This invention relates to novel pyrethroid-like insecticides which effectively control infestations of undesirable insects and acarids and simultaneously dis¬ play remarkably low toxicity to fish. Synthetic pyre- throids have been the focus of intensive research activ¬ ity for more than a decade. The pioneering work of Elliott, as described in U.S. 4,024,163, established that synthetic pyrethroids could be synthesized with sufficient stability to light to be commercially attrac¬ tive. The vast majority of these new pyrethroids are esters of substituted cyclopropanecarboxylic acids similar to those described by Elliott. Initially, co - pounds having the aforementioned structure were thought to be required for insecticidal activity; however, con¬ siderable effort has been successfully directed toward defining compounds which are nominally described as pyrethroids based upon similarities in molecular geom- etry and insecticidal activity. In some of these com¬ pounds only the ester linkage has been retained; in others the substituted cyclopropane ring has been retained; and in yet others neither the substituted cyclopropane ring nor the ester linkage has been retained. In the current invention an unsubstituted cyclopropane group is incorporated into pyrethroid-like compounds. These novel compounds lack the substituted cyclopropanecarboxylic acid moiety typical of the com¬ pounds described by Elliott and those who followed him. Further, these compounds display pyrethroid-like insecticidal activity while possessing remarkably low toxicity to fish in comparison with the notorious toxicity to fish exhibited by cyclopropanecarboxylates. United States Patent 4,397,864 discloses a class of pyrethroid-like compounds having the following sub- generic formula:

R

wherein

Ar is optionally substituted phenyl, optionally substituted naphthyl, or l,3-benzodioxol-5-yl; R is lower alkyl; Y is O or S;

Z is O, S, or a carbonyl or methylene group; R' is H, F, lower alkyl, or lower alkoxy; and n is 1-5. These compounds are alleged to have high insecticidal activity and low toxicity to fish.

United States Patent 4,073,812 covers a closely related series of compounds having the generic formula:

wherein

R is halogen, lower alkyl, or lower alkoxy; m is 1 or 2;

R ¹ is branched chain alkyl of 3-6 carbon atoms;

R ² is hydrogen or alkynyl of 2-4 carbon atoms;

R ³ is -fluorine; and n is 0 or 1.

In all examples R ¹ is isopropyl. All compounds are asserted to be insecticidal, some more than others, but there is no indication or assertion about the degree of toxicity to fish.

United States Patent 4,562,213 covers another similar series of compounds of the formula:

wherein R ¹ is hydrogen, halogen, or methyl; R ² is hydrogen or fluorine; is CH or N;

A is oxygen, methylene, or imino; X and Y are both methyl or taken together form an optionally substituted cyclopropane ring;

R ³ and R ⁴ may be the same or different and are hydrogen, halogen, lower alkyl, lower alkoxy, lower fluoroalkoxy, or taken together form a methylenedioxy bridge.

In all cases where A is oxygen, X and Y are taken together to form a cyclopropane ring or a substituted cyclopropane ring. These compounds are asserted to be insecticidal and acaricidal without any assertion relating to fish toxicity.

United Kingdom patent application GB 2 120 664A discloses a class of aromatic-substituted alkane deriva¬ tives having the following generic formula:

wherein

Ar stands for a substituted or unsubstituted phenyl or naphthyl group; R ¹ stands for a methyl, ethyl, or isopropyl group and R ² stands for a hydrogen atom or a methyl group or R ¹ and R ² taken together with the carbon to which 5 they are attached represent a substituted or

_. unsubstituted cycloalkyl group; and R ³ stands for the residue of an alcohol, R ³ OH, commonly found in natural or synthetic pyrethroids. _Q Examples of substituted or unsubstituted cycloalkyl groups named or exemplified by taking R ¹ and R ² together with the carbon to which they are attached are- cyclo- propyl, 2,2-dichlorocyclopropyl-, cyclobutyl, cyclo- pentyl, and cyclohexyl. These compounds are asserted to _g be highly insecticidal and acaricidal and to have low toxicity to mammals and fish.

Belgian patent 902147 discloses a class of compounds having the following generic formula:

0

Rl Ar-C-CR ³ =CR ⁴ CHDR _B

± ²

5

wher in

Ar represents a substituted or unsubstituted phenyl or naphthyl group; R ¹ and R ² taken together with the carbon atom to which they are attached represent a substituted or unsubstituted cycloalkyl group of 3-6 carbon atoms; R ³ and R ⁴ , which may be the same or different, are hydrogen, halogen, or C1-C alkyl; _β represents the residue of an alcohol, R _B CHDOH, which provides significant insecticidal activ¬ ity when esterified with lR,c_is-3-(2,2-dibromo- ethenyl)-2,2-dimethylcyclopropanecarboxylic acid; and D is hydrogen or cyano.

The compounds of this invention may be described as 2-(optionally substituted aryl)-2-cyclopropylethyl sub- stituted-benzyl ethers and thioethers and 1-(optionally substituted aryl)-l-cyclopropyl-4-(substituted aryl)- butanes. These compounds contain an asymmetric carbon atom; the invention thus includes individual stereo- isomers as well as racemic and non-racemic mixtures of enantiomers of the instant compounds.

This invention also encompasses insecticidal compo¬ sitions containing the pyrethroid ethers, thioethers, and butanes and their use for controlling insects-. The compounds of this invention are effective for control of a wide variety of insects and acarids and may be expected to be useful in any situation for which pyre¬ throid insecticides are indicated. The compounds of this invention find particular utility in applications where there is a possibility of significant contamina¬ tion of streams, rivers, and lakes by insecticidal material. Their low toxicity to fish will obviate concern about potential ecological problems associated

with the use of pyrethroids in environments where such contamination is possible.

The 2-(optionally substituted aryl)-2-cyclopropyl- ethyl substituted-benzyl ethers, thioethers,. and the 1- (optionally substituted aryl)-l-cyclopropyl-4-(substitu¬ ted aryl)butanes have the general formula:

in which Ar is a substituted or unsubstituted phenyl, naphthyl, or thienyl. A substituted Ar may have one or two, not necessarily identical, substituents. Prefer¬ ably Ar is phenyl and is monosubstituted at the 4-position. Preferred substituents include, but are not limited to, (Cι_ ₆ )alkyl, halo, (Cι_4)haloalkyl, ^* ( ^c l-4)alkoxy, (C^_4)haloalkoxy. Halo includes fluoro, chloro, and bro o. The term alkyl includes straight and branched chain alkyl groups having 1-6 carbon atoms, preferably 1-4 carbon atoms. The terms haloalkyl and haloalkoxy include ^" alkyl and alkoxy groups in which one or more hydrogen atoms have been replaced by fluorine, chlorine, or bromine atoms including all combinations thereof. Further, the substituent may have the struc¬ ture -A-(CR ¹ R ² ) _n -A- where R ¹ and R ² are independently, hydrogen, halogen, or (Cι_ ₂ )alkyl, n is 1 or 2, and each .A, which may be O, S, or CH ₂ , is bonded to a carbon atom of the aromatic ring, the carbons to which the A groups are attached being adjacent to each other in the ring. Illustrative of this mode of substitution are compounds in which Ar is 1,3-benzodioxolyl, 2,2-difluoro-l,3- benzodioxolyl, or 2,3-dihydro-2,2-dimethylbenzofuranyl.

Typical Ar groups include: phenyl, fluorophenyl, chlorophenyl, bromophenyl, preferably, 4-chlorophenyl; methylphenyl, ethylphenyl, propylphenyl, isopropyl- phenyl, butylphenyl, isobutylphenyl, sec-butylphenyl, tert-butylphenyl, preferably methylphenyl; methoxyphenyl, ethoxyphenyl, propoxyphenyl, isoprop- oxyphenyl, butoxyphenyl, isobutoxyphenyl, sec-butoxy- phenyl, or tert-butoxyphenyl, preferably methoxyphenyl or ethoxyphenyl; fluoromethylphenyl, chloromethylphenyl, trifluoro- methylphenyl, difluoromethylphenyl, fluoroethylphenyl, chloroethylphenyl, preferably trifluoromethylphenyl; difluoromethoxyphenyl, trifluoromethoxyphenyl, 2-fluoroethoxyphenyl, 1,1,2,2-tetrafluoroethoxyphenyl, 2-bromo-l-l,2,2-tetrafluoroethoxyphenyl, preferably trifluoromethoxyphenyl or difluoromethoxyphenyl;

1, ^' 3-benzodioxol-5-yl, 2,2-difluoro-1,3-benzodioxol- 5-yl, naphthyl, thienyl, 2,3-dihydro-2,2-dimethylbenzo- furan-5-yl, 2,2,3,3-tetrafluorobenzofuran-5-yl, and 2,3-dihydro-2,2-dimethylbenzofuran-7-yl;

Z is oxygen, sulfur, or methylene;

Ar ¹ is 2-methyl[l,l'-biphenyl]-3-yl, 3-phenoxy- phenyl, 4-fluoro-3-phenoxyphenyl, and 6-phenoxy-2- PY ^r idyl, preferably 4-fluoro-3-phenoxyphenyl. Substitu¬ tion of the phenyl, pyridyl, or phenoxy moieties with halogen or lower alkyl is within the scope of this invention.

The ether and thioether compounds of this invention are prepared by reacting an appropriate 2,2-disubsti- tuted ethanol or thioethanol with sodium hydride, thus preparing the corresponding sodium ethoxide. The ethoxide or thioethoxide can, in turn, be reacted with an appropriately substituted benzyl halide to prepare the insecticidal ether or thioether. Example 1

describes the reaction of 2-cyclopropyl-2-(4-chloro- phenyl) thanol with sodium hydride in tetrahydrofuran and the reaction of the resulting sodium salt with (4- fluoro-3-phenoxyphenyl) ethyl chloride to prepare (4- fluoro-3-phenoxyphenyl) ethyl 2-cyclopropyl-2-(4-chloro- phenyl)ethyl ether,' Compound 16 of Table 1.

Numerous references describe the preparation of the substituted halides or preparation of the corresponding alcohols from which the halides may be prepared by con- ventional methods. The halides may be selected from chlorides, bromides, or iodides. Other leaving groups that may be readily displaced by a substituted ethoxide or thioethoxide may be substituted for the halogen atom of the benzyl hal-ide. Examples of such leaving groups include, but are not limited to, methanesulfonate, tri- fluoromethanesulfonate, and p-toluenesulfonate.

The alcohol intermediates may be prepared from the aryl cyclopropyl ketones by conventional methods. In Example 1 the 4-chlorophenyl cyclopropyl ketone is reacted with sodium hydride and methyl triphenyl- phosphonium bromide to prepare l-(4-chlorophenyl)-1- cyclopropylethene. Hydroboration of this olefin with bis(3-methyl-2-butyl)borane, followed by treatment with aqueous sodium hydroxide and hydrogen peroxide completes the synthesis of the ethanol from which the ether may be prepared as described above.

The substituted ethanol may be converted to the • corresponding ethanethiol by reacting triphenylphosphine with diisopropyl azodicarboxylate and then reacting the resulting intermediate with the substituted ethanol.

Quenching this reaction with thiolacetic acid produces the thiolacetate. Reduction of the thiolacetate pro¬ duces the substituted thiol from which the thioether can be prepared by the same method described above for the ethers. Example 2 details the synthesis of (4-fluoro-3-

phenoxy) ethyl 2-cyclopropyl-2-(4-chlorophenyl)ethyl thioether, Compound 21 of Table 1 by this method.

Separation of the optical isomers can be effected by first preparing the 2,2-disubstituted acetic acid. One 5 method for this preparation is to react the aryl cyclo¬ propyl ketone with the anion prepared from 2-trimethyl- silyl-l,3-dithiane and n-butyllithium. The resulting 2- [ (aryl)cyclopropylmethylene]-l,3-dithiane may then be reacted with mercury (II) chloride, water, and methanol, 0 producing methyl 2-aryl-2-cyclopropylacetate. Hydroly¬ sis of the acetate to the acid and preparation of the _' acid chloride may be followed by reaction with (S)-4-(l- methylethyl)-2-oxazolidinone, previously prepared by reacting (S) -2-amino-3-methyl-l-butanol with phosgene. 5 The two diastereomers of N-(2-aryl-2-cyclopropylacetyl)- 4-(l-methylethyl)-2-oxazoli.dinone may then be separated chromatographically. Reduction of the individual dias¬ tereomers of the oxazolidinone with lithium aluminum hydride produces the (S) or (R)-2-aryl-2-cyclopropyl- o ethanols, each substantially free of the other antipode. In Example 3 details are provided for this method of preparing the two stereoisomers of (4-fluoro-3-phenoxy- phenyl)methyl 2-cyclopropyl-2-(4-chlorophenyl)ethyl ether, Compounds 17 and 18 of Table 1. The saturated, hydrocarbon compounds of this inven¬ tion are prepared by reacting a substituted-phenyl cyclopropyl ketone with vinylmagnesium bromide to pre¬ pare the corresponding 1-(substituted phenyl) -1-cyclo- propyl-2-propen-l-ol. Oxidation of this unsaturated _Q alcohol yields 3-(substituted phenyl)-3-cyclopropyl- propenal. The reaction of triphenylphosphine and a substituted-benzyl bromide yields the corresponding substituted benzyltriphenylphosphonium bromide which, in turn, can be reacted with the 3-(substituted phenyl)-3- ₅ cyclopropylpropenal in the presence of n-butyllithium to

yield a 1-(substituted phenyl)-l-cyclopropyl-4-(substi¬ tuted phenyl)butadiene. Hydrogenation of this butadiene produces the saturated insecticidal compounds of Formula I. Example 4 details the synthesis of l-(4-chloro- 5 phenyl)-l-cyclopropyl-4-(3-phenoxyphenyl)butane. Compound 88 of Table 1, by this method.

