USH1838H - Insecticidal N-(arylalkyl)-4-[Bis(substituted aryl)hydroxymethyl]azabicyclo[3.3.1.]nonanes and [3.2.1.]octanes - Google Patents

Insecticidal N-(arylalkyl)-4-[Bis(substituted aryl)hydroxymethyl]azabicyclo[3.3.1.]nonanes and [3.2.1.]octanes Download PDF

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USH1838H
USH1838H US09/212,223 US21222398A USH1838H US H1838 H USH1838 H US H1838H US 21222398 A US21222398 A US 21222398A US H1838 H USH1838 H US H1838H
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ocf
nhco
pyrid
sup
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US09/212,223
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Thomas G. Cullen
Ian Robert Silverman
Walter H. Yeager
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FMC Corp
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FMC Corp
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D451/00—Heterocyclic compounds containing 8-azabicyclo [3.2.1] octane, 9-azabicyclo [3.3.1] nonane, or 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring systems, e.g. tropane or granatane alkaloids, scopolamine; Cyclic acetals thereof
    • C07D451/02—Heterocyclic compounds containing 8-azabicyclo [3.2.1] octane, 9-azabicyclo [3.3.1] nonane, or 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring systems, e.g. tropane or granatane alkaloids, scopolamine; Cyclic acetals thereof containing not further condensed 8-azabicyclo [3.2.1] octane or 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring systems, e.g. tropane; Cyclic acetals thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/20—N-Aryl derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D451/00—Heterocyclic compounds containing 8-azabicyclo [3.2.1] octane, 9-azabicyclo [3.3.1] nonane, or 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring systems, e.g. tropane or granatane alkaloids, scopolamine; Cyclic acetals thereof
    • C07D451/14—Heterocyclic compounds containing 8-azabicyclo [3.2.1] octane, 9-azabicyclo [3.3.1] nonane, or 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring systems, e.g. tropane or granatane alkaloids, scopolamine; Cyclic acetals thereof containing 9-azabicyclo [3.3.1] nonane ring systems, e.g. granatane, 2-aza-adamantane; Cyclic acetals thereof

Definitions

  • the present invention relates to novel pesticidal compounds, intermediates therefor, formulations thereof, and to methods for controlling insects, acarids and the like.
  • the invention relates to certain N-( arylalkyl)-4-[bis(substituted aryl)hydroxymethyl]azabicyclo[3.3.1.]nonanes and [3.2.1.]octanes, to methods for control of insects with such compounds or formulations thereof, and to certain novel intermediates in the preparation of such insecticidal compounds.
  • the compounds of this invention are N-(substituted arylalkyl) 4-[bis(substituted aryl)hydroxymethyl]azabicyclo[3.3.1.]nonanes and [3.2.1.]octanes, their N-oxides, N-(substituted-oxy) derivatives thereof, and agriculturally acceptable salts thereof. More particularly the compounds of this invention are compounds of the formula: ##STR2## in which m is 2 or 3; n is 0 or 1;
  • W is hydrogen or alkoxy
  • X is hydrogen, alkoxy, cycloalkylalkoxy, alkoxycarbonyl, alkoxycarbonylamino, alkoxyimino, haloalkoxyimino, or a five-or six-membered heteroaryl or heteroaryloxy in which one or more hetero atoms may be optionally substituted with an alkyl;
  • R 1 and R 2 are independently selected from hydrogen, haloalkyl, halothio, or haloalkoxy;
  • Y represents (a) an N-oxide of the ring nitrogen or (b) an agriculturally acceptable anionic salt of the ring nitrogen; or (c) forms an OR 3 linkage in which R 3 is selected from hydrogen, alkyl, alkoxycarbonylalkyl, hydroxycarbonylethyl, in association with an agriculturally acceptable anion resulting in an anionic salt, or R 3 is an oxycarbonylalkyl group bearing a negative charge resulting in an inner salt.
  • Alkyl means lower alkyl having 1 to 4 carbon atoms which may have a branched or unbranched chain.
  • Heteroaryl refers to an aromatic (unsaturated) ring structure having 1 to 4 nitrogen atoms as hetero ring components, the balance being carbon atoms.
  • Halo or “halide” refers to one or more halogen atoms selected from chlorine, fluorine, bromine or iodine, with fluorine being the preferred atom when appended to an alkyl or this group.
  • “Anion”, “anionic” or “anionic salt” refers to negatively charged ions which form salts with a positively charged ring nitrogen, including but not limited to, halides, salicylates and alkylsulfonates.
  • the preferred insecticidal compounds are those wherein W is hydrogen; X is propoxy, methoxycarbonylamino, or 2-ethyltetrazol-5-yl; R 1 and R 2 are 4-trifluoromethyl or 4-trifluoromethoxy; and R 3 is methyl or ethoxycarbonylethyl in association with an agriculturally acceptable anionic salt, or an oxycarbonylalkyl group bearing a negative charge resulting in an inner salt.
  • insecticidal compounds of the present invention may be prepared by methods known to one skilled in the art. A suitable route for preparation of these compounds are shown in Schema 1 set forth below.
  • an appropriately substituted phenylmethyl azabicycloalkan-3-one (SM1) was reacted with tosylmethyl isocyanide under basic conditions to form the appropriate 3-cyanophenylmethylazabicycloalkane (A).
  • the nitrile (A) was in turn treated with an alcohol, for example ethanol, in the presence of hydrogen chloride gas, yielding the appropriate alkyl N-(substituted phenylmethylazabicycloalkyl)carboxylate (B), for example ethyl N-(9-phenylmethyl-9-azabicyclo[3.3.1]nonane-3-yl)carboxylate.
  • the so-prepared alkyl carboxylate (B) was then reacted with a two or three molar excess of the Grignard reagent of an appropriately substituted halide, for example 1-trifluoromethyl-4-bromobenzene, to form the targeted phenylmethyl- ⁇ , ⁇ -bis(substituted phenyl)azabicycloalkane-3-methanol (I), for example 9-phenyhnethyl- ⁇ , ⁇ -bis(4-trifluoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol.
  • I phenyhnethyl- ⁇ , ⁇ -bis(4-trifluoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol.
  • Example 1 provides the detailed procedure for this route.
  • the ⁇ , ⁇ -bis(substituted phenyl)azabicycloalkane-3-methanol (II) was then reacted with the appropriately substituted phenylmethyl halide, for example 4-propoxyphenylmethyl chloride, affording the targeted (substituted phenyl)methyl- ⁇ , ⁇ -bis(substituted phenyl)azabicycloalkane-3-methanol (III), for example 9-(4-propoxyphenyl)methyl- ⁇ , ⁇ -bis(4-trifluoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol.
  • the appropriately substituted phenylmethyl halide for example 4-propoxyphenylmethyl chloride
  • the 3-methanol (III) (can then be reacted with an oxidizing agent, such as hydrogen peroxide or 3-chloroperoxybenzoic acid, to yield the targeted (substituted phenyl)methyl- ⁇ , ⁇ -bis(substituted phenyl)-azabicycloalkane-3-methanol N-oxide (IV), for example 9-(4-propoxyphenyl)methyl- ⁇ , ⁇ -bis(4-trifiuoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol N-oxide.
  • an oxidizing agent such as hydrogen peroxide or 3-chloroperoxybenzoic acid
  • the methanol (III) can also be reacted with the appropriate acids, such as hydrochloric or ethanesulfonic acid, yielding the targeted salts (V).
  • Additional salts (VI) can be prepared by reacting the N-oxide (IV) with an appropriate halide, such as 3-bromopropionic acid, or with a sulfate or sulfonate.
  • Even more salts (VII) can be prepared by reacting the N-oxide (IV) with the appropriate acid, such as hydrochloric, ethanesulfonic, or salicylic. Examples 2, 3, 4, 5, 6, and 7 described the detailed procedures for this route. ##STR4##
  • Tables 1, 2, 3 and 4 below illustrate the insecticidal compounds of this invention.
  • the compounds of this invention may be used to combat, control, or prevent infestations of insect pests such as Lepidoptera, Diptera, Homoptera, Coleoptera, and Diabrotica such as corn rootworms as well as other invertebrate pests such as Acarids.
  • insect pests such as Lepidoptera, Diptera, Homoptera, Coleoptera, and Diabrotica
  • corn rootworms such as corn rootworms
  • invertebrate pests such as Acarids.
  • the compounds of the invention may be used to control insects and acarids found in agricultural crops, horticulture, and animal husbandry. They are also useful in forestry, storage and preservation of products of vegetable origin, and for controlling those insect and acarine pests associated with transmission of diseases of man and animals.
  • pest species some or all of which may be effectively controlled by the compounds of the invention include Myzus persicae (aphid), Aphis gossypii (aphid), Aedes aegypti (mosquito), Anopheles species (mosquitoes), Culex species (mosquitoes), Dysdercus faciatus (capsid), Musca domestica (housefly), Pieris brassicae (white butterfly), Plutella xylostella (black diamond moth), Phaedon cochleariae (mustard beetle), Aonidiella species (scale insects), Trialeurodes species (white flies), Bemisia tabaci (white fly), Blatella germanica (cockroach), Periplaneta americana (cockroach), Blatta orientalis (cockroach), Spodoptera littoralis (cotton leafworm), Heliothis virescens (tobacco budworm, Chortiocetes terminifera (locus
  • the insecticides of this invention are normally formulated into compositions which include a pesticidally effective amount of the active ingredient of this invention in addition to suitable compatible and inert diluents, carriers, surfactants and the like.
  • Such compositions are generally applied to the locus where control is desired, which may include the soil in which plants are or are to be grown or stored, to plants or animals themselves, or to other loci where control or prevention of infestation is required.
  • the formulations in which the compounds of the invention may suitably be applied include such formulations as dusts, wettable powders, granules, solutions, emulsions suspensions, and various concentrates such as solution concentrates or suspension concentrates, and also as controlled release compositions such as microencapsulated granules or suspensions.
  • Such formulations are well known to those skilled in the art.
  • the compounds of the invention may be used alone as a single active ingredient of such formulations or in combination with other known pesticides, such as other insecticides, acaricides, fungicides, plant growth and development regulators, herbicides and combinations of such other active ingredients.
  • Step A 3-cyano-9-phenylmethyl-9-azabicyclo[3.3.1]nonane as an intermediate.
  • reaction mixture was allowed to cool to ambient temperature were it stirred for about 18 hours.
  • the reaction mixture was analyzed by gas chromatography (GC), which indicated the reaction was incomplete.
  • GC gas chromatography
  • the above procedure was repeated and an additional 1.7 grams (0.007 mole) of 9-phenylmethyl-9-azabicyclo[3.3.1]nonane-3-one was added.
  • the reaction mixture was heated to 55° C. where it stirred for two hours. After this time, the reaction mixture was again analyzed by GC, which indicated the reaction was incomplete.
  • the reaction mixture was heated at about 50° C. for an additional three hours and then cooled to ambient temperature where it stirred for about 18 hours.
  • the reaction mixture was poured into 150 ml of an aqueous saturated sodium chloride solution, and the resulting mixture was extracted with ethyl acetate. The organic layer was separated from the aqueous layer, dried with sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure to yield 4.5 grams of crude product.
  • the crude product was purified by column chromatography, yielding 0.41 grams of the above identified intermediate. The NMR spectrum was consistent with the proposed structure.
  • Step B Ethyl N-(9-phenylmethyl-9-azabicyclo[3.3.1]nonane-3-yl)carboxylate as an intermediate.
  • the organic layer was separated from the aqueous layer, dried with sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure to yield the crude product.
  • the crude product was purified by column chromatography, yielding 0.3 gram of the above identified intermediate. The NMR spectrum was consistent with the proposed spectrum.
  • Step A 9-phenylmethyl- ⁇ , ⁇ -bis(4-trifluoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol hydrochloride salt as an intermediate.
  • Step B ⁇ , ⁇ -bis(4-trifiuoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol as an intermediate.
  • the reaction mixture was poured into a mixture consisting of 100 ml of an aqueous saturated sodium bicarbonate solution, 20 ml of an aqueous 10% sodium hydroxide solution, and 300 ml of ethyl acetate.
  • the organic layer was separated, washed with one 100 ml portion of an aqueous saturated sodium chloride solution, dried with sodium sulfate, and filtered.
  • the filtrate was concentrated under reduced pressure to yield a yellow oil.
  • the yellow oil was taken up in ethyl acetate, and the resulting solution was filtered through a silica gel plug.
  • the filtrate was concentrated under reduced pressure, yielding 1.4 grams of crude product.
  • the crude product was purified by column chromatography, yielding 1.3 grams of Compound 2, m.p. 109-111° C.
  • the NMR spectrum was consistent with the proposed structure.
  • the larvae were selected at a stage of growth at which they uniformly weigh about 5 mg each.
  • a sheet of clear plastic was heat-sealed over the top of the tray using a common household flat iron.
  • the trays were held at 25° C. at 60% relative humidity for five days in a growth chamber. Lighting was set at 14 hours of light and 10 hours of darkness. After the 5-day exposure period, mortality counts were taken, and the surviving insects were weighed. From the weights of the surviving insects that fed on the treated diet as compared to those insects that fed on the untreated diet, the percent growth inhibition caused by each test chemical was determined.
  • the negative log of the concentration of the test chemical that provided 50% growth inhibition was determined by linear regression, when possible, for each test chemical.
  • the negative log of the concentration of the test chemical that provided 50% mortality (pLC 50 ) was determined.
  • the compounds of the present invention inhibited the growth of the tobacco budworm, as shown in the following table of data for selected compounds:
  • the four chick pea plants in each replicate treated with test chemical as described above were removed from their pots by cutting the stems just above the soil line.
  • the excised leaves and stems from the four plants in each replicate were placed in individual 8-ounce paper cups, which contained a moistened filter paper.
  • Five second-instar (4-5 days old) tobacco budworms were counted into each cup, taking care not to cause injury.
  • An opaque plastic lid was placed on each cup, which was then held in a growth chamber for a 96 hour exposure period at 25° C. and 50% relative humidity. At the end of the 96 hour exposure period the cups were opened, and the numbers of dead and live insects were counted. Moribund larvae which were disoriented or unable to crawl normally were counted as dead.
  • the compounds of the present invention also provide insecticidal activity in foliar evaluations against the beet armyworm (Spodoptera exigua [Hubner]) and the cabbage looper (Trichoplusia ni [Hubner]), and various other insects and acarids described above.

