfonyl, C1-C4 haloalkylsulfonyl, C2-C5 alkylcarbonyl, C2--C4 alkenyl, C1-C4 haloalkylthio, C₃-Cg cycloalkyl, phenyl, monosubstituted phenyl, pyridyloxy, C2-C4 alkyleneoxy, C]-C₄ alkylenedioxy, Cj-C₃haloalkylenedioxy, C2-C4 alkylene, amido, nitro, cyano, up to two C]-<4 alkyl thio groups, up to three C1-C4 alkoxy groups, up to three C1-C4

15 haloalkoxy groups, up to three C1-C4 alkyl groups, up to three C1-C4 haloalkyl groups, or up to five halogens;

R₂ is methyl; ethyl; n-propyl; C3-O7 branched alkyl; Cj-Cg haloalkyl, cyclopropyl optionally substituted with up to 4 methyl groups or up to 2 halogens, cyclobutyl, cyano, C₂-C₄ alkoxyalkyl, C2-C3 alkenyl or

20 C2-C3 haloalkenyl; and (a)

AP 0 0 0 1 5 0

30 R4 is hydrogen or halo;

Rg is hydrogen, methyl, fluoro or ethynyl; and R₇ is (i)

PR-7713/7874/7924/8029/8443A in which D and E are each carbon or nitrogen provided that both D and E are not nitrogen, and further provided that if any of A, B or C is nitrogen, then D and E are both carbon; and

in which R8 is hydrogen or halogen; or (iii) -OCH2-CH=CH2 '-^(R1O)4 in which (i) R9 is 4-fluoro, 4-methoxymethyl, or 4-propargyl, and R10 is fluoro or (ii) R9 is 3- or 4-allyl, 3- or 4-propargyl, or 3- or 4-(monoor dihalo)allyl, and R10 is hydrogen or fluoro;

(c) —CH2

PR-7713/7874/7924/8029/8443A (d) 4-phenoxy-2-butyn-2-yl;

(e) 3-bromo-4-f luorobenzyl ;

(f) 4-(benzyloxy)-benzyl;

(g) 4-(4-fluorobenzyloxy)benzyl;

(h) 4-(4-trifluoromethyl-2-pyridyloxyJbenzyl; or (i) R; is not 2,3-dichlorophenyl, 2,6-difluorophenyl, 2,6-di(Cj-C4 alkyl)phenyl, 2,4,6-tribromophenyl or 2,4,6-tri(C1-C4 alkoxy) phenyl;

(ii) when R2 is tertiary butyl, R-| is not phenyl, 3-methylphenyl, 4-(n-butyl)phenyl or 4-(t-butyl)phenyl; and (iii) when R2 is a C5 alkyl group, R·, is not 4-isopropylphenyl.

2. A oonpound according to Claim 1 in which R1 is

Riy^—⁷

APO 00150 wherein R-j 1 is hydrogen, halogen, C]-C4 alkyl, Cf-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, CJ-C4 alkylthio, Cj-<4 haloalkylthio, C2-C5 carboalkoxy, C2“<5 alkylcarbonyl, nitro or cyano; R^ is hydrogen, halogen, C1-C4 alkyl, CJ-C4 haloalkyl, C1-C4 alkoxy, C;-C4 haloalkoxy, C1-C4 alkylthio, nitro, cyano, C1-C4 alkylsulfonyl, C2-C5 alkylcarbonyl or C2-C5 carboalkoxy; and R13 is hydrogen, halogen, C1-C4 haloalkyl or C1-C4 alkoxy, or R11 and R12 taken together are C2-C4 alkylene, C1-C4 alkyleneoxy, C1-C4 alkylenedioxy or halo-C;-C3 alkylenedioxy; provided that R]1, R12 and R13 are not all hydrogen.

3. A conpound according to Claim 2 in which R13 is hydrogen and R^ 1 and R-,2 are other than hydrogen.

4. A conpound according to Claim 2 in which R]j and Rj3 are hydrogen.

98 PR-7713/7874/7924/8029/8443A

5. A oonpound according to Claim 2 in which R]₂ and R]₃ are hydrogen.

6. A compound according to Claim 2 in which R]₂ is halogen and 5 R13 is hydrogen.

7. A oonpound according to Claim 2 in which R-μ is chloro, R^₂is fluoro and R13 is hydrogen.

10

8. A compound according to Claim 1 in which R-, is in which R]₄ is halogen and R15 is hydrogen or halogen.

9. A oonpound according to any of Claims 1-8 in vhich R3 is

10. A oonpound according to any of Claims 1-9 in which R3 is

11. A compound according to any of Claims 1-8 or 10 in which R₄and R5 are both hydrogen.

12. A compound according to any of Claims 1-8 or 10 in which R₄and R5 are both 4-fluoro.

13. A oonpound according to any of Claims 1-8 or 10 in which R4

35 is 4-fluoro and R5 is 4-chloro.

99 PR-7713/7874/7924/8029/8443A

14. A conpound according to any of Claims 1-8 or 10 in which ie hydrogen and Rj is 4-halo.

15. A conpound according to any of Claims 1-8 or 10 in which 5 is 4-fluoro and Rg is hydrogen.

16. A compound according to Claim 14 in which R3 is -.0^

R4 is hydrogen and R5 is hydrogen or 4-halo.

