EP1409440A4 - Procede d'inhibition de reponses de l'ethylene chez des vegetaux - Google Patents

Procede d'inhibition de reponses de l'ethylene chez des vegetaux

Info

Publication number
EP1409440A4
EP1409440A4 EP02707944A EP02707944A EP1409440A4 EP 1409440 A4 EP1409440 A4 EP 1409440A4 EP 02707944 A EP02707944 A EP 02707944A EP 02707944 A EP02707944 A EP 02707944A EP 1409440 A4 EP1409440 A4 EP 1409440A4
Authority
EP
European Patent Office
Prior art keywords
mmol
added
cyclopropene
water
dried over
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02707944A
Other languages
German (de)
English (en)
Other versions
EP1409440A1 (fr
Inventor
Richard Martin Jacobson
Martha Jean Kelly
Fiona Linette Wehmeyer
Karen Anderson Evans
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rohm and Haas Co
Original Assignee
Rohm and Haas Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rohm and Haas Co filed Critical Rohm and Haas Co
Publication of EP1409440A1 publication Critical patent/EP1409440A1/fr
Publication of EP1409440A4 publication Critical patent/EP1409440A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/325—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • 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
    • A01N27/00—Biocides, pest repellants or attractants, or plant growth regulators containing hydrocarbons
    • 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
    • A01N29/00—Biocides, pest repellants or attractants, or plant growth regulators containing halogenated hydrocarbons
    • A01N29/04—Halogen directly attached to a carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/04—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a three-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C07C17/2632—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions involving an organo-magnesium compound, e.g. Grignard synthesis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C23/00—Compounds containing at least one halogen atom bound to a ring other than a six-membered aromatic ring
    • C07C23/02—Monocyclic halogenated hydrocarbons
    • C07C23/04—Monocyclic halogenated hydrocarbons with a three-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/24—Halogenated aromatic hydrocarbons with unsaturated side chains
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
    • C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • C07C309/66—Methanesulfonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/73—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/12—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms
    • C07C321/20—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
    • C07C321/28—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/01—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton
    • C07C323/09—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton having sulfur atoms of thio groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/416—Henkel reaction and related reactions, i.e. rearrangement of carboxylate salt groups linked to six-membered aromatic rings, in the absence or in the presence of CO or CO2, (e.g. preparation of terepholates from benzoates); no additional classification for the subsequent hydrolysis of the salt groups has to be given
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/62—Halogen-containing esters
    • C07C69/65—Halogen-containing esters of unsaturated acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/40—2,5-Pyrrolidine-diones
    • C07D207/416—2,5-Pyrrolidine-diones with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to other ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/80—Acids; Esters in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/16—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/04—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having less than three double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/04—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D277/06—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/06—1,2,3-Thiadiazoles; Hydrogenated 1,2,3-thiadiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/182—Radicals derived from carboxylic acids
    • C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
    • C07D295/28—Nitrogen atoms
    • C07D295/30—Nitrogen atoms non-acylated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C07D307/84—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C07D307/85—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/12—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

  • the present invention generally relates to methods of inhibiting ethylene responses in plants and plant materials, and particularly relates to methods of inhibiting various ethylene responses including plant maturation and degradation, by exposing plants to cyclopropene derivatives and compositions thereof wherein at least one substituent on the cyclopropene ring contains a carbocyclic or heterocyclic ring.
  • ethylene can cause the premature death of plants or plant parts including, for example, flowers, leaves, fruits, and vegetables. Ethylene also promotes leaf yellowing and stunted growth as well as premature fruit, flower, and leaf drop. Such activities are understood to be achieved through interaction with a specific ethylene receptor in the plant. Many compounds other than ethylene interact with this receptor: some mimic the action of ethylene; others prevent ethylene from binding and thereby counteract its action. To address these ethylene-induced effects, very active and intense research presently concerns the investigation of ways to prevent or reduce the deleterious effects of ethylene on plants.
  • the new compounds will avoid the explosive hazards of 1 -methylcyclopropene and, in addition, provide alternative means of delivery, such as through liquid or solid formulations.
  • n is an integer from 1 to 12; ii) each L is independently selected from a member of the group Dl , D2, E, or J wherein: Dl is of the formula:
  • D2 is of the formula:
  • each X and Y is independently a group of the formula: -(L) m -Z;
  • each Z is independently selected from:
  • G is an unsubstituted or substituted; unsaturated, partially saturated, or saturated; monocyclic, bicyclic, tricyclic, or fused; 4 to 14 membered carbocyclic or heterocyclic ring system wherein;
  • each heteroatom is independently selected from N, O, and S; 4) the number of substituents is from 0 to 5 and each substituent is independently selected from X; b) the total number of non-hydrogen atoms in each compound is 50 or less; and c) the total number of heteroatoms in -(L) n -Z is from 0 to 4; and d) either; i) R' or R contains at least one group G; or ii) at least one L group is an E group; or iii) at least one of R 1 , R 2 , R 3 , and R 4 contains one to four non-hydrogen atoms and at least one of R 1 , R , R , and R 4 contains more than four non-hydrogen atoms; and its enantiomers, stereoisomers, salts, and mixtures thereof; or a composition thereof.