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Abstract

Compounds for control of insects and arcarids are disclosed and exemplified which are N-(arylalkyl)-4-[bis(substituted aryl)hydroxymethyl]azabicyclo[3.3. 1 .]nonanes and [3.2.1.]octanes, including N-oxides thereof, N-(substituted-oxy) derivatives thereof, and agriculturally acceptable salts thereof, having the formula: ##STR1## Certain novel intermediates for these pesticidal compounds are also disclosed.

Description

This application claims benefit of provisional application Ser. No. 60/068,001 filed Dec. 17, 1997.
The present invention relates to novel pesticidal compounds, intermediates therefor, formulations thereof, and to methods for controlling insects, acarids and the like. In particular, the invention relates to certain N-( arylalkyl)-4-[bis(substituted aryl)hydroxymethyl]azabicyclo[3.3.1.]nonanes and [3.2.1.]octanes, to methods for control of insects with such compounds or formulations thereof, and to certain novel intermediates in the preparation of such insecticidal compounds.
In general the compounds of this invention are N-(substituted arylalkyl) 4-[bis(substituted aryl)hydroxymethyl]azabicyclo[3.3.1.]nonanes and [3.2.1.]octanes, their N-oxides, N-(substituted-oxy) derivatives thereof, and agriculturally acceptable salts thereof. More particularly the compounds of this invention are compounds of the formula: ##STR2## in which m is 2 or 3; n is 0 or 1;
W is hydrogen or alkoxy;
X is hydrogen, alkoxy, cycloalkylalkoxy, alkoxycarbonyl, alkoxycarbonylamino, alkoxyimino, haloalkoxyimino, or a five-or six-membered heteroaryl or heteroaryloxy in which one or more hetero atoms may be optionally substituted with an alkyl;
R1 and R2 are independently selected from hydrogen, haloalkyl, halothio, or haloalkoxy; and
When n is 1, Y represents (a) an N-oxide of the ring nitrogen or (b) an agriculturally acceptable anionic salt of the ring nitrogen; or (c) forms an OR3 linkage in which R3 is selected from hydrogen, alkyl, alkoxycarbonylalkyl, hydroxycarbonylethyl, in association with an agriculturally acceptable anion resulting in an anionic salt, or R3 is an oxycarbonylalkyl group bearing a negative charge resulting in an inner salt.
Unless otherwise specifically indicated to the contrary, the foregoing terms have the following meanings. "Alkyl" means lower alkyl having 1 to 4 carbon atoms which may have a branched or unbranched chain. "Heteroaryl" refers to an aromatic (unsaturated) ring structure having 1 to 4 nitrogen atoms as hetero ring components, the balance being carbon atoms. "Halo" or "halide" refers to one or more halogen atoms selected from chlorine, fluorine, bromine or iodine, with fluorine being the preferred atom when appended to an alkyl or this group. "Anion", "anionic" or "anionic salt" refers to negatively charged ions which form salts with a positively charged ring nitrogen, including but not limited to, halides, salicylates and alkylsulfonates.
Of the compounds described above, the preferred insecticidal compounds are those wherein W is hydrogen; X is propoxy, methoxycarbonylamino, or 2-ethyltetrazol-5-yl; R1 and R2 are 4-trifluoromethyl or 4-trifluoromethoxy; and R3 is methyl or ethoxycarbonylethyl in association with an agriculturally acceptable anionic salt, or an oxycarbonylalkyl group bearing a negative charge resulting in an inner salt.
The following are novel intermediates of the invention: ##STR3## in which m is 2 or 3; and R1 and R2 are 4-trifluoromethyl or 4-trifluoromethoxy.
The insecticidal compounds of the present invention may be prepared by methods known to one skilled in the art. A suitable route for preparation of these compounds are shown in Schema 1 set forth below.
As depicted in Schema 1, an appropriately substituted phenylmethyl azabicycloalkan-3-one (SM1) was reacted with tosylmethyl isocyanide under basic conditions to form the appropriate 3-cyanophenylmethylazabicycloalkane (A). The nitrile (A) was in turn treated with an alcohol, for example ethanol, in the presence of hydrogen chloride gas, yielding the appropriate alkyl N-(substituted phenylmethylazabicycloalkyl)carboxylate (B), for example ethyl N-(9-phenylmethyl-9-azabicyclo[3.3.1]nonane-3-yl)carboxylate. The so-prepared alkyl carboxylate (B) was then reacted with a two or three molar excess of the Grignard reagent of an appropriately substituted halide, for example 1-trifluoromethyl-4-bromobenzene, to form the targeted phenylmethyl-α,α-bis(substituted phenyl)azabicycloalkane-3-methanol (I), for example 9-phenyhnethyl-α,α-bis(4-trifluoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol. Example 1 provides the detailed procedure for this route.
The methanol (I) was reacted with hydrogen chloride gas in the presence of diethyl ether and then hydrogenated with methanol in the presence of 10% palladium on carbon, affording the targeted α,α-bis(substituted phenyl)azabicycloalkane-3-methanol (II). The α,α-bis(substituted phenyl)azabicycloalkane-3-methanol (II) was then reacted with the appropriately substituted phenylmethyl halide, for example 4-propoxyphenylmethyl chloride, affording the targeted (substituted phenyl)methyl-α,α-bis(substituted phenyl)azabicycloalkane-3-methanol (III), for example 9-(4-propoxyphenyl)methyl-α,α-bis(4-trifluoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol. The 3-methanol (III) (can then be reacted with an oxidizing agent, such as hydrogen peroxide or 3-chloroperoxybenzoic acid, to yield the targeted (substituted phenyl)methyl-α,α-bis(substituted phenyl)-azabicycloalkane-3-methanol N-oxide (IV), for example 9-(4-propoxyphenyl)methyl-α,α-bis(4-trifiuoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol N-oxide. The methanol (III) can also be reacted with the appropriate acids, such as hydrochloric or ethanesulfonic acid, yielding the targeted salts (V). Additional salts (VI) can be prepared by reacting the N-oxide (IV) with an appropriate halide, such as 3-bromopropionic acid, or with a sulfate or sulfonate. Even more salts (VII) can be prepared by reacting the N-oxide (IV) with the appropriate acid, such as hydrochloric, ethanesulfonic, or salicylic. Examples 2, 3, 4, 5, 6, and 7 described the detailed procedures for this route. ##STR4##
Tables 1, 2, 3 and 4 below illustrate the insecticidal compounds of this invention.
              TABLE 1                                                     
______________________________________                                    
Insecticidal N-(Phenylmethylazabicyclo)benzhydryl Alcohols                
 ##STR5##                                                                 
N---Y is N-Oxide when n is 1                                              
No.  W         X             R.sup.1                                      
                                    R.sup.2                               
                                           n                              
______________________________________                                    
1    H         H             3 4-CF.sub.3                                 
                                    4-CF.sub.3                            
                                           0                              
2    H              OC.sub.3 H.sub.7                                      
                               3 4-CF.sub.3                               
                                     4-CF.sub.3                           
                                            0                             
3    H              OC.sub.3 H.sub.7                                      
                               3 4-CF.sub.3                               
                                     4-CF.sub.3                           
                                            1                             
4    H              H            2 4-OCF.sub.3                            
                                     4-OCF.sub.3                          
                                             0                            
5    H              OC.sub.2 H.sub.5                                      
                               2 4-OCF.sub.3                              
                                     4-OCF.sub.3                          
                                             0                            
6    H              OC.sub.3 H.sub.7                                      
                               2 4-OCF.sub.3                              
                                     4-OCF.sub.3                          
                                             0                            
7    H              OC.sub.3 H.sub.7                                      
                               2 4-OCF.sub.3                              
                                     4-OCF.sub.3                          
                                             1                            
8    H              OC.sub.4 H.sub.9                                      
                               2 4-OCF.sub.3                              
                                     4-OCF.sub.3                          
                                             0                            
9    H              NHCO.sub.2 CH.sub.3                                   
                               2 4-OCF.sub.3                              
                                     4-OCF.sub.3                          
                                             0                            
10   --OC.sub.3 H.sub.7                                                   
                 H               2 4-OCF.sub.3                            
                                     4-OCF.sub.3                          
                                             0                            
11   H             CO.sub.2 CH(CH.sub.3).sub.2                            
                              2 4-CF.sub.3                                
                                     4-CF.sub.3                           
                                            0                             
12   H             CO.sub.2 CH(CH.sub.3).sub.2                            
                              3 4-CF.sub.3                                
                                     4-CF.sub.3                           
                                            1                             
13   H             CO.sub.2 CH(CH.sub.3).sub.2                            
                              3 4-CF.sub.3                                
                                     4-CF.sub.3                           
                                            0                             
14   H             CO.sub.2 CH(CH.sub.3).sub.2                            
                              3 4-CF.sub.3                                
                                      4-CF.sub.3                          
                                             1                            
15   H          CO.sub.2 CH(CH.sub.3).sub.2                               
                               2 4-OCF.sub.3                              
                                     4-OCF.sub.3                          
                                            0                             
16   H          CO.sub.2 CH(CH.sub.3).sub.2                               
                               2 4-OCF.sub.3                              
                                     4-OCF.sub.3                          
                                            1                             
17   H          CO.sub.2 CH(CH.sub.3).sub.2                               
                               3 4-OCF.sub.3                              
                                     4-OCF.sub.3                          
                                            0                             
18   H          CO.sub.2 CH(CH.sub.3).sub.2                               
                               3 4-OCF.sub.3                              
                                     4-OCF.sub.3                          
                                            1                             
19   H          CO.sub.2 CH(CH.sub.3).sub.2                               
                               2 4-SF.sub.5                               
                                     4-SF.sub.5                           
                                            0                             
20   H          CO.sub.2 CH(CH.sub.3).sub.2                               
                               2 4-SF.sub.5                               
                                     4-SF.sub.5                           
                                            1                             
21   H          CO.sub.2 CH(CH.sub.3).sub.2                               
                               3 4-SF.sub.5                               
                                     4-SF.sub.5                           
                                            0                             
22   H          CO.sub.2 CH(CH.sub.3).sub.2                               
                               3 4-SF.sub.5                               
                                     4-SF.sub.5                           
                                            1                             
23   H          NHCO.sub.2 CH.sub.3                                       
                                2 4-CF.sub.3                              
                                     4-CF.sub.3                           
                                            0                             
24   H          NHCO.sub.2 CH.sub.3                                       
                                2 4-CF.sub.3                              
                                     4-CF.sub.3                           
                                            1                             
25   H          NHCO.sub.2 CH.sub.3                                       
                                3 4-CF.sub.3                              
                                     4-CF.sub.3                           
                                            0                             
26   H          NHCO.sub.2 CH.sub.3                                       
                                3 4-CF.sub.3                              
                                     4-CF.sub.3                           
                                            1                             
27   H          NHCO.sub.2 CH.sub.3                                       
                                 2 4-OCF.sub.3                            
                                     4-OCF.sub.3                          
                                            0                             
28   H          NHCO.sub.2 CH.sub.3                                       
                                 2 4-OCF.sub.3                            
                                     4-OCF.sub.3                          
                                            1                             
29   H          NHCO.sub.2 CH.sub.3                                       
                                 3 4-OCF.sub.3                            
                                     4-OCF.sub.3                          
                                            0                             
30   H          NHCO.sub.2 CH.sub.3                                       
                                 3 4-OCF.sub.3                            
                                     4-OCF.sub.3                          
                                            1                             
31   H          NHCO.sub.2 CH.sub.3                                       
                                   2 4-SF.sub.5                           
                                     4-SF.sub.5                           
                                            0                             
32   H          NHCO.sub.2 CH.sub.3                                       
                                2 4-SF.sub.5                              
                                     4-SF.sub.5                           
                                            1                             
33   H          NHCO.sub.2 CH.sub.3                                       
                                3 4-SF.sub.5                              
                                     4-SF.sub.5                           
                                            0                             
34   H          NHCO.sub.2 CH.sub.3                                       
                                3 4-SF.sub.5                              
                                     4-SF.sub.5                           
                                            1                             
35   H          NHCO.sub.2 CH.sub.3                                       
                                2 4-CF.sub.3                              
                                     4-CF.sub.3                           
                                            0                             
36   H          NHCO.sub.2 CH(CH.sub.3).sub.2                             
                              2 4-CF.sub.3                                
                                     4-CF.sub.3                           
                                            1                             
37   H          NHCO.sub.2 CH(CH.sub.3).sub.2                             
                              3 4-CF.sub.3                                
                                     4-CF.sub.3                           
                                            0                             
38   H          NHCO.sub.2 CH(CH.sub.3).sub.2                             
                              3 4-CF.sub.3                                
                                     4-CF.sub.3                           
                                            1                             
39   H          NHCO.sub.2 CH(CH.sub.3).sub.2                             
                               2 4-OCF.sub.3                              
                                     4-OCF.sub.3                          
                                            0                             
40   H          NHCO.sub.2 CH(CH.sub.3).sub.2                             
                               2 4-OCF.sub.3                              
                                     4-OCF.sub.3                          
                                            1                             
41   H          NHCO.sub.2 CH(CH.sub.3).sub.2                             
                                3 4-OCF.sub.3                             
                                      4-OCF.sub.3                         
                                                  0                       
42   H          NHCO.sub.2 CH(CH.sub.3).sub.2                             
                                3 4-OCF.sub.3                             
                                      4-OCF.sub.3                         
                                                  1                       
43   H          NHCO.sub.2 CH(CH.sub.3).sub.2                             
                                2 4-SF.sub.5                              
                                      4-SF.sub.5                          
                                                  0                       
44   H          NHCO.sub.2 CH(CH.sub.3).sub.2                             
                                2 4-SF.sub.5                              
                                      4-SF.sub.5                          
                                                  1                       
45   H          NHCO.sub.2 CH(CH.sub.3).sub.2                             
                                3 4-SF.sub.5                              
                                      4-SF.sub.5                          
                                                  0                       
46   H          NHCO.sub.2 CH(CH.sub.3).sub.2                             
                                3 4-SF.sub.5                              