17. A conpound having the formula

R)-iX?=C *17 \

^R18

2-=—A-ccHpo«nd-aeeordif»g-to-Claim-4 in which R] is ,

r₁₃^ wherein R^ is hydrogen, halogen, C^-C₄ alkyl, C]-C₄ haloalkyl, Cj-C₄alkoxy, Cj-C₄ haloaltoxy, C]-<₄ alkylthio, Cj-C₄ haloalkyl thio, Cj-Cg carxKslkoxy, C2-C5 alkylcarbonyl, nitro or cyano; R₁₂ is hydrogen^

25 halogen, C]-C₄ alkyl, C^-C₄ haloalkyl, C]-C₄ alkoxy, C]-C₄ haloalkoxy, C-|-C₄ alkylthio, nitro, cyano, Cj-C₄ alkylsulfonyl, C2-C5 alkylcarbonyl

C2-C5 carboalkoxy; and R^ is hydrogen, halogen, C^-C₄ haloalkyl or Cj-C,· alkoxy, or R^j and R^₂ taken together are C₂-C₄ alkylene, C|-C₄alkyleneoxy, C^-C₄ alkylenedioxy or halo-C^-<3 alkylenedioxy; provided.--:;υ

0 ς V 0 0 0 dV

18. A process for preparing a eanpound according to Cl.u.a 17 ;cnprising reacting an amide having the formula r-— -n BAD ORIGINAL

R1NHCR2

V

100 PR-7713/7874/7924/8029/8443A with a base and a tri valent phosphorus conpound, in the presence of a halogen, in which R₂ is methyl; ethyl; n-propyl; C3-C7 branched alkyl other than those having no alpha-hydrogen atoms; Cj-Cg haloalkyl, cyclopropyl optionally substituted with up to 4 methyl groups or up to 2 halo5 gens, cyclobutyl, C₂-C4 alkoxyalkyl, C₂-C₃ alkenyl or C₂-C₃ haloalkenyl.

Claim

19. A process for the production of a conpound according to comprising reaction of a conpound having the formula

Z ''

Ri-N=C=C ¹ \ ^r18 with an alcohol having the formula R3OH in the presence of an alkali metal base in which R17 and Rig are independently hydrogen, C]-Cg alkyl, halo, Cj-Cg haloalkyl, C1-C3 alkoxy, C₂ alkenyl or C₂ haloalkenyl or R17 and R]g taken together are a C₂-C₃ alkylene chain optionally substituted by up to four methyl groupe or up to two halogens.

20. A conpound having the formula c=nh₂-hx

RjO^ in which

R₂ is methyl; ethyl; n-propyl; C3-C7 branched alkyl; Cj-Cg haloalkyl, cyclopropyl optionally substituted with up to 4 methyl groups or up to 2 halogens, cyclobutyl, C₂-C4 alkoxyalkyl, C₂-C₃ alkenyl or C₂-C₃haloalkenyl; and (a)

101

PR-7713/7874/7924/8029/8443A

R4 is hydrogen or halo;

R$ is hydrogen, methyl, fluoro or ethynyl; and

R7 is (i)

R5 in which D and E are each carbon or nitrogen provided that both D and E are not nitrogen, and further provided that if any of A, B or C is nitrogen, then D and E are both carbon; and

R5 is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, trifluoromethyl, cyano, C^-C^ alkylthio, C1-C4 alkylsulfonyl, or mono- or polyhalo;

(ii) in which Rg is hydrogen or halogen; or (iii) -O-CH₂“O1=Q32

AP 0 0 0 1 5 0 (i) Rg is 4-fluoro, 4-methoxymethyl, or 4-propargyl, and R^q is fluoro or (ii) R9 is 3- or 4-allyl, 3- or 4-propargyl, or 3- or 4-(monoor dihalo) allyl, and R]q is hydrogen or fluoro;

102

PR-7713/7874/7924/8029/8443A (c) —ch₂ (d) 4-phenoxy-2-butyn-2-yl;

(e) 3-bromo-4-fluorobenzyl;

(f) 4-(benzyloxy)benzyl;

(g) 4-(4-fluorobenzyloxy Jbenzyl (h) 4-(4-trifluoromethyl-2-pyridyloxy)benzyl; or

HX represents a mineral acid.

; and

21. An insecticidal conposition oonprising (a) an insecticidal15 ly effective amount of a conpound according to any of Claims 1-16, and (b) an insecticidally suitable diluent or carrier.

22. A method for controlling insects oonprising applying to an insect, the locus of an insect or a locus at which insecticidal control is

20 desired, an insecticidally effective amount of a conpound or conposition according to any of Claims 1-16 or 21.

23. A method for controlling insects according to Claim 22 in which the insect is a member of the order Lepidoptera.

24. A method for controlling insects according to Claim 22 in vhich the insect is a member of the order Coleoptera.

25. A method for controlling insects according to Claim 22 in 30 which the insect is a member of the order Hemiptera.

103

IV

26. A compound of the general formula I set out in claim 1 substantially as herein described with reference to the examples and tables 1 S 2.

27. A process for the production of a compound of the general formula I set out in claim 1 substantially as herein described with reference to the examples and tables 1 & 2.

28. An insecticidal composition comprising an insecticidally effective amount of a compound according to claim 26 and a suitable diluent or carrier.

29. A method for controlling insects comprising applying to the insect or the locus thereof or of the desired control zone a compound according to claim 26 or a composition according to claim 28.