# US 6,720,450 B2 · Pesticidal activity of functionalized cyclopropanes > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 6,720,450 B2 - Document ID: US6720450B2 - Status: Granted - Kind: B2 - Application number: 10/020,835 - Filed: 2001-12-13 - Published: 2003-08-07 - Granted: 2004-04-13 - Earliest claimed: 2001-12-13 - Assignees: North Carolina State University - Inventors: Russell J. Linderman - Web page: https://patentgrep.com/patent/US6720450B2 ## CPC - C07C 57/46: containing six-membered aromatic rings and other rings, e.g. cyclohexylphenylacetic acid - A01N 37/10: Aromatic or araliphatic carboxylic acids, or thio analogues thereof; Derivatives thereof - A01N 37/18: containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof - C07C 51/09: from carboxylic acid esters or lactones - C07C 51/353: by isomerisation; by change of size of the carbon skeleton - C07C 51/36: by hydrogenation of carbon-to-carbon unsaturated bonds - C07C 51/38: by decarboxylation - C07C 53/132: containing rings - C07C 53/134: monocyclic - C07C 57/26: containing rings other than six-membered aromatic rings - C07C 57/42: having unsaturation outside the rings - C07C 2601/02: with a three-membered ring - C07C 2601/14: The ring being saturated - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - A01N: PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF (preservation of food or foodstuff A23); BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES (preparations for medical, dental or toiletry purposes which kill or prevent the growth or proliferation of unwanted organisms A61K); PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS ## Abstract The present invention provides functionalized cyclopropane compounds that have pesticidal and/or TMOF activity. The pesticidal compounds and other compounds of the present invention are usefully employed in the control of pests, particularly insect pests such as mosquitoes, which ingest blood. ## Claims ### Claim 1 A method for controlling an insect pest, comprising administering to said insect pest an insect pest-controlling effective amount of a compound selected from the group consisting of compounds of formula I, and salt, acid and ester forms thereof: wherein: X is cyclopropyl; Z is selected from the group consisting of —OH, —NH2, —NHR6 and —OR6 wherein R6 is C1-C6 alkyl, alkenyl, optionally substituted cycloalkylalkyl, and optionally substituted aralkyl; m≧0 and n≧1 and (m+n) can have any integer value from 1 to 12 inclusive; the ring bearing substituents R1, R2, R3, R4 and R5 is a phenyl ring or a cyclohexyl ring, or a corresponding ring wherein one or more ring carbon atom(s) has been replaced by nitrogen atom(s); R1, R2, R3, R4, and R5 are each independently selected from the group consisting of—H, —OH, halo, C1-C6 alkyl, C1-C6 alkoxy, nitro, amino, and phenyl; subject to the proviso that: when the ring is a phenyl ring, a pair of R1 and R2, R2 and R3, or R3 and R4 on the phenyl ring may together represent —CR7═CR8-CR9═CR10−, to form with the phenyl ring illustrated above a naphthyl ring system, wherein R7, R8, R9, and R10 are each independently selected from the group consisting of —H, —OH, halo, nitro, amino, C1-C6 alkyl, and C1-C6 alkoxy. ### Claim 2 (depends on 1) A method according to claim 1, wherein said compound of Formula I has the formula ### Claim 3 (depends on 1) The method according to claim 1, wherein said compound of Formula I has the formula: ### Claim 4 (depends on 1) The method according to claim 1, wherein said compound of Formula I has the formula: where Ph is phenyl. ### Claim 5 (depends on 1) A method according to claim 1, wherein R1 is selected from the group consisting of hydroxy, bromo, fluoro, methyl, methoxy, propoxy, and ethoxy. ### Claim 6 (depends on 1) A method according to claim 1, wherein R1 is selected from the group consisting of bromo and propoxy. ### Claim 7 (depends on 1) A method according to claim 1, wherein Z is OH. ### Claim 8 (depends on 1) A method according to claim 1, wherein Z is