                                      4-SF.sub.5                          
                                                  1                       
47   H          2-methyltetrazol-5-yl                                     
                                   2 4-CF.sub.3                           
                                      4-CF.sub.3                          
                                                  0                       
48   H          2-methyltetrazol-5-yl                                     
                                   2 4-CF.sub.3                           
                                      4-CF.sub.3                          
                                                  1                       
49   H          2-methyltetrazol-5-yl                                     
                                   3 4-CF.sub.3                           
                                      4-CF.sub.3                          
                                                  0                       
50   H          2-methyltetrazol-5-yl                                     
                                   3 4-CF.sub.3                           
                                      4-CF.sub.3                          
                                                  1                       
51   H          2-methyltetrazol-5-yl                                     
                                    2 4-OCF.sub.3                         
                                      4-OCF.sub.3                         
                                                  0                       
52   H          2-methyltetrazol-5-yl                                     
                                    2 4-OCF.sub.3                         
                                      4-OCF.sub.3                         
                                                  1                       
53   H          2-methyltetrazol-5-yl                                     
                                    3 4-OCF.sub.3                         
                                      4-OCF.sub.3                         
                                                  0                       
54   H          2-methyltetrazol-5-yl                                     
                                    3 4-OCF.sub.3                         
                                      4-OCF.sub.3                         
                                                  1                       
55   H          2-methyltetrazol-5-yl                                     
                                   2 4-SF.sub.5                           
                                      4-SF.sub.5                          
                                                  0                       
56   H          2-methyltetrazol-5-yl                                     
                                   2 4-SF.sub.5                           
                                      4-SF.sub.5                          
                                                  1                       
57   H          2-methyltetrazol-5-yl                                     
                                   3 4-SF.sub.5                           
                                      4-SF.sub.5                          
                                                  0                       
58   H          2-methyltetrazol-5-yl                                     
                                   3 4-SF.sub.5                           
                                      4-SF.sub.5                          
                                                  1                       
59   H          2-ethyltetrazol-5-yl                                      
                                   2 4-CF.sub.3                           
                                      4-CF.sub.3                          
                                                  0                       
60   H          2-ethyltetrazol-5-yl                                      
                                   2 4-CF.sub.3                           
                                      4-CF.sub.3                          
                                                  1                       
61   H          2-ethyltetrazol-5-yl                                      
                                   3 4-CF.sub.3                           
                                      4-CF.sub.3                          
                                                  0                       
62   H          2-ethyltetrazol-5-yl                                      
                                   3 4-CF.sub.3                           
                                      4-CF.sub.3                          
                                                  1                       
63   H          2-ethyltetrazol-5-yl                                      
                                    2 4-OCF.sub.3                         
                                      4-OCF.sub.3                         
                                                  0                       
64   H          2-ethyltetrazol-5-yl                                      
                                    2 4-OCF.sub.3                         
                                      4-OCF.sub.3                         
                                                  1                       
65   H          2-ethyltetrazol-5-yl                                      
                                   3 4-OCF.sub.3                          
                                     4-OCF.sub.3                          
                                                 0                        
66   H          2-ethyltetrazol-5-yl                                      
                                   3 4-OCF.sub.3                          
                                     4-OCF.sub.3                          
                                                 1                        
67   H          2-ethyltetrazol-5-yl                                      
                               2 4-SF.sub.5                               
                                     4-SF.sub.5                           
                                            0                             
58   H          2-ethyltetrazol-5-yl                                      
                               2 4-SF.sub.5                               
                                     4-SF.sub.5                           
                                            1                             
69   H          2-ethyltetrazol-5-yl                                      
                                     4-SF.sub.5ub.5                       
                                            0                             
70   H          2-ethyltetrazol-5-yl                                      
                               3 4-SF.sub.5                               
                                     4-SF.sub.5                           
                                            1                             
71   H          pyrid-2-yl     2 4-CF.sub.3                               
                                     4-CF.sub.3                           
                                            0                             
72   H          pyrid-2-yl      2 4-CF.sub.3                              
                                     4-CF.sub.3                           
                                            1                             
73   H          pyrid-2-yl      3 4-CF.sub.3                              
                                     4-CF.sub.3                           
                                            0                             
74   H          pyrid-2-yl      3 4-CF.sub.3                              
                                     4-CF.sub.3                           
                                            1                             
75   H          pyrid-2-yl       2 4-OCF.sub.3                            
                                     4-OCF.sub.3                          
                                            0                             
76   H          pyrid-2-yl       2 4-OCF.sub.3                            
                                     4-OCF.sub.3                          
                                            1                             
77   H          pyrid-2-yl      3 4-OCF.sub.3                             
                                      4-OCF.sub.3                         
                                                  0                       
78   H          pyrid-2-yl      3 4-OCF.sub.3                             
                                      4-OCF.sub.3                         
                                                  1                       
79   H          pyrid-2-yl      2 4-SF.sub.5                              
                                      4-SF.sub.5                          
                                                  0                       
80   H          pyrid-2-yl      2 4-SF.sub.5                              
                                      4-SF.sub.5                          
                                                  1                       
81   H          pyrid-2-yl      3 4-SF.sub.5                              
                                      4-SF.sub.5                          
                                                  0                       
82   H          pyrid-2-yl      3 4-SF.sub.5                              
                                      4-SF.sub.5                          
                                                  1                       
83   H          pyrid-2-yloxy                                             
                               2 4-CF.sub.3                               
                                      4-CF.sub.3                          
                                                  0                       
84   H          pyrid-2-yloxy                                             
                                2 4-CF.sub.3                              
                                      4-CF.sub.3                          
                                                  1                       
85   H          pyrid-2-yloxy                                             
                                3 4-CF.sub.3                              
                                      4-CF.sub.3                          
                                                  0                       
86   H          pyrid-2-yloxy                                             
                                3 4-CF.sub.3                              
                                      4-CF.sub.3                          
                                                  1                       
87   H          pyrid-2-yloxy                                             
                                 2 4-OCF.sub.3                            
                                      4-OCF.sub.3                         
                                                  0                       
88   H          pyrid-2-yloxy                                             
                                 2 4-OCF.sub.3                            
                                      4-OCF.sub.3                         
                                                  1                       
89   H          pyrid-2-yloxy                                             
                                 3 4-OCF.sub.3                            
                                      4-OCF.sub.3                         
                                                  0                       
90   H          pyrid-2-yloxy                                             
                                 3 4-OCF.sub.3                            
                                      4-OCF.sub.3                         
                                                  1                       
91   H          pyrid-2-yloxy                                             
                                2 4-SF.sub.5                              
                                      4-SF.sub.5                          
                                                  0                       
92   H          pyrid-2-yloxy                                             
                                2 4-SF.sub.5                              
                                      4-SF.sub.5                          
                                                  1                       
93   H          pyrid-2-yloxy                                             
                                3 4-SF.sub.5                              
                                     4-SF.sub.5                           
                                            0                             
94   H          pyrid-2-yloxy                                             
                               3 4-SF.sub.5                               
                                     4-SF.sub.5                           
                                            1                             
95   H          cyclopropylmethoxy                                        
                              2 4-CF.sub.3                                
                                     4-CF.sub.3                           
                                            0                             
96   H          cyclopropylmethoxy                                        
                                2 4-CF.sub.3                              
                                     4-CF.sub.3                           
                                            1                             
97   H          cyclopropylmethoxy                                        
                                3 4-CF.sub.3                              
                                     4-CF.sub.3                           
                                            0                             
98   H          cyclopropylmethoxy                                        
                                3 4-CF.sub.3                              
                                     4-CF.sub.3                           
                                            1                             
99   H          cyclopropylmethoxy                                        
                                 2 4-OCF.sub.3                            
                                     4-OCF.sub.3                          
                                            0                             
100  H         cyclopropylmethoxy                                         
                                  2 4-OCF.sub.3                           
                                     4-OCF.sub.3                          
                                            1                             
101  H         cyclopropylmethoxy                                         
                                 3 4-OCF.sub.3                            
                                      4-OCF.sub.3                         
                                                  0                       
102  H         cyclopropylmethoxy                                         
                                 3 4-OCF.sub.3                            
                                      4-OCF.sub.3                         
                                                  1                       
103  H         cyclopropylmethoxy                                         
                                 2 4-SF.sub.5                             
                                      4-SF.sub.5                          
                                                  0                       
104  H         cyclopropylmethoxy                                         
                                 2 4-SF.sub.5                             
                                      4-SF.sub.5                          
                                                  1                       
105  H         cyclopropylmethoxy                                         
                                 3 4-SF.sub.5                             
                                      4-SF.sub.5                          
                                                  0                       
106  H         cyclopropylmethoxy                                         
                                 3 4-SF.sub.5                             
                                      4-SF.sub.5                          
                                                  1                       
107  H          N═O--CH.sub.3                                         
                               3 4-CF.sub.3                               
                                       4-CF.sub.3                         
                                            0                             
108  H          N═O--CH.sub.3                                         
                               2 4-CF.sub.3                               
                                     4-CF.sub.3                           
                                            0                             
109  H          N═O--CH.sub.3                                         
                               3 4-CF.sub.3                               
                                     4-CF.sub.3                           
                                            1                             
110  H          N═O--CH.sub.3                                         
                               2 4-CF.sub.3                               
                                     4-CF.sub.3                           
                                            1                             
111  H          N═O--CH.sub.3                                         
                               3 4-OCF.sub.3                              
                                     4-OCF.sub.3                          
                                            0                             
112  H          N═O--CH.sub.3                                         
                               3 4-OCF.sub.3                              
                                     4-OCF.sub.3                          
                                            1                             
113  H          N═O--CH.sub.2 CH.sub.3                                
                              3 4-CF.sub.3                                
                                     4-CF.sub.3                           
                                            0                             
114  H          N═O--CH.sub.2 CH.sub.3                                
                              3 4-CF.sub.3                                
                                     4-CF.sub.3                           
                                            1                             
115  H          N═O--CH.sub.2 CH.sub.3                                
                              3 4-OCF.sub.3                               
                                     4-OCF.sub.3                          
                                            0                             
116  H          N═O--CH.sub.2 CH.sub.3                                
                              3 4-OCF.sub.3                               
                                     4-OCF.sub.3                          
                                            1                             
117  H          N═O--CH.sub.2 CH.sub.3 F                              
                             3 4-OCF.sub.3                                
                                     4-OCF.sub.3                          
                                            0                             
______________________________________                                    