Alternatively, the saturated, hydrocarbon compounds may be synthesized by reacting an appropriately substi¬ tuted benzaldehyde with ethoxycarbonylmethylene- 0 triphenylphosphorane, producing the corresponding ethyl 3-(substituted aryl)acrylate. Reduction of this ester with lithium aluminum hydride yields the corresponding 3-(substituted aryl)propanol. Reaction of this alcohol with phosphorous tribromide yields the propyl bromide 5 ^' which, in turn, is reacted with triphenylphosphine, producing the corresponding 3-(substituted aryl)propyl- triphenylphosphonium bromide. The intermediate l-(sub¬ stituted phenyl)-l-cyclopropyl-4-(substituted aryl)-l- butene is prepared by reaction of the phosphonium 0 bromide with the appropriate substituted-phenyl cyclo¬ propyl ketone in the presence of n-butyllithium. Catalytic hydrogenation with Raney nickel completes the synthesis. By this method l-(4-chlorophenyl)-1-cyclo- propyl-4-(3-phenoxyphenyl)butane, Compound 88 of Table 5 1, was synthesized as described in Example 7.

Certain substituted-phenyl cyclopropyl ketones, e.g. , 4-chlorophenyl cyclopropyl ketone, are commer¬ cially available. Others can be synthesized by starting with an appropriately substituted benzoic acid which can 0 be converted to the acid chloride by the usual methods, e.g., by reaction with oxalyl chloride. Reaction of the acid chloride with N-methoxy-N-methylamine hydrochloride yields the corresponding substituted N-methoxy-N-methyl- benzamide. The desired substituted-phenyl cyclopropyl

-r. ketone is then obtained by reacting the benzamide with

cyclopropylmagnesium bromide. Example 5, Steps A-C, representative of this method, provide ^' details for the synthesis of cyclopropyl (4-trifluoromethylphenyl) ketone. Alternatively, the substituted-phenyl cyclopropyl ketones may be prepared by reacting cyclopropane¬ carboxylic acid chloride with an appropriately substi¬ tuted-phenyl compound in the presence of a Friedel- Crafts catalyst, e.g., aluminum chloride. In Example 6, Step A, cyclopropanecarboxylic acid chloride is reacted with ethoxybenzene in the presence of aluminum chloride, yielding cyclopropyl (4-ethoxyphenyl) ketone. The intermediate butadienes of the formula:

Ar-C=CH-CH=CH-Ar'

wherein Ar and Ar' are defined as above are themselves insecticidal and acaricidal. Table 2 lists these compounds.

Also, the intermediate butenes of the formula:

Ar-C=CH-CH ₂ -CH ₂ -Ar ^»

wherein Ar and Ar ¹ are defined as above are insecticidal and acaricidal. Table 3 lists these compounds. These olefins may exist in two configurations, the E and Z isomers. In the E isomer the cyclopropyl group and the -CH ₂ CH ₂ Ar' moiety are in a cis configuration in relation

to the double bond and in the Z isomer these same moie¬ ties are situated in a trans configuration. In one instance an example of a Z isomer, Compound B13, was- separated by rotating disk thin layer chromatography from" a mixture of E and Z isomers. This enriched the residue, Compound B12, in the E isomer relative to the Z isomer. Comparisons of the insecticidal data for these compounds indicate that E isomers are significantly more active than the Z isomers. The following examples provide additional details of the synthetic methods used to prepare the insecticidal ethers, thioethers, and hydrocarbons of this invention. Tables 1, 2, and 3 list these compounds. The compound numbers shown in each example are those assigned in these tables.

Example 1 Synthesis of (4-fluoro-3-phenoxyphenyl)methyl 2-cyclopropyl-2-(4-chlorophenyl)ethyl ether [Compound 16]

Step A Synthesis of l-cyclopropyl-l-(4-chlorophenyl)- ethene as an intermediate Under a nitrogen atmosphere, a stirred suspension of 1.6 grams (0.063 mole) of 97% sodium hydride in 50 mL of dimethyl sulfoxide was heated at 80°C for 90 minutes. The reaction mixture was cooled to ambient temperature, and 20.8 grams (0.056 mole) of methyl triphenyl- phosphonium bromide was added portionwise. Upon completion of addition, an additional 20 mL of dimethyl- sulfoxide was added to the reaction mixture which was then stirred at ambient temperature for 30 minutes and then at 60°C for 30 minutes. The reaction mixture was cooled to ambient temperature, and 10.2 grams (0.056 mole) of cyclopropyl (4-chlorophenyl) ketone was added

-. portionwise during a 15 minute period. Upon completion of addition, an additional 20 mL of di ethylsulfoxide was added, and the reaction mixture was stirred at ambient temperature for 18 hours. The reaction mixture was stirred with 100 mL of water which caused the pre¬ cipitation of the by-product triphenylphosphine oxide. The aqueous layer and the precipitate were extracted with five 100 mL portions of hexane. The combined extracts were washed first with 80 mL of 1:1 dimethyl- sulfoxide:water and then with 80 mL of an aqueous, saturated sodium chloride solution. The organic layer was dried with magnesium sulfate and filtered. The filtrate was concentrated, yielding 10.9 grams of resid¬ ual oil. A 1.2 gram sample from a previous run of this reaction was combined with the product of the reaction, and the 12.1 gram sample was distilled under reduced pressure, yielding 8.2 grams of 1-cyclopropyl-l-(4- chlorophenyl)ethen ^' e; . b.p. 100-105°C/34 mm. The nmr and ir spectra were consistent with the proposed structure.

Step B Synthesis of 2-cyclopropyl-2-(4-chlorophenyl)- ethanol as an intermediate

Under a nitrogen atmosphere, a stirred solution of

3.5 grams (0.019 mole) of 1-cyclopropyl-l-(4-chloro- phenyl)ethene in 10 L of distilled tetrahydrofuran was cooled to 0°C, and 29.5 mL (0.020 mole) of 0.68 M bis(3-

^• methyl-2-butyl)borane in tetrahydrofuran was added via syringe during a 10 minute period. Upon completion of addition,* the reaction mixture was stirred at 0°C for 1.3 hours, at ambient temperature for 2.5 hours, and at

60°C for 0.75 hour. The reaction mixture was cooled to

0°C, and 17 mL-of methanol, 8.8 mL of aqueous 10% sodium hydroxide solution, and 8.0 mL of aqueous 30% hydrogen peroxide solution were sequentially added. Upon comple- tion of addition, the reaction mixture was stirred, at •

ambient temperature for 18 hours^. The reaction mixture was heated at 60°C for 30 minutes and then was cooled, after which 30 mL of an aqueous solution saturated with potassium carbonate was added. The aqueous laye was separated and extracted with three 30 mL portions of diethyl ether. The organic materials were combined and washed with 30 mL of an aqueous, saturated potassium carbonate solution. The organic layer was dried with magnesium sulfate/potassium carbonate and filtered. The " filtrate was concentrated under reduced pressure, yield¬ ing 3.8 grams of 2-cyclopropyl-2-(4-chlorophenyl)- ethanol. The nmr and i spectra were consistent with the proposed structure.

Step C Synthesis of (4-fluoro-3-phenoxyphenyl)methyl

2-cyclopropyl-2-(4-chlorophenyl)ethyl ether A stirred suspension of 0.1 gram (0.0044 mole) of sodium hydride in 5 mL of tetrahydrofuran was cooled to 0°C, and a solution of 0.8, gram (0.0041 mole) of 2- cyclopropyl-2-(4-chlorophenyl)ethanol in 2.5 mL of tetrahydrofuran was added via syringe during a two minute period. Upon completion of addition, the reac¬ tion mixture was allowed to warm to ambient temperature where it stirred for 30 minutes and then was heated to 55°C where it stirred for 1.5 hours. The reaction mix¬ ture was cooled to ambient temperature, and a solution of 1.0 gram (0.0043 mole) of (4-fluoro-3-phenoxyphenyl)- methyl chloride in 2.5 m_L of tetrahydrofuran was added via syringe. Upon completion of addition, the reaction mixture stirred at ambient temperature for 20 hours and then was warmed to 60°C where it stirred for 30 minutes. The reaction mixture was cooled, and 15 mL of water was added. The aqueous layer was removed and extracted with three 25 mL portions of hexanes. The organic materials were combined and dried with magnesium sulfate. The

ixture was filtered, and the filtrate was concentrated under reduced pressure to a residual oil. The oil was purified by rotating disk thin layer chromatography using 5-10% ethyl acetate in hexanes for elution. The appropriate fractions were combined and concentrated under reduced pressure, yielding 0.65 gram of (4-fluoro- 3-phenoxyphenyl)methyl 2-cyclopropyl-2-(4-chlorophenyl)- ethyl ether. The nmr and the ir spectra were consistent with the proposed structure.

Example 2

Synthesis of (4-fluoro-3-phenoxyphenyl)methyl

2-cyclopropyl-2-(4-chlorophenyl)ethyl thioether

[Compound 21]

Step A Synthesis of 2-cyclopropyl-2-(4-chlorophenyl)- ethyl thiolacetate as an intermediate A stirred solution of 11.7 grams (.0.045 mole) of triphenylphosphine in 75 mL of dry tetrahydrofuran was cooled to 0°C, and 9.0 grams (0.045 mole) of diisopropyl azodicarboxylate was added dropwise. Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature where it stirred for 30 minutes. Successively, 4.4 grams (0.022 mole) of 2-cyclopropyl-2- (4-chlorophenyl)ethanol (prepared in Example 1, Step B) and 3.4 grams (0.045 mole) of thiolacetic acid were then added. The exothermic reaction caused the reaction mixture temperature to rise to 39°C. After cooling to ambient temperature the reaction mixture was stirred for 16 hours. The reaction mixture was then concentrated under reduced pressure to a residual oil. The oil was subjected to chromatography on silica gel using methyl¬ ene chloride:heptane (1:4) as eluant. The appropriate fractions were combined and concentrated under reduced pressure, yielding 4.6 grams of 2-cyclopropyl-2-(4-

chlorophenyl)ethyl thiolacetate as an oil. The nmr and the ir spectra were consistent with the proposed structure.

Step B Synthesis of 2-cyclopropyl-2-(4-chlorophenyl)- ethanethiol as an intermediate Under a nitrogen atmosphere a mixture of 1.2 grams (0.032 mole) of lithium aluminum hydride in dry tetra¬ hydrofuran was stirred, and a solution of 4.1 grams (0.016 mole) of 2-cyclopropyl-2-(4-chlorophenyl) thyl thiolacetate in 3 mL of tetrahydrofuran was added drop- wise. Upon completion of addition, the reaction mixture was stirred at ambient temperature for 16 hours. Water was then carefully added dropwise to destroy excess lithium aluminum hydride. After the hydride was destroyed, ^" 50 mL of additional water was added. The reaction mixture was extracted with several portions of diethyl ether. The combined extracts were dried with magnesium sulfate and filtered. The filtrate was con- centrated under reduced pressure, yielding 3.4 grams of 2-cyclopropyl-2-(4-chlorophenyl)ethanethiol. The nmr and the ir spectra were consistent with the proposed structure.

Procedures analogous to Steps A and B are reported in Tetrahedron Letters , Vol. 22, No. 33, p 3119-3122, 1981.

Step C Synthesis of (4-fluoro-3-phenoxyphenyl)methyl

2-cyclopropyl-2-(4-chlorophenyl)ethyl thioether This compound was prepared in a manner analogous to that of Example 1, Step C, using 1.0 gram (0.0046 mole) of-2-cyclopropyl-2-(4-chlorophenyl)ethanethiol, 0.97 gram (0.0041 mole) of (4-fluoro-3-phenoxyphenyl)methyl chloride, and 0.22 gram (0.0055 mole) of sodium hydride in 12 mL of dry tetrahydrofuran. The yield of (4-

fluoro-3-phenoxyphenyl)methyl 2-cyclopropyl-2-(4-chloro- phenyl)ethyl thioether was 1.2 grams as an oil. The nmr and the ir spectra were consistent with the proposed structure.