  • each open bond indicates a bond to another L group, a Z group, or the cyclopropene moiety.
  • the structural representation - ⁇ — indicates an oxygen atom with bonds to two other atoms; it does not represent a dimethyl ether moiety.
  • Typical R 1 , R 2 , R 3 , and R 4 groups include, for example: alkenyl, alkyl, alkynyl, acetylaminoalkenyl, acetylaminoalkyl, acetylaminoalkynyl, alkenoxy, alkoxy, alkynoxy, alkoxyalkoxyalkyl, alkoxyalkenyl, alkoxyalkyl, alkoxyalkynyl, alkoxycarbonylalkenyl, alkoxycarbonylalkyl, alkoxycarbonylalkynyl, alkylcarbonyl, alkylcarbonyloxyalkyl, alkyl(alkoxyimino)alkyl, carboxyalkenyl, carboxyalkyl, carboxyalkynyl, dialkylamino, haloalkoxyalkenyl, haloalkoxyalkyl, haloalkoxyalkynyl, haloalkenyl
  • G groups include, for example: saturated or unsaturated cycloalkyl, bicyclic, tricyclic, polycyclic, saturated or unsaturated heterocyclic, unsubstituted or substituted phenyl, naphthyl, or heteroaryl ring systems such as, for example, cyclopropyl, cyclobutyl, cyclopent-3-en-l-yl, 3-methoxycyclohexan-l-yl, phenyl, 4-chlorophenyl, 4-fluorophenyl, 4- bromophenyl, 3-nitrophenyl, 2-mefhoxyphenyl, 2-methylphenyl, 3-methyphenyl, 4- methylphenyl, 4-ethylphenyl, 2-methyl-3-methoxyphenyl, 2,4-dibromophenyl, 3,5- difluorophenyl, 3,5-dimethylphenyl, 2,4,6-trichlorophenyl, 4-methoxyphenyl, naphth
  • R 1 , R 2 , R 3 , and R 4 are hydrogen. More preferably, R 1 and R 2 are hydrogen or R and R are hydrogen. Even more preferably, R , R , and R are hydrogen or R 1 , R 2 , and R 3 are hydrogen. Most preferably, R , R , and R 4 are hydrogen.
  • n is from 0 to 8. Most preferably, n is from 1 to 7.
  • m is 0 to 4. Most preferably, m is from 0 to 2.
  • Dl is -CXY-, -CO-, or -CS-. More preferably Dl is -CXY-.
  • D2 is -O- or -NX-.
  • E is -S-, -SiXY-,, or -S0 2 -.
  • X and Y are independently H, halo, OH, SH, -C(0)(C ⁇ -C 4 )alkyl -, -C(0)0(C ⁇ -C 4 )alkyl -, -O- (C ⁇ -C 4 )alkyl, -S-(C ⁇ -C 4 )alkyl, or substituted or unsubstituted (C ⁇ -C 4 )alkyl.
  • Z is H, halo, or G. More preferably, Z is H or G.
  • each G is independently a substituted or unsubstituted; five, six, or seven membered; aryl, heteroaryl, heterocyclic, or cycloalkyl ring. More preferably, each G is independently a substituted or unsubstituted phenyl, pyridyl, cyclohexyl, cyclopentyl, cycloheptyl, pyrolyl, furyl, thiophenyl, triazolyl, pyrazolyl, 1,3-dioxolanyl, or mo ⁇ holinyl.
  • G is unsubstituted or substituted phenyl, cyclopentyl, cycloheptyl, or cyclohexyl. Most preferably, G is cyclopentyl, cycloheptyl, cyclohexyl, phenyl, or substituted phenyl wherein the substituents are independently selected from 1 to 3 of methyl, methoxy, and halo.
  • Another aspect of the present invention is a method of blocking ethylene receptors in plants by applying to the plants an effective ethylene receptor-blocking amount of the cyclopropene derivative or a composition thereof.
  • the methods described herein may be carried out in a variety of ways, such as by contacting the plant with a cyclopropene derivative or a composition thereof, whether in solid, liquid, or gaseous form, or by exposing the plant, cut flower, picked fruit or picked vegetable in an atmosphere infused with the cyclopropene derivative or a composition thereof.
  • contacting means to bring the cyclopropene and a plant into intimate association with each other such that a sufficient number of ethylene receptors are effected by the cyclopropene.