              TABLE 2                                                     
______________________________________                                    
Salts of Insecticidal N-(Phenylmethylazabicyclo)benzhydryl Alcohols       
 ##STR6##                                                                 
No.  X             m     R.sup.1                                          
                                R.sup.2                                   
                                      A.sup.-                             
______________________________________                                    
118  OC.sub.3 H.sub.7                                                     
                   3     4-CF.sub.3                                       
                                4-CF.sub.3                                
                                      Chloride                            
119   OC.sub.3 H.sub.7                                                    
                      3   4-CF.sub.3                                      
                                4-CF.sub.3                                
                                        Ethylsulfonate                    
120   CO.sub.2 CH(CH.sub.3).sub.2                                         
                     2    4-CF.sub.3                                      
                                4-CF.sub.3                                
                                        Chloride                          
121   CO.sub.2 CH(CH.sub.3).sub.2                                         
                     2    4-CF.sub.3                                      
                                4-CF.sub.3                                
                                        Ethylsulfonate                    
122   CO.sub.2 CH(CH.sub.3).sub.2                                         
                     3    4-CF.sub.3                                      
                                4-CF.sub.3                                
                                        Chloride                          
123   CO.sub.2 CH(CH.sub.3).sub.2                                         
                     3    4-CF.sub.3                                      
                                4-CF.sub.3                                
                                        Ethylsulfonate                    
124   CO.sub.2 CH(CH.sub.3).sub.2                                         
                     2    4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                       Chloride                           
125   CO.sub.2 CH(CH.sub.3).sub.2                                         
                     2    4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                       Ethylsulfonate                     
126   CO.sub.2 CH(CH.sub.3).sub.2                                         
                     3    4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                       Chloride                           
127   CO.sub.2 CH(CH.sub.3).sub.2                                         
                     3    4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                       Ethylsulfonate                     
128   NHCO.sub.2 CH.sub.3                                                 
                      2   4-CF.sub.3                                      
                                4-CF.sub.3                                
                                        Chloride                          
129   NHCO.sub.2 CH.sub.3                                                 
                      2   4-CF.sub.3                                      
                                4-CF.sub.3                                
                                        Ethylsulfonate                    
130   NHCO.sub.2 CH.sub.3                                                 
                      3   4-CF.sub.3                                      
                                4-CF.sub.3                                
                                        Chloride                          
131   NHCO.sub.2 CH.sub.3                                                 
                      3   4-CF.sub.3                                      
                                4-CF.sub.3                                
                                        Ethylsulfonate                    
132   NHCO.sub.2 CH.sub.3                                                 
                      2   4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                       Chloride                           
133   NHCO.sub.2 CH.sub.3                                                 
                       2  4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                                      Ethylsulfonate      
134   NHCO.sub.2 CH.sub.3                                                 
                       3  4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                          Chloride                        
135   NHCO.sub.2 CH.sub.3                                                 
                       3  4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                          Ethylsulfonate                  
136   NHCO.sub.2 CH(CH.sub.3).sub.2                                       
                     2    4-CF.sub.3                                      
                                4-CF.sub.3                                
                                             Chloride                     
137   NHCO.sub.2 CH(CH.sub.3).sub.2                                       
                     2    4-CF.sub.3                                      
                                4-CF.sub.3                                
                                           Ethylsulfonate                 
138   NHCO.sub.2 CH(CH.sub.3).sub.2                                       
                     3    4-CF.sub.3                                      
                                4-CF.sub.3                                
                                             Chloride                     
139   NHCO.sub.2 CH(CH.sub.3).sub.2                                       
                     3    4-CF.sub.3                                      
                                4-CF.sub.3                                
                                           Ethylsulfonate                 
140   NHCO.sub.2 CH(CH.sub.3).sub.2                                       
                     2    4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                            Chloride                      
141   NHCO.sub.2 CH(CH.sub.3).sub.2                                       
                     2    4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                          Ethylsulfonate                  
142   NHCO.sub.2 CH(CH.sub.3).sub.2                                       
                     3    4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                            Chloride                      
143   NHCO.sub.2 CH(CH.sub.3).sub.2                                       
                     3    4-OCF.sub.3                                     
                                4-OCH.sub.3                               
                                      Ethylsulfonate                      
144   2-methyltetrazol-5-yl                                               
                       2  4-CF.sub.3                                      
                                4-CF.sub.3                                
                                             Chloride                     
145   2-methyltetrazol-5-yl                                               
                       2  4-CF.sub.3                                      
                                4-CF.sub.3                                
                                           Ethylsulfonate                 
146   2-methyltetrazol-5-yl                                               
                       3  4-CF.sub.3                                      
                                4-CF.sub.3                                
                                             Chloride                     
147   2-methyltetrazol-5-yl                                               
                       3  4-CF.sub.3                                      
                                4-CF.sub.3                                
                                           Ethylsulfonate                 
148   2-methyltetrazol-5-yl                                               
                       2  4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                            Chloride                      
149   2-methyltetrazol-5-yl                                               
                       2  4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                          Ethylsulfonate                  
150   2-methyltetrazol-5-yl                                               
                       3  4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                            Chloride                      
151   2-methyltetrazol-5-yl                                               
                       3  4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                          Ethylsulfonate                  
152   2-methyltetrazol-5-yl                                               
                       2  4-CF.sub.3                                      
                                4-CF.sub.3                                
                                             Chloride                     
153   2-ethyltetrazol-5-yl                                                
                      2   4-CF.sub.3                                      
                                4-CF.sub.3                                
                                           Ethylsulfonate                 
154   2-ethyltetrazol-5-yl                                                
                      3   4-CF.sub.3                                      
                                4-CF.sub.3                                
                                             Chloride                     
155   2-ethyltetrazol-5-yl                                                
                      3   4-CF.sub.3                                      
                                4-CF.sub.3                                
                                           Ethylsulfonate                 
156   2-ethyltetrazol-5-yl                                                
                      2   4-OCF.sub.3 --                                  
                                4-OCF.sub.3                               
                                                   Chloride               
157   2-ethyltetrazol-5-yl                                                
                       2 4-OCF.sub.3                                      
                                4-OCF.sub.3                               
                                          Ethylsulfonate                  
158   2-ethyltetrazol-5-yl                                                
                       3 4-OCF.sub.3                                      
                                4-OCF.sub.3                               
                                            Chloride                      
159   2-ethyltetrazol-5-yl                                                
                       3 4-OCF.sub.3                                      
                                4-OCF.sub.3                               
                                          Ethylsulfonate                  
160   pyrid-2-yl        2                                                 
                         4-CF.sub.3                                       
                                4-CF.sub.3                                
                                             Chloride                     
161   pyrid-2-yl        2                                                 
                         4-CF.sub.3                                       
                                4-CF.sub.3                                
                                           Ethylsulfonate                 
162   pyrid-2-yl        3                                                 
                         4-CF.sub.3                                       
                                4-CF.sub.3                                
                                             Chloride                     
163   pyrid-2-yl        3                                                 
                         4-CF.sub.3                                       
                                4-CF.sub.3                                
                                           Ethylsulfonate                 
164   pyrid-2-yl        2                                                 
                                4-OCF.sub.3.3                             
                                      Chloride                            
165   pyrid-2-yl        2                                                 
                         4-OCF.sub.3                                      
                                4-OCF.sub.3                               
                                          Ethylsulfonate                  
166   pyrid-2-yl        3                                                 
                         4-OCF.sub.3                                      
                                4-OCF.sub.3                               
                                            Chloride                      
167   pyrid-2-yl        3                                                 
                         4-OCF.sub.3                                      
                                4-OCF.sub.3                               
                                          Ethylsulfonate                  
168   pyrid-2-yloxy                                                       
                        2                                                 
                         4-CF.sub.3                                       
                                4-CF.sub.3                                
                                             Chloride                     
169   pyrid-2-yloxy                                                       
                        2                                                 
                         4-CF.sub.3                                       
                                4-CF.sub.3                                
                                           Ethylsulfonate                 
170   pyrid-2-yloxy                                                       
                        3                                                 
                         4-CF.sub.3                                       
                                4-CF.sub.3                                
                                             Chloride                     
171   pyrid-2-yloxy                                                       
                        3                                                 
                         4-CF.sub.3                                       
                                4-CF.sub.3                                
                                           Ethylsulfonate                 
172   pyrid-2-yloxy                                                       
                        2                                                 
                         4-OCF.sub.3                                      
                                4-OCF.sub.3                               
                                      Chloride                            
173   pyrid-2-yloxy                                                       
                        2                                                 
                         4-OCF.sub.3                                      
                                4-OCF.sub.3                               
                                          Ethylsulfonate                  
174   pyrid-2-yloxy                                                       
                        3                                                 
                         4-OCF.sub.3                                      
                                4-OCF.sub.3                               
                                            Chloride                      
175   pyrid-2-yloxy                                                       
                        3                                                 
                         4-OCF.sub.3                                      
                                4-OCF.sub.3                               
                                          Ethylsulfonate                  
176   cyclopropylmethoxy                                                  
                       2 4-CF.sub.3                                       
                                4-CF.sub.3                                
                                             Chloride                     
177   cyclopropylmethoxy                                                  
                       2 4-CF.sub.3                                       
                                4-CF.sub.3                                
                                           Ethylsulfonate                 
178   cyclopropylmethoxy                                                  
                       3 4-CF.sub.3                                       
                                4-CF.sub.3                                
                                             Chloride                     
179   cyclopropylmethoxy                                                  
                       3 4-CF.sub.3                                       
                                4-CF.sub.3                                
                                           Ethylsulfonate                 
180   cyclopropylmethoxy                                                  
                       2 4-OCF.sub.3                                      
                                4-OCF.sub.3                               
                                      Chloride                            
181   cyclopropylmethoxy                                                  
                         4-OCF.sub.3                                      
                                4-OCF.sub.3                               
                                       Ethylsulfonate                     
182   cyclopropylmethoxy                                                  
                         3                                                
                         4-OCF.sub.3                                      
                                4-OCF.sub.3                               
                                         Chloride                         
183    cyclopropylmethoxy                                                 
                         3                                                
                         4-OCF.sub.3                                      
                                4-OCF.sub.3                               
                                            Ethylsulfonate                
184  ═NCOCH.sub.2 CH.sub.3                                            
                         4-OCF.sub.3                                      
                                4-OCF.sub.3                               
                                            Ethylsulfonate                
185   ═NOCH.sub.3                                                     
                         4-OCF.sub.3                                      
                                4-OCF.sub.3                               
                                            Ethylsulfonate                
186  ═NOCH.sub.2 CH.sub.2 F                                           
                         4-OCF.sub.3                                      
                                4-OCF.sub.3                               
                                            Ethylsulfonate                
187  ═NOCH.sub.2 CH.sub.2 F                                           
                         2                                                
                         4-OCF.sub.3                                      
                                4-OCF.sub.3                               
                                            Ethylsulfonate                
188   ═NOCH.sub.3                                                     
                         4-CF.sub.3                                       
                                4-CF.sub.3                                
                                             Ethylsulfonate               
189   ═NOCH.sub.3                                                     
                         4-CF.sub.3                                       
                                4-CF.sub.3                                
                                             Ethylsulfonate               
190  ═NOCH.sub.2 CH.sub.3                                             
                         4-CF.sub.3                                       
                                4-CF.sub.3                                
                                             Ethylsulfonate               
191  ═NOCH.sub.2 CH.sub.3                                             
                         4-CF.sub.3                                       
                                4-CF.sub.3                                
                                             Ethylsulfonate               
192  ═NOCH.sub.2 CH.sub.2 F                                           
                           4-CF.sub.3                                     
                                4-CF.sub.3                                
                                            Ethylsulfonate                
193  ═NOCH.sub.2 CH.sub.2 F                                           
                         2                                                
                           4-CF.sub.3                                     
                                4-CF.sub.3                                
                                                Ethylsulfonate            
______________________________________                                    