Example 3

Synthesis of the stereoisomers (A) and (B) of

(4-fluoro-3-phenoxyphenyl)methyl 2-cyclopropyl-

2-(4-chlorophenyl)ethyl ether [Compounds 17 and 18, respectively]

Step A Synthesis of 2-[ (4-chlorophenyl)cyclopropyl- methylene]-1,3-dithiane as an intermediate

A solution of 16.0 grams (0.083 mole) of 2-tri- methylsilyl-1,3-dithiane in 80 L of tetrahydrofuran was cooled to 0°C, and 39 mL (0.083 mole) of n-butyllithium (2.1 M in hexane) was added. The reaction mixture was stirred for 15 minutes, and 15.0 grams (0.083 mole) of cyclopropyl (4-chlorophenyl) ketone in 40 mL of tetra¬ hydrofuran was added via syringe during a five minute period. Upon completion of addition, the reaction mixture was stirred at 0°C for 15 minutes and then was allowed to warm for 30 minutes. The reaction mixture was stirred with 100 L of an aqueous solution saturated with sodium chloride, and then the two phases were separated. The aqueous phase was extracted with one portion of diethyl ether. The ether extract was com¬ bined with the organic phase, and this mixture was dried with magnesium sulfate and filtered through a pad of silica gel. The filtrate was concentrated under reduced pressure, yielding 24.0 grams of 2-[ (4-chlorophenyl)- cyclopropylmethylene]τi,3-dithiane as a solid, m.p. 91-95°C. The nmr spectrum was consistent with the proposed structure.

Step B Synthesis of methyl 2-cyclopropyl-2-(4-chloro- phenyl)acetate as an intermediate A mixture of 10.0 grams (0.036 mole) of 2-[(4- chlorophenyl)cyclopropylmethylene]-1,3-dithiane, 24.0 grams (0.086 mole) of mercury (II) chloride, and 5 mL of water in 50 mL of methanol was stirred at ambient tem¬ perature for 18 hours. The reaction mixture was heated at reflux for one hour, cooled, and then was diluted with diethyl ether. The mixture was filtered through diatomaceous earth and then was dried with magnesium sulfate. The mixture was filtered through silica gel, and the filtrate was concentrated under reduced pres¬ sure, yielding 5.9 grams of methyl 2-cyclopropyl-2-(4- chlorophenyl)acetate as an oil. The nmr spectrum was consistent with the proposed structure. The reaction was run again to produce an additional 7.1 grams of the acetate.

Step C Synthesis of 2-cyclopropyl-2-(4-chlorophenyl)- acetic acid as an intermediate

A mixture of 13.0 grams ^' (0.058 mole) of methyl 2- cyclopropyl-2-(4-chlorophenyl)acetate and 5.0 grams of an aqueous; 50% sodium hydroxide solution in 50 mL of methanol was stirred at ambient _^ ,temperature for 18 hours. The reaction mixture was diluted with 150 mL of water, and the solution was decanted from a solid residue. The liquid portion was washed with three por¬ tions of diethyl ether. The combined ether washes were, in turn, washed with an aqueous, dilute sodium hydroxide solution. The combined aqueous layers were made acidic by the slow addition of aqueous, 10% hydrochloric acid. The acidified mixture was extracted with five portions of methylene chloride. The combined extracts were dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, yielding 7.4 grams

of 2-cyclopropyl-2-(4-chlorophenyl)acetic acid as a solid, m.p-. 95-96°C

Step D Synthesis of (S)-4-(1-methylethyl)-2-oxazol- idinone as an intermediate

A mixture of 9.4 grams (0.091 mole) of (S)-2-amino- 3-methyl-l-butanol, 36 grams (0.0546 mole) of 85% potas¬ sium hydroxide, 175 mL of toluene, and 240 mL of water was stirred rapidly as 140 mL (0.273 mole) of a toluene solution containing 20% phosgene was added dropwise during a 15 minute period. Upon completion of addition, the resulting hot solution was stirred an additional 30 minutes. The reaction mixture was cooled, and the organic and aqueous layers were separated. . The organic layer was washed with water and dried with magnesium sulfate. The mixture was filtered, and the filtrate was concentrated under reduced pressure, yielding 15.0 grams of (S)-4-(l-methylethyl)-2-oxazolidinone as a solid. Recrystallization from cyclohexane yielded purer com¬ pound, m.p. 7l.5-72.5°C.

Step E Synthesis of (S) -N-[2-(4-chlorophenyl) -2-cyclo- propylacetyl]-4-(1-methylethyl)-2-oxazolidinone and separation of its diastereomers (A) and (B) for use as intermediates A solution of 3.3 grams (0.016 mole) of 2-cyclo- propyl-2-(4-chlorophenyl)acetic acid (prepared in Step C) , 1.36 mL (0.016 mole) of oxalyl chloride, and two drops of N,N-dimethylformamide in 70 mL of diethyl ether was stirred at 0°C for one hour. The reaction mixture was then allowed to warm to ambient temperature where it stirred for one hour.

In a separate reaction vessel a stirred solution of 2.0 grams (0.016 mole) of (S)-4-(1-methylethyl)-2- oxazolidinone in 50 mL of tetrahydrofuran was cooled to

-78°C, and 6.25 mL (0.016 mole) of n-butyllithium (2.5 molar in hexane) was added dropwise. Upon completion of addition, the reaction mixture was stirred for 30 minutes, and then the 2-cyclopropyl-2-(4-chlorophenyl)- acetyl chloride, prepared above, was added dropwise during several minutes. Upon completion of addition, the reaction mixture was stirred for an additional 30 minutes and then was poured into water. The organic layer was separated and washed with one portion of aqueous sodium bicarbonate. The organic layer was. dried with magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to a residual oil. The oil was subjected to chromatography on silica gel using hexane:diethyl ether (3:1) as eluant. The appro- priate fractions were combined and concentrated under reduced pressure, yielding 0.85 gram of diastereomer (A)- and 0.8 gram of diastereomer (B) of (S)-N-[2-(4-chloro- phenyl)-2-cyclopropylacetyl]-4-(1-methylethyl)-2-oxazo- lidinone. Upon standing, diastereomer (A) crystallized to a solid, m.p. 61-64°C.

Step F Synthesis of stereoisomer (A) of 2-cyclopropyl- 2-(4-chlorophenyl)ethanol as an intermediate A stirred suspension of 0.31 gram (0.008 mole) of lithium aluminum hydride in 5 mL of tetrahydrofuran was cooled to 0°C, and 0.85 gram (0.0026 mole) of diaster¬ eomer (A) of (S)-N-[2-(4-chlorophenyl)-2-cyclo- propylacetyl]-4-(1-methylethyl)-2-oxazolidinone was added. Upon completion of addition, the reaction ix- ture was stirred for 45 minutes, and then 15 mL of hexane was added to the reaction mixture. This was followed by the careful addition of 0.3 mL of water, 0.3 L of aqueous 15% sodium hydroxide, and 0.9 mL of water.- The reaction mixture was stirred with magnesium sulfate and filtered through a pad of silica gel. The filtrate

was concentrated under reduced pressure to a residual oil. The oil was subjected to chromatography on silica gel using diethyl ether:hexane (1:1) as eluant. The appropriate fractions were combined and concentrated under reduced pressure, yielding 0.4 gram of stereo- iso er (A) of 2-cyclopropyl-2-(4-chlorophenyl)ethanol as an oil.

Step G Synthesis of stereoisomer (A) of (4-fluoro-3- phenoxyphenyl)methyl 2-cyclopropyl-2-(4-chloro- phenyl)ethyl ether

Under a nitrogen atmosphere a suspension of 0.06 gram (0.0024 mole) of 97% sodium hydride in 2.2 L of dimethylfo-rmamide was stirred, and a solution of 0.40 gram (0.002 mole) of stereoisomer (A) of 2-cyclopropyl- 2-(4-chlorophenyl)ethyl ethanol in 1.0 L of dimethyl- formamide was slowly added. Upon completion of addi¬ tion, the reaction mixture was stirred for 1.5 hours, and then a solution of 0.46 gram (0.0019 mole) of (4- fluoro-3-phenoxyphenyl)methyl chloride in 1.0 mL of dimethylformamide was added. Upon completion of addi¬ tion, the reaction mixture was stirred for one hour, and then 2-3 L of water was added. The mixture was poured into 75 mL of aqueous, 10% hydrochloric acid and then was extracted with two 50 L portions of hexane. The combined hexane layers were washed with 25 L of a sat¬ urated, aqueous solution of sodium chloride. The or¬ ganic layer was dried with. sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to a residual oil. The oil was subjected to rotating disk thin layer chromatography on silica gel using diethyl ether: hexane (19:1) as eluant. The appropriate frac¬ tions were combined and concentrated under reduced pres¬ sure, yielding 0.55 gram of stereoisomer (A) of (4- fluoro-3-phenoxyphenyl) ethyl 2-cyclopropyl-2-(4-chloro- phenyl) ethyl ether as an oil. The nmr spectrum was consistent with the proposed structure. [α] ⁵ =(+) 22.19°

Step H Synthesis of stereoisomer (B) of 2-cyclopropyl- 2-(4-chlorophenyl)ethanol as an intermediate This compound was prepared in a manner analogous to that of Step F, using 0.80 gram (0.0025 mole) of dias- 5 tereomer (B) of (S)-N-[2-(4-chlorophenyl)-2-cyclo- propylacetyl]-4-(1-methylethyl)-2-oxazolidinone (pre¬ pared in Example 3, Step E) and 0.30 gram (0.008 mole) of lithium aluminum hydride in 15 mL of tetrahydrofuran. The yield of stereoisomer (B) of 2-cyclopropyl-2-(4- 0 chlorophenyl)ethanol was 0.45 gram as an oil.

Step I Synthesis of stereoisomer (B) of (4-fluoro-3- phenoxyphenyl)methyl 2-cyclopropyl-2-(4-chloro- phenyl) 5 This compound was prepared in a manner analogous to that of Step G, using 0.40 gram (0.0020 mole) of stereo¬ isomer (B) of 2-cyclopropyl-2-(4-chlorophenyl)ethanol (prepared in Step H) , 0.46 gram (0.0019 mole) of (4- fluoro-3-phenoxyphenyl)methyl chloride, and 0.06 gram o (0.0024 mole) of sodium hydride in 4.2 mL of dimethyl- formamide. The yield of stereoisomer (B) of (4-fluoro- 3-phenoxyphenyl)methyl 2-cyclopropyl-2-(4-chlorophenyl)- ethyl ether was 0.56 gram as an oil. The nmr spectrum was consistent with the proposed structure. 5 [α]25=(-)20.64θ

Example 4 Synthesis of l-(4-chlorophenyl)-1-cyclopropyl- -(3-phenoxyphenyl)butane 0 [Compound 88]

Step A Synthesis of l-(4-chlorophenyl)-1-cyclopropyl- 2-propen-l-ol as an intermediate A 1.0 M solution of vinylmagnesium bromide in tetra- _ ₅ hydrofuran (110 mL, 0.11 mole) was stirred, and a solu¬ tion of 18.1 grams (0.1 mole) of commercially available

4-chlorophenyl cyclopropyl ketone in 50 mL of dry tetra¬ hydrofuran was added dropwise during a one hour period. The exothermic reaction caused the reaction mixture to warm to 45°C. Upon completion of addition, the reaction mixture was stirred for two hours as it cooled to ambient temperature. The reaction was quenched with the addition of 50 mL of a _. saturated, aqueous solution of ammonium chloride. The mixture was extracted with two 50 mL portions of diethyl ether. The combined extracts were dried with potassium carbonate and filtered.. The filtrate was concentrated under reduced pressure, yield¬ ing 20.0 grams of 1-(4-chlorophenyl)-l-cyclopropyl-2- propen-1-ol.

Step B Synthesis of 3-(4-chlorophenyl) -3-cyclopropyl¬ propenal as an intermediate To a stirred solution of 40.3 grams (0.192 mole) of pyridinium chlorochromate in 210 mL of methylene chlor¬ ide was added a solution of 20.0 grams (0.096 mole) of l-(4-chlorophenyl)-l-cyclopropyl-2-propen-l-ol in 25 mL of methylene chloride in one portion. Upon completion of addition, the reaction mixture was stirred for two hours. A supernatent layer was decanted from a residue, and the residue was extracted with diethyl ether. The supernatent layer was combined with the ether extracts, and the combination was washed with two 100 mL portions of an aqueous 5% sodium hydroxide solution, 100 L of an aqueous 5% hydrochloric acid solution, and then with 50 L of an aqueous solution saturated with sodium bicar- bonate. The organic layer was dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to a residue. The residue was sub¬ jected to column chromatography on silica gel. Elution was accomplished using 5% diethyl ether in hexane. The appropriate fractions were combined and concentrated

under reduced pressure, yielding 6.8 grams of 3-(4- chlorophenyl)-3-cyclopropylpropenal.

Step C Synthesis of 3-phenoxyphenylmethyltriphenyl- phosphonium chloride as an intermediate

A stirred solution of 5.0 grams (0.0228 mole) of 3- phenoxyphenylmethyl chloride and 5.6 grams (0.0217 mole) of triphenyl phosphine in 50 mL of dry toluene was heated at reflux for 8 hours. The reaction mixture was cooled and filtered to collect a solid. The solid was washed with pentane and dried, yielding 4.6 grams of 3- phenoxyphenylmethyltriphenylphosphonium chloride. The nmr spectrum was consistent with the proposed structure.

