USH1996H1 - Insecticidal photostable acid salt derivatives of N-benzyl-4-benzhydrolpiperidines - Google Patents

Insecticidal photostable acid salt derivatives of N-benzyl-4-benzhydrolpiperidines Download PDF

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USH1996H1
USH1996H1 US09/196,880 US19688098A USH1996H US H1996 H1 USH1996 H1 US H1996H1 US 19688098 A US19688098 A US 19688098A US H1996 H USH1996 H US H1996H
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tetrazol
acid
ethyl
alkyl
halogen
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US09/196,880
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Clinton J. Peake
Thomas G. Cullen
II Robert N. Henrie
Jane A. Dybas
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FMC Corp
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FMC Corp
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Assigned to FMC CORPORATION reassignment FMC CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CULLEN, THOMAS G., DYBAS, JANE A., HENRIE, ROBERT N., II, PEAKE, CLINTON J.
Priority to PCT/US1999/005275 priority patent/WO2000031034A1/en
Priority to AU30778/99A priority patent/AU3077899A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • 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
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D211/20—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by singly bound oxygen or sulphur atoms
    • C07D211/22—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by singly bound oxygen or sulphur atoms by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
    • C07D211/94—Oxygen atom, e.g. piperidine N-oxide

Definitions

  • This invention relates generally to insecticidal compounds for use in controlling insects.
  • it pertains to certain agriculturally acceptable organic and inorganic acid salt derivatives of N-benzyl-4-benzhydrolpiperidines and their corresponding N-oxides having improved photostability while providing insecticidal activity generally equivalent to the parent compound.
  • This invention also pertains to the insecticidal compositions of these salt derivatives, and a method of controlling insects at a locus which comprises applying to that locus a compound of the invention or an insecticidal composition containing the compound.
  • Insecticides are useful for controlling insects which may otherwise cause significant damage to crops such as wheat, corn, soybeans, potatoes, and cotton to name a few.
  • crops such as wheat, corn, soybeans, potatoes, and cotton to name a few.
  • insecticides are desired which can control the insect pests without damaging the crops, and which have no deleterious effects to mammals and other living organisms.
  • Photostable insecticides are advantageous in that they promote residual insecticidal activity which increases the effectiveness of the insecticidally active material.
  • U.S. Pat. No. 5,569,664 and U.S. Pat. No. 5,639,763 disclose a class of piperidine derivatives, the corresponding N-oxides and agriculturally acceptable salts for use as insecticides:
  • U is —(CH 2 ) n — where n is 1, 2, or 3;
  • R is selected from a heterocycle having 5 or 6 ring atoms, optionally fused to a benzene ring, and
  • V, W, Y, and Z are hydrogen;
  • X is hydrogen, hydroxy, halogen, alkyl, alkoxyalkyl, alkoxy, cycloalkylalkoxy, haloalkoxy, alkenyloxy, haloalkenyloxy, alkynyloxy, alkylsilyloxy, alkylthio, haloalkylthio, cyano, cyanoalkoxy, nitro, amino, monoalkylamino, dialkylamino, alkylaminoalkoxy, alkylcarbonylamino, alkylcarbonyl, alkoxycarbonylamino, alkoxycarbonyl, alkylaminocarbonyl, aminocarbonyloxy, phenyl, phenylalkoxy, phenoxy, phenoxyalkyl, or a five- or six-membered heterocycl; each cycloalkyl moiety, heterocycle, or phenyl ring is optionally substituted with halogen, alkoxy, or haloalkoxy;
  • W and X taken together may be —OCH 2 CH 2 O—, —CH 2 C(CH 3 ) 2 O—, —OC(CH 3 ) 2 O—, —N ⁇ C(C 2 H 5 )O—, or —CH ⁇ CHCH ⁇ C—;
  • R 1 and R 2 are independently selected from phenyl substituted with one or more haloalkyl or haloalkoxy.
  • R, R 1 , and n are as defined below.
  • Preferred compounds include those where R is 2-alkyl-2H-tetrazol-5-yl; R 1 is trifluoromethyl, or trifluoromethoxy; n is 1; and said salts are derived from hydrochloric acid, or a sulfonic acid.
  • R is alkoxycarbonyl, alkoxycarbonylamino, cycloalkylalkoxy, 2-alkyl-2H-tetrazol-5-yl, or 2-haloalkyl-2H-tetrazol-5-yl;
  • R 1 is trihaloalkyl, or trihaloalkoxy
  • n 0, or 1;
  • salts are derived from hydrochloric acid; hydrobromic acid; boric acid; phosphoric acid, maleic acid, fumaric acid, phthalic acid; salicylic acid optionally substituted with alkyl or halogen; D-glucuronic acid; the sulfonic acid R 2 SO 3 H where R 2 is alkyl, haloalkyl, hydroxyalkyl, D-10-camphoryl, or phenyl optionally substituted with alkyl or halogen; the carboxylic acid R 3 CO 2 H where R 3 is hydrogen, alkyl, trihaloalkyl, carboxyl, phenyl optionally substituted with alkyl or halogen, or pyridyl; the boronic acid R 4 B(OH) 2 where R 4 is alkyl or phenyl optionally substituted with alkyl or halogen; the phosphonic acid R 5 PO 3 H 2 where R 5 is alkyl, haloalkenyl, or phenyl optionally substituted with
  • Preferred compounds are those where R is alkoxycarbonyl, alkoxycarbonylamino, cycloalkylalkoxy, 2-alkyl-2H-tetrazol-5-yl, or 2-haloalkyl-2H-tetrazol-5-yl; R 1 is trihaloalkyl, or trihaloalkoxy; n is 0, or 1; and, wherein said salts are derived from hydrochloric acid, salicylic acid optionally substituted with alkyl or halogen, D-glucuronic acid, or the sulfonic acid R 2 SO 3 H where R 2 is alkyl, haloalkyl, hydroxyalkyl, D-10-camphoryl, or phenyl optionally substituted with alkyl or halogen.
  • Particularly preferred compounds are those where R is 2-ethyl-2H-tetrazol-5-yl; R 1 is trifluoromethyl; n is 1; and said salts are derived from hydrochloric acid, or the sulfonic acid R 2 SO 3 H where R 2 is alkyl, or hydroxyalkyl.
  • alkyl and alkoxy used alone or as part of a larger moiety includes 1 to 6 carbon atoms either straight or branched chain.
  • Alkenyl refers to 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, either straight or branched chain.
  • Cycloalkyl refers to 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms.
  • Halogen or “Halo” refer to chlorine, bromine, and fluorine.
  • HPLC refers to high pressure liquid chromatography
  • DMSO dimethyl sulfoxide.
  • N-benzyl-4-benzhydrolpiperidines and their corresponding N-oxides of formula I may be prepared by methods described below or by methods similar to those known in the art for similar compounds.
  • the parent N-benzyl-4-benzhydrolpiperidines may be prepared as described in U.S. Pat. No. 5,569,664 by reacting a 4-benzhydrolpiperidine with a benzyl halide.