                                  TABLE 3                                 
__________________________________________________________________________
Inner Salts of Insecticidal N-(Phenylmethylazabicylo)benzhydryl Alcohols  
 ##STR7##                                                                 
No X         m R.sup.1                                                    
                   R.sup.2                                                
                       R.sup.3   A.sup.-                                  
__________________________________________________________________________
194                                                                       
   CO.sub.2 CH(CH.sub.3).sub.2                                            
             2 4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                       CH.sub.3  Iodide                                   
195                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              2                                                           
                4-CF.sub.3                                                
                   4-CF.sub.3                                             
                            CH.sub.2 CH.sub.3 COO.sup.-                   
                                    Inner Salt                            
196                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              2                                                           
                4-CF.sub.3                                                
                   4-CF.sub.3                                             
                            CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5    
                                   Iodide                                 
197                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              2                                                           
                4-CF.sub.3                                                
                   4-CF.sub.3                                             
                            CH.sub.3                                      
                                       Bromide                            
198                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              2                                                           
                4-CF.sub.3                                                
                   4-CF.sub.3                                             
                            CH.sub.2 CH.sub.3 COO.sup.-                   
                                    Inner Salt                            
199                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              2                                                           
                4-CF.sub.3                                                
                   4-CF.sub.3                                             
                            CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5    
                                   Bromide                                
200                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              2                                                           
                4-OCF.sub.3                                               
                   4-OCF.sub.3                                            
                           CH.sub.3                                       
                                       Iodide                             
201                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              2                                                           
                4-OCF.sub.3                                               
                   4-OCF.sub.3                                            
                           CH.sub.2 CH.sub.3 COO.sup.-                    
                                    Inner Salt                            
202                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              2                                                           
                4-OCF.sub.3                                               
                   4-OCF.sub.3                                            
                           CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5     
                                   Iodide                                 
203                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              2                                                           
                4-OCF.sub.3                                               
                   4-OCF.sub.3                                            
                           CH.sub.3                                       
                                       Bromide                            
204                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              2                                                           
                4-OCF.sub.3                                               
                   4-OCF.sub.3                                            
                           CH.sub.2 CH.sub.3 COO.sup.-                    
                                    Inner Salt                            
205                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              2                                                           
                4-OCF.sub.3                                               
                   4-OCF.sub.3                                            
                           CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5     
                                   Bromide                                
206                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              3                                                           
                4-CF.sub.3                                                
                   4-CF.sub.3                                             
                           CH.sub.3                                       
                                       Iodide                             
207                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              3                                                           
                4-CF.sub.3                                                
                   4-CF.sub.3                                             
                           CH.sub.2 CH.sub.3 COO.sup.-                    
                                    Inner Salt                            
208                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              3                                                           
                4-CF.sub.3                                                
                   4-CF.sub.3                                             
                           CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5     
                                   Iodide                                 
209                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              3                                                           
                4-CF.sub.3                                                
                   4-CF.sub.3                                             
                           CH.sub.3                                       
                                       Bromide                            
210                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              3                                                           
                4-CF.sub.3                                                
                   4-CF.sub.3                                             
                           CH.sub.2 CH.sub.3 COO.sup.-                    
                                    Inner Salt                            
211                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              3                                                           
                4-CF.sub.3                                                
                   4-CF.sub.3                                             
                           CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5     
                                   Bromide                                
212                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              3                                                           
                4-OCF.sub.3                                               
                   4-OCF.sub.3                                            
                           CH.sub.3                                       
                                       Iodide                             
213                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              3                                                           
                4-OCF.sub.3                                               
                   4-OCF.sub.3                                            
                           CH.sub.2 CH.sub.3 COO.sup.-                    
                                    Inner Salt                            
214                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              3                                                           
                4-OCF.sub.3                                               
                   4-OCF.sub.3                                            
                           CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5     
                                   Iodide                                 
215                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              3                                                           
                4-OCF.sub.3                                               
                   4-OCF.sub.3                                            
                              CH.sub.3                                    
                                       Bromide                            
216                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              3                                                           
                4-OCF.sub.3                                               
                   4-OCF.sub.3                                            
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                            Inner Salt                    
217                                                                       
    CO.sub.2 CH(CH.sub.3).sub.2                                           
              3                                                           
                4-OCF.sub.3                                               
                   4-OCF.sub.3                                            
                             CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5   
                                   Bromide                                
218                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             2 4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.3                                 
                                        Iodide                            
219                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             2 4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
220                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             2 4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Iodide                                 
221                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             2 4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.3                                 
                                        Bromide                           
222                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             2 4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
223                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             2 4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Bromide                                
224                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             2 4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Iodide                            
225                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             2 4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
226                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             2 4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2        
                       H.sub.5     Iodide                                 
227                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             2 4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Bromide                           
228                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             2 4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.3 COO.sup.-               
                                     Inner Salt                           
229                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             2 4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2        
                       H.sub.5     Bromide                                
230                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             3 4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                        Iodide                            
231                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             3 4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
232                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             3 4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Iodide                                 
233                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             3 4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.3                                 
                                        Bromide                           
234                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             3 4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
235                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             3 4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Bromide                                
236                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             3 4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Iodide                            
237                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             3 4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
238                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             3 4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2        
                       H.sub.5     Iodide                                 
239                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             3 4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Bromide                           
240                                                                       
    NHCO.sub.2 CH.sub.3                                                   
             3 4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.3 COO.sup.-               
                                     Inner Salt                           
241                                                                       
   NHCO.sub.2 CH.sub.3                                                    
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
242                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-CF.sub.3   2                                             
                   4-CF.sub.3                                             
                                 CH.sub.3                                 
                                        Iodide                            
243                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
244                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Iodide                                 
245                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.3                                 
                                        Bromide                           
246                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
247                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Bromide                                
248                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Iodide                            
249                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
250                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2        
                       H.sub.5     Iodide                                 
251                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Bromide                           
252                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.3 COO.sup.-               
                                     Inner Salt                           
253                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2        
                       H.sub.5     Bromide                                
254                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                        Iodide                            
255                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
256                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Iodide                                 
257                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.3                                 
                                        Bromide                           
258                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
259                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Bromide                                
260                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Iodide                            
261                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
262                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2        
                       H.sub.5     Iodide                                 
263                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Bromide                           
264                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.3 COO.sup.-               
                                     Inner Salt                           
265                                                                       
   NHCO.sub.2 CH(CH.sub.3).sub.2                                          
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Bromide                                
266                                                                       
   2-methyltetrazol-5-                                                    
               4-CF.sub.3 2                                               
                   4-CF.sub.3                                             
                                 CH.sub.3                                 
                                        Iodide                            
267                                                                       
   2-methyltetrazol-5-                                                    
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
268                                                                       
   2-methyltetrazol-5-                                                    
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Iodide                                 
269                                                                       
   2-methyltetrazol-5-                                                    
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.3                                 
                                        Bromide                           
270                                                                       
   2-methyltetrazol-5-                                                    
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
271                                                                       
   2-methyltetrazol-5-                                                    
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Bromide                                
272                                                                       
   2-methyltetrazol-5-                                                    
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Iodide                            
273                                                                       
   2-methyltetrazol-5-                                                    
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
274                                                                       
   2-methyltetrazol-5-                                                    
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2        
                       H.sub.5     Iodide                                 
275                                                                       
   2-methyltetrazol-5-                                                    
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Bromide                           
276                                                                       
   2-methyltetrazol-5-                                                    
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.3 COO.sup.-               
                                     Inner Salt                           
277                                                                       
   2-methyltetrazol-5-                                                    
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2        
                       H.sub.5     Bromide                                
278                                                                       
   2-methyltetrazol-5-                                                    
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                        Iodide                            
279                                                                       
   2-methyltetrazol-5-                                                    
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
280                                                                       
   2-methyltetrazol-5-                                                    
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Iodide                                 
281                                                                       
   2-methyltetrazol-5-                                                    
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.3                                 
                                        Bromide                           
282                                                                       
   2-methyltetrazol-5-                                                    
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
283                                                                       
   2-methyltetrazol-5-                                                    
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Bromide                                
284                                                                       
   2-methyltetrazol-5-                                                    
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Iodide                            
285                                                                       
   2-methyltetrazol-5-                                                    
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
286                                                                       
   2-methyltetrazol-5-                                                    
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2        
                       H.sub.5     Iodide                                 
287                                                                       
   2-methyltetrazol-5-                                                    
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Bromide                           
288                                                                       
   2-methyltetrazol-5-                                                    
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.3 COO.sup.-               
                                     Inner Salt                           
289                                                                       
   2-methyltetrazol-5-                                                    
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Bromide                                
290                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                       CH.sub.3  Iodide                                   
291                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
292                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Iodide                                 
293                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.3                                 
                                        Bromide                           
294                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
295                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Bromide                                
296                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Iodide                            
297                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
298                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2        
                       H.sub.5     Iodide                                 
299                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Bromide                           
300                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.3 COO.sup.-               
                                     Inner Salt                           
301                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2        
                       H.sub.5     Bromide                                
302                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                        Iodide                            
303                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
304                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Iodide                                 
305                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.3                                 
                                        Bromide                           
306                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
307                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Bromide                                
308                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Iodide                            
309                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
310                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2        
                       H.sub.5     Iodide                                 
311                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Bromide                           
312                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.3 COO.sup.-               
                                     Inner Salt                           
313                                                                       
   2-ethyltetrazol-5-yl                                                   
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Bromide                                
314                                                                       
   pyrid-2-yll                                                            
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                       CH.sub.3  Iodide                                   
315                                                                       
   pyrid-2-yl                                                             
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                       CH.sub.2 CH.sub.3 COO.sup.-                        
                                 Inner Salt                               
316                                                                       
   pyrid-2-yl                                                             
               4-CF.sub.3          2                                      
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Iodide                                 
317                                                                       
   pyrid-2-yl                                                             
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.3                                 
                                        Bromide                           
318                                                                       
   pyrid-2-yl                                                             
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
319                                                                       
   pyrid-2-yl                                                             
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Bromide                                
320                                                                       
   pyrid-2-yl                                                             
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Iodide                            
321                                                                       
   pyrid-2-yl                                                             
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
322                                                                       
   pyrid-2-yl                                                             
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2        
                       H.sub.5     Iodide                                 
323                                                                       
   pyrid-2-yl                                                             
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Bromide                           
324                                                                       
   pyrid-2-yl                                                             
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.3 COO.sup.-               
                                     Inner Salt                           
325                                                                       
   pyrid-2-yl                                                             
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2        
                       H.sub.5     Bromide                                
326                                                                       
   pyrid-2-yll                                                            
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                        Iodide                            
327                                                                       
   pyrid-2-yl                                                             
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
328                                                                       
   pyrid-2-yl                                                             
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Iodide                                 
329                                                                       
   pyrid-2-yl                                                             
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.3                                 
                                        Bromide                           
330                                                                       
   pyrid-2-yl                                                             
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
331                                                                       
   pyrid-2-yl                                                             
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Bromide                                
332                                                                       
   pyrid-2-yll                                                            
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Iodide                            
333                                                                       
   pyrid-2-yl                                                             
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
334                                                                       
   pyrid-2-yl                                                             
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2        
                       H.sub.5     Iodide                                 
335                                                                       
   pyrid-2-yl                                                             
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Bromide                           
336                                                                       
   pyrid-2-yl                                                             
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.3 COO.sup.-               
                                     Inner Salt                           
337                                                                       
   pyrid-2-yl                                                             
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Bromide                                
338                                                                       
   pyrid-2-yloxy                                                          
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                       CH.sub.3  Iodide                                   
339                                                                       
   pyrid-2-yloxy                                                          
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
340                                                                       
   pyrid-2-yloxy                                                          
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Iodide                                 
341                                                                       
   pyrid-2-ylxoy                                                          
              2                                                           
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.3                                 
                                        Bromide                           
342                                                                       
   pyrid-2-yloxy                                                          
              2                                                           
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
343                                                                       
   pyrid-2-yloxy                                                          
              2                                                           
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Bromide                                
344                                                                       
   pyrid-2-yloxy                                                          
              2                                                           
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Iodide                            
345                                                                       
   pyrid-2-yloxy                                                          
              2                                                           
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
346                                                                       
   pyrid-2-yloxy                                                          
              2                                                           
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2        
                       H.sub.5     Iodide                                 
347                                                                       
   pyrid-2-yloxy                                                          
              2                                                           
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Bromide                           
348                                                                       
   pyrid-2-yloxy                                                          
              2                                                           
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.3 COO.sup.-               
                                     Inner Salt                           
349                                                                       
   pyrid-2-yloxy                                                          
              2                                                           
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2        
                       H.sub.5     Bromide                                
350                                                                       
   pyrid-2-yloxy                                                          
              3                                                           
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                        Iodide                            
351                                                                       
   pyrid-2-yloxy                                                          
              3                                                           
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
352                                                                       
   pyrid-2-yloxy                                                          
              3                                                           
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Iodide                                 
353                                                                       
   pyrid-2-yloxy                                                          
              3                                                           
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.3                                 
                                        Bromide                           
354                                                                       
   pyrid-2-yloxy                                                          
              3                                                           
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
355                                                                       
   pyrid-2-yloxy                                                          
              3                                                           
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Bromide                                
356                                                                       
   pyrid-2-yloxy                                                          
              3                                                           
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Iodide                            
357                                                                       
   pyrid-2-yloxy                                                          
              3                                                           
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
358                                                                       
   pyrid-2-yloxy                                                          
              3                                                           
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2        
                       H.sub.5     Iodide                                 
359                                                                       
   pyrid-2-yloxy                                                          
              3                                                           
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Bromide                           
360                                                                       
   pyrid-2-yloxy                                                          
              3                                                           
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.3 COO.sup.-               
                                     Inner Salt                           
361                                                                       
   pyrid-2-yloxy                                                          
              3                                                           
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Bromide                                
362                                                                       
   cyclopropyloxy                                                         
             2 4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                       CH.sub.3  Iodide                                   
363                                                                       
   cyclopropyloxy                                                         
             2 4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                       CH.sub.2 CH.sub.3 COO.sup.-                        
                                 Inner Salt                               
364                                                                       
   cyclopropyloxy                                                         
             2 4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Iodide                                 
365                                                                       
   cyclopropyloxy                                                         
             2 4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.3                                 
                                        Bromide                           
366                                                                       
   cyclopropyloxy                                                         
               4-CF.sub.3          2                                      
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
367                                                                       
   cyclopropyloxy                                                         
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Bromide                                
368                                                                       
   cyclopropyloxy                                                         
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Iodide                            
369                                                                       
   cyclopropyloxy                                                         
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
370                                                                       
   cyclopropyloxy                                                         
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2        
                       H.sub.5     Iodide                                 
371                                                                       
   cyclopropyloxy                                                         
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Bromide                           
372                                                                       
   cyclopropyloxy                                                         
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.3 COO.sup.-               
                                     Inner Salt                           
373                                                                       
   cyclopropyloxy                                                         
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2        
                       H.sub.5     Bromide                                
374                                                                       
   cyclopropyloxy                                                         
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                        Iodide                            
375                                                                       
   cyclopropyloxy                                                         
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
376                                                                       
   cyclopropyloxy                                                         
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Iodide                                 
377                                                                       
   cyclopropyloxy                                                         
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.3                                 
                                        Bromide                           
378                                                                       
   cyclopropyloxy                                                         
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
379                                                                       
   cyclopropyloxy                                                         
               4-CF.sub.3                                                 
                   4-CF.sub.3                                             
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Bromide                                
380                                                                       
   cyclopropyloxy                                                         
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Iodide                            
381                                                                       
   cyclopropyloxy                                                         
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                 CH.sub.2 CH.sub.3 COO.sup.-              
                                     Inner Salt                           
382                                                                       
   cyclopropyloxy                                                         
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2        
                       H.sub.5     Iodide                                 
383                                                                       
   cyclopropyloxy                                                         
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.3                                  
                                        Bromide                           
384                                                                       
   cyclopropyloxy                                                         
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                CH.sub.2 CH.sub.3 COO.sup.-               
                                     Inner Salt                           
385                                                                       
   cyclopropyloxy                                                         
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                                 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2       
                       H.sub.5     Bromide                                
386                                                                       
   OC.sub.3 H.sub.7                                                       
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                       CH.sub.2 CH.sub.3 COO.sup.-                        
                                 Inner Salt                               
387                                                                       
   ═N--O--CH.sub.3                                                    
              3                                                           
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                       CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.2         
                                 Bromide                                  
388                                                                       
   ═N--O--CH.sub.3                                                    
              3                                                           
               4-OCF.sub.3                                                
                   4-OCF.sub.3                                            
                       CH.sub.2 CH.sub.2 COO                              
                                 Inner Salt                               
__________________________________________________________________________