Step D Synthesis of l-(4-chlorophenyl)-1-cyclopropyl-

4-(3-phenoxyphenyl)-1,3-butadiene (Compound A5) as an intermediate A stirred solution of 4.4 mL (0.011 mole) of n- butyllithium (2.5 molar in hexane) in 100 mL of dry tetrahydrofuran was cooled to -78°C, and 4.6 grams (0.01 mole) of 3-phenoxyphenylmethyltriphenylphosphonium chloride was quickly added. Upon completion of addi¬ tion, the reaction mixture was stirred at -78°C for one hour and then was allowed to warm to -20°C where it stirred for one hour. The reaction mixture was cooled to -78°C, and 2.1 grams (0.01 mole) of 3-(4-chloro- phenyl)-3-cyclopropylpropenal (prepared in Step B) in 10 L of tetrahydrofuran was added during a 15 minute period. Upon completion of addition, the reaction mix- ture was allowed to warm to ambient temperature where it stirred for two hours. -The reaction was quenched with the addition of 15 mL of aqueous 10% hydrochloric acid solution. The mixture was extracted with diethyl ether. The combined extracts were dried with sodium sulfate and filtered. The filtrate was concentrated under reduced

pressure to a residue. The residue was subjected to column chromatography on silica gel. Elution was accom¬ plished using 5% -diethyl ether in hexane. The appro¬ priate fractions were combined and concentrated under reduced pressure, yielding 3.2 grams of l-(4-chloro- phenyl)-l-cyclopropyl-4-(3-phenoxyphenyl)-1,3-butadiene.

Step E Synthesis of l-(4-chlorophenyl)-1-cyclopropyl- 4-(3-phenoxyphenyl)butane (Compound 88) A mixture of 2.3 grams (0.006 mole) of l-(4-chloro- phenyl)-l-cyclopropyl-4-(3-phenoxyphenyl) -1,3-butadiene, 2.3 grams (0.002 mole) of 10% palladium.on carbon, 0.25 gram (0.0002 mole) of tris(triphenylphosphine)rhodium (I) chloride, and 25 mL of benzene in 100 mL of ethanol was hydrogenated at 40°C using a Parr hydrogenator.

Upon completion of the uptake of the theoretical amount of hydrogen (two hours) , the reaction mixture was cooled and filtered. The filtrate was concentrated under reduced pressure to a residue. The residue was taken up in hexane and filtered. The filtrate was dried with sodium sulfate and filtered again. The filtrate was concentrated under reduced pressure to a residue. The residue was subjected to rotating disk thin layer chromatography. Elution was accomplished using 20% toluene in hexane. The appropriate fractions were com¬ bined and concentrated under reduced pressure, yielding 0.52 gram of 1-(4-chlorophenyl)-l-cyclopropyl-4-(3- phenoxyphenyl)butane as an oil. The nmr spectrum was consistent with the proposed structure.

Example 5 Synthesis of 1-cyclopropyl-l-(4-trifluoromethylphenyl)- 4-(4-fluoro-3-phenoxyphenyl)butane [Compound 99]

Step A Synthesis of 4-trifluoromethylbenzoyl chloride as an intermediate A stirred solution of 20.0 grams (0.105 mole) of 4- trifluoromethylbenzoic acid and four drops of dimethyl- formamide in 300 mL of methylene chloride was cooled to 0-10°C, and 14.7 grams (0.116 mole) of oxalyl chloride was added. Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature where it stirred for 18 hours. The reaction mixture was then concentrated under reduced pressure, yielding 21.9 grams of 4-trifluoromethylbenzoyl chloride as a. semi-solid. The reaction was repeated.

Step B Synthesis of N-methoxy-N-methy1-4-trifluoro- methylbenzamide as an intermediate

To a stirred suspension of 19.9 grams (0.204 mole) ^• of N-methoxy-N-methylamine hydrochloride in 500 mL of methylene chloride was added 39.3 grams (0.388 mole) of triethylamine. Upon completion of addition, the reac- tion mixture was stirred for ten minutes, and a solution of 38.4 grams (0.185 mole) of 4-trifluoromethylbenzoyl chloride in 25 mL of methylene chloride was added drop¬ wise. Upon completion of addition, the reaction mixture was stirred at ^" ambient temperature for ^■ 18 hours. The reaction mixture was then stirred vigorously with 300 L of water. The aqueous layer was separated from the organic layer and washed with three portions of methyl¬ ene chloride. The washes were combined with the organic layer, and the combination was dried with magnesium sulfate. The mixture was filtered, and the filtrate was concentrated under reduced pressure, yielding 42.5 grams of .N-methoxy-N-methyl-4-trifluoromethylbenzamide as an oil. The nmr spectrum was consistent with the proposed structure.

Step C Synthesis of cyclopropyl (4-trifluoromethyl¬ phenyl) ketone as an intermediate Under a nitrogen atmosphere a vigorously stirred solution of 42.5 grams (0.182 mole) of N-methoxy-N- methyl-4-trifluoromethylbenzamide in 250 mL of dry tetrahydrofuran was cooled to 0-10°C, and 41.7 grams (0.0287 mole) of freshly prepared cyclopropylmagnesium bromide in 170 mL of tetrahydrofuran was added rapidly dropwise. Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature where it stirred for 60 hours. The reaction mixture was then concentrated under reduced pressure to a residue. The residue was taken up in water and extracted with four portions of methylene chloride. The combined extracts were dried with magnesium sulfate and filtered. - The filtrate was passed through a pad of silica gel and was concentrated under reduced pressure yielding, 34.6 grams of cyclopropyl (4-trifluoromethylphenyl) ketone. The nmr spectrum was consistent with the proposed structure.

Step D Synthesis of 1-cyclopropyl-l-(4-trifluoro¬ methylphenyl)-2-propen-l-ol as an intermediate This compound was prepared in a manner analogous to that of Example 4, Step A, using 10.0 grams (0.05 mole) of cyclopropyl (4-trifluoromethylphenyl) ketone and 50 L (0.05 mole) of vinylmagnesium bromide (1.0 M in tetrahydrofuran) and 25 L of tetrahydrofuran. The yield of 1-cyclopropyl-l-(4-trifluoromethylphenyl) -2- propen-1-ol was 11.6 grams. The nmr spectrum was con¬ sistent with the proposed structure.

Step E Synthesis of 3-cyclopropyl-3-(4-trifluoro¬ methylphenyl)propenal as an intermediate This compound was prepared in a manner analogous to that of Example 4, Step B, using 11.1 grams (0.046 mole)

of 1-cyclopropyl-l-(4-trifluoromethylphenyl)-2-propen-l- ol and 19.7 grams (0.091 mole) of pyridinium chloro- chromate in 100 mL of methylene chloride. The yield of 3-cyclopropyl-3-(4-trifluoromethylphenyl)propenal was 5.5 grams

Step F Synthesis of 4-fluoro-3-phenoxyphenylmethanol as an intermediate To a stirred suspension of 1.4 grams (0.0375 mole) of lithium aluminum hydride in 50 mL of anhydrous diethyl ether was added dropwise during a one hour period a solution of 21.6 grams (0.1 mole) of 4-fluoro- 3-phenoxybenzaldehyde in 50 mL of anhydrous diethyl ether. Upon completion of addition, the reaction mix¬ ture was heated at reflux for 1.0 hour. The reaction mixture was cooled to 15°C, and 1.4 mL of water was cautiously added dropwise. Upon completion of addition, the reaction mixture was again cooled to 15°C, and 1.4 mL of an aqueous, 15% sodium hydroxide solution was added dropwise, followed by an additional 4.2 mL of water. The mixture was filtered through diatomaceous earth, and the filtrate was concentrated under reduced pressure, yielding 19.5 grams of 4-fluoro-3-phenoxy- phenylmethanol as an oil.

Step G Synthesis of 4-fluoro-3-phenoxyphenylmethyl chloride ^" as an intermediate To a stirred solution of 12.6 grams (0.106 mole) of thionyl chloride and a catalytic amount of pyridine in 25 mL of toluene was added dropwise during a 45 minute period a solution of 19.5 grams (0.88 mole) of 4-fluoro- 3-phenoxyphenylmethanoi (prepared in Step F) in 30 mL of toluene. The reaction mixture temperature was main¬ tained at 25-35°C throughout the addition. Upon comple¬ tion of addition, the reaction mixture was warmed to

45°C where it stirred for one hour. The reaction mix¬ ture was cooled and then was concentrated under reduced pressure, yielding 23.5 grams of semi-solid. The semi- solid was combined with 114.2 grams of identical semi- solid obtained from a large run of the present reaction. The 136.6 grams of semi-solid was distilled under reduced pressure. The appropriate fractions were com¬ bined, yielding 100.3 grams of 4-fluoro-3-phenoxyphenyl- methyl chloride, b.p. 98-105°C/0.03-0.13 mm Hg.

Step H Synthesis of. (4-fluoro-3-phenoxyphenyl)methyl- triphenylphosphonium chloride as an intermediate This compound was prepared in a manner analogous to that of Example 4, Step C, using 11.8 grams (0.05 mole) of 4-fluoro-3-phenoxyphenylmethyl chloride and 13.1 grams (0.05 mole) of triphenylphosphine in 100 mL of tetrahydrofuran. The yield of (4-fluoro-3-phenoxy¬ phenyl)methyltriphenylphosphonium chloride was 15.0 grams.

Step I Synthesis of l^cyclopropyl-1-(4-trifluoro¬ methylphenyl)-4-(4-fluoro-3-phenoxyphenyl) -1,3- butadiene (Compound A13) as an intermediate This compound was prepared in a manner analogous to that of Example 4, Step D, using 1.7 grams (0.0069 mole) of 3-cyclopropyl-3-(4-trifluoromethylphenyl)propenal (prepared in Step E of the present example), 3.4 grams (0.0069 mole) of (4-fluoro-3-phenoxyphenyl)methyltri- phenylphosphoniu chloride (prepared in Step H of the present example), and 2.8 mL (0.0069 mole) of n-butyl¬ lithium (2.5 molar in hexane) in 69 mL of dry tetra¬ hydrofuran. The yield of 1-cyclopropyl-l-(4-trifluoro¬ methylphenyl)-4-(4-fluoro-3-phenoxyphenyl)-1,3-butadiene was 1.8 grams. The nmr spectrum was consistent with the proposed structure.

Step J Synthesis of 1-cyclopropyl-l-(4-trifluoro¬ methylphenyl)-4-(4-fluoro-3-phenoxyphenyl)- butane (Compound 99) This compound was prepared in a manner analogous to that of Example 4, Step E, by the hydrogenation of 0.98 gram (0.0023 mole) of 1-cyclopropyl-l-(4-trifluoro¬ methylphenyl)-4-(4-fluoro-3-phenoxyphenyl)-1,3-butadiene in the presence of 0.2 gram (0.00023 mole) of Raney nickel in 50 L of ethanol. The yield of 1-cyclopropyl- 1-(4-trifluoromethylphenyl)-4-(4-fluoro-3-phenoxy¬ phenyl)butane was 0.65 gram as an oil. The nmr spectrum was consistent with the proposed structure.

Example 6 Synthesis of l-cyclopropyl-l-(4-ethoxyphenyl)-

4-(3-phenoxyphenyl)butane- [Compound 104]

Step A Synthesis of cyclopropyl (4-ethoxyphenyl) ketone as an intermediate Under an argon atmosphere a stirred suspension of 36.7 grams (0.275 mole) of aluminum chloride in 225 mL of carbon disulfide was cooled to 0°C, and 22.7 mL (0.25 mole) of cyclopropanecarboxylic acid chloride was added dropwise during a 15 minute period. During the addition and for 30 minutes after its completion the reaction mixture temperature was maintained at 0-15°C. Then 34.8 mL of ethoxybenzene was added dropwise during a one hour period. The reaction mixture temperature was maintained at 5-10°C during this addition. Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature as it stirred for one hour. Petro¬ leum ether, 250 L, was added to the reaction mixture, and the suspension was stirred for ten minutes. The

solid was collected by filtration and washed with petro¬ leum ether. The solid was returned to the reaction vessel and, with stirring, was cooled to 0-10°C while 50 mL of water was added dropwise during a 30 minute 5 period. Upon completion of addition, the mixture was stirred until the evolution of hydrogen chloride ceased. An additional 250 mL of water was then added, and the mixture was stirred at ambient temperature for 30 minutes. It was then warmed to 80°C where it stirred 0 for an additional 30 minutes. The mixture was cooled, and a solid was collected by filtration. The solid was dissolved in methylene chloride, and the solution was dried with sodium sulfate. The mixture was filtered, and the filtrate was concentrated under reduced pressure 5 to a residual solid. The solid was recrystallized from heptane, yielding, in two crops, 44.0 grams of cyclo¬ propyl (4-ethoxyphenyl) ketone, m.p. 67-70°C. The nmr spectrum was consistent with the'proposed structure.

o Step B Synthesis of 1-cyclopropyl-l-(4-ethoxyphenyl)- 2-propen-l-ol as an intermediate This compound was prepared in a manner analogous to that of Example 4, Step A, using 5.7 grams (0.03 mole) of cyclopropyl (4-ethoxyphenyl) ketone and 33 mL (0.033 5 mole) of vinylmagnesium bromide (1.0 M in tetrahydro¬ furan) in 30 mL of dry tetrahydrofuran. The yield of 1- cyclopropyl-1-(4-ethoxyphenyl) -2-propen-l-ol was 6.5 grams as an oil.