  • This patent also describes a method for oxidizing the N-benzyl-4-benzhydrolpiperidines by treatment with, for example, 50% 3-chloroperoxybenzoic acid in a suitable solvent, to give the corresponding N-benzyl-4-benzhydrolpiperidine N-oxides.
  • the acid salts of formula I may then be obtained by treatment of an appropriately substituted N-benzyl-4-benzhydrolpiperidine in a solvent with an acid, to give the corresponding acid salts of N-benzyl-4-benzhydrolpiperidine I.
  • R R 1 n R 3 58 2-ethyl-2H-tetrazol-5-yl CF 3 1 H 59 2-ethyl-2H-tetrazol-5-yl CF 3 1 CH 3 60 2-ethyl-2H-tetrazol-5-yl CF 3 1 CF 3 61 2-ethyl-2H-tetrazol-5-yl CF 3 1 CO 2 H 62 2-ethyl-2H-tetrazol-5-yl CF 3 1 4-Cl-phenyl 63 2-ethyl-2H-tetrazol-5-yl CF 3 1 4-CH 3 -phenyl 64 2-ethyl-2H-tetrazol-5-yl CF 3 1 pyridin-2-yl Salt Derived From R 4 B(OH) 2 Cmpd.
  • the remaining coverslips are then placed in the water-cooled chamber of the exposure platform of a Suntest CPS illuminator (Heraeus Instruments GmbH; Signal Original Hanau, Hersaeusstrasse R-14, Postfach 1563, D-6450 Hanau 1).
  • the exposure platform is covered with a quartz plate and maintained at about 25° C. for the duration of the test.
  • the Suntest CPS illuminator employs a filtered xenon lamp, which provides illumination of a similar spectrum and intensity as sunlight.
  • Four coverslips for each test compound are removed from the illuminator at the end of each illumination period described above.
  • the four coverslips from each of the illumination periods are treated as described above and the acetonitrile extract is analyzed by HPLC.
  • the average HPLC peak area from each of the illumination periods represents a diminished amount of test compound when compared to the initial level of test compound as determined from the zero hour illumination sample.
  • the percents of test compound remaining from each of these illumination periods are used to generate a degradation curve from which a half life in hours is determined for each test compound.
  • Table 3 shows the improved photostability of representative compounds of the present invention when compared to the photostability of their non-ionic amino parent.
  • the test compounds are identified by numbers which correspond to those in Table 1.
  • Representative compounds of the present invention were shown to be about 2.5 to 4 times more photostable than their non-ionic parents in the tests conducted.
  • Candidate insecticides are evaluated for activity against tobacco budworm ( Heliothis virescens [Fabricius]) by applications to the surface of a wheat germ-based artificial insect diet.
  • Solutions of the candidate insecticides are prepared for testing by diluting a standard 50 millimolar DMSO solution of each candidate insecticide with DMSO, then further diluting with a 1:1 water/acetone solution (V/V). Forty microliters of this solution of calculated concentration is then pipetted onto the surface of the diet in each of six containers, to provide six replicates for each rate of application. Once treated, the contents of the containers are allowed to dry, leaving the calculated concentration ( in millimoles) of candidate insecticide on the surface of the diet.
  • each container In each container is placed one second instar tobacco budworm larvea. The container is sealed with a transparent film, and then held in a growth chamber for five days. After the five-day exposure period the insecticidal activity of the candidate insecticide is recorded as percent mortality when compared to the total number of insects infested.
  • Insecticidal activity at a concentration of candidate insecticide of 0.0025 millimoles on the surface of the diet is given for various compounds of this invention in Table 4.
  • the active compounds are formulated into insecticidal compositions by admixture in insecticidally effective amount with adjuvants and carriers normally employed in the art for facilitating the dispersion of active ingredients for the particular utility desired, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the material in a given application.
  • the present insecticidal compounds may be formulated as granules of relatively large particle size, as water-soluble or water-dispersible granules, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, or as any of several other known types of formulations, depending on the desired mode of application.
  • insecticidal compositions may be applied either as water-diluted sprays, or dusts, or granules to the areas in which insect control is desired. These formulations may contain as little as 0.1%, 0.2% or 0.5% to as much as 95% or more by weight of active ingredient.
  • Dusts are free flowing admixtures of the active ingredients with finely divided solids such as talc, natural clays, kieselguhr, flours such as walnut shell and cottonseed flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant; these finely divided solids have an average particle size of less than about 50 microns.
  • a typical dust formulation useful herein is one containing 1.0 part or less of the insecticidal compound and 99.0 parts of talc.
  • Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersant.
  • the wettable powder is ultimately applied to the locus where insect control is desired either as a dry dust or as an emulsion in water or other liquid.
  • Typical carriers for wettable powders include Fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wet, inorganic diluents. Wettable powders normally are prepared to contain about 5-80% of active ingredient, depending on the absorbency of the carrier, and usually also contain a small amount of a wetting, dispersing, or emulsifying agent to facilitate dispersion.
  • a useful wettable powder formulation contains 80.8 parts of the insecticidal compound, 17.9 parts of Palmetto clay, and 1.0 part of sodium lignosulfonate and 0.3 part of sulfonated aliphatic polyester as wetting agents.
  • ECs emulsifiable concentrates
  • ECs emulsifiable concentrates
  • ECs emulsifiable concentrates
  • these concentrates are dispersed in water or other liquid carrier, and normally applied as a spray to the area to be treated.
  • the percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises 0.5 to 95% of active ingredient by weight of the insecticidal composition.
  • SCs Suspension Concentrates
  • ECs are similar to ECs except that the active ingredient is suspended in a liquid carrier, generally water.
  • SCs may include a small amount of a surfactant, and contain active ingredient in the range of 0.5 to 95%, frequently from 5 to 50%, by weight of the composition.
  • SCs may be diluted in water or other liquid vehicle, and are normally applied as a spray to the area to be treated.
  • Typical wetting, dispersing, or emulsifying agents used in agricultural formulations include, but are not limited to, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; alkylaryl polyether alcohols; sulfated higher alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition product of long-chain mercaptans and ethylene oxide.
  • alkylaryl polyether alcohols sulfated higher alcohols
  • polyethylene oxides polyethylene oxides
  • sulfonated animal and vegetable oils sulfonated petroleum oils
  • fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters and the addition product of long-chain mercaptans and ethylene oxide.
  • the surface-active agents when used, normally comprise from 1 to 15% by weight of the composition.
  • compositions include suspensions of the active ingredient in a relatively non-volatile solvent such as corn oil, kerosene, propylene glycol, or other suitable solvents.
  • Still other useful formulations for insecticidal applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene, or other organic solvents.
  • Granular formulations, wherein the toxicant is carried on relatively coarse particles, are of particular utility for aerial distribution or for penetration of cover crop canopy.
  • Pressurized sprays, typically aerosols wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as carbon dioxide, propane, or butane, may also be used.
  • Water-soluble or water-dispersible granules are also useful formulations for insecticidal application of the present compounds.
  • Such granular formulations are free-flowing, non-dusty, and readily water-soluble or water-miscible.
  • the soluble or dispersible granular formulations described in U.S. Pat. No. 3,920,442 are useful herein with the present insecticidal compounds.