              TABLE 4                                                     
______________________________________                                    
Salts of Insecticidal N-(Phenylmethylazabicyclo)benshydryl Alcohols       
 ##STR8##                                                                 
N    X              m     R.sup.1                                         
                                R.sup.2                                   
                                      A.sup.-                             
______________________________________                                    
389  2-ethyltetrazol-5-yl                                                 
                    3     4-CF.sub.3                                      
                                4-CF.sub.3                                
                                      Ethylsulfonate                      
390  2-ethyltetrazol-5-yl                                                 
                    3     4-CF.sub.3                                      
                                4-CF.sub.3                                
                                      Ethylsulfonate                      
391  2-ethyltetrazol-5-yl                                                 
                    3     4-CF.sub.3                                      
                                4-CF.sub.3                                
                                      Hydrochloride                       
392  2-ethyltetrazol-5-yl                                                 
                    3     4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                      Salicylate                          
393  2-ethyltetrazol-5-yl                                                 
                    3     4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                      Ethylsulfonate                      
394  2-ethyltetrazol-5-yl                                                 
                    3     4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                      Hydrochloride                       
395  2-ethyltetrazol-5-yl                                                 
                    2     4-CF.sub.3                                      
                                4-CF.sub.3                                
                                      Salicylate                          
396  2-ethyltetrazol-5-yl                                                 
                    2     4-CF.sub.3                                      
                                4-CF.sub.3                                
                                      Ethylsulfonate                      
397  2-ethyltetrazol-5-yl                                                 
                    2     4-CF.sub.3                                      
                                4-CF.sub.3                                
                                      Hydrochloride                       
398  2-ethyltetrazol-5-yl                                                 
                    2     4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                      Salicylate                          
399  2-ethyltetrazol-5-yl                                                 
                    2     4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                      Ethylsulfonate                      
400  2-ethyltetrazol-5-yl                                                 
                    2     4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                      Hydrochloride                       
401  2-methyltetrazol-5-yl                                                
                    3     4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                      Salicylate                          
402  2-methyltetrazol-5-yl                                                
                    2     4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                      Ethylsulfonate                      
403  2-methyltetrazol-5-yl                                                
                    3     4-CF.sub.3                                      
                                4-CF.sub.3                                
                                      Ethylsulfonate                      
404  2-methyltetrazol-5-yl                                                
                    2     4-CF.sub.3                                      
                                4-CF.sub.3                                
                                      Ethylsulfonate                      
405  pyrid-2-yloxy  3     4-CF.sub.3                                      
                                4-CF.sub.3                                
                                      Ethylsulfonate                      
406  pyrid-2-yloxy  3     4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                      Ethylsulfonate                      
407  pyrid-2-yloxy  2     4-CF.sub.3                                      
                                4-CF.sub.3                                
                                      Ethylsulfonate                      
408  pyrid-2-yloxy  2     4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                      Ethylsulfonate                      
409  NHCO.sub.2 CH.sub.3                                                  
                    3     4-CF.sub.3                                      
                                4-CF.sub.3                                
                                      Ethylsulfonate                      
410  NHCO.sub.2 CH.sub.3                                                  
                    3     4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                      Ethylsulfonate                      
411  NHCO.sub.2 CH.sub.3                                                  
                    2     4-CF.sub.3                                      
                                4-CF.sub.3                                
                                      Ethylsulfonate                      
412  NHCO.sub.2 CH.sub.3                                                  
                    2     4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                      Ethylsulfonate                      
413  CO.sub.2 CH(CH.sub.3).sub.2                                          
                    3     4-CF.sub.3                                      
                                4-CF.sub.3                                
                                      Ethylsulfonate                      
414  CO.sub.2 CH(CH.sub.3 0.sub.2                                         
                    3     4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                      Ethylsulfonate                      
415  CO.sub.2 CH(CH.sub.3).sub.2                                          
                    2     4-CF.sub.3                                      
                                4-CF.sub.3                                
                                      Ethylsulfonate                      
416  CO.sub.2 CH(CH.sub.3 0.sub.2                                         
                    2     4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                      Ethylsulfonate                      
417  ═N--O--CH.sub.3                                                  
                    3     4-CF.sub.3                                      
                                4-CF.sub.3                                
                                      Ethylsulfonate                      
418  ═N--O--CH.sub.3                                                  
                    3     4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                      Ethylsulfonate                      
419  ═N--O--CH.sub.3                                                  
                    2     4-CF.sub.3                                      
                                4-CF.sub.3                                
                                      Ethylsulfonate                      
420  ═N--O--CH.sub.3                                                  
                    2     4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                      Ethylsulfonate                      
421  ═N--O--CH.sub.2 CH.sub.3                                         
                    3     4-CF.sub.3                                      
                                4-CF.sub.3                                
                                      Ethylsulfonate                      
422  ═N--O--CH.sub.2 CH.sub.3                                         
                    3     4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                      Ethylsulfonate                      
423  ═N--O--CH.sub.2 CH.sub.3                                         
                    2     4-CF.sub.3                                      
                                4-CF.sub.3                                
                                      Ethylsulfonate                      
424  ═N--O--CH.sub.2 CH.sub.3                                         
                    2     4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                      Ethylsulfonate                      
425  ═N--O--CH.sub.2 CH.sub.2 F                                       
                    3     4-CF.sub.3                                      
                                4-CF.sub.3                                
                                      Ethylsulfonate                      
426  ═N--O--CH.sub.2 CH.sub.2 F                                       
                    3     4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                      Ethylsulfonate                      
427  ═N--O--CH.sub.2 CH.sub.2 F                                       
                    2     4-CF.sub.3                                      
                                4-CF.sub.3                                
                                      Ethylsulfonate                      
428  ═N--O--CH.sub.2 CH.sub.2 F                                       
                    2     4-OCF.sub.3                                     
                                4-OCF.sub.3                               
                                      Ethylsulfonate                      
429  OC.sub.3 H.sub.7                                                     
                    3     4-CF.sub.3                                      
                                4-CF.sub.3                                
                                      Ethylsulfonate                      
______________________________________
The compounds of this invention may be used to combat, control, or prevent infestations of insect pests such as Lepidoptera, Diptera, Homoptera, Coleoptera, and Diabrotica such as corn rootworms as well as other invertebrate pests such as Acarids. In general the compounds of the invention may be used to control insects and acarids found in agricultural crops, horticulture, and animal husbandry. They are also useful in forestry, storage and preservation of products of vegetable origin, and for controlling those insect and acarine pests associated with transmission of diseases of man and animals.
Examples of pest species some or all of which may be effectively controlled by the compounds of the invention include Myzus persicae (aphid), Aphis gossypii (aphid), Aedes aegypti (mosquito), Anopheles species (mosquitoes), Culex species (mosquitoes), Dysdercus faciatus (capsid), Musca domestica (housefly), Pieris brassicae (white butterfly), Plutella xylostella (black diamond moth), Phaedon cochleariae (mustard beetle), Aonidiella species (scale insects), Trialeurodes species (white flies), Bemisia tabaci (white fly), Blatella germanica (cockroach), Periplaneta americana (cockroach), Blatta orientalis (cockroach), Spodoptera littoralis (cotton leafworm), Heliothis virescens (tobacco budworm, Chortiocetes terminifera (locust), Diabrotica species (rootworms), Asrotis species (cutworms), Chilo partellus (maize stem borer), Nilaparvata lus`ens (planthopper, Nephotettix cincticeps (leafhopper), Panonychus ulmi (European red mite), Panonychus citri (citrus red mite), Tetranychus urticae (two-spotted spider mite), Tetranychus cinnabarinus (carmine spider mite, Phylocoptruta oleivora (citrus rust mite), Polyphagotarsonemus latus (broad mite) and various Brevapalpus species (mites).
In accordance with the method for controlling such pests, the insecticides of this invention are normally formulated into compositions which include a pesticidally effective amount of the active ingredient of this invention in addition to suitable compatible and inert diluents, carriers, surfactants and the like. Such compositions are generally applied to the locus where control is desired, which may include the soil in which plants are or are to be grown or stored, to plants or animals themselves, or to other loci where control or prevention of infestation is required.
It will be appreciated by those skilled in the art that the formulations in which the compounds of the invention may suitably be applied include such formulations as dusts, wettable powders, granules, solutions, emulsions suspensions, and various concentrates such as solution concentrates or suspension concentrates, and also as controlled release compositions such as microencapsulated granules or suspensions. Such formulations are well known to those skilled in the art. It will also be appreciated by those skilled in the art that the compounds of the invention may be used alone as a single active ingredient of such formulations or in combination with other known pesticides, such as other insecticides, acaricides, fungicides, plant growth and development regulators, herbicides and combinations of such other active ingredients.
The examples set forth below further demonstrate the preparation and use of selected compounds of the invention for illustration purposes only and not by way of limitation on the scope and content of that which the inventors regard as their invention.
EXAMPLE 1 Synthesis of 9-phenylmethyl-α,α-bis(4-trifiuoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol (Compound 1)
Step A: 3-cyano-9-phenylmethyl-9-azabicyclo[3.3.1]nonane as an intermediate.
To a stirred solution of 2.0 grams (0.009 mole) of 9-phenylmethyl-9-azabicyclo[3.3.1]nonane-3-one (prepared in the manner disclosed by Lowe et al., (J.Med. Chem., 1994 37, 2831-2840) in 55 ml of 1,1-dimethoxyethane was added 3.06 grams (0.016 mole) of tosylmethyl isocyanide. Upon completion of addition, the mixture was cooled to 0° C. and 1.17 ml (0.020 mole) of ethanol was added followed by 3.42 grams (0.031 mole) of potassium t-butoxide in four portions. Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature and then heated to 50° C. where it stirred for five hours. After this time, the reaction mixture was allowed to cool to ambient temperature were it stirred for about 18 hours. The reaction mixture was analyzed by gas chromatography (GC), which indicated the reaction was incomplete. The above procedure was repeated and an additional 1.7 grams (0.007 mole) of 9-phenylmethyl-9-azabicyclo[3.3.1]nonane-3-one was added. The reaction mixture was heated to 55° C. where it stirred for two hours. After this time, the reaction mixture was again analyzed by GC, which indicated the reaction was incomplete. The reaction mixture was heated at about 50° C. for an additional three hours and then cooled to ambient temperature where it stirred for about 18 hours. The reaction mixture was poured into 150 ml of an aqueous saturated sodium chloride solution, and the resulting mixture was extracted with ethyl acetate. The organic layer was separated from the aqueous layer, dried with sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure to yield 4.5 grams of crude product. The crude product was purified by column chromatography, yielding 0.41 grams of the above identified intermediate. The NMR spectrum was consistent with the proposed structure.
Step B: Ethyl N-(9-phenylmethyl-9-azabicyclo[3.3.1]nonane-3-yl)carboxylate as an intermediate.
In a 100 ml roundbottom flask, 250 ml of ethanol was saturated with hydrochloric gas for 40 minutes. After this time, 0.41 gram (0.002 mole) of 3-cyano-9-phenylmethyl-9-azabicyclo[3.3.1]nonane was taken up in 12 ml of the saturated ethanol. The solution was heated to reflux and 0.2 ml of water was added. Upon completion of addition, the reaction mixture was heated at reflux for about 18 hours. At the conclusion of this period, the ethanol was removed under reduced pressure and the hydrochloric gas was neutralized with an aqueous 5% sodium hydroxide solution. The resulting mixture was extracted with methylene chloride and washed with an aqueous saturated sodium chloride solution. The organic layer was separated from the aqueous layer, dried with sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure to yield the crude product. The crude product was purified by column chromatography, yielding 0.3 gram of the above identified intermediate. The NMR spectrum was consistent with the proposed spectrum.
Step C: Compound 1