0 Step C Synthesis of 3-cyclopropyl-3-(4-ethoxyphenyl)- propenal as an intermediate This compound was prepared in a manner analogous to that of Example 4, Step B, using 6.5 grams (0.029 mole) of 1-cyclopropyl-l-(4-ethoxyphenyl)-2-propen-1-ol and 15.3 grams (0.029 mole) of pyridinium dichromate in 40 5

mL of methylene chloride. The yield of 3-cyclopropyl-3- (4-ethoxyphenyl)propenal was 4.2 grams as an oil.

Step D Synthesis of l-cyclopropyl-l-(4-ethoxyphenyl) - 4-(3-phenoxyphenyl) -1,3-butadiene (Compound

A15) as an intermediate This compound was prepared in a manner analogous to that of Example 4, Step D, using 4.2 grams (0.019 mole) of 3-cyclopropyl-3-(4-ethoxyphenyl)propenal, 9.1 grams (0.019 mole) of 3-phenoxyphenylmethyltriphenyl- phosphonium bromide (prepared as in Example 4, Step H) , and 7.5 mL (0.019 mole) of n-butyllithium (2.5 M.in tetrahydrofuran) in 100 mL of dry tetrahydrofuran. The yield of l-cyclopropyl-l-(4-ethoxyphenyl) -4-(3-phenoxy- phenyl) -1,3-butadiene was 2.5 grams.

Step E Synthesis of l-cyclopropyl-l-(4-ethoxyphenyl) - 4-(3-phenoxyphenyl)butane (Compound 104) This compound was prepared in a manner analogous to that of Example 4, Step E, by the hydrogenation of 1.5 grams (0.0039 mole) of 1-cyclopropyl-l-(4-ethoxyphenyl) - 4-(3-phenoxyphenyl) -1, 3-butadiene in the presence of 0.3.4 gram of Raney nickel in 70 L of ethanol. The yield of l-cyclopropyl-l-(4-ethoxyphenyl) -4-(3-phenoxy- phenyl)butane was 1.2 grams as an oil. The nmr spectrum was consistent with the proposed structure.

Example 7 Synthesis of l-(4-chlorophenyl) -1-cyclopropyl- 4-(3-phenoxyphenyl)butane

[Compound 88]

Step A Synthesis of ethyl 3-(3-phenoxyphenyl) acrylate To a stirred solution of 23.4 g (0.188 mole) of 3- phenoxybenzaldehyde in 175 mL of 1,4-dioxane was added

45.2 grams (0.130 mole) of ethoxycarbonylmethylenetri- phenylphosphorane in one portion. The reaction was allowed to stir at ambient temperature overnight. The solvent was evaporated under reduced pressure, leaving a 5 residue which was dissolved in ethyl acetate. Approx¬ imately 30 grams of silica gel was mixed with this solu¬ tion. This solvent was evaporated under reduced pres¬ sure, and the silica gel was placed in a sintered glass filter. The silica gel was eluted with 1000 mL of 0 heptane/ethyl acetate (3:1). The solvent was evaporated under reduced pressure, leaving an oil. This oil was dissolved in 150 mL of heptane/ethyl acetate (9:1), treated with 15 grams of silica gel, and filtered. The filtrate was evaporated under reduced pressure, leaving 5 26.7 grams of ethyl 3-(3-phenoxyphenyl)acrylate as an oil. The nmr spectrum was consistent with the proposed structure.

Step B Synthesis of 3-(3-phenoxypftenyl)propanol o To a stirred mixture of 7.4 grams (0.196 mole) of lithium aluminum hydride in 300 mL of dry diethyl ether under a nitrogen atmosphere was added 26.2 grams (0.098 mole) of ethyl 3-(3-phenoxyphenyl)acrylate in 300 mL of dry diethyl ether. The addition required 9.0 minutes to 5 complete, and the reaction mixture was stirred overnight at ambient temperature. It was then cooled in an ice/ water bath, and sequentially 14 mL of water, 14 mL of a 15% aqueous solution of sodium hydroxide, and 42 mL of water were all added dropwise. This mixture was fil- _Q tered, and the filtrate was dried over anhydrous sodium sulfate. After being filtered, the solvent was evap¬ orated under reduced pressure, leaving 21.9 grams of 3- (3-phenoxyphenyl)propanol as an oil. The nmr spectrum was consistent with the proposed structure. 5

Step C Synthesis of 3-(3-phenoxyphenyl)propyl bromide

To a mixture of 21.0 grams (0.092 mole) of 3-(3- phenoxyphenyl)propanol and 1 mL of pyridine which had been cooled to 0°C was added .dropwise during a 20 minute period 8.27 grams (0.031 mole) of phosphorus tribromide. This mixture was stirred at 0°C for 90 minutes and then at ambient temperature overnight. The reaction mixture was then diluted with 200 mL of diethyl ether, and the solution was washed successively twice with 50 L of water, four times with 25 L of a saturated, aqueous solution of sodium bicarbonate, once with 50 mL of water, and once with an aqueous solution of sodium chloride. After being dried over anhydrous sodium sulfate and filtered, the solvent was evaporated under reduced pressure, leaving 18.9 grams of 3-(3-phenoxy¬ phenyl)propyl bromide -as an oil. The nmr spectrum was consistent with the proposed structure.

Step D. Synthesis of 3-(3-phenoxyphenyl)propyltri- phenylphosphonium bromide

Under nitrogen a mixture of 2.9 grams (0.01 mole) of 3-(3-phenoxyphenyl)propyl bromide and 2.9 grams (0.01 mole) of triphenylphosphine in 25 mL of acetonitrile was heated at reflux overnight. The solvent was evaporated under reduced pressure. Toluene was added to the residue, and this mixture was heated at reflux for 90 minutes during which a solid formed. Filtration yielded 4.2 grams of 3-(3-phenoxyphenyl)propyltriphenyl- phosphonium bromide, m.p. 198-200°C.

Step E Synthesis of l-(4-chlorophenyl)-l-cyclopropyl- 4-(3-phenoxyphenyl)-l-butene (Compound B7) Under an argon atmosphere a slurry of 4.2 grams (0.0076 mole) of 3-phenoxyphenyl)propyltriphenyl- phosphonium bromide in 75 mL of freshly distilled tetra¬ hydrofuran was cooled to 0°C with stirring. To this

mixture was added 5.4 mL (0.0079 mole^) of a 1.55 M solution of n-butyllithium in hexanes in 0.5 mL portions using a syringe during a 20 minute period. An addi¬ tional 2.0 mL (0.0031 mole) of the n-butyllithium solu- tion was then added slowly, causing a red solution to form. This solution was allowed to warm to ambient temperature at which it was stirred for 60 minutes. This solution was again cooled to 0°C, and 1.3 grams (0.0072 mole) 4-chlorophenyl cyclopropyl ketone in 5 mL of tetrahydrofuran was added portionwise using a syringe. Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature. A precipitate formed. After two hours the reaction mix¬ ture was filtered. To the filtrate was added 1 L of water with stirring to decompose any residual n-butyl¬ lithium. The filtrate was dried over anhydrous sodium sulfate and was filtered. The filtrate was evaporated under reduced pressure, leaving a mixture of a solid and an oil as the residue. To this -residue was added heptane/ethyl acetate (1:2) with stirring. A solid was removed by filtration, and the filtrate was concentrated under reduced pressure. Additional solid was removed by filtration from the concentrated solution. The filtrate was placed on a column of silica gel, eluting with 500 mL of heptane/ ethyl acetate (9:1). The appropriate fractions were combined, and the solvent was evaporated under reduced pressure, yielding 1.2 grams of l-(4- chlorophenyl)-l-cyclopropyl-4-(3-phenoxyphenyl) -1-butene as an oil. The nmr spectrum was consistent with the proposed structure.

Analysis for C ₂ 5H ₂₃ C10 Calc'd: C 80.09; H 6.18;

Found: C 80.15; H 5.98.

Step F Synthesis of l-(4-chlorophenyl)-1-cyclopropyl- 4-(3-phenoxyphenyl)butane (Compound 88) This compound was prepared in a manner analogous to that of Example 4, Step E, by hydrogenation of 1.0 gram (0.0027 mole) of 1-(4-chlorophenyl)-l-cyclopropyl-4-(3- phenoxyphenyl)-1-butene in the presence of 0.35 gram of Raney nickel in 75 L of ethanol. This procedure yielded 0.8 gram of l-(4-chlorophenyl)-l-cyclopropyl-4- (3-phenoxyphenyl)butane as an a oil. The nmr spectrum was consistent with the proposed structure.

In accordance with the composition aspect of the invention, the compounds are generally not applied full strength but are typically applied as formulations which may be applied as such or further diluted for applica¬ tion. Typical formulations include compositions of the active ingredient in combination with one or more agri¬ culturally acceptable adjuvants, carriers or diluents, preferably with a surface active agent, and optionally with other active ingredients. Suitable formulations include solid compositions such as dusts,, wettable powders, and granules or liquid compositions such as solutions, dispersions, suspensions, and emulsifiable concentrates, the choice varying with the type of pest and environmental factors present at the particular locus of infestation.

A typical formulation may vary widely in concentra¬ tion of active ingredient and other ingredients depend¬ ing upon the particular agent used, the additives and carriers used, other active ingredients, the desired mode of application, and numerous other factors well known to those skilled in formulating compositions for use in agriculture.

With due consideration to these factors, the active ingredient of a typical formulation may, for example.

comprise 0.01 percent to 1 percent by weight up to about 95 percent by weight, preferably 1 percent up to 90 or 95 percent by weight, of the formulation. Agricul¬ turally acceptable carriers, diluents, adjuvants, sur- face active agents, and optionally other suitable active ingredients comprise the balance of the formulation. Thus a typical formulation may contain from 0.01 to 95 (preferably 1 to 95) percent by weight active ingre¬ dient, from 0 to 30 percent by weight surface active agent, and from 5 to 99.99 (preferably 5 to 99) percent by weight of an inert agriculturally acceptable carrier or diluent.

Provided below is a general description of exemplary types of formulations which may be employed for applica- tion of the compounds of the present, invention.

SOLID OR DRY FORMULATIONS Dry formulations are mixtures of a liquid or solid active ingredient with a solid carrier to form a partic- ulate product comprising discrete solid particles of various sizes. Solid or dry compositions may take the form of dusts, . wettable powders and granules having average particle sizes varying from about 5 microns to about 5000 microns. These compositions employ solid or dry carriers and/or diluents which may be selected from one or more of the following:

1. Attapulgite Clay: Characterized as hydrated aluminum-magnesium silicate, with or without free water, and possessing sorptive capacity of at least 35% w/w.

2. Kaolin or Kaolinite Clay: Characterized as hydrated aluminum silicate, and including the species dickite, nakrite, and halloysite, and further character¬ ized by having low values for cation exchange capacity.

3. Montmorillonite: Characterized as hydrous aluminum silicate derived by natural modification of mica and pyrophyllite, and further sub-divided into swelling (sodium form) and non-swelling (calcium form) .

4. Pyrophyllite (Talc): Characterized as hydrous magnesium or aluminum silicate and having neutral to basic pH, and further characterized by low to moderate sorptive capacity. 5. Diatomite: Class of opaline silica skeletal remains of aquatic species which includes diatomaceous earth, tripolite, kieselguhr, and fossil flour, charac¬ terized by high (85-93%) silica content, and having high absorptive and low adsorptive capacity. 6. Silica: Diverse origin materials characterized by very high (98-100%) silica content and high (75-100%) sorptive capacity (synthetic) , or low sorptive capacity, such as sand.

7. Botanicals: Any material of plant origin cap- able of being processed into particles of the desired size, including nut shell flours, wood and cellulose flours, corncobs, and the like.

8. Calcium Carbonate

Dust formulations are finely divided solid compositions of active ingredient in admixture with a solid carrier. In most cases dust formulations have an average particle size of less than about 50 microns, typically 5 to 40 microns, an active ingredient content of 1 to 30-percent by weight, and from 70 to 99 percent by weight of one or more of the solid diluents or car¬ riers described above. Since dust formulations are generally applied as such or mixed with other solids for application, they generally do not require a-surface active agent or other adjuvants. The following exem¬ plify typical dust formulations:

1% Dust % W/ ' W

Active Ingredient 1-. , 0

Finely Divided Silica 99 . . 0

100. 0

10% Dust % W/W

Active Ingredient 10.0

Kaolin 90.0

100.0 30% Dust

Active Ingredient 30.0

Montmorillonite 30.0

Talc 40.0

100.0 Wettable powders are finely divided solid composi¬ tions which disperse readily in water or other liquid vehicles. The wettable powder may be applied as a dry dust or as a dispersion in water or other liquid. Thus, wettable powders are essentially a dust or powder formu- lation containing a surface active agent in addition to the active ingredient and solid carrier normally employed in dusts.

A wettable powder may thus typically contain from 1 to 95 percent by weight active ingredient, from 1 to 15 percent surface active agent, and from 4 to 98 percent by weight of one or mqre of the inert solid or dry carriers or diluents described above.

Suitable surface active agents may be selected from the following: 1. Salts or esters of sulfated or sulfonated fatty acids.