  • the granular formulations, emulsifiable concentrates, flowable concentrates, solutions, etc. may be diluted with water to give a concentration of active ingredient in the range of say 0.1% or 0.2% to 1.5% or 2%.
  • the active insecticidal compounds of this invention may be formulated and/or applied with other insecticides, fungicides, nematicides, plant growth regulators, fertilizers, or other agricultural chemicals.
  • an effective amount and concentration of the active compound is applied to the locus where control is desired.
  • the locus may be, e.g., the insects themselves, plants upon which the insects feed, or the insect habitat.
  • the composition of the active compound may be applied to and optionally incorporated into the soil.
  • the effective amount may be as low as, e.g. about 10 to 500 g/ha, preferably about 100 to 250 g/ha.

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Abstract

It has now been found that certain novel photostable agriculturally acceptable organic or inorganic salts of formula I are useful as insecticides:whereR is alkoxycarbonyl, alkoxycarbonylamino, cycloalkylalkoxy, 2-alkyl-2H-tetrazol-5-yl, or 2-haloalkyl-2H-tetrazol-5-yl; R1 is trihaloalkyl, or trihaloalkoxy; n is 0, or 1; and, wherein said salts are derived from hydrochloric acid; hydrobromic acid; boric acid; phosphoric acid; maleic acid; fumaric acid; phthalic acid; salicylic acid optionally substituted with alkyl or halogen; D-glucuronic acid; the sulfonic acid R2SO3H where R2 is alkyl, haloalkyl, hydroxyalkyl, D-10-camphoryl, or phenyl optionally substituted with alkyl or halogen; the carboxylic acid R3CO2H where R3 is hydrogen, alkyl, trihaloalkyl, carboxyl, phenyl optionally substituted with alkyl or halogen, or pyridyl; the boronic acid R4B(OH)2 where R4 is alkyl or phenyl optionally substituted with alkyl or halogen; the phosphonic acid R5PO3H2 where R5 is alkyl, haloalkenyl, or phenyl optionally substituted with alkyl or halogen; the sulfuric acid R6OSO3H where R6 is hydrogen or alkyl; or the alkanoic acid X-(CH2)qCO2H where q is 0 to 11, X is halogen, trihaloalkyl, haloalkenyl, cyano, aminocarbonyl, or CO2R7 where R7 is hydrogen or alkyl. Preferred compounds include those where R is 2-ethyl-2H-tetrazol-5-yl; R1 is trifluoromethyl; n is 1; and said salts are derived from hydrochloric acid, or the sulfonic acid R2SO3H where R2 is alkyl, or hydroxyalkyl.

Description

This application derives priority from verified provisional application No. 60/067,072 filed Nov. 20, 1997, now abandoned.
BACKGROUND OF THE INVENTION
This invention relates generally to insecticidal compounds for use in controlling insects. In particular, it pertains to certain agriculturally acceptable organic and inorganic acid salt derivatives of N-benzyl-4-benzhydrolpiperidines and their corresponding N-oxides having improved photostability while providing insecticidal activity generally equivalent to the parent compound. This invention also pertains to the insecticidal compositions of these salt derivatives, and a method of controlling insects at a locus which comprises applying to that locus a compound of the invention or an insecticidal composition containing the compound.
There is a continuing demand for new insecticides that are safer, more effective, and less costly. Insecticides are useful for controlling insects which may otherwise cause significant damage to crops such as wheat, corn, soybeans, potatoes, and cotton to name a few. For crop protection, insecticides are desired which can control the insect pests without damaging the crops, and which have no deleterious effects to mammals and other living organisms. Photostable insecticides are advantageous in that they promote residual insecticidal activity which increases the effectiveness of the insecticidally active material.
U.S. Pat. No. 5,569,664 and U.S. Pat. No. 5,639,763 disclose a class of piperidine derivatives, the corresponding N-oxides and agriculturally acceptable salts for use as insecticides:
Figure USH0001996-20011002-C00002
in which, among others,
U is —(CH2)n— where n is 1, 2, or 3;
Q is hydroxy;
R is selected from a heterocycle having 5 or 6 ring atoms, optionally fused to a benzene ring, and
Figure USH0001996-20011002-C00003
where
V, W, Y, and Z are hydrogen; and,
X is hydrogen, hydroxy, halogen, alkyl, alkoxyalkyl, alkoxy, cycloalkylalkoxy, haloalkoxy, alkenyloxy, haloalkenyloxy, alkynyloxy, alkylsilyloxy, alkylthio, haloalkylthio, cyano, cyanoalkoxy, nitro, amino, monoalkylamino, dialkylamino, alkylaminoalkoxy, alkylcarbonylamino, alkylcarbonyl, alkoxycarbonylamino, alkoxycarbonyl, alkylaminocarbonyl, aminocarbonyloxy, phenyl, phenylalkoxy, phenoxy, phenoxyalkyl, or a five- or six-membered heterocycl; each cycloalkyl moiety, heterocycle, or phenyl ring is optionally substituted with halogen, alkoxy, or haloalkoxy;
W and X taken together may be —OCH2CH2O—, —CH2C(CH3)2O—, —OC(CH3)2O—, —N═C(C2H5)O—, or —CH═CHCH═C—;
R1 and R2 are independently selected from phenyl substituted with one or more haloalkyl or haloalkoxy.
The '664 and '763 patents do not disclose improved photostablility of agriculturally acceptable salts of piperidines or piperidine N-oxides.
SUMMARY OF THE INVENTION
It has now been found that certain novel agriculturally acceptable organic and inorganic acid salts of N-benzyl-4-benzhydrolpiperidines and their corresponding N-oxides have improved photostablility, and are useful as insecticides. These compounds are represented by formula I:
Figure USH0001996-20011002-C00004
wherein R, R1, and n are as defined below. Preferred compounds include those where R is 2-alkyl-2H-tetrazol-5-yl; R1 is trifluoromethyl, or trifluoromethoxy; n is 1; and said salts are derived from hydrochloric acid, or a sulfonic acid.
DETAILED DESCRIPTION OF THE INVENTION
Certain novel photostable agriculturally acceptable organic and inorganic acid salts of N-benzyl-4-benzhydrolpiperidines and their corresponding N-oxides are useful in controlling insects. These compounds are represented by formula I:
Figure USH0001996-20011002-C00005
where
R is alkoxycarbonyl, alkoxycarbonylamino, cycloalkylalkoxy, 2-alkyl-2H-tetrazol-5-yl, or 2-haloalkyl-2H-tetrazol-5-yl;
R1 is trihaloalkyl, or trihaloalkoxy;
n is 0, or 1; and,
wherein said salts are derived from hydrochloric acid; hydrobromic acid; boric acid; phosphoric acid, maleic acid, fumaric acid, phthalic acid; salicylic acid optionally substituted with alkyl or halogen; D-glucuronic acid; the sulfonic acid R2SO3H where R2 is alkyl, haloalkyl, hydroxyalkyl, D-10-camphoryl, or phenyl optionally substituted with alkyl or halogen; the carboxylic acid R3CO2H where R3 is hydrogen, alkyl, trihaloalkyl, carboxyl, phenyl optionally substituted with alkyl or halogen, or pyridyl; the boronic acid R4B(OH)2 where R4 is alkyl or phenyl optionally substituted with alkyl or halogen; the phosphonic acid R5PO3H2 where R5 is alkyl, haloalkenyl, or phenyl optionally substituted with alkyl or halogen; the sulfuric acid R6OSO3H where R6 is hydrogen or alkyl; or the alkanoic acid X-(CH2)qCO2H where q is 0 to 11, X is halogen, trihaloalkyl, haloalkenyl, cyano, aminocarbonyl, or CO2R7where R7 is hydrogen or alkyl.