Under a nitrogen atmosphere, 0.42 gram (0.0174 mole) of turnings magnesium was taken up in 5.0 ml of anhydrous tetrahydrofuran. The resulting solution was heated to about 60° C. to effect dissolution. The tetrahydrofuran was removed via a syringe and the magnesium was dried at about 60° C. for five minutes. After this time, the magnesium was allowed to cool to ambient temperature and an additional 5.0 ml of tetrahydrofuran was added followed by 0.5 (0.0022 mole) of 1-trifluoromethyl-4-bromobenzene. To this solution was added an additional 2.0 ml of tetrahydrofuran and one small crystal of iodine. The resulting solution was heated until the iodine color disappeared. In an independent separatory funnel, 3.42 grams (0.0153 mole) of 1-trifluoromethyl-4-bromobenzene was taken up in 20 ml of tetrahydrofuran. To this solution was added a solution of 2.0 grams (0.007 mole) of ethyl N-(9-phenylmethyl-9-azabicyclo[3.3.1]nonane-3-yl)carboxylate in 28 ml of tetrahydrofuran. The resulting mixture was added dropwise to the iodine solution. Upon completion of addition, the reaction mixture was heated to 60° C. where it stirred for 2.5 hours. The reaction mixture was allowed to cool to ambient temperature where it stirred for about 18 hours. At the conclusion of this period, 50 ml of ammonium chloride was added, and the resulting mixture was extracted with two portions of ethyl acetate. The combined ethyl acetate extracts were dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, yielding 4.6 grams of crude product. The crude product was purified by column chromatography, yielding 2.3 grams of 9-phenylmethyl-α,α-bis(4-trifluoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol (Compound 1) as a yellow oil. The NMR spectrum was consistent with the proposed spectrum.
EXAMPLE 2 9-(4-propoxyphenyl)methyl-α,α-bis(4-trifluoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol (Compound 2)
Step A: 9-phenylmethyl-α,α-bis(4-trifluoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol hydrochloride salt as an intermediate.
A stirred solution of 2.3 grams (0.0043 mole) of 9-phenylmethyl-α,α-bis(4-trifluoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol in 30 ml of diethyl ether was cooled to 0° C. and 30 ml of a hydrochloric acid and diethyl ether mixture was added dropwise. Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature and 100 ml of pentane was added. The solvent was removed under reduced pressure, yielding 2.5 grams of the above identified intermediate. The NMR spectrum was consistent with the proposed structure
Step B: α,α-bis(4-trifiuoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol as an intermediate.
Under a nitrogen atmosphere, a stirred solution of 2.49 grams (0.0044 mole) of 9-phenylmethyl-α,α-bis(4-trifluoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol hydrochloride salt in 40 ml of absolute methanol was treated with 0.75 grams of 10% palladium in carbon in 52 ml of absolute methanol. The reaction mixture was heated to 65° C. where it stirred for 1.5 hours. After this time, the reaction mixture was cooled to ambient temperature, filtered through diatomaceous earth, and the resulting filter cake was washed with 200 ml of methylene chloride. The filtrate was concentrated under reduced pressure, and the resulting residue was taken up in a 5% aqueous sodium hydroxide solution. The solution was extracted with three 100 ml portions of chloroform. The organic layer was separated from the aqueous layer and concentrated under reduce pressure, yielding 1.6 grams of the above identified intermediate structure, m.p. 172-179° C. The NMR spectrum was consistent with the proposed spectrum.
Step C: (Compound 2)
Under a nitrogen atmosphere, 1.3 grams (0.0029 mole) of α,α-bis(4-trifluoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol was taken up in 15 ml of dimethyl sulfoxide. To this solution was added a solution of 0.6 gram (0.0032 mole) of 4-propoxyphenylmethyl chloride in 6 ml of dimethyl sulfoxide. The resulting solution was stirred for five minutes and then 1.5 grams (0.0116 mole) of N,N-diisopropylethylamine was added via syringe. Upon completion of addition, the reaction mixture was stirred at ambient temperature for 20 hours. At the conclusion of this period, the reaction mixture was poured into a mixture consisting of 100 ml of an aqueous saturated sodium bicarbonate solution, 20 ml of an aqueous 10% sodium hydroxide solution, and 300 ml of ethyl acetate. The organic layer was separated, washed with one 100 ml portion of an aqueous saturated sodium chloride solution, dried with sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure to yield a yellow oil. The yellow oil was taken up in ethyl acetate, and the resulting solution was filtered through a silica gel plug. The filtrate was concentrated under reduced pressure, yielding 1.4 grams of crude product. The crude product was purified by column chromatography, yielding 1.3 grams of Compound 2, m.p. 109-111° C. The NMR spectrum was consistent with the proposed structure.
EXAMPLE 3 9-(4-propoxyphenyl)methyl-α,α-bis(4-trifluoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol N-oxide (Compound 3)
A stirred solution of 0.8 gram (0.0014 mole) of 9-(4-propoxyphenyl)-methyl- α,α-bis(4-trifluoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol in 20 ml of chloroform was cooled to about 10° C. and 0.43 gram (0.0015 mole) of 60% 3-chloroperoxybenzoic acid was added. Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature where it stirred for about 18 hours. After this time, an additional 150 ml of chloroform was added, and the resulting solution was washed with one 100 ml portion of a cold aqueous 5% sodium hydroxide solution. The organic layer was separated from the aqueous, dried with sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure, yielding 0.69 gram of Compound 3, m.p. 179-184° C. The NMR spectrum was consistent with the proposed structure.
EXAMPLE 4 9-(4-propoxyphenyl)methyl-α,α-bis(4-trifluoromethylphenyl)-9-azabicyclo [3.3.1.]nonane-3-methanol hydrochloride (Compound 118)
To a stirred suspension of 0.65 gram (0.0011 mole) of 9-(4-propoxyphenyl)-methyl-α,α-bis(4-triluoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol in 10 ml of diethyl ether is added dropwise a solution of 2.2 ml (0.022 mole) of hydrochloric acid in 20 ml of diethyl ether. Upon completion of addition, the reaction mixture is stirred at ambient temperature for about 18 hours. After this time, the diethyl ether is removed under reduced pressure to yield a residue. This residue when triturated with pentane and dried under reduced pressure, will yield Compound 118.
EXAMPLE 5 Ethanesulfonate salt of 9-(4-propoxyphenyl)methyl-α,α-bis(4-trifluoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol (Compound 119)
To a stirred suspension of 0.65 gram (0.0011 mole) of 9-(4-propoxyphenyl)-methyl-α,α-bis(4-trifluoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol in 10 ml of diethyl ether is added dropwise a solution of 0.18 ml (0.022 mole) of ethanesulfonic acid in 20 ml of diethyl ether. Upon completion of addition, the reaction mixture is stirred at ambient temperature for five hours. After this time, the diethyl ether is removed under reduced pressure to yield a brown oil. The oil is then up in 20 ml of methylene chloride, and the resulting solution is washed with one five ml portion of water. The organic layer is separated from the aqueous layer, dried with sodium sulfate, and filtered. The filtrate when concentrated under reduced pressure, will yield the Compound 119.
EXAMPLE 6 9-(4-propoxyphenyl)methyl-α,α-bis(4-trifluoromethylphenyl)-9-(2-carboxyethoxy)-9-azabicyclo[3.3.1.]nonane-3-methanol N-oxide (Compound 386)
Under a nitrogen atmosphere, a solution of 0.61 gram (0.001 mole) of 9-(4-propoxyphenyl)methyl- α,α-bis(4-trifluoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol N-oxide, 0.15 gram (0.001 mole) of 3-bromopropionic acid, and a 1:1 mixture of acetonitrile and chloroform is stirred at ambient temperature for about 48 hours. The reaction mixture is then filtered. The filtrate when concentrated under reduced pressure, will then yield Compound 386.
EXAMPLE 7 Ethanesulfonate salt of 9-(4-propoxyphenyl)methyl-α,α-bis(4-trifluoromethylphenyl)-9azabicyclo[3.3.1]nonane-3-methanol N-oxide (Compound 429)
Under a nitrogen atmosphere, to a stirred suspension of 0.61 gram (0.001 mole) of 9-(4-propoxyphenyl)methyl-α,α-bis(4-trifluoromethylphenyl)-9-azabicyclo[3.3.1.]nonane-3-methanol N-oxide in 1 ml of ethanol is added dropwise a solution of 0.22 gram (0.002 mole) of ethanesulfonic acid in 0.5 ml of ethanol. Upon completion of addition, the reaction mixture is stirred at ambient temperature for 12 hours. After this time, the reaction mixture is washed with one 15 ml portion of heptane. The resulting solid may the be separated from the aqueous layer, dried with sodium sulfate, and filtered. The filtrate, when concentrated under reduced pressure, will yield Compound 429.
EXAMPLE 8 Insecticidal activity against the tobacco budworm (Heliothis virescens [Fabricius])
Stock solutions of test chemical in dimethylsulfoxide were prepared for each rate of application. The rates of application, expressed as the negative log of the molar concentration, and the corresponding concentrations of the stock solution prepared for each rate are shown below:
______________________________________                                    
Stock Solution                                                            
              Rate of Application                                         
______________________________________                                    
50 micromolar 4                                                           
5             5                                                           
0.5           6                                                           
0.05          7                                                           
0.005         8                                                           
______________________________________
One hundred microliters of each of the stock solutions was manually stirred into 50 ml of a molten (65-70° C.) wheat germ-based artificial diet. The 50 ml of molten diet containing the test chemical was poured evenly into twenty wells in the outer four rows of a twenty-five well, five row plastic tray. Each well in the tray was about 1 cm in depth, with an opening of 3 cm by 4 cm at the lip. Molten diet containing only dimethylsulfoxide at the levels used in the test chemical-treated diet was poured into the five wells in the third row of the tray. Each tray therefore contained one test chemical at a single rate of application, together with an untreated control. Single second instar tobacco budworm larvae were placed in each well. The larvae were selected at a stage of growth at which they uniformly weigh about 5 mg each. Upon completion of infestation, a sheet of clear plastic was heat-sealed over the top of the tray using a common household flat iron. The trays were held at 25° C. at 60% relative humidity for five days in a growth chamber. Lighting was set at 14 hours of light and 10 hours of darkness. After the 5-day exposure period, mortality counts were taken, and the surviving insects were weighed. From the weights of the surviving insects that fed on the treated diet as compared to those insects that fed on the untreated diet, the percent growth inhibition caused by each test chemical was determined. From these data, the negative log of the concentration of the test chemical that provided 50% growth inhibition (p150) was determined by linear regression, when possible, for each test chemical. Where possible, the negative log of the concentration of the test chemical that provided 50% mortality (pLC50) was determined.
Generally, the compounds of the present invention inhibited the growth of the tobacco budworm, as shown in the following table of data for selected compounds:
______________________________________                                    
             Rate of   % Growth                                           
No.          Application.sup.1                                            
                       Inhibition.sup.2                                   
______________________________________                                    
1            5         53.sup.3                                           
2            5         97.sup.3                                           
3            5         97                                                 
4            5         98                                                 
5            5         100.sup.3                                          
6            5         100.sup.3                                          
7            5         101                                                
8            5         99                                                 
9            5         99                                                 
10           5         94                                                 
26           5         100                                                
29           5         59                                                 
50           5         100                                                
54           5         99                                                 
62           5         98                                                 
65           5         95                                                 
85           5         99                                                 
86           5         99                                                 
89           5         98                                                 
90           5         99                                                 
131          5         99                                                 
151          5         100                                                
283          5         100                                                
288          5         97                                                 
289          5         100                                                
389          5         100                                                
______________________________________                                    
 .sup.1 The rate of application is expressed as the negative log og the   
 molar concentration of the test compound in the diet.                    
 .sup.2 Precent growth inhibition is derived from the total weight of the 
 insects (IW) at each rate of application in the test relative to the tota
 weight of the insects in an untreated control:                           
 ##STR9##                                                                 
 .sup.3 Average of two results
EXAMPLE 9 Insecticidal activity in foliar evaluations against the tobacco budworm.
In these tests against the tobacco budworm, nine-day-old chick pea plants (Cicer arietinum) were sprayed at 20 psi to runoff on both upper and lower leaf surfaces with solutions of test chemical to provide application rates as high as 1000 ppm of test chemical. The solvent used to prepare the solutions of test chemical was 10% acetone or methanol (v/v) and 0.1% of the surfactant octylphenoxypolyethanol in distilled water. Four replicates, each containing four chick pea plants, for each rate of application of test chemical were sprayed. The treated plants were transferred to a hood where they were kept until the spray had dried.
The four chick pea plants in each replicate treated with test chemical as described above were removed from their pots by cutting the stems just above the soil line. The excised leaves and stems from the four plants in each replicate were placed in individual 8-ounce paper cups, which contained a moistened filter paper. Five second-instar (4-5 days old) tobacco budworms were counted into each cup, taking care not to cause injury. An opaque plastic lid was placed on each cup, which was then held in a growth chamber for a 96 hour exposure period at 25° C. and 50% relative humidity. At the end of the 96 hour exposure period the cups were opened, and the numbers of dead and live insects were counted. Moribund larvae which were disoriented or unable to crawl normally were counted as dead. Using the insect counts, the efficacy of the test chemical was expressed in percent mortality. The condition of the test plants was also observed for phytotoxicity and for reduction of feeding damage as compared to an untreated control. Where applicable, computer- generated LC50 values were determined from the percentages of insect mortality. The resulting data are presented in the following table:
______________________________________                                    
            Rate of   Percent Control.sup.1                               
Cmpd No.    Application                                                   
                      TBW                                                 
______________________________________                                    
4           300       65                                                  
6           300       100                                                 
7           300       100                                                 
8           300       100                                                 
______________________________________                                    
 .sup.1 Percent control is derived from the total number of dead insects  
 (TD) plus the total number of moribound insects (TM) relative to the     
 number of insects (TI) used in the test.                                 
 ##STR10##
The compounds of the present invention also provide insecticidal activity in foliar evaluations against the beet armyworm (Spodoptera exigua [Hubner]) and the cabbage looper (Trichoplusia ni [Hubner]), and various other insects and acarids described above.