2. Salts or esters of ethylene oxide condensates of sulfated or sulfonated fatty acids.

3. Salts or amine derivatives of various resin and fatty acids including, but not restricted to, palmitic and myristic acids, tall oils, and taurine.

4. Salts of alkylarylsulfonates including alkyl- naphthalenesulfonates and dialkylnaphthalenesulfonates.

5. Ethylene oxide .condensates of mixed fatty and resin acids.

6. Ethylene oxide condensates of linear or branched chain glycols, secondary alcohols, or alkylaryl alcohols.

7. Mixed ethylene oxide and propylene oxide con¬ densates of linear and branched chain glycols.

8. Salts of sulfonated naphthalene-formaldehyde condensates.

9. Salts of carboxylated poly-electrolytes.

10. Salts of polymerized alkylnaphthalenesulfonic acids.

11. Salts of lignin sulfonates.

12. Fatty alcohol polyglycol ethers.

13. Materials of classes 1, 2, 5, 6, 7 above when sorbed onto a sorptive, water compatible carrier. 14. Inorganic salts such as tripolyphosphate and hexametaphosphat .

15. Salts and esters of orthophosphoric acid.

16. Fatty acid esters of sorbitan.

17. Ethylene oxide condensates with fatty acid esters of sorbitan.

Ϊ8. Alkylated alkene mono- and polyhydric alcohols..

19. Sulfonated castor oil.

20. Ethylene oxide condensate with lanolin.

21. Coconut alkanolamides.

22. Sulfated sperm oil.

23. Salts of linear alkyl sulfonates.

24. Tall oil ethoxylates.

The following are typical wettable powders: 1% Powder % W/W

Active Ingredient 1.0

Sodium lignosulfonate 7.5

Sodium laurylsulfate 1.5

Talc 96.0

Total 100.0

5% Powder

Active Ingredient 5.0

Sodium lignosulfonate 1.5

Sodium alkylnaphthylene 1.5 sulfonate

Attaclay 92.0

Total 100.0

25% Powder Active Ingredient 25.0

Sodium lignosulfonate 1.5

Sodium laurylsulfate 1.5

Montmorillonite 72.0

Total 100.0

90% Powder

Active Ingredient 90.0

Sodium dibutylnaphthalene- sulfonate 0.5

Sodium lignosulfonate 3.5

Kaolin clay 6.0

Total 100.0

Granules are solid or dry compositions of active ingredient deposited on or in a large particle. Granules usually have an average particle size in the range of 150 to 5000 microns, typically 425 to 850 microns. Granular formulations generally contain from 1 to 50 percent by weight of active ingredient, from 1 to 15 percent by weight of one or more of the surface active agents described above, and from 50 to 98 percent by weight of one or more of the inert solid or dry carriers of diluents described above.

Granular formulations may be of several types. Impregnated granules are those in which the active ingredient is applied,, normally as a solution, to large

particles of an absorbent diluent or carrier such as attapulgite or kaolin clay, corncobs or expanded mica. Surface coated granules are granules produced by adher¬ ing an active ingredient in finely divided form on the surface of a generally non-absorbent particle or by applying a solution of active ingredient to the surface of such a carrier. The carrier or core may be water soluble, such as prilled fertilizer or urea, or insol¬ uble, such as sand, marble chips, corncobs, or coarse talc, as -described above. Particularly useful are granules wherein a wettable powder is adhered as a sur¬ face coating to a sand or other insoluble particle, so that the wettable powder may be dispersed on contact of the granule with moisture. Granules may also be pro- duced by agglomeration of dusts or powders, by compac¬ tion, by extrusion through a die, or by use of a granu¬ lation disk.

The following are typical granular formulations: 1% Granule % W/W Active Ingredient 1.0

Attapulgite 99.0

Total 100.0

5% Granule Active Ingredient 5.0

Attapulgite - 95.0

Total 100.0

The granules above may be prepared by dissolving the active ingredient in a volatile solvent such as methyl- ene chloride, coating large particles of attapulgite clay with the solution, then allowing the solvent to evaporate.

As indicated above, granules may also be adhered to a nonabsorbent core material. The following are typical formulations:

5% Sand-Core Granule % W/W

75% Powder Base 6.64

Active compound 75. .0

Sodium alkylnaphthaiene- - sulfonate 1, .0

Sodium lignosulfonate 4. ,0

Barden clay 20. ,0

Dilute Polyvinylacetate 1.75

Silica (425-850) 91.61 0 Total 100.00

47.5% Sand-Core Granule % W/W

95% Powder Base - 50.0

Active compound 95.0 5 Sodium aIky1naphthalene- sulfonate 1.0

Sodium lignosulfonate . 4.0 Dilute Polyvinylacetate 2.0 adherent o Silica (425-850) 48.00

Total 100.00

The foregoing sand-core granules may be prepared by incorporating the active compound into the base, then adhering the base to sand, utilizing an adhesive such as polyvinylacetate to assure adhesion.

LIQUID AND SEMI-LIQUID FORMULATIONS Liquid formulations are those which contain the active ingredient dissolved or dispersed in one or more inert liquid carriers or diluents, containing from 0.01 to about 95% active ingredient. Carriers suitable for use in liquid formulations may be selected from the following:

1. Water.

2. Aliphatic petroleum solvents including kero¬ sene, light refined mineral oils, and diesel oils.

3. Aromatic petroleum solvents including coal tar fractions yielding xylene, toluene, and benzene; light, medium, and heavy aromatic naphthas; and alkylated mixed naphthenics. 4. Alcohols such as ethanol and isopropyl alcohol.

5. Alkyl ethers of glycols.

6. Esters including dibutyl phthalate, di-2-ethyl- hexyl phthalate, and ethyl acetate.

7. Ketones including cyclohexanone, methyl iso- butyl ketone, acetone, diacetone, and isophorone.

8. Chlorinated hydrocarbons including ethylene dichloride, methylene chloride, chlorobenzene, chlori¬ nated toluene, and chlorinated xylene.

9. Vegetable oils including cottonseed, soybean, pine, sesame, and palm oils.

10. Aqueous solutions of natural origin such as liquors obtained in processing natural sugar products,

' and fermentation broths.

Solutions are liquid compositions containing from about 0.01 to 95 percent by weight active ingredient .and from 1 to 99.99 percent by weight of one or more of the inert liquid diluents or carriers described above. These may be applied as such or further diluted for application. Suspensions or dispersions (also sometimes called flowable formulations) are liquid formulations contain¬ ing from 0.01 to 95 percent by weight active ingredient and from 1 to 99.99 percent by weight of an inert liquid diluent or carrier, in which the active ingredient" is wholly or partially insoluble in the diluent or carrier at the concentration level employed. Suspension or dispersion is frequently facilitated by incorporating from 1 to 30 percent by weight of one or more surface active agents described above, alone or together with a

thickener or suspending agent. Like solutions, disper¬ sions may be used as such or further diluted with a liquid carrier for application.

The following illustrate suspensions suitable for use in the present invention:

25% Oil Suspension: % W/W

Active ingredient 25.0 polyoxyethylene sorbitol hexaoleate 5.0 aliphatic hydrocarbon oil 70.0

Total 100.0

1% Aqueous Suspension: W/W

Active ingredient 1 , 0

Polyacrylic acid thickener 0 , 3

Sodium alkylnaphthalenesulfonate 1 , 0

Sodium lignosulfonate 4 , 0

Polyvinyl alcohol suspending agent 1. 0

Water 92 . 7

Total 100 . 0

20% Aσueous Suspension:

Active ingredient 20 . 0

Polyacrylic acid thickener 0 . 3

Sodium alkylnaphthalenesulfonate 1. 0

Sodium lignosulfonate 4. 0

Polyvinyl alcohol suspending agent 1. 0

Water 73 . 7

Total 100 . 0

40% Aqueous Suspension: Active ingredient 40.0 Polyacrylic acid thickener 0.3 Dodecylphenol polyethylene glycol ether 0.5 Disodium phosphate 1.0

Monosodium phosphate 0.5

Polyvinyl alcohol 1.0

Water 56.7

Total 100.0 Emulsifiable concentrates (EC's) are homogeneous liquid compositions, containing the active ingredient dissolved in a liquid carrier. Commonly used liquid carriers include xylene, heavy aromatic naphthas, isophorone, and other nonvolatile or slightly volatile organic solvents. For application these concentrates are dispersed in water, or other liquid vehicle, forming an emulsion, and .are normally applied as a spray to the area to be treated. The concentration of the essential active ingredient in EC*s may vary according to the manner in which the composition is to be applied, but, in general, is in. the range of 0.01 to 95 percent by weight of active ingredient. Also included in the com¬ position are from 1 to 30 percent by weight surface active agent and from 4 to 97.99 percent of one or more of the inert liquid carriers described above. The following are typical EC compositions:

1% Emulsifiable Concentrate % W/W Active Ingredient 1.0

Anionic calcium dodecylbenzene- sulfonate 4.2

Nonionic polyethoxylated nonylphenol (Mol. Wt. 450-500) 0.4 Nonionic polyethoxylated nonylphenol (Mol. Wt. 1400-1600) 1.1 Nonionic paste of 100% poly- alkylene glycol ether 0.4

Xylene 92. 9

Total 100. 0

5% Emulsifiable Concentrate

Active Ingredient 5.0

Anionic calcium dodecylbenzene- sulfonate 4.2 Nonionic polyethoxylated nonylphenol (Mol. Wt. 450-500) 0.4 Nonionic polyethoxylated nonylphenol (Mol. Wt. 1450-1600) 1.1

Nonionic paste of 100% poly- alkylene glycol ether 0.4

Xylene 88.9

Total 100.0

10% Emulsifiable Concentrate % W/W Active Ingredient 10.0 Blend of alkylnaphthalenesulfonate and polyoxyethylene ethers 4.0

Xylene 86.0

Total 100.0

50% Emulsifiable Concentrate

Active Ingredient 50.0

Blend of alkylnaphthalenesulfonate and polyoxyethylene ethers 6.0 Epoxidized soybean oil 1.0

Xylene 43.0

Total 100.0

75% Emulsifiable Concentrate Active Ingredient 75.0

Blend of alkylnaphthalenesulfonate and.polyoxyethylene ethers 4.0

Xylene 21.0

Total 100.0

Other useful formulations include simple solutions of the active ingredient in a relatively non-volatile solvent such as corn oil, kerosene, propylene glycol, or other organic solvents. This type of formulation is particularly useful for ultra low volume application. The concentration of the active ingredient in use dilution is normally in the range of about 2% to about 0.1%. Many variations of spraying, dusting, and con¬ trolled or slow release compositions in the art may be used by substituting or adding a compound of this inven¬ tion into compositions known or apparent to the art. These compositions may be formulated and applied with other suitable active ingredients, including nematicides, insecticides, acaricides, fungicides, plant regulators, herbicides, fertilizers, etc.

In applying the foregoing chemicals, an effective insect controlling amount of active ingredient must be applied, sometimes referred to herein as an insecticidal amount. While the application rate will vary widely depending on the choice of compound, the formulation and mode of application, the plant species being protected and the planting density, a suitable use rate may be in the range of _. 0.10 to 0.50 kg per hectare, preferably 0.25 to about 1.5 kg/hectare. The compounds of this invention may be applied by incorporating or applying a formulation thereof to a food source for the insects to be controlled, i.e. the locus where control is required, including application to the above ground portions of plants on which the insects feed, to the soil in which plants are or are about to be planted in order to provide control of soil- borne insects, or in a bait-type formulation for appli¬ cation to surfaces on which insects normally do not feed. When applying the compounds to the soil, the compounds may be broadcast broadly over the planted area

or the area to be planted or by limiting the application to a small area or band in the root zone where plants are or are to be planted. When either method of soil application is used, sufficient compound must be applied to provide an insect controlling concentration of the compound in the soil in the root zone. For the present a suitable concentration is about 0.2 to about 50 parts by weight of compound per million parts of soil.

The insecticidal activity of the pyrethroid-like compound of this invention was evaluated as follows: Foliar Evaluation

The compound was tested by foliar application at various concentrations in aqueous solutions containing 10% acetone and 0.25% octyl phenoxypolyethoxy ethanol. The evaluation utilized Mexican bean beetle (Epilachna varivestis) , southern armyworm (Spodoptera eridania) , pea aphid (Acyrthosiphon pisum) , cabbage looper (Trichoplusia ni) , beet armyworm (Spodoptera exigua) , and twospotted spider mite (Tetranychus urticae) . For all insects except pea aphid, pinto bean

(Phaseolus vulqaris) plants were' placed on a revolving turntable in a hood, and the test solutions were applied with a sprayer. The test solutions were applied to the upper and lower surfaces of the plant leaves to runoff. The plants were then allowed to dry and were severed at the base of the stem before being placed in cups. Ten individuals of the appropriate insect species were placed in each cup and the cup covered. Mortality was read 48 hours later. Fava bean was substituted for pinto bean in the case of pea aphid, and the treated, potted plants were placed in cups infested with ten individuals and covered. Mortality was read 48 hours later.