Preferred compounds are those where R is alkoxycarbonyl, alkoxycarbonylamino, cycloalkylalkoxy, 2-alkyl-2H-tetrazol-5-yl, or 2-haloalkyl-2H-tetrazol-5-yl; R1 is trihaloalkyl, or trihaloalkoxy; n is 0, or 1; and, wherein said salts are derived from hydrochloric acid, salicylic acid optionally substituted with alkyl or halogen, D-glucuronic acid, or the sulfonic acid R2SO3H where R2 is alkyl, haloalkyl, hydroxyalkyl, D-10-camphoryl, or phenyl optionally substituted with alkyl or halogen.
Particularly preferred compounds are those where R is 2-ethyl-2H-tetrazol-5-yl; R1 is trifluoromethyl; n is 1; and said salts are derived from hydrochloric acid, or the sulfonic acid R2SO3H where R2 is alkyl, or hydroxyalkyl.
As used in this specification and unless otherwise indicated the term “alkyl” and “alkoxy” used alone or as part of a larger moiety includes 1 to 6 carbon atoms either straight or branched chain. “Alkenyl” refers to 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, either straight or branched chain. “Cycloalkyl” refers to 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms. “Halogen” or “Halo” refer to chlorine, bromine, and fluorine. “HPLC” refers to high pressure liquid chromatography, and “DMSO” refers to dimethyl sulfoxide.
The photostable, agriculturally acceptable acid salts of N-benzyl-4-benzhydrolpiperidines and their corresponding N-oxides of formula I may be prepared by methods described below or by methods similar to those known in the art for similar compounds. In general, the parent N-benzyl-4-benzhydrolpiperidines may be prepared as described in U.S. Pat. No. 5,569,664 by reacting a 4-benzhydrolpiperidine with a benzyl halide. This patent also describes a method for oxidizing the N-benzyl-4-benzhydrolpiperidines by treatment with, for example, 50% 3-chloroperoxybenzoic acid in a suitable solvent, to give the corresponding N-benzyl-4-benzhydrolpiperidine N-oxides. The acid salts of formula I may then be obtained by treatment of an appropriately substituted N-benzyl-4-benzhydrolpiperidine in a solvent with an acid, to give the corresponding acid salts of N-benzyl-4-benzhydrolpiperidine I.
A procedure for a method useful to prepare compounds of this invention is given in the example below.
EXAMPLE Synthesis of N-[4-(2-ethyl-2H-tetrazol-5-yl)phenylmethyl]-4-[bis(4-trifluoro-methylphenyl)hydroxymethyl]piperidine N-oxide ethanesulfonic acid salt (Compound 33)
A suspension of 10.0 grams (0.017 mole) of N-[4-(2-ethyl-2H-tetrazol-5-yl)phenylmethyl]-4-[bis(4-trifluoromethylphenyl)hydroxymethyl]piperidine N-oxide in 10 mL of ethanol was stirred, and 3.0 mL (0.037 mole) of ethanesulfonic acid was added dropwise. Upon completion of addition the reaction mixture was stirred at ambient temperature for about 10 minutes, diluted with 500 mL of diethyl ether, and then stirred for an additional 30 minutes. After this time a white solid was collected by filtration. The solid was washed with diethyl ether and dried at 60 ° C., yielding 10.5 grams of Compound 33, mp 187-193 ° C. The NMR spectrum was consistent with the proposed structure.
Elemental Analyses: C32H35N5O5SF6
Carbon Hydrogen Nitrogen Fluorine
% Theoretical 53.70 4.93 9.79 15.93
% Found 53.46 4.83 9.68 16.20
Table 1 below shows representative compounds of the present invention.
TABLE 1
Figure USH0001996-20011002-C00006
Salt Derived From
R2SO3H or Other Acid
Cmpd. No. R R1 n R2 Acid
 1 CO2CH(CH3)2 OCF3 0 — HCl
 2 CO2CH(CH3)2 OCF3 0 C2H5 —
 3 2-methyl-2H-tetrazol-5-yl CF3 0 — HCl
 4 2-methyl-2H-tetrazol-5-yl OCF3 0 — HCl
 5 2-methyl-2H-tetrazol-5-yl OCF3 0 C2H5 —
 6 2-ethyl-2H-tetrazol-5-yl CF3 0 — HCl
 7 2-ethyl-2H-tetrazol-5-yl CF3 0 C2H5 —
 8 2-ethyl-2H-tetrazol-5-yl OCF3 0 — HCl
 9 2-ethyl-2H-tetrazol-5-yl OCF3 0 C2H5 —
10 2-(2-fluoroethyl)-2H-tetrazol-5-yl OCF3 0 — HCl
11 cyclopropylmethoxy CF3 1 — HCl
12 cyclopropylmethoxy CF3 1 C2H5 —
13 cyclopropylmethoxy CF3 1 C2H4OH —
14 cyclopropylmethoxy CF3 1 — salicylic acid
15 cyclopropylmethoxy CF3 1 — D-glucuronic acid
16 NHCO2CH3 OCF3 1 — HCl
17 NHCO2CH3 OCF3 1 C2H5 —
18 NHCO2CH3 OCF3 1 C2H4OH —
19 NHCO2CH3 OCF3 1 — salicylic acid
20 NHCO2CH3 OCF3 1 — D-glucuronic acid
21 NHCO2CH(CH3)2 CF3 1 — HCl
22 NHCO2CH(CH3)2 CF3 1 C2H5 —
23 NHCO2CH(CH3)2 CF3 1 C2H4OH —
24 NHCO2CH(CH3)2 CF3 1 — salicylic acid
25 NHCO2CH(CH3)2 CF3 1 — D-glucuronic acid
26 2-methyl-2H-tetrazol-5-yl CF3 1 — HCl
27 2-methyl-2H-tetrazol-5-yl CF3 1 C2H5 —
28 2-methyl-2H-tetrazol-5-yl CF3 1 C2H4OH —
29 2-methyl-2H-tetrazol-5-yl CF3 1 — salicylic acid
30 2-methyl-2H-tetrazol-5-yl CF3 1 — D-glucuronic acid
31 2-ethyl-2H-tetrazol-5-yl CF3 1 — HCl
32 2-ethyl-2H-tetrazol-5-yl CF3 1 CH3 —
33 2-ethyl-2H-tetrazol-5-yl CF3 1 C2H5 —
34 2-ethyl-2H-tetrazol-5-yl CF3 1 C5H11 —
35 2-ethyl-2H-tetrazol-5-yl CF3 1 C6H13 —
36 2-ethyl-2H-tetrazol-5-yl CF3 1 CF3 —