NH2. ### Claim 9 (depends on 1) A method according to claim 1, wherein m is 2 to 12. ### Claim 10 (depends on 1) A method according to claim 1, wherein m is 3 to 10. ### Claim 11 (depends on 1) A method according to claim 1, wherein m is 4 to 8. ### Claim 12 (depends on 1) A method according to claim 1, wherein m is 4 to 6. ### Claim 13 (depends on 1) The method according to claim 1, wherein n is 2 to 12. ### Claim 14 (depends on 1) A method according to claim 1, wherein n is 3 to 10. ### Claim 15 (depends on 1) A method according to claim 1, wherein n is 4 to 8. ### Claim 16 (depends on 1) A method according to claim 1, wherein n is 4 to 6. ### Claim 17 (depends on 1) A method according to claim 1, wherein R2 is H. ### Claim 18 (depends on 1) A method according to claim 1, wherein R3 is H. ### Claim 19 (depends on 1) A method according to claim 1, wherein R5 is H. ### Claim 20 (depends on 1) A method according to claim 1, wherein R2 and R3 are both H. ### Claim 21 (depends on 1) A method according to claim 1, wherein R2 and R5 are both H. ### Claim 22 (depends on 1) A method according to claim 1, wherein R3 and R5 are both H. ### Claim 23 (depends on 1) A method according to claim 1, wherein R2, R3 and R5 are all H. ### Claim 24 (depends on 1) A method according to claim 1, wherein R1 is a halogen. ### Claim 25 (depends on 1) A method according to claim 1, wherein R3 is a halogen. ### Claim 26 (depends on 1) A method according to claim 1, wherein R1 is an C1—C6 alkoxy. ### Claim 27 (depends on 1) A method according to claim 1, wherein R3 is C1-C6 alkoxy. ### Claim 28 (depends on 1) A method according to claim 1, wherein R1 and R3 are both a halogen. ### Claim 29 (depends on 1) A method according to claim 1, wherein R1 and R3 are both an C1—C6 alkoxy. ### Claim 30 (depends on 1) A method according to claim 1, wherein said pest is an insect selected from the group consisting of coleopterans, lepidopterans, and dipterans. ### Claim 31 (depends on 1) A method according to claim 1, wherein said pest is a blood-sucking insect. ### Claim 32 (depends on 1) A method according to claim 1, wherein said pest is an insect of the suborder Nematocera. ### Claim 33 (depends on 1) A method according to claim 1, wherein said pest is an insect of the family Colicidae. ### Claim 34 (depends on 1) A method according to claim 1, wherein said pest is an insect of a subfamily selected from the group consisting of Culicinae, Corethrinae, Ceratopogonidae and Simuliidae. ### Claim 35 (depends on 1) A method according to claim 1, wherein said pest is an insect of a genus selected from the group consisting of Culex, Theobaldia, Aedes, Anopheles, Aedes, Forciponiyia, Culicoides and Helea. ### Claim 36 (depends on 1) A method according to claim 1, wherein said pest is an insect species selected from the group consisting of: Aedes aegypti, Culex quinquefasciatus, Anopheles albimanus, Anopheles quadrimaculatus, Lutzomyia ant hrophora, Culicoides variipennis, Stomoxys calcitrans, Musca domestica, Ctenocephalidesfeliz, and Heliothis virescens. ### Claim 37 (depends on 1) A method according to claim 1, wherein said pest is selected from the group consisting of flies, fleas, ticks, and lice. ### Claim 38 (depends on 1) A method according to claim 1, wherein said pest is a mosquito. ### Claim 39 (depends on 1) A method according to claim 1, wherein said pest is selected from the group consisting of beetles, caterpillars, and mites. ### Claim 40 (depends on 1) A method according to claim 1, wherein said pest is selected from the group consisting of ants and cockroaches. ### Claim 41 A method of initiating a TMOF receptor-mediated biological response, comprising contacting to a TMOF receptor in vivo or in vitro for a time and in an amount sufficient to initiate a TMOF receptor-mediated biological response a compound selected from the group consisting of compounds of formula I, and salt, acid and ester forms thereof: wherein: X is cyclopropyl; Z is selected from the group consisting of —OH, —NH2, —NHR6 and —OR6 wherein R6 is C1-C6 alkyl, alkenyl, optionally substituted cycloalkylalkyl, and optionally substituted aralkyl; m≧0 and n≧1 and (m+n) can have any integer value from 1 to 12 inclusive; the ring bearing substituents R1, R2, R3, R4 and R5 is a phenyl ring or a cyclohexyl ring, or a corresponding ring wherein one or more ring carbon atom(s) has been replaced by nitrogen atom(s); R1, R2, R3, R4, and R5 are each independently selected from the group consisting of—H, —OH, halo, C1-C6 alkyl, C1-C6 alkoxy, nitro, amino, and phenyl; subject to the proviso that: when the ring is a phenyl ring, a pair of R1 and R2, R2 and R3, or R3 and R4 on the phenyl ring may together represent —CR7═CR8-CR9═CR10—, to form with the phenyl ring illustrated above a naphthyl ring system, wherein R7, R8, R9, and R10 are each independently selected from the group consisting of —H, —OH, halo, nitro, amino, C1-C6 alkyl, and C1-C6 alkoxy. ### Claim 42 (depends on 41) A method according to claim 41, wherein said compound of Formula I has the formula ### Claim 43 The method according to claim wherein said compound of Formula I has the formula: ### Claim 44 (depends on 41) The method according to claim 41, wherein said compound of Formula I has the formula: where Ph is phenyl. ### Claim 45 (depends on 41) A method according to claim 41, wherein said biological response is inhibition of biosynthesis of trypsin. ### Claim 46 (depends on 41) A method according to claim 41, wherein said contacting step is carried out in vivo in an insect pest. ### Claim 47 A pest control composition comprising a pesticidal carrier and a pesticidal compound selected from the group consisting of compounds of formula I, and salt, acid and ester forms thereof: wherein: X is cyclopropyl; Z is selected from the group consisting of —OH, —NH2, —NHR6 and —OR6 wherein R6 is C1-C6 alkyl, alkenyl, optionally substituted cycloalkylalkyl, and optionally substituted aralkyl; m≧0 and n≧1 and (m+n) can have any integer value from 1 to 12 inclusive; the ring bearing substituents R1, R2, R3, R4 and R5 is a phenyl ring or a cyclohexyl ring, or a corresponding ring wherein one or more ring carbon atom(s) has been replaced by nitrogen atom(s); R1, R2, R3, R4, and R5 are each independently selected from the group consisting of —H, —OH, halo, C1-C6 alkyl, C1-C6 alkoxy, nitro, amino, and phenyl; subject to the proviso that: when the ring is a phenyl ring, a pair of R1 and R2, R2 and R3, or R3 and R4 on the phenyl ring may together represent —CR7═CR8-CR9═CR10—, to form with the phenyl ring illustrated above a naphthyl ring system, wherein R7, R8, R9, and R10 are each independently selected from the group consisting of —H, —OH, halo, nitro, amino, C1-C6 alkyl and C1-C6 alkoxy. ### Claim 48 (depends on 47) A composition according to claim 47, herein said composition is a liquid composition, and wherein said liquid composition is selected from the group consisting of aqueous compositions nonaqueous compositions, and combinations thereof. ### Claim 49 (depends on 43) A composition according to claim 43, wherein said pesticidal carrier is included in said composition in an amount from 0.1% to 99.9999% by weight. ### Claim 50 (depends on 43) A composition according to claim 43, wherein said pesticidal carrier comprises an aqueous solution. ### Claim 51 A composition according to 43, wherein said pesticidal carrier comprises an emulsion. ### Claim 52 (depends on 47) A composition according to claim 47, wherein said composition is a bait granule. ### Claim 53 (depends on 47) A composition according to claim 47, wherein said compound of Formula I has the formula ### Claim 54 (depends on 47) A composition according to claim 47, wherein said compound of Formula I has the formula: ### Claim 55 (depends on 47) The composition according to claim 47, wherein said compound of Formula I has the formula: where Ph is phenyl. ### Claim 56 A compound selected from the group consisting of compounds of formula I, and salt, acid and ester forms thereof: wherein: X is