  • Agricultural compositions comprising the compounds of this invention are also encompassed by the invention.
  • compositions comprise 0.005% to 99%, by weight; preferably 1% to 95%, by weight; more preferably 2% to 90%, by weight; even more preferably 3% to 80%, by weight; or most preferably 4% to 70%, by weight, of the active compounds of the present invention.
  • These compositions may comprise one or more adjuvants, such as, for example, carriers, extenders, binders, lubricants, surfactants and/or dispersants, wetting agents, spreading agents, dispersing agents, stickers, adhesives, defoamers, thickeners, and emulsifying agents.
  • adjuvants commonly used in the art can be found in the John W. McCutcheon, Inc.
  • organic solvents may be used as carriers for the active compounds of the present invention such as, for example, hydrocarbons such as hexane, benzene, toluene, xylene, kerosene, diesel oil, fuel oil and petroleum naphtha, ketones such as acetone, methyl ethyl ketone and cyclohexanone, chlorinated hydrocarbons such as methylene chloride, esters such as ethyl acetate, amyl acetate and butyl acetate, ethers, e.g., ethylene glycol monomethyl ether and diethylene glycol monomethyl ether, alcohols, e.g., ethanol, methanol, isopropanol, amyl alcohol, ethylene glycol, propylene glycol, butyl carbitol acetate and glycerine.
  • hydrocarbons such as hexane, benzene, toluene, xylene, kerosene,
  • Solid, liquid, and gaseous formulations can be prepared by various conventional procedures.
  • the active ingredient, in finely divided form if a solid may be tumbled together with finely divided solid carrier.
  • the active ingredient in liquid form including mixtures, solutions, dispersions, emulsions and suspensions thereof, may be admixed with a solid carrier in finely divided form.
  • the active ingredient in solid form may be admixed with a liquid carrier to form a mixture, solution, dispersion, emulsion, suspension or the like.
  • the active compounds of the present invention can be applied to plants by various suitable means.
  • an active compound may be applied alone in gaseous, liquid, or solid form by contacting the compound with the plant to be treated. Additionally the active compound may be converted to the salt form, and then applied to the plants.
  • compositions containing one or more active compounds of the present invention may be formed. The compositions may be applied in gaseous, liquid, or solid form by contacting the composition with the plant to be treated. Such compositions may include an inert carrier. Similarly, when in gaseous form, the compound may be dispersed in an inert gaseous carrier to provide a gaseous solution.
  • the active compound may also be suspended in a liquid solution such as an organic solvent or an aqueous solution that may serve as the inert carrier.
  • Solutions containing the active compound may be heterogeneous or homogeneous and may be of various forms including mixtures, dispersions, emulsions, suspensions and the like.
  • the cyclopropenes may also be encapsulated into a molecular encapsulation agent.
  • Preferred encapsulating agents include cyclodextrins, crown ethers, polysiloxanes, and zeolites. More preferred encapsulating agents include ⁇ -cyclodextrin, ⁇ -cyclodextrin, and ⁇ -cyclodextrin. The most preferred encapsulating agent will vary depending upon the size of the R substituents. However, as one skilled in the art will appreciate, any cyclodextrin or mixture of cyclodextrins, cyclodextrin polymers as well as modified cyclodextrins can also be utilized pursuant to the present invention.
  • Cyclodextrins are available from Wacker Biochem Inc., Adrian, MI or Cerestar USA, Hammond, IN, as well as other vendors. When encapsulated, the preferred concentrations of the cyclopropenes will typically be less than in other compositions due to the capacity limitations of molecular encapsulation agents.
  • the active compounds and compositions thereof can also be applied as aerosols, e.g., by dispersing them in air using a compressed gas such as, for example, nitrogen, carbon dioxide, dichlorodifluoromethane, trichlorofluoromefhane, or other halocarbons.
  • a compressed gas such as, for example, nitrogen, carbon dioxide, dichlorodifluoromethane, trichlorofluoromefhane, or other halocarbons.
  • the amount of the cyclopropene needed to inhibit ethylene effects will vary depending upon the particular cyclopropene, the type and amount of plant material present, the cyclopropene composition used, and the volume to be treated. Generally, a gas treatment (measured volume/volume) concentration of the cyclopropene in the treated chamber of from about 0.1 part per billion ("ppb") to 1000 parts per million (“ppm”) provides adequate ethylene inhibition. Likewise, an applied spray treatment (measured weight/weight) concentration of the cyclopropene of from about 0.01 part per billion (“ppb") to 1000 parts per million (“ppm”) provides adequate ethylene inhibition.
  • plant is used in a generic sense herein, and includes, for example, woody- stemmed plants such as trees and shrubs; herbs; vegetables, fruits, and agricultural crop;, and ornamental plants. Plants to be treated by the methods described herein include whole plants and any portions thereof, such as field crops, potted plants, seeds, cut flowers (stems and flowers), and harvested fruits and vegetables.