37 2-ethyl-2H-tetrazol-5-yl CF3 1 C6H5 —
38 2-ethyl-2H-tetrazol-5-yl CF3 1 4-(CH3)C6H4 —
39 2-ethyl-2H-tetrazol-5-yl CF3 1 2,4,6-(CH3)3C6H2 —
40 2-ethyl-2H-tetrazol-5-yl CF3 1 D-10-camphor —
41 2-ethyl-2H-tetrazol-5-yl CF3 1 C2H4OH —
42 2-ethyl-2H-tetrazol-5-yl CF3 1 — —
43 2-ethyl-2H-tetrazol-5-yl CF3 1 — 5-Cl-salicylic acid
44 2-ethyl-2H-tetrazol-5-yl CF3 1 — D-glucuronic acid
45 2-ethyl-2H-tetrazol-5-yl CF3 0 CH3 —
46 2-ethyl-2H-tetrazol-5-yl CF3 0 — HBr
47 2-ethyl-2H-tetrazol-5-yl CF3 0 4-(CH3)C6H4 —
48 2-ethyl-2H-tetrazol-5-yl CF3 0 — D-glucuronic acid
49 2-ethyl-2H-tetrazol-5-yl CF3 0 C2H4OH —
50 2-ethyl-2H-tetrazol-5-yl CF3 0 — salicylic acid
51 2-ethyl-2H-tetrazol-5-yl CF3 1 — 3-CH3-salicylic acid
52 2-ethyl-2H-tetrazol-5-yl CF3 1 4-ClC6H4 —
53 2-ethyl-2H-tetrazol-5-yl CF3 1 — H3BO3
54 2-ethyl-2H-tetrazol-5-yl CF3 1 — H3PO4
55 2-ethyl-2H-tetrazol-5-yl CF3 1 — maleic acid
56 2-ethyl-2H-tetrazol-5-yl CF3 1 — fumaric acid
57 2-ethyl-2H-tetrazol-5-yl CF3 1 — phthalic acid
Salt Derived From R3CO2H
Cmpd. No. R R1 n R3
58 2-ethyl-2H-tetrazol-5-yl CF3 1 H
59 2-ethyl-2H-tetrazol-5-yl CF3 1 CH3
60 2-ethyl-2H-tetrazol-5-yl CF3 1 CF3
61 2-ethyl-2H-tetrazol-5-yl CF3 1 CO2H
62 2-ethyl-2H-tetrazol-5-yl CF3 1 4-Cl-phenyl
63 2-ethyl-2H-tetrazol-5-yl CF3 1 4-CH3-phenyl
64 2-ethyl-2H-tetrazol-5-yl CF3 1 pyridin-2-yl
Salt Derived From R4B(OH)2
Cmpd. No. R R1 n R4
65 2-ethyl-2H-tetrazol-5-yl CF3 1 CH3
66 2-ethyl-2H-tetrazol-5-yl CF3 1 4-Cl-phenyl
67 2-ethyl-2H-tetrazol-5-yl CF3 1 4-CH3-phenyl
Salt Derived From R5PO3H2
Cmpd. No. R R1 n R5
68 2-ethyl-2H-tetrazol-5-yl CF3 1 CH3
69 2-ethyl-2H-tetrazol-5-yl CF3 1 4-Cl-phenyl
70 2-ethyl-2H-tetrazol-5-yl CF3 1 4-CH3-phenyl
71 2-ethyl-2H-tetrazol-5-yl CF3 1 CH2CF═CF2
Salt Derived From R6OSO3H
Cmpd. No. R R1 n R6
72 2-ethyl-2H-tetrazol-5-yl CF3 1 H
73 2-ethyl-2H-tetrazol-5-yl CF3 1 CH3
Salt Derived From
X-(CH2)qCO2H
Cmpd. No. R R1 n q X
74 2-ethyl-2H-tetrazol-5-yl CF3 1 2 Cl
75 2-ethyl-2H-tetrazol-5-yl CF3 1 2 CF3
76 2-ethyl-2H-tetrazol-5-yl CF3 1 1 CF═CF2
77 2-ethyl-2H-tetrazol-5-yl CF3 1 1 CN
78 2-ethyl-2H-tetrazol-5-yl CF3 1 2 CONH2
Salt Derived From
X-(CH2)qCO2H
Cmpd. No. R R1 n q X R7
79 2-ethyl-2H-tetrazol-5-yl CF3 1 4 CO2R7 H
80 2-ethyl-2H-tetrazol-5-yl CF3 1 8 CO2R7 CH3
TABLE 2
Characterizing Data
Cmpd No Melting Point ° C.
1 SOLID
2 123-128
3 178-185
4 SOLID
5 136-140
6 178-185
7 160-173
8 SOLID
9 126-130
10 112-116
11 171-175
16 160-165
31 214-216
33 187-193
45 82-85
47 138-140
50 75-77
PHOTOSTABILITY TESTING
Compounds of the present invention were subjected to determinations of their photostability in side-by-side tests with their non-ionic parent analogs. These photostability tests are conducted as follows:
For each compound tested, four glass microscope coverslips (12 mm in diameter) for each illumination period (0, 3, 6, 12, 24, 48, and 96 hours) are spotted with 10 microliters of a one mg/mL acetonitrile or methanol solution of test compound. The solutions are allowed to evaporate leaving a thin film of test compound on each coverslip. The four coverslips representing the zero hour illumination period are placed in a 20 mL scintillation vial. In the vile is placed one mL of acetonitrile, which extracts the test chemical from the coverslip. The solution is then transferred to a two dram vile for analysis by HPLC. The average HPLC peak area generated by this sample defines the initial level of test compound. The remaining coverslips are then placed in the water-cooled chamber of the exposure platform of a Suntest CPS illuminator (Heraeus Instruments GmbH; Bereich Original Hanau, Hersaeusstrasse R-14, Postfach 1563, D-6450 Hanau 1). The exposure platform is covered with a quartz plate and maintained at about 25° C. for the duration of the test. The Suntest CPS illuminator employs a filtered xenon lamp, which provides illumination of a similar spectrum and intensity as sunlight. Four coverslips for each test compound are removed from the illuminator at the end of each illumination period described above. The four coverslips from each of the illumination periods are treated as described above and the acetonitrile extract is analyzed by HPLC. The average HPLC peak area from each of the illumination periods represents a diminished amount of test compound when compared to the initial level of test compound as determined from the zero hour illumination sample. The percents of test compound remaining from each of these illumination periods are used to generate a degradation curve from which a half life in hours is determined for each test compound.
Table 3 shows the improved photostability of representative compounds of the present invention when compared to the photostability of their non-ionic amino parent. The test compounds are identified by numbers which correspond to those in Table 1.
Photostability Data
Compound Number Half-life (Hrs)
 7 23.0
A* 5.5
33 34.0
B* 13.9
*A is the non-ionic amino parent of Cmpd. 7
*B is the non-ionic amino N-oxide parent of Cmpd. 33
Representative compounds of the present invention were shown to be about 2.5 to 4 times more photostable than their non-ionic parents in the tests conducted.
BIOLOGICAL TESTING
Candidate insecticides are evaluated for activity against tobacco budworm (Heliothis virescens [Fabricius]) by applications to the surface of a wheat germ-based artificial insect diet. Solutions of the candidate insecticides are prepared for testing by diluting a standard 50 millimolar DMSO solution of each candidate insecticide with DMSO, then further diluting with a 1:1 water/acetone solution (V/V). Forty microliters of this solution of calculated concentration is then pipetted onto the surface of the diet in each of six containers, to provide six replicates for each rate of application. Once treated, the contents of the containers are allowed to dry, leaving the calculated concentration ( in millimoles) of candidate insecticide on the surface of the diet. In each container is placed one second instar tobacco budworm larvea. The container is sealed with a transparent film, and then held in a growth chamber for five days. After the five-day exposure period the insecticidal activity of the candidate insecticide is recorded as percent mortality when compared to the total number of insects infested.
It is expected that all formulations normally employed in applications of insecticides would be usable with the compounds of the present invention. These include wettable powders, emulsifiable concentrates, suspension concentrates, water suspensions, flowable concentrates, and the like.
Insecticidal activity at a concentration of candidate insecticide of 0.0025 millimoles on the surface of the diet is given for various compounds of this invention in Table 4.
Insecticidal Activity of Candidate Insecticide Applied
to the Surface of the Diet of Tobacco Budworm
Cmpd. No
1 2 3 4 5 6 7 8
Percent 100 100 100 100 100 100 100 100
Mortality
Cmpd. No
9 10 11 16 31 33 A* B*
Percent 100 100 100 100 100 100 100
Mortality
*A is the non-ionic amino parent of Cmpd. 7
*B is the non-ionic amino N-oxide parent of Cmpd. 33
For insecticidal application, the active compounds are formulated into insecticidal compositions by admixture in insecticidally effective amount with adjuvants and carriers normally employed in the art for facilitating the dispersion of active ingredients for the particular utility desired, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the material in a given application. Thus, for agricultural use the present insecticidal compounds may be formulated as granules of relatively large particle size, as water-soluble or water-dispersible granules, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, or as any of several other known types of formulations, depending on the desired mode of application.
These insecticidal compositions may be applied either as water-diluted sprays, or dusts, or granules to the areas in which insect control is desired. These formulations may contain as little as 0.1%, 0.2% or 0.5% to as much as 95% or more by weight of active ingredient.
Dusts are free flowing admixtures of the active ingredients with finely divided solids such as talc, natural clays, kieselguhr, flours such as walnut shell and cottonseed flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant; these finely divided solids have an average particle size of less than about 50 microns. A typical dust formulation useful herein is one containing 1.0 part or less of the insecticidal compound and 99.0 parts of talc.
Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersant. The wettable powder is ultimately applied to the locus where insect control is desired either as a dry dust or as an emulsion in water or other liquid. Typical carriers for wettable powders include Fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wet, inorganic diluents. Wettable powders normally are prepared to contain about 5-80% of active ingredient, depending on the absorbency of the carrier, and usually also contain a small amount of a wetting, dispersing, or emulsifying agent to facilitate dispersion. For example, a useful wettable powder formulation contains 80.8 parts of the insecticidal compound, 17.9 parts of Palmetto clay, and 1.0 part of sodium lignosulfonate and 0.3 part of sulfonated aliphatic polyester as wetting agents.
Other useful formulations for insecticidal applications are emulsifiable concentrates (ECs) which are homogeneous liquid compositions dispersible in water or other dispersant, and may consist entirely of the insecticidal compound and a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone, or other non-volatile organic solvent. For insecticidal application these concentrates are dispersed in water or other liquid carrier, and normally applied as a spray to the area to be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises 0.5 to 95% of active ingredient by weight of the insecticidal composition.
Suspension Concentrates (SCs) are similar to ECs except that the active ingredient is suspended in a liquid carrier, generally water. SCs, like ECs, may include a small amount of a surfactant, and contain active ingredient in the range of 0.5 to 95%, frequently from 5 to 50%, by weight of the composition. For application, SCs may be diluted in water or other liquid vehicle, and are normally applied as a spray to the area to be treated.
Typical wetting, dispersing, or emulsifying agents used in agricultural formulations include, but are not limited to, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; alkylaryl polyether alcohols; sulfated higher alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition product of long-chain mercaptans and ethylene oxide. Many other types of useful surface-active agents are available in commerce. The surface-active agents, when used, normally comprise from 1 to 15% by weight of the composition.
Other useful formulations include suspensions of the active ingredient in a relatively non-volatile solvent such as corn oil, kerosene, propylene glycol, or other suitable solvents.
Still other useful formulations for insecticidal applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene, or other organic solvents. Granular formulations, wherein the toxicant is carried on relatively coarse particles, are of particular utility for aerial distribution or for penetration of cover crop canopy. Pressurized sprays, typically aerosols wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as carbon dioxide, propane, or butane, may also be used. Water-soluble or water-dispersible granules are also useful formulations for insecticidal application of the present compounds. Such granular formulations are free-flowing, non-dusty, and readily water-soluble or water-miscible. The soluble or dispersible granular formulations described in U.S. Pat. No. 3,920,442 are useful herein with the present insecticidal compounds. In use by the farmer on the field, the granular formulations, emulsifiable concentrates, flowable concentrates, solutions, etc., may be diluted with water to give a concentration of active ingredient in the range of say 0.1% or 0.2% to 1.5% or 2%.
The active insecticidal compounds of this invention may be formulated and/or applied with other insecticides, fungicides, nematicides, plant growth regulators, fertilizers, or other agricultural chemicals. In using an active compound of this invention, whether formulated alone or with other agricultural chemicals, to control insects, an effective amount and concentration of the active compound is applied to the locus where control is desired. The locus may be, e.g., the insects themselves, plants upon which the insects feed, or the insect habitat. When the locus is the soil, e.g., soil in which agricultural crops have been or will be planted, the composition of the active compound may be applied to and optionally incorporated into the soil. For most applications the effective amount may be as low as, e.g. about 10 to 500 g/ha, preferably about 100 to 250 g/ha.