Claims (6)

We claim:
1. A compound of the formula: ##STR11## in which m is 2 or 3; n is 0 or 1;
W is hydrogen or alkoxy;
X is hydrogen, alkoxy, cycloalkylalkoxy, alkoxycarbonyl, alkoxycarbonylamino, alkoxyimino, haloalkoxyimino, or a five-or six-membered heteroaryl or heteroaryloxy in which one or more hetero atoms may be optionally substituted with an alkyl;
R1 and R2 are independently selected from hydrogen, haloalkyl, halothio, or haloalkoxy; and
when n is 1, Y represents (a) an N-oxide of the ring nitrogen or (b) an agriculturally acceptable anionic salt of the ring nitrogen; or (c) forms an OR3 linkage in which R3 is selected from hydrogen, alkyl, alkoxycarbonylalkyl, hydroxycarbonylethyl, in association with an agriculturally acceptable anion resulting in an anionic salt, or R3 is an oxycarbonylalkyl group bearing a negative charge resulting in an inner salt.
2. The compound claim 1 in which W is hydrogen or propoxy, X is hydrogen, ethoxy, propoxy, butoxy, (C1-C3 alkoxy)carbonyl, (C1-C3 alkoxy)carbonylamino, 2-(C1-C2 alkyl)tetrazol-5-yl, pyridyl-2-yl, pyridyl-2-yloxy, or cyclopropylmethoxy; R1 and R2 are 4-trifluoromethyl or 4-trifluorormethoxy.
3. The insecticidal compounds of claim 1 in which W is hydrogen; X is propoxy, methoxycarbonylamino, or 2-ethyltetrazol-5-yl; R1 and R2 are 4-trifluoromethyl or 4-trifluoromethoxy; R3 is methyl, ethoxycarbonylethyl, or an oxycarbonylethyl group, and the associated anionic or inner salts thereof.
4. An insecticidal composition comprising an insecticidally effective amount of the compound of claim 1 in admixture with an agriculturally acceptable diluent carrier, excipient, adjuvant or combination thereof.
5. A method for controlling insects comprising applying to a locus where control is desired an insecticidally effective amount of the compound of claim 1 or an agriculturally acceptable formulation thereof.
6. Compounds of the formula: ##STR12## in which m is 2 or 3; and R1 and R2 are 4-trifluoromethyl or 4-trifluoromethoxy.
US09/212,223 1997-12-17 1998-12-16 Insecticidal N-(arylalkyl)-4-[Bis(substituted aryl)hydroxymethyl]azabicyclo[3.3.1.]nonanes and [3.2.1.]octanes Abandoned USH1838H (en)

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Cited By (1)

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US20050176410A1 (en) * 2001-03-22 2005-08-11 Brooking Michael A. Method and system for providing message services in a communication system

Citations (1)

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Publication number Priority date Publication date Assignee Title
GB2319524A (en) * 1996-11-25 1998-05-27 Zeneca Ltd Nortropane derivatives for use as insecticides

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2319524A (en) * 1996-11-25 1998-05-27 Zeneca Ltd Nortropane derivatives for use as insecticides

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050176410A1 (en) * 2001-03-22 2005-08-11 Brooking Michael A. Method and system for providing message services in a communication system

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