cyclopropyl; Z is selected from the group consisting of —OH, —NH2, —NHR6 and —OR6 wherein R6 is C1-C6 alkyl, alkenyl, optionally substituted cycloalkylalkyl, and optionally substituted aralkyl; m≧0 and n≧1 and together total an integer from 1 to 12; the ring bearing substituents R1, R2, R3, R4 and R5 is a phenyl ring or a cyclohexyl ring, or a corresponding ring wherein one or more ring carbon atom(s) has been replaced by nitrogen atom(s); R1, R2, R3, R4, and R5 are each independently selected from the group consisting of —H, —OH, halo, C1-C6 alkyl, C1-C6 alkoxy, nitro, amino, and phenyl; subject to the proviso that: when the ring is a phenyl ring, a pair of R1 and R2, R2 and R3, or R3 and R4 on the phenyl ring may together represent —CR7═CR8-CR9═CR10—, to form with the phenyl ring illustrated above a naphthyl ring system, wherein R7, R8, R9, and R10 are each independently selected from the group consisting of —H, —OH, halo, nitro, amino, C1-C6 alkyl, and C1-C6 alkoxy. ### Claim 57 (depends on 56) The compound according to claim 56, wherein said compound of Formula I has the formula ### Claim 58 (depends on 56) The compound according to claim 56, wherein said compound of Formula I has the formula: ### Claim 59 (depends on 56) The compound according to claim 56, wherein said compound of Formula I has the formula: where Ph is phenyl. ### Claim 60 (depends on 56) The compound according to claim 56, wherein R1 is selected from the group consisting of hydroxy, bromo, fluoro, methyl, methoxy, propoxy, and ethoxy. ### Claim 61 (depends on 56) The compound according to claim 56, wherein R1 is selected from the group consisting of bromo and propoxy. ### Claim 62 (depends on 56) The compound according to claim 56, wherein Z is OH. ### Claim 63 (depends on 56) The compound according to claim 56, wherein Z is NH2. ### Claim 64 (depends on 56) The compound according to claim 56, wherein m is 2 to 12. ### Claim 65 (depends on 56) The compound according to claim 56, wherein m is 3 to 10. ### Claim 66 (depends on 56) The compound according to claim 56, wherein m is 4 to 8. ### Claim 67 (depends on 56) The compound according to claim 56, wherein m is 4 to 6. ### Claim 68 (depends on 56) The compound according to claim 56, wherein n is 2 to 12. ### Claim 69 (depends on 56) The compound according to claim 56, wherein n is 3 to 10. ### Claim 70 (depends on 56) The compound according to claim 56, wherein n is 4 to 8. ### Claim 71 (depends on 56) The compound according to claim 56, wherein n is 4 to 6. ### Claim 72 (depends on 56) The compound according to claim 56, wherein R2 is H. ### Claim 73 (depends on 56) The compound according to claim 56, wherein R3 is H. ### Claim 74 (depends on 56) The compound according to claim 56, wherein R5 is H. ### Claim 75 (depends on 56) The compound according to claim 56, wherein R2 and R3 are both H. ### Claim 76 (depends on 56) The compound according to claim 56, wherein R2 and R5 are both H. ### Claim 77 (depends on 56) The compound according to claim 56, wherein R3 and R5 are both H. ### Claim 78 (depends on 56) The compound according to claim 56, wherein R2, R3 and R5 are all H. ### Claim 79 (depends on 56) The compound according to claim 56, wherein R1 is a halogen. ### Claim 80 (depends on 56) The compound according to claim 56, wherein R3 is a halogen. ### Claim 81 (depends on 56) The compound according to claim 56, to R1 is C1-C6 alkoxy. ### Claim 82 (depends on 56) The compound according to claim 56, wherein R3 is C1-C6 alkoxy. ### Claim 83 (depends on 56) The compound according to claim 56, wherein R1 and R3 are both halogen. ### Claim 84 (depends on 56) The compound according to claim 56, wherein R1 and R3 are both C1-C6 alkoxy. ### Claim 85 (depends on 1) A method according to claim 1, wherein the pest-controlling effective amount is a pesticidally effective amount of said compound. ### Claim 86 (depends on 1) A method according to claim 1, wherein the pest-controlling effective amount is a pest-repelling effective amount of said compound.