It is apparent that various modifications may be made in the formulation and application of the compounds of this invention without departing from the inventive concepts herein as defined in the claims

Claims (18)

We claim:
1. An insecticidal, photostable, agriculturally acceptable acid salt of an organic or inorganic acid having the formula:
Figure USH0001996-20011002-C00007
where
R is alkoxycarbonyl, alkoxycarbonylamino, cycloalkylalkoxy, 2-alkyl-2H-tetrazol-5-yl, or 2-haloalkyl-2H-tetrazol-5-yl;
R1 is trihaloalkyl, or trihaloalkoxy;
n is 0,or 1; and,
wherein said salt is at least about 2.5 times more photostable than its non-ionic parent and is derived from hydrochloric acid, hydrobromic acid, boric acid, phosphoric acid, maleic acid, fumaric acid, phthalic acid, D-glucuronic acid; the sulfonic acid R2SO3H where R2 is alkyl, haloalkyl, hydroxyalkyl, D-10-camphoryl, or phenyl optionally substituted with alkyl or halogen; the carboxylic acid R3CO2H where R3 is hydrogen, alkyl, trihaloalkyl, carboxyl, phenyl optionally substituted with alkyl or halogen, or pyridyl; the boronic acid R4B(OH)2 where R4 is alkyl or phenyl optionally substituted with alkyl or halogen; the phosphonic acid R5PO3H2 where R5 is alkyl, haloalkenyl, or phenyl optionally substituted with alkyl or halogen: the sulfuric acid R6OSO3H where R6 is hydrogen or alkyl; or the alkanoic acid X-(CH2)qCO2H where q is 0 to 11, X is halogen, trihaloalkyl, haloalkenyl, cyano, aminocarbonyl, or CO2R7 where R7 is hydrogen or alkyl; and
wherein further, the following terms whether used alone or as part of a larger moiety refer to the associated number of carbon atoms: (1) “alkyl” or “alkoxy” refers to 1 to 6 carbon atoms, (2) “alkenyl” refers to 2 to 12 carbon atoms; and (3) “cycloalkyl” refers to 3 to 8 carbon atoms.
2. The acid salt of claim 1 where R is alkoxycarbonyl, alkoxycarbonylamino, cycloalkylalkoxy, 2-alkyl-2H-tetrazol-5-yl, or 2-haloalkyl-2H-tetrazol-5-yl;
R1 is trihaloalkyl, or trihaloalkoxy;
n is 0, or 1; and,
wherein said salt is derived from D-glucuronic acid, or the sulfonic acid R2SO3H where R2 is alkyl, haloalkyl, hydroxyalkyl, D-10-camphoryl, or phenyl optionally substituted with alkyl or halogen.
3. The acid salt of claim 1 where R is 2-ethyl-2H-tetrazol-5-yl; R1 is trifluoromethyl; n is 1; and said salt is derived from the sulfonic acid R2SO3H where R2 is alkyl, or hydroxyalkyl.
4. An insecticidal composition comprising an insecticidally effective amount of an acid salt of claim 1, and an insecticidally compatible carrier.
5. An insecticidal composition comprising an insecticidally effective amount of an acid salt of claim 2, and an insecticidally compatible carrier.
6. An insecticidal composition comprising an insecticidally effective amount of an acid salt of claim 3, and an insecticidally compatible carrier.
7. A method of controlling insects, comprising application of an insecticidally effective amount of a composition of claim 4 to a locus where insect control is desired.
8. A method of controlling insects, comprising application of an insecticidally effective amount of a composition of claim 5 to a locus where insect control is desired.
9. A method of controlling insects, comprising application of an insecticidally effective amount of a composition of claim 6 to a locus where insect control is desired.
10. An insecticidal, photostable, agriculturally acceptable salt of an organic or inorganic acid having the formula:
Figure USH0001996-20011002-C00008
wherein the acid employed to form said salt, and n, q, X, R, R1, R2, R3, R4, R5, R6, and R7 are as set forth in the following table:
Photostable N-Benzyl-4-benzhydrol- piperidine Salt Derived From The Sulfonic Acid R2SO3H or Other Acid, Wherein: Cmpd. No. is R is R1 is n is R2 is Other Acid is 1 CO2CH(CH3)2 OCF3 0 — HCl 2 CO2CH(CH3)2 OCF3 0 C2H5 — 3 2-methyl-2H-tetrazol-5-yl CF3 0 — HCl 4 2-methyl-2H-tetrazol-5-yl OCF3 0 — HCl 5 2-methyl-2H-tetrazol-5-yl OCF3 0 C2H5 — 6 2-ethyl-2H-tetrazol-5-yl CF3 0 — HCl 7 2-ethyl-2H-tetrazol-5-yl CF3 0 C2H5 — 8 2-ethyl-2H-tetrazol-5-yl OCF3 0 — HCl 9 2-ethyl-2H-tetrazol-5-yl OCF3 0 C2H5 — 10 2-(2-fluoroethyl-2H-tetrazol-5-yl OCF3 0 — HCl 11 Cyclopropylmethoxy CF3 1 — HCl 12 Cyclopropylmethoxy CF3 1 C2H5 — 13 Cyclopropylmethoxy CF3 1 C2H4OH — 15 Cyclopropylmethoxy CF3 1 — D-glucuronic acid 16 NHCO2CH3 OCF3 1 — HCl 17 NHCO2CH3 OCF3 1 C2H5 — 18 NHCO2CH3 OCF3 1 C2H4OH — 20 NHCO2CH3 OCF3 1 — D-glucuronic acid 21 NHCO2CH(CH3)2 CF3 1 — HCl 22 NHCO2CH(CH3)2 CF3 1 C2H5 — 23 NHCO2CH(CH3)2 CF3 1 C2H4OH — 25 NHCO2CH(CH3)2 CF3 1 — D-glucuronic acid 26 2-methyl-2H-tetrazol-5-yl CF3 0 — HCl 27 2-methyl-2H-tetrazol-5-yl CF3 0 C2H5 — 28 2-methyl-2H-tetrazol-5-yl CF3 0 C2H4OH — 30 2-methyl-2H-tetrazol-5-yl CF3 1 — D-glucuronic acid 31 2-ethyl-2H-tetrazol-5-yl CF3 1 — HCl 32 2-ethyl-2H-tetrazol-5-yl CF3 1 CH3 — 33 2-ethyl-2H-tetrazol-5-yl CF3 1 C2H5 — 34 2-ethyl-2H-tetrazol-5-yl CF3 1 C5H11 — 35 2-ethyl-2H-tetrazol-5-yl CF3 1 C6H11 — 36 2-ethyl-2H-tetrazol-5-yl CF3 1 CF3 — 37 2-ethyl-2H-tetrazol-5-yl CF3 1 C6H5 — 38 2-ethyl-2H-tetrazol-5-yl CF3 1 4-(CH3)C6H4 — 39 2-ethyl-2H-tetrazol-5-yl CF3 1 2,4,6-(CH3)3C6H2 — 40 2-ethyl-2H-tetrazol-5-yl CF3 1 D-10-camphor — 41 2-ethyl-2H-tetrazol-5-yl CF3 1 C2H4OH — 44 2-ethyl-2H-tetrazol-5-yl CF3 1 — D-glucuronic acid 45 2-ethyl-2H-tetrazol-5-yl CF3 0 CH3 — 46 2-ethyl-2H-tetrazol-5-yl