Acaricidal tests were performed using the following procedure: Leaves infested with adult twospotted spider

mites (Tetranychus urticae) were removed from culture plants and cut into segments containing 50-75 female mites. Each segment was placed on the upper leaf surface of a whole pinto bean plant. After the mites had migrated to the under surfaces of the leaves, the leaf segments used to infest were removed, and each plant was sprayed with test chemical as described above. After the plants had dried, the entire plant and pot were placed in metal trays in a hood, a supply of water in the tray keeping the plants turgid. After 48 hours the living and dead mites were counted, and percent mortal¬ ity was calculated.

The results of these tests are shown in Table 4. Soil Evaluation A stock solution of the test compound was prepared by dissolving 9.6 mg- in 10 mL of acetone and diluting with 90 L of acetone/water (1:9). The addition of 5 mL of this stock solution to 30 grams of air-dried, clay loam soil in a three ounce plastic cup provided a con- centration of 16 ppm of the test compound in the soil. Serial dilution of the stock solution was used to pro¬ vide concentrations of the test compound in soil of 8, 4, 2, 1, 0.5, and 0.25 ppm. In all cases 5 mL of a solution having the required concentration was added to 30 grams of soil. The treated soil was allowed to stand uncovered in a hood for 0.5 hour to evaporate the ace¬ tone. Before infesting the soil with southern corn rootworm larvae (Diabrotica undecimpunctata howardi Barber) the soil was mixed thoroughly, and two three- day-old corn sprouts were planted in it. Ten early third-stage (9-10 days old) southern corn rootworm larvae were placed in the cup which was covered with a plastic bag. After storage at 74-78°F ^" for 48 hours, the mortality of the larvae was determined by removing the

cup from the plastic bag, removing the cover, and plac¬ ing the cup in a modified Berlese polyethylene funnel fitted with an 18-mesh screen. The funnels were placed over containers of an aqueous detergent solution. Incandescent lights (100 watts) were placed 36 cm above the soil samples. The heat from these lights slowly dried the soil causing larvae that had not been affected by the test compound to emerge from the soil and drop into the detergent solution. The percent mortality was determined in this manner for each concentration.

Results of these tests are reported in Table 5. Fish Toxicity

The toxicity towards fish was determined in a 48 hour static bioassay using the bluegill sunfish (Lepomis macrochirus) . Three fish ranging in size from 1 to 2 inches were placed in a 0.95 liter jar containing the specified concentration of the compound. Two replicates were used for each concentration. After 48 hours the percent kill was determined. Concentrations of chemi¬ cals used were 6.3 ppm, 3.1 ppm, and occasionally 1.7 ppm. Compound 16, the compound of Example 1 and a preferred compound of this invention, exhibited 83% kill at 6.3 ppm. Another preferred compound, Compound 24, killed only 50% of the fish at the same concentration. By way of comparison, cypermethrin, a conventional pyre- throid insecticide used widely for crop protection, displays 100% kill at! a concentration of 0.01 ppm.

The remarkably low toxicity towards fish of the pyrethroid-like compounds is certainly unexpected, and this factor, in combination with the demonstrated insecticidal activity, should make them appropriate compounds for control of insect infestations in_ aquatic environments, such as rice paddies.

TABLE 1 - TABLE OF ETHERS, THIOETHERS, AND BUTANE DERIVATIVES

Ar-CH-CH ₂ -Z-CH ₂ -Ar'

Cmpd

No. Ar Z Ar'

1 phenyl 0 2-methyl[l,l' -biphenyl] -3- ^■ yl

2 phenyl 0 3-phenoxyphenyl

3 phenyl 0 4-fluoro-3-phenoxyphenyl

4 4-fluorophenyl 0 2-methyl[1,1' -biphenyl']-3• -yl

5 4-fluorophenyl 0 3-phenoxyphenyl

6 4-fluorophenyl 0 4-fluoro-3-phenoxyphenyl

7 2-chlorophenyl 0 2-methyl[1,1 ' -biphenyl]-3 ^■ -yl

8 2-chlorophenyl 0 3-phenoxyphenyl

9 2-chlorophenyl 0 4-fluoro-3-phenoxyphenyl

10 3-chlorophenyl 0 2-me hyl[1,1' -biphenyl] -3- -yl

11 3-chlorophenyl 0 3-phenoxyphenyl

12 3-chlorophenyl 0 4-fluoro-3-phenoxyphenyl

13 4-chlorophenyl 0 2-methyl[1,1' -biphenyl] -3 -yl

14 4-chlorophenyl 0 3-phenoxyphenyl

15 4-chlorophenyl 0 3-phenoxyphenyl

(Stereoisomer B) ^a

16 4-chlorophenyl 0 4-fluoro-3-phenoxyphenyl

17 4-chlorophenyl 0 4-fluoro-3-phenoxyphenyl (Stereoisomer A)" '

18 4-chlorophenyl 0 4-fluoro-3-phenoxyphenyl (Stereoisomer B) ^c

19 4-chlorophenyl S 2-methyl[1,1' -biphenyl] -3 -yl

20 4-chlorophenyl S -phenoxyphenyl

21 4-chlorophenyl S 4-fluoro-3-phenoxyphenyl

22 4-bromopheny1 0 2-me hyl[1,1' -biphenyl] -3 -yl

23 4-bromophenyl 0 3-phenoxyphenyl

Table 1 (continued)

Cmpd

No. Ar _Z. Ar'

24 4-bromophenyl 0 4-fluoro-3-phenoxyphenyl

25 4-methylphenyl 0 2-methyl[1,1' -biphenyl] -3-yl

26 4-methylpheny1 0 3-phenoxyphenyl

27 4-methylphenyl 0 4-fluoro-3-phenoxyphenyl

28 3-ethylpheny1 0 2-methyl[1,1' -biphenyl] -3-yl

29 3-ethylphenyl 0 3-phenoxyphenyl

30 3-ethylpheny1 0 4-fluoro-3-phenoxyphenyl

31 4-ethylpheny1 0 2-methyl[1,1' -biphenyl] -3-yl

32 4-ethylpheny1 0 3-phenoxyphenyl

33 4-ethylphenyl 0 4-fluoro-3-phenoxyphenyl

34 4-t-butylphenyl 0 2-methyl[1,1' -biphenyl] -3-yl

35 4-t-butylphenyl 0 3-phenoxyphenyl

36 4-t-butylphenyl 0 4-fluoro-3-phenoxyphenyl

37 4-trifluorometh lphenyl 0 2-methyl[1,1' -biphenyl] -3-yl

38 4-trifluoromethylphenyl 0 3-phenoxyphenyl

39 4-trifluoromethylphenyl 0 -fluoro-3-phenoxyphenyl

40 4-methoxyphenyl 0 2-methyl[1,1' -biphenyl] -3-yl

41 4-me hoxyphenyl 0 3-phenoxyphenyl

42 .4-methoxyphenyl - 0 4-fluoro-3-phenoxyphenyl

43 4-ethoxyphenyl 0 2-methyl[1,1' -biphenyl] -3-yl

44 4-ethoxyphenyl 0 3-phenoxyphenyl

45 4-ethoxyphenyl 0 -fluoro-3-phenoxyphenyl

46 -difluoromethoxyphenyl 0 2-methyl[1,1' -biphenyl] -3-yl

47 4-difluoromethoxyphenyl 0 3-phenoxyphenyl

48 4-difluorome hoxyphenyl 0 4-fluoro-3-phenoxyphenyl

49 4-trifluoromethoxyphenyl 0 2-methyl[1,1' -biphenyl] -3-yl

50 4-trifluoromethoxyphenyl 0 3-phenoxyphenyl

51 4-trifluoromethoxyphenyl 0 4-fluoro-3-phenoxyphenyl

52 4- (2-fluoroethoxy)phenyl 0 2-methyl[1,1' -biphenyl] - -yl

53 4- (2-fluoroethoxy) henyl 0 3-phenoxyphenyl

54 4- (2-fluoroethoxy) henyl 0 4-fluoro-3-phenoxyphenyl

55 4-trifluoromethylthiophenyl 0 2-methyl[1,1' -biphenyl] -3-yl

56 4-trifluoromethylthiophenyl 0 3-phenoxyphenyl

Table 1 (continued)

Cmpd

No. Ar Z Ar'

57 4-tri-fluoromethylthiophenyl 0 4-fluoro-3-phenoxyphenyl

58 4- ri luoromethylsul Inylphenyl 0 2-methyl[1,1' -biphenyl] -3-yl

59 4- rifluoromethylsulfinylphenyl 0 3-phenoxyphenyl

60 4-trifluoromethylsulfInylphenyl 0 4-fluoro-3-phenoxyphenyl

61 4-trifluoromethylsulfonylphenyl 0 2-methyl[1,1' -biphenyl] -3-yl

62 4- rifluoromethylsulfonylphenyl 0 3-phenoxyphenyl

63 4- rifluoromethylsulfonylphenyl 0 4-fluoro-3-phenoxyphenyl

64 1,3-benzodioxol-5-yl 0 2-methyl[1,1' -biphenyl] -3-y1

65 1,3-benzodioxol-5-yl 0 3-phenoxyphenyl

66 1,3-benzodioxol-5-yl 0 4-fluoro-3-phenoxyphenyl

67 2,2-difluoro-l,3-benzo- 0 2-methyl[1,1' -biphenyl] -3-yl dioxol-5-yl

68 2,2-difluoro-1,3-benzo- 0 3-phenoxyphenyl dioxol-5-yl

69 2,2-difluoro-1,3-benzo¬ 0 4-fluoro-3-phenoxyphenyl dioxol-5-yl

70 3-chloro-4-methoxyphenyl 0 2-methyl[1,1' -biphenyl] -3-yl

71 2,3-dihydro-2,2-dimethyl- 0 2-methyl[1,1' -biphenyl] -3-yl benzofuran-5-yl

72 2,3-dihydro-2,2-dimethyl- 0 3-phenoxyphenyl benzofuran-5-yl

73 2,3-dihydro-2,2-dime hyl- 0 4-fluoro-3-phenoxyphenyl benzofuran-5- l

74 2,2,3,3- etrafluoro- 0 2-methyl[1,1 ' -biphenyl] -3-yl benzofuran-5-yl

75 2,2,3,3-tetrafluoro- 0 3-phenoxyphenyl benzofuran-5-y1

76 2,2,3,3-tetrafluoro- 0 4-fluoro-3-phenoxyphenyl benzofuran-5-yl

77 2-thienyl .0 2-methyl[1,1' -biphenyl] -3-yl

78 -thienyl 0 3-phenoxyphenyl

79 ^~"" -----_ 2-thienyl 0 4-fluoro-3-phenoxyphenyl

80 4-chlorophenyl 0 6-phenoxy-2-pyridyl

Table 1 (continued)

Cmpd

No. Ar Ar'

81 4-ethoxypheny1 0 6-phenoxy-2-pyridyl

82 2-chlorophenyl CH2 3-phenoxyphenyl

83 2-chlorophenyl CH2 4-fluoro-3-phenoxyphenyl

84 3-chlorophenyl CH ₂ 2-me hyl[1,1' -biphenyl] -3-yl

85 3-chlorophenyl CH ₂ 3-phenoxyphenyl

86 3-chlorophenyl CH 4-fluoro-3-phenoxyphenyl

87 4-chlorophenyl CH ₂ 2-methyl[1,1' -biphenyl] -3-yl

88 4-chlorophenyl CH ₂ 3-phenoxyphenyl

89 -chlorophenyl CH 4-fluoro-3-phenoxyphenyl

90 4-chlorophenyl CH 6-phenoxy-2-pyridyl

91 -bromophenyl CH ₂ 2-methyl[1,1' -biphenyl] -3-yl

92 4-bromophenyl CH ₂ 3-phenoxyphenyl

93 4-bromophenyl CH ₂ 4-fluoro-3-phenoxyphenyl

94 4-methylphenyl CH ₂ 2-methyl[1,1' -biphenyl] -3-yl

95 4-meth Iphenyl CH ₂ 3-phenoxyphenyl

96 4-methylphenyl CH 4-fluoro-3-phenoxyphenyl

97 4 -trifluoromethylphenyl CH ₂ 2-me hyl[1,1' -biphenyl] -3-yl

98 4 -trifluoromethylphenyl CH 3-phenoxyphenyl

99 4 - rifluoromethylphenyl CH 4-fluoro-3- henoxyphenyl

100 4-methoxypheny1 CH ₂ 2-methyl[1,1' -biphenyl] -3-yl

101 4-methoxyphenyl CH 3-phenoxyphenyl

102 4-methoxyphenyl CH 4-fluoro-3-phenoxyphenyl

103 4-ethoxyphenyl CH ₂ 2-methyl[1,1' -biphenyl] -3-yl

104 4-ethoxyphenyl CH 3-phenoxyphenyl

105 4-ethoxyphenyl CH 4-fluoro-3-phenoxyphenyl

106 4 -difluoromethoxyphenyl CH ₂ 2-methyl[l,l' -biphenyl] -3-yl

107 4 -difluoromethoxyphenyl CH 3-phenoxyphenyl

108 4 -difluoromethoxyphenyl CH 4-fluoro-3-phenoxyphenyl

109 4-trifluoromethoxyphenyl CH ₂ 2-methyl[1,1' -biphenyl] -3-yl

110 4-t i luoromethoxyphenyl CH ₂ 3-phenoxyphenyl

111 4-trifluoromethoxyphenyl CH ₂ 4-fluoro-3-phenoxyphenyl

112 4- (2-fluoroethoxy)phenyl CH ₂ 2-methyl[l,l' -biphenyl] -3-yl

113 4- (2-fluoroethoxy) henyl CH ₂ 3-phenoxyphenyl

Table 1 (continued)

Cmpd

No. Ar Ar' 114 4-(2-fluoroethoxy)phenyl CH ₂ 4-fluoro-3-phenoxyphenyl 115- 1,3-benzodioxol-5-yl CH ₂ 2-methyl[1,1' -biphenyl] -3-yl 116 1,3-benzodioxol-5-yl CH ₂ 3-phenoxyphenyl 117 1,3-benzodioxol-5-yl CH ₂ 4-fluoro-3-phenoxyphenyl 118 2,2-difluoro-1,3-benzo- CH ₂ 2-methyl[1,1' -biphenyl] -3-yl dioxol-5-yl

119 2,2-difluoro-1,3-benzo- CH ₂ 3-phenoxyphenyl dioxol-5-yl

120 2,2-difluoro-1,3-benzo- CH 4-fluoro-3-phenoxyphenyl dioxol-5-yl

121 4-trifluoromethylthiophenyl CH ₂ 2-methyl[l,l' -biphenyl] -3-yl 122 4-trifluoromethylthiophenyl CH ₂ 3-phenoxyphenyl 123 4-trifluorometh lthiophenyl CH 4-fluoro-3-phenoxyphenyl 124 2,3-dihydro-2,2-dimethyl- CH ₂ 2-methyl[1,1' -biphenyl] -3-yl benzofuran-5-yl

125 2,3-dihydro-2,2-dimethyl- CH ₂ 3-phenoxyphenyl_ benzofuran-5- l

126 2,3-dih dro-2,2-dimeth l CH ₂ 4-fluoro-3-phenoxyphenyl benzofuran-5-yl

.127 2,2,3,3-tetrafluoro- CH ₂ 2-methyl[1,1' -biphenyl] -3-yl benzofuran-5-yl

128 2,2,3,3-tetrafluoro- CH ₂ 3-phenoxyphenyl benzofuran-5-yl

129 2,2,3,3-tetrafluoro- _CH ₂ 4- luoro-3-phenoxyphenyl benzofuran-5-yl

130 2-thienyl CH ₂ 3-phenoxyphenyl 131 2-thienyl CH ₂ 4-fluoro-3-phenoxyphenyl 132 4-ethoxyphenyl CH ₂ 6-phenoxy-2-p ridy1

b. [ ] ⁵ =(+)22.19° in CHCI3 c. in CHCI3

TABLE 2 - INSECTICIDAL AND ACARICIDAL 1,4-DIARYL- 1-CYCLOPROPYL-1,3-BUTADIENE DERIVATIVES

C pd No Ar Ar'

Al 3-chlorophenyl 2-methyl[1,1' -biphenyl] -3-yl

A2 3-chlorophenyl 3-phenoxyphenyl

A3 3-chlorophenyl 4-fluoro-3-phenoxyphenyl

A4 4-chlorophenyl 2-methyl[1,1' -biphenyl] -3-yl

A5 4-chlorophenyl 3-phenoxyphenyl

A6 4-chlorophenyl 4-fluoro-3-phenoxyphenyl

A7 4-chlorophenyl 6-phenoxy-2-pyridyl

A8 4-me hyIphen l 2-methyl[1,1' -biphenyl] -3-yl

A9 4-methyIphenyl 3-phenoxyphenyl

A10 4-methyIphen l 4-fluoro-3-phenoxyphen l

All 4-trifluoromethylphenyl 2-methyl[1,1' -biphenyl] -3-yl

A12 4-trifluoromethylphenyl 3-phenoxyphenyl

A13 4-trifluoromethylphenyl 4-fluoro-3-phenoxyphenyl

A14 4-ethoxyphenyl 2-methyl[1,1' -biphenyl] -3-yl

A15 4-ethoxyphenyl 3-phenoxyphenyl

A16 4-ethoxyphenyl 4-fluoro-3-phenoxyphenyl

A17 4-trifluoromethoxyphenyl 2-methyl[1,1' -biphenyl] -3-yl

A18 4-trifluoromethoxyphenyl 3-phenoxyphenyl

A19 4- rifluoromethoxyphenyl 4-fluoro-3-phenoxyphenyl

A20 1,3-benzodioxol-5-yl 2-methyl[1,1' -biphenyl] -3-yl

A21 1,3-benzodioxol-5-yl 3-phenoxyphenyl

A22 1,3-benzodioxol-5-yl 4-fluoro-3-phenoxyphenyl

A23 2,3-dihydro-2,2-dimethyl- 2-methyl[1,1' -biphenyl] -3-yl benzofuran-5-yl

A24 2,3-dihydro-2,2-dimethy1- 3-phenoxypheny1 benzofuran-5-yl

Table 2 - (continued)

Cmυd No. Ar Ar'

A25 2,3-dihydro-2,2-dimethyl- 4-fluoro-3-phenoxyphenyl benzofuran-5- ^" yl

A26 2-thienyl 2-me hyl[1,1-biphenyl] -3-yl

A27 2-thienyl 3-phenoxyphenyl

A28 2-thienyl 4-fluoro-3-phenoxyphen l

TABLE 3 - INSECTICIDAL AND ACARICIDAL 1,4-DIARYL- CYCLOPROPYL-1-BUTENE DERIVATIVES

Ar-C-CH-CH ₂ -CH -Ar'

Cmpd No Ar- Ar'

Bl phenyl 4-fluoro-3-phenoxyphen l

B2 4-fluorophenyl 3-phenoxyphenyl

B3 4-fluorophen l 4-fluoro-3-phenoxyphenyl

B4 2-chlorophenyl 2-methyl[1,1' -biphenyl] -3-yl

B5 2-chlorophenyl 3-phenoxyphenyl

B6 2-chlorophenyl 4-fluoro-3-phenoxyphenyl

B7 4-chlorophenyl 3-phenoxyphen l

B8 4-chlorophenyl 4-fluoro-3-phenoxyphen l

B9 4-bromophenyl 3-phenoxyphenyl

BIO 4-ethyIphenyl 2-methyl[l,l' -biphenyl] -3-yl

Bll 4-ethylphen 1 4-fluoro-3-phenoxyphenyl

*B12 4-methoxyphen 1 3-phenoxyphenyl

**B13 4-methoxypheny1 3-phenoxyphenyl

B14 4 -difluoromethoxyphenyl 2-methyl[1,1' -biphenyl] -3-yl

B15 4 -difluoromethoxyphenyl 3-phenoxyphenyl

B16 4 -difluoromethoxyphenyl 4-fluoro-3-phenoxyphenyl

B17 4- (2-fluoroethox )phen l 3-phenoxyphenyl

B18 4- (2-fluoroethox )phenyl 4-fluoro-3-phenoxyphen l

B19 4-trifluoromethylthiophenyl 2-methyl[1,1' -biphenyl] -3-yl

B20 4-trifluoromethylthiophenyl 3-phenoxyphenyl

B21 4-trifluoromethylthiophenyl 4-fluoro-3-phenoxyphen l

B22 2 ,2-difluoro-1,3-benzo- 2-methyl[1,1' -biphenyl] -3-yl dioxol-5-yl

B23 2 , ,2-difluoro-1,3-benzo- 3-phenoxyphenyl dioxol-5-yl

B24 _. 2, ,2-difluoro-l,3-benzd- 4-fluoro-3-phenoxyphenyl dioxol-5-yl

Table 3 (continued)

Cmpd No. Ar ArJ

B25 2,2,3,3-tetrafluorobenzo- 2-methyl[1,1' -biphenyl] -3-yl fur n-5-yl

B26 2,2,3,3-tetrafluorobenzo- 3-phenoxyphenyl furan-5-yl

B27 _. 2,2,3,3-tetrafluorobenzo- 4-fluoro-3-phenoxyphenyl furan-5-yl

* Mixture of 57% Z isomer and 43% E isomer by gas chromatographic analysis (area %) ** Mixture of 86% Z isomer and 14% E isomer by gas chromatographic analysis (area %)

TABLE 4 - FOLIAR INSECTICIDAL TEST RESULTS

Cmpd Rate % Kill No. (ppm) BAW MBB SAW TSM . CL PA

1 500

100 45 20

2 500 23

100 95 95 55

3 500 20 25

100 100 100 85

4 10O0 15

250 85 85

5 500 70

250 100 95

6 1000 60

250. 100 100

10 1000 35 29 95 50

11 1000 100 55 100 100

12 1000 100 100 100 . 90

13 1000 100 100 100 100 100 90 50

14 1000 100 100 90 ^a 100 100 100 95

15 1000 100 100 90

Table 4 (continued)

Cmpd Rate % Kill

No. .(ppm) BAW MBB SAW TSM CL PA

16 1000 100 100 100 100

100 100 100

17 500 38 100

100 75 95

50 90 95

18 500 83 100

100 100 100

50 100 100

19 1000 11

500 45

250 100 20

20 500 12

250 95 100 75

21 500 15

250 100 100 90

22 1000 100 80 60 70

500 95

23 1000 100 100 77 100

500 100

24 1000 100 100 100 80

500 100

Table 4 (continued)

Cmpd Rate % Kill

No. (PPm) BAW MBB SAW TSM CL P

25 1000 100 0 35

500 100 100

26 1000 100 45

500 100 100

27 1000 100 40 35

500 100 100

34 500 25

100 35 70 16 10

35 500 99 ^a 90

10.0 55 100

36 500 100 60

100 55 100 45

37 1000 100 100 100 100

38 1000 100 100 100 100

39 1000 100 100 95 90

40 1000 100 100 40 80

500 75

41 1000 100 100 100

500 95 85

Table 4 (continued)

Cmpd Rate % Kill

No. (ppm) BAW MBB SAW TSM CL PA

42 1000 75 100 0 - 100

500 100 100

43 500 100 100 100

44 500 100 100 100 60

45 1000 100 500 100 100 100 90

46 1000 80 100 95 90

47 1000 70 100 . 100 100

48 1000 95 100 100 100

49 1000 100 100 100 100

50 1000 100 100 100 100

51 1000 100 100 100 100

52 1000 250 75 85

53 1000 55 250 100 100

Table 4 (continued)

Cmpd Rate % Kill No. (ppm) BAW MBB SAW TSM CL PA 54 1000 65 250 90 100

55 1000 100 100 100 75

56 1000 100 100 100 95

57 1000 100 100 100 90

58 1000 75 100 100

59 1000 100 100 100 90

60 1000 100 100 100 80

61 1000 60 94 100

62 1000 100 100 80 80

63 1000 100 100 100 95

64 500 23 250 85 100 80

65 500 250 90 100 70

66 250 100 11 100 65

70 500 100 80 40

77 500 14 0 100 0

Table 4 (continued)

Cmpd Rate % Kill

No. (ppm) BAW MBB SAW TSM CL PA

78 500 11 0

100 20 0 0

79 500 10

100 45 15 0

80 1000 95 96 100 100

84 1000 95 21 90 65

85 1000 100 14 100 95

86 1000 80 92 100 85

87 1000 100 97 100 90

88 1000 100 100 100 80

89 1000 100 100 100 100

^' 94 1000 100 63 100 35

95 1000 100 50 100 55

96 1000 100 100 100 40

97 1000 100 99 100 100

98 1000 100 100 100 100

99 1000 100 100 100 100

Table 4 (continued)

Cmpd Rate % Kill

No. (ppm) BAW MBB SAW TSM CL

103 1000 95 100 85 95

104 1000 100 89 100 60

105 1000 100 100 100 95

109 1000 100 100 100 80

110 1000 100 100 100 100

111 1000 100 100 100 100

A4 1000 63 ^a

A6 1000 68 ^a 25

A8 1000 0

A9 1000

A10 1000 30

All 1000 68 ^a 88 ^a

A12 1000 78 ^a 68 ^a

A13 1000 95 ^a 0 100 ^a

A15 1000 55 60

B7 1000 90 500 95 30

Table 4 (continued)

Cmpd Rate % Kill

No. (ppm) BAW MBB SAW TSM CL PA

B8 1000 0 100

500 95 100 100

B9 1000 65

500 100 35

B12 500 100 100 20 30

^* B13 1000 65

a. Average of two tests

BAW = beet armyworm

MBB = Mexican bean beetle

SAW = southern armyworm

TSM = twospotted spider mite

CL = cabbage looper

PA = pea aphid

TABLE 5 - SOIL INSECT]:CIDAL TEST RESULTS

Cmpd. Rate Initial % Kill

No. (ppm). SCR

13 16 15

14 2 25

16 16 50

22 16 35

26 16 90

27 16 70

40. 16 45

41 16 ^' 65

42 16 75 ^a

48 15 100

57 15 100

80 15 85

85 15 Ab

88 15 A

89 15 80

94 ^" 15 A

95 15 A

96 15 A

99 15 A

103 15 85

105 15 A

110 15 A

B7 15 60

B8 15 60

B9 15 30

a. = Average of two tests. b. = A = active = >75% kill

SCR = southern corn rootworm