  • Plants treated with the compounds and by the methods of the present invention are preferably treated with a non-phytotoxic amount of the active compound.
  • the present invention can be employed to modify a variety of different ethylene responses such as, for example, the ripening and/or senescence of flowers, fruits, and vegetables; abscission of foliage, flowers, and fruit; the shortening of life of ornamentals such as potted plants, cut flowers, shrubbery, seeds, and dormant seedlings; in some plants (e.g., pea) the inhibition of growth, the stimulation of growth (e.g., rice), auxin activity, inhibition of terminal growth, control of apical dominance, increase in branching, increase in tillering, changing the mo ⁇ hology of plants, modifying the susceptibility to plant pathogens such as fungi, changing bio-chemical compositions of plants (such as increasing leaf area relative to stem area), abortion or inhibition of flowering and seed development, lodging effects, stimulation of seed germination and breaking of dormancy, and hormone or epinasty effects.
  • plants e.g., pea
  • the inhibition of growth e.g., the
  • Active compounds of the present invention have proven to be unexpectedly potent inhibitors of ethylene action on plants, fruits and vegetables, even when applied at low concentrations.
  • compounds of the present invention may result in a longer period of insensitivity to ethylene than compounds found in the prior art. This longer period of insensitivity may occur even when compounds of the present invention are applied at a lower concentration than previous compounds.
  • Another embodiment of this invention relates to members of the class of cyclopropenes which are newly discovered compounds. These compounds include compounds of the formula:
  • R 1 and R 3 are H and R 2 , R 4 , and the other of R 1 and R 3 are independently selected from H and a group of the formula:
  • n is an integer from 1 to 12; ii) each L is independently selected from a member of the group Dl, D2, E, or J wherein:
  • Dl is of the formula:
  • D2 is of the formula:
  • each X and Y is independently a group of the formula: -(L) m -Z;
  • each Z is independently selected from:
  • G is an unsubstituted or substituted; unsaturated, partially saturated, or saturated; monocyclic, bicyclic, tricyclic, or fused; 4 to 14 membered carbocyclic or heterocyclic ring system wherein;
  • each heteroatom is independently selected from N, O, and S; 4) the number of substituents is from 0 to 5 and each substituent is independently selected from X; b) the total number of non-hydrogen atoms in each compound is 50 or less; and c) the total number of heteroatoms in -(L) ⁇ -Z is from 0 to 4; and d) either; i) R 1 or R 3 contains at least one group G; or ii) at least one L group is an E group; or iii) at least one of R 1 , R 2 , R 3 , and R 4 contains one to four non-hydrogen atoms and at least one of R 1 , R 2 , R 3 , and R 4 contains more than four non-hydrogen atoms; andits enantiomers, stereoisomers, salts, and mixtures thereof; or a composition thereof; provided that: a) -(L) n -Z is other than trimethylsilyl, trimethylsilylsulf
  • the compounds of this invention can be prepared by a number of methods.
  • the cyclopropenyllithium can be reacted with electrophiles to give derivatived cyclopropenes. Examples of such electrophiles include alkylating agents, trisubstituted chlorosilanes, borates, dialkyl or diaryl disulfides, ketones, aldehydes, esters, amides and nitriles.
  • the bromo-olefins can be prepared by standard methods. Chloro-olefins can be used in place of bromo-olefins.
  • the tribrominated cyclopropanes can also be converted to mono-brominated cyclopropanes with reducing agents such as diethylphosphite. Other reducing agents could be used.
  • a 1 , 1 -disubstituted olefin can also react with dibromocarbene to give a dibrominated intermediate. This can be reduced with zinc to the mono-brominated cyclopropane. Elimination of the bromide with base gives the cyclopropene (reference Binger, P. Synthesis 1974, 190).
  • Cyclopropene can be deprotonated with a strong base such as sodium amide in liquid ammonia and reacted with an alkyl halide or other electrophiles to give a substituted cyclopropene (reference: Schipperijn, A. J.; Smael, P.; Reel Trav. Chim. Pays-Bas, 1973, 92, 1159).
  • Substituted cyclopropenes can be deprotonated with alkyllithium reagents and reacted with electrophiles.
  • Tribromocyclopropanes or cyclopropenes containing an alcohol can be converted to a good leaving group such as a sulfonate derivative.
  • the leaving group can be displaced with nucleophiles to give other substituted cyclopropenes.
  • a l-trialkylsilyl-2-hydroxycyclopropane, generated from vinyltrialkylsilane, can serve as a precursor to a cyclopropene (Mizojiri, R.; Urabe, H.; Sato, F. J. Org Chem. 2000, 65, 6217).
  • l-Trialkylsilyl-2-halocyclopropanes also undergo a fluoride catalyzed elimination to give cyclopropenes (Billups, W. E.; Lee, G-A; Arney, B. E.; Whitmire, K. H. J. Am. Chem. Soc, 1991, 775, 7980. and Banwell, M. G.; Corbett, M.; Gulbis, J.; Mackay, M.F.; Reum, M. E. J. Chem. Soc. Perkin Trans. 1, 1993, 945).
  • the esters can be hydrolyzed to the carboxylic acid.
  • dihalocarbenes can be added to acetylenes to give l-alkyl-3,3- dihalocyclopropenes (Bessard, Y.; Schlosser, M.; Tetrahedron, 1991, 47, 7323).
  • a solution of 8 ml (0.0622 mol) of 2,3-dibromopropene in 50 ml diethyl ether was placed under a nitrogen atmosphere by use of a Firestone valve. While cooling in an ice water bath, a solution of 62 ml (0.062 mol) of IM 4-chlorophenylmagnesium bromide in diethyl ether was added slowly via addition funnel. After stirring for 2 hours while warming to room temperature, the reaction was recooled in an ice bath and 50 ml of 1 N hydrochloric acid was then added via syringe. The resulting mixture was transferred to a separatory funnel and the phases were separated. The organic layer was dried over MgS0 4 and filtered.
  • the Grignard reagent of 2-bromothiophene was prepared, and converted to 1 -( 2- thienyl)methyl-cyclopropene by the same reaction sequence as was used for the preparation of compound 1.
  • EXAMPLE 3 Preparation of 2-(3-Cvcloprop-l-enyl-propyl)- l ,31dioxane (Compound 3) The Grignard reagent of 2-(2-bromoethyl)-l,3-dioxane was prepared, and converted to 2-(3-cycloprop-l-enyl-propyl)-[l,3]dioxane by the same reaction sequence as was used for the preparation of compound 1.
  • EXAMPLE 4 Preparation of l-(6-(Phenyldimethylsilyl)-hexyl)-cvclopropene (Compound 3)
  • N,N'-dibenzyl-N,N,N',N'-tetramethylethylenediammonium dibromide and N,N'- dibenzyl-N,N,N',N'-tetraethylethylenediammonium dibromide Phase transfer catalysts
  • N,N,N',N'-tetraethylethylenediamine one obtains N,N'- dibenzyl-N,N,N',N'-tetraethylethylenediammonium dibromide, a white solid mp 190-193°C, decomposes.
  • EXAMPLE 5 Preparation of l-( ⁇ , ⁇ -dimethylbenzyl)-cvclopropene (Compound 5) a. ⁇ , ⁇ -dimefhylbenzylcyanide Into a 1000 ml 3 necked flask with mechanical stirring, an external water bath, an internal thermometer, a condenser and an addition funnel was added 250 g of dimethyl sulfoxide, 59 g (504 mmol) of benzyl cyanide, and 160 g (1127 mmol) of methyl iodide. The internal temperature was raised to +45 °C and then 83 g of 50% aqueous NaOH was added at 0.7 drops per second. After two hours the addition was complete.
  • the thick slurry was cooled, diluted with 1000 ml of water and 500 ml of diethyl ether and 500 ml of hexane.
  • the organic layer was separated and concentrated. It contained mono and dimethylated compounds.
  • To this concentrate was further added 250 g of dimethyl sulfoxide, 60 g of methyl iodide, and 37 g of 50% aqueous NaOH for two hours as above.
  • Extractive workup with diethyl ether gave a mixture of l-( ⁇ , ⁇ -dimethylbenzyl)-l-chloroethylene and l-( ⁇ , ⁇ - dimethylbenzyl)-l,l-dichloroethane.
  • Vacuum distillation gave purified l-( ⁇ , ⁇ - dimethylbenzyl)-l-chloroethylene bp (23 torr) 110-120 °C. d.
  • reaction was quenched with 0.5 ml of methanol, rapidly evaporated in vacuo with a bath temperature of +25 °C, partitioned between diethyl ether and dilute aqueous hydrochloric acid, dried with anhydrous magnesium sulfate and re- evaporated in vacuo yielding 1.3 g of l-methyl-2- benzylcyclopropene.
  • EXAMPLE 10 2-(2-Benzenesulfonyloxyethyl)-cvclopropene (Compound 10) A solution of 0.745 g (0.00150 mol) of l,l,2-tribromo-2-(2- benzenesulfonyloxyethyl)-cyclopropane in 4 ml of diethyl ether was placed under a nitrogen atmosphere by use of a Firestone valve.
  • EXAMPLE 12 Preparation of 7-(l -Imidazole)- 1-heptylcvclopropene (Compound 12) a. 1 -( 1 -Ethoxyethoxy)-6-bromohexane
  • N,N'-dibenzyl-N,N,N',N'-tetraethylethylenediammonium dibromide 42 g of 45% potassium hydroxide (337 mmol), 93 g of bromoform (368 mmol) and 280 g of methylene chloride were rapidly stirred at room temperature for two days.
  • the reaction mixture was transferred to a separatory funnel and washed with water.
  • the methylene chloride phase was transferred to a flask and treated with the same amount of the phase transfer catalyst and 45% potassium hydroxide as above, then stirred at room temperature for an additional 3 days.
  • the reaction mixture was washed with water, the methylene chloride phase was dried with magnesium sulfate, and then stripped.
  • the product was treated with 320 ml of methanol and 40 ml of IN HCI for 1 hour at room temperature. The methanol was stripped, ethyl acetate was added. The organic phase was washed with water and brine, then treated with 200 ml of silica gel. Filtration followed by a strip gave 38 g of black product. This was chromatographed on silica gel to give 19.0 g of l,l,2-tribromo-2-(7- hydroxyheptyl)cyclopropane as a pale yellow liquid. d.
  • EXAMPLE 14 Preparation of 1 -Cyclohexylcyclopropene (Compound 14) l-Cyclohexyl-2-(trimethylsilyl)cyclopropanol was prepared from methyl cyclohexylcarboxylate and vinyltrimethylsilane as described in Mizojiri, R.; Urabe, H.; Sato, F. J. Org Chem. 2000, 65, 6217. This material was converted to the cyclopropene in an analogous manner to that described in the same reference.
  • EXAMPLE 15 Preparation of l-((2-Carboxy-N-mo ⁇ holino)ethyl)-cyclopropene a. 2-(2-Bromo-allyl)-malonic acid diethyl ester
  • EXAMPLE 17 Preparation of l-(3-trifluoromethylphenoxymethyl)-2- ethylcvclopropene (Compound 37) a. 1,1 ,2-Tribromo-2-efhylcyclopropane l,l,2-Tribromo-2-ethylcyclopropane was prepared from 2-bromo-l-butene by the same method used in example 4 c. b. 1 -(Hydroxymethyl)-2-ethylcyclopropene
  • Example 2Q l-PhenyI-2,3.3-trichlorocvclopropene (Compound 41) l-Phenyl-2,3,3-trichlorocyclopropene was prepared by the method described in Eicher, theophil; Huch, VolkerJ Schneider, VolkerJ Veith, Michael.
  • Example 21 l-(4-Methylphenylcarbonyloxybutyl)-cvclopropene (Compound 44) a. 5,6-Dibromo-hexan-l-ol To an ice bath cooled solution of 5-hexen-l-ol (ll.23g, 112.3mmol) in about
  • the reaction was heated to 60 °C for about 2 hours then cooled to room temperature. After about 15 hours, 50% aqueous potassium carbonate (30 g, 107 mmol) and 30 g water were added and the reaction was heated to 60 °C for about 2 hours then cooled to room temperature. The reaction mixture was concentrated in vacuo, then the resulting residue was extracted with diethyl ether. The organic layer was washed with basified water (pHlO.) The phases were separated and the organic phase was dried over magnesium sulfate then dried in vacuo.
  • Example 23 l-Benzyl-2-chlorocyclopropene (Compound 46) a. l-(2-Bromo-allyl)-benzene l-(2-Bromo-ally ⁇ )-benzene was prepared from 2,3-dibromopropene and phenylmagnesium bromide by the method shown in Example la. b. l-Benzyl-l-bromo-2,2-dichlorocyclopropane
  • the methylene chloride phase was transferred to a flask and treated with the same amount of the phase transfer catalyst and 45% potassium hydroxide as before, then stirred at room temperature for an additional 3 days.
  • the reaction mixture was washed with water, the methylene chloride phase was dried with magnesium sulfate, and then stripped.
  • the product was treated with 320 ml of methanol and 40 ml of IN HCI for 1 hour at room temperature. The methanol was stripped, ethyl acetate was added.
  • the organic phase was washed with water and brine, then treated with 200 ml of silica gel. Filtration followed by a strip gave 38 g of black product.
  • Ethyl 4-bromopent-4-enoate was prepared by the method described in Mori, M.; et al. Journal of Organic Chemistry, 1983, 48, 4058-4067. b. 3-(l,2,2-Tribromo-cyclopropyl)-propionic acid ethyl ester
  • Example 27 l-(8-Benzenesulfonyloxyoctyl)-cvclopropene (Compound 56) a. 9,10-Dibromo-decan-l-ol
  • Example 28 l-(4-Methylphenylthiooctyl)-cvclopropene (Compound 57) a.
  • l-(Benzenesulfonyloxyoctyl)-cyclopropene l-(Benzenesulfonyloxyoctyl)-cyclopropene is prepared from 1- (benzenesulfonyloxyoctyl)- 1,2,2-tribromo-cyclopropane by the method shown in Example 27. b. l-(4-Methylphenylthiooctyl)-cyclopropene
  • Example 29 l-(lH-1.2.4-triazol-2-ylthiooctyl)-cvclopropene (Compound 58) a. l-(Benzenesulfonyloxyoctyl)-cyclopropene l-(Benzenesulfonyloxyoctyl)-cyclopropene is prepared from 1-
  • 3-(4-Chlorophenyl)-pyridaz-6-one can be prepared as described in Example 3 of DE Pat. No. 2435244 (1976.)
  • b. l-(Methanesulfonyloxymethyl)-2-ethylcyclopropene
  • l-(Methanesulfonyloxymethyl)-2-ethylcyclopropene is prepared from by the method shown in Example 17c.
  • N,N'-dibenzyl-N,N,N',N'-tetramethylethylenediammonium dibromide and N,N'- dibenzyl-N,N,N',N'-tetraethylethylenediammonium dibromide Phase transfer catalysts.
  • N,N,N',N'-tetraethylethylenediamine one obtains N,N'- dibenzyl-N,N,N',N'-tetraethylethylenediammonium dibromide, a white solid mp 190-193°C, decomposes.
  • the methylene chloride phase was placed in a reaction flask and treated with an additional 0.47 g of 45% aqueous potassium hydroxide solution (3.8 mmol) and 75 mg N,N'-dibenzyl- N,N,N',N'-tetraethylethylenediammonium dibromide.
  • the reaction mixture was stirred overnight, then water and additional methylene chloride were added and the phases were separated.
  • the methylene chloride phase was dried over magnesium sulfate, and stripped. A small amount of heptane was added during the strip to help remove remaining bromoform.
  • Column chromatography gave 390 mg of 2-triethylsilylmethyl- 1 , 1 ,2-tribromocyclopropane as a colorless liquid, e) 1 -Triethylsilylmethylcyclopropene
  • EXAMPLE 33 Preparation of l-Trimethylsilylmethylcyclopropene (Compound 64) Commercially available 3-trimethylsilyl-2-bromopropene was converted to 1- trimethylsilylmethylcyclopropene in a similar manner as described for Example 1.
  • EXAMPLE 34 Preparation of 6-(Trimethylsilyl)-hexylcycloprop-2-ene (Compound 65) a. 2-Bromo-8-(trimethylsilyl)-oct-l-ene
  • 2-Bromodec-l-ene Into a 500 ml 3 necked flask equipped with magnetic stirring, an addition funnel, and a reflux condenser was added 17 g (700 mmol) of magnesium turnings. The atmosphere was exchanged for dry nitrogen and the turnings were covered with 20 ml of diethyl ether. 2 g of 1 ,2-dibromoethane was added whereon a reaction occurred as evidenced by some bubbling and cloudiness. After 5 minutes, 200 ml of diethyl ether was added and the mixture brought to reflux. Slow addition of 90 g (503 mmol) of 1-bromoheptane in 100 ml of diethyl ether at a rate sufficient to maintain reflux took 50 minutes. The reaction was further refluxed for 30 minutes yielding a solution of heptyl magnesium bromide.
  • the methylene chloride phase was transferred to a flask and treated with the same amount of the phase transfer catalyst and 45% potassium hydroxide as before, then stirred at room temperature for an additional 3 days.
  • the reaction mixture was washed with water, the methylene chloride phase was dried with magnesium sulfate, and then stripped.
  • the product was treated with 320 ml of methanol and 40 ml of IN HCI for 1 hour at room temperature. The methanol was stripped, ethyl acetate was added.
  • the organic phase was washed with water and brine, then treated with 200 ml of silica gel. Filtration followed by a strip gave 38 g of black product.
  • 2-Octyl- 1 , 1 ,2-tribromocyclopropane Into a 125 ml single necked flask with magnetic stirring was added 20 g (91 mmol) of 2-bromodec-l-ene, 75 g (297 mmol) of bromoform, 200 g of methylene chloride, 2.2 g of N,N'-dibenzyl-N,N,N',N'-tetramethylethylenediammonium dibromide, and 20 g (161 mmol) of 45% aqueous potassium hydroxide.
  • This compound was prepared in a similar manner to compound 2. It was obtained as a mixture of 40% 3-methyl-3-nonyl-cyclopropene, 30% 1 -methyl- 1-nonyl- cyclopropane and 20% l-methyl-l-nonyl-2-bromocyclopropane.
  • EXAMPLE 43 Preparation of 1 -Heptyl-2-methyl-cyclopropene (Compound 74) A solution of 1 mg of 1,10-phenanthroline, 1.74 ml of tetramethylethylenediamine, and 20 ml of tetrahydrofuran was placed under a nitrogen atmosphere via use of a Firestone valve.
  • 1,1 ,2-Tribromo-2-(2-(carbo(acetoxylmethyl))ethyl-cyclopropene To a solution of 0.800 g (0.00228 mol) of 3-1,1, 2-tribromo -2-(2-(carboxy))ethyl- cyclopropene in about 2 ml anhydrous N,N-dimefhylformamide was added 0.224 ml (0.00228 mol) of bromomethyl acetate then 0.396 ml (0.00228 mol) of diisopropylethylamine. After heating to 60 °C for 2 hours, water and diethyl ether were added.
  • EXAMPLE 45 Preparation of l-Bromo-2-(2-(carboethoxy)-ethyl-cvclopropene (Compound 76) l-Bromo-2-(2-(carboethoxy)-ethyl-cyclopropene was prepared from 1,1,2- tribromo-2-(2-(carboethoxy)-ethyl-cyclopropene in a manner similar to the preparation 1- bromo-2-(2-(carbo(acetoxylmethyl))-ethyl-cyclopropene from 1 , 1 ,2-tribromo-2-(2- (carbo(acetoxylmethyl))-efhyl-cyclopropene (Example 5).
  • EXAMPLE 46 Preparation of l-Bromo-2-(2-(carboxy)-ethyl-cvclopropene (Compound 77) To a solution of 200 mg (0.913 mmol) of l-bromo-2-(2-(carboethoxy)-ethyl- cyclopropene in 2 ml of absolute ethanol was added 0.0768 g (1.37 mmol) of potassium hydroxide. After stirring for 1 hour, diethyl ether and water were added. The resulting mixture was transferred to a separatory funnel and the phases were separated. After the isolated aqueous layer was acidified by addition of 1 N hydrochloric acid, diethyl ether was added.
  • EXAMPLE 47 Preparation of l-Octyl-3-carboxy-cvclopropene (Compound 78): a. 1 -Octyl-3-(carboxyethoxy)-cyclopropene l-Octyl-3-(carboxyethoxy)-cyclopropene was prepared from 1-decyne and ethyl diazoacetate by the method of Mueller, P.; Pautex, N. Helv. Chim Acta 1990, 73, 1233. b.
  • l-Octyl-3-carboxy-cyclopropene l-Octyl-3-(carboxyethoxy)-cyclopropene (1.12g, 5 mmol) and 100 ml of 0.2 N potassium hydroxide were stirred at room temperature for one week. Ether was added and the phases were separated. The aqueous phase was acidified and extracted with methylene chloride. The organic phase was dried over magnesium sulfate and stripped to give 0.8 g of l-octyl-3-carboxy-cyclopropene.
  • EXAMPLE 48 Preparation of l-Trimethylsilyl-2,3,3-trimethylcyclopropene (Compound 79) Compound 79 was prepared as a 36% solution in ether from 2-bromo-3-mefhyl-2-butene by the same method used to prepare Compound 5 from 2-bromodec-l-ene.
  • EXAMPLE 49 Preparation of l-(Butyldimethylsilyl)-2-methylcvclopropene (Compound 80)
  • Compound 80 was prepared from 2-bromopropene by the same method used to prepare Compound 5 from 2-bromodec-l-ene.
  • EXAMPLE 50 Preparation of l-Triethylsilyl-2 -methylcyclopropene (Compound 81)
  • Compound 81 was prepared from 2-bromopropene by the same method used to prepare Compound 5 from 2-bromodec-l-ene.
  • EXAMPLE 51 Preparation of 1 -(7-T-butyldimethylsilyloxyheptyl)-cyclopropene (Compound 82) a. 1 -(7-Hydroxyheptyl)-cyclopropene l-(7-Hydroxyheptyl)-cyclopropene was prepared by the same method already described in example 7. b. 1 -(7-T-butyldimethylsilyloxyheptyl)-cyclopropene
  • EXAMPLE 52 Preparation of 1 -(Methanesulfonyloxymethyl)-2-ethylcvclopropene (Compound 83) a. 1,1 ,2-Tribromo-2-efhylcyclopropane l,l,2-Tribromo-2-ethylcyclopropane was prepared from 2-bromo-l-butene by the same method used in example 5. b. l-(Hydroxymethyl)-2-ethylcyclopropene
  • EXAMPLE 53 Preparation of l-(Diethoxy-thiophosphorylthiomethyl)-2- ethylcvclopropene (Compound 84) a. l-(Methanesulfonyloxymethyl)-2-ethylcyclopropene l-(Methanesulfonyloxymethyl)-2-ethylcyclopropene was prepared from 1- (hydroxymethyl)-2-ethyl cyclopropene by the same method used in example 13. b.
  • Tomato Epinasty