CF3 0 — HBr 47 2-ethyl-2H-tetrazol-5-yl CF3 0 4-(CH3)C6H4 — 48 2-ethyl-2H-tetrazol-5-yl CF3 0 — D-glucuronic acid 49 2-ethyl-2H-tetrazol-5-yl CF3 0 C2H4OH — 52 2-ethyl-2H-tetrazol-5-yl CF3 1 4-ClC6H4 — 53 2-ethyl-2H-tetrazol-5-yl CF3 1 — H3BO3 54 2-ethyl-2H-tetrazol-5-yl CF3 1 — H3PO4 55 2-ethyl-2H-tetrazol-5-yl CF3 1 — maleic acid 56 2-ethyl-2H-tetrazol-5-yl CF3 1 — fumaric acid 57 2-ethyl-2H-tetrazol-5-yl CF3 1 — phthalic acid Photostable N-Benzyl-4-benzhydrol- piperidine Salt Derived From The Carboxilic Acid R3CO2H, Wherein: Cmpd. No. is R is R1 is n is R3 is 58 2-ethyl-2H-tetrazol-5-yl CF3 1 H 59 2-ethyl-2H-tetrazol-5-yl CF3 1 CH3 60 2-ethyl-2H-tetrazol-5-yl CF3 1 CF3 61 2-ethyl-2H-tetrazol-5-yl CF3 1 CO2H 62 2-ethyl-2H-tetrazol-5-yl CF3 1 4-Cl-phenyl 63 2-ethyl-2H-tetrazol-5-yl CF3 1 4-CH3-phenyl 64 2-ethyl-2H-tetrazol-5-yl CF3 1 pyridin-2-yl 65 2-ethyl-2H-tetrazol-5-yl CF3 1 CH3 66 2-ethyl-2H-tetrazol-5-yl CF3 1 4-Cl-phenyl 67 2-ethyl-2H-tetrazol-5-yl CF3 1 4-CH3-phenyl Photostable N-Benzyl-4-benzhydrol- piperidine Salt Derived From The Phosphonic Acid R5PO3H2, Wherein: Cmpd. No. is R is R1 is n is R5 is 68 2-ethyl-2H-tetrazol-5-yl CF3 1 CH3 69 2-ethyl-2H-tetrazol-5-yl CF3 1 4-Cl-phenyl 70 2-ethyl-2H-tetrazol-5-yl CF3 1 4-CH3-phenyl 71 2-ethyl-2H-tetrazol-5-yl CF3 1 CH2CF═CF2 Photostable N-Benzyl-4-benzhydrol- piperidine Salt Derived From The Sulfuric Acid R6OSO3H, Wherein: Cmpd. No. is R is R1 is n is R6 is 72 2-ethyl-2H-tetrazol-5-yl CF3 1 H 73 2-ethyl-2H-tetrazol-5-yl CF3 1 CH3 Photostable N-Benzyl-4-benzhydrol- piperidine Salt Derived From The Alkanoic Acid X—(CH2)qCO2H, Wherein: Cmpd. No. is R is R1 is n is q is X is R7 is 74 2-ethyl-2H-tetrazol-5-yl CF3 1 2 Cl — 75 2-ethyl-2H-tetrazol-5-yl CF3 1 2 CF3 — 76 2-ethyl-2H-tetrazol-5-yl CF3 1 1 CF═CF2 — 77 2-ethyl-2H-tetrazol-5-yl CF3 1 1 CN — 78 2-ethyl-2H-tetrazol-5-yl CF3 1 2 CONH2 — 79 2-ethyl-2H-tetrazol-5-yl CF3 1 4 CO2R7 H 80 2-ethyl-2H-tetrazol-5-yl CF3 1 8 CO2R7 CH3;
and wherein said salt is at least about 2.5 times more photostable than its non-ionic parent.
11. An insecticidal composition comprising an insecticidally effective amount of an acid salt of claim 10, and an insecticidally compatible carrier.
12. A method of controlling insects, comprising application of an insecticidally effective amount of a composition of claim 10 to a locus where insect control is desired.
13. A method for enhancing the photostability of a N-benzyl-4-benzhydrolpiperidine or its corresponding N-oxide, comprising forming said piperidine or N-oxide as an agriculturally acceptable organic or inorganic acid salt, with the proviso that salts formed with salicylic acid, 5-chlorosalicylic acid, or 3,5-dichlorosalicylic acid are excluded.
14. The method of claim 13, wherein said piperidine or N-oxide thereof have the formula
Figure USH0001996-20011002-C00009
where R is alkoxycarbonyl, alkoxycarbonylamino, cycloalkylalkoxy, 2-alkyl-2H-tetrazol-5-yl, or 2-haloalkyl-2H-tetrazol-5-yl; R1 is trihaloalkyl, or trihaloalkoxy; and n is 0, or 1.
15. The method of claim 14, wherein R is 2-ethyl-2H-tetrazol-5-yl; R1 is trifluoromethyl; and n is 1.
16. The method of claim 13, wherein said salt is derived from hydrochloric acid, hydrobromic acid, boric acid, phosphoric acid, maleic acid, fumaric acid, phthalic acid, D-glucuronic acid; the sulfonic acid R2SO3H where R2 is alkyl, haloalkyl, hydroxyalkyl, D-10-camphoryl, or phenyl optionally substituted with alkyl or halogen; the carboxylic acid R3CO2H where R3 is hydrogen, alkyl, trihaloalkyl, carboxyl, phenyl optionally substituted with alkyl or halogen, or pyridyl; the boronic acid R4B(OH)2 where R4 is alkyl or phenyl optionally substituted with alkyl or halogen; the phosphonic acid R5PO3H2 where R5 is alkyl, haloalkenyl, or phenyl optionally substituted with alkyl or halogen: the sulfuric acid R6OSO3H where R6 is hydrogen or alkyl; or the alkanoic acid X-(CH2)qCO2H where q is 0 to 11, X is halogen, trihaloalkyl, haloalkenyl, cyano, amino-carbonyl, or CO2R7 where R7 is hydrogen or alkyl.
17. The method of claim 16, wherein said salt is derived from hydrochloric acid, D-glucuronic acid, or the sulfonic acid wherein R2 is alkyl, haloalkyl, hydroxyalkyl, D-10-camphoryl, or phenyl optionally substituted with alkyl or halogen.
18. The method of claim 13, wherein R is 2-ethyl-2H-tetrazol-5-yl; R1 is trifluoromethyl; n is 1; and said salts are derived from hydrochloric acid, D-glucuronic acid, or the sulfonic acid wherein R2 is alkyl or hydroxyalkyl.
US09/196,880 1997-11-20 1998-11-20 Insecticidal photostable acid salt derivatives of N-benzyl-4-benzhydrolpiperidines Abandoned USH1996H1 (en)

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US5569664A (en) * 1995-02-16 1996-10-29 Fmc Corporation Insecticidal n-(substituted arylmethyl)-4-[bis(substituted phenyl) methyl]pi
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US5639763A (en) * 1994-03-01 1997-06-17 Fmc Corporation Insecticidal N-(substituted arylmethyl)-4-[bis(substituted phenyl)methyl]piperidines
US5569664A (en) * 1995-02-16 1996-10-29 Fmc Corporation Insecticidal n-(substituted arylmethyl)-4-[bis(substituted phenyl) methyl]pi
WO1996036228A1 (en) 1995-05-19 1996-11-21 Fmc Corporation Insecticidal n-(substituted arylmethyl)-4-[bis(substituted phenyl or pyridyl)methyl]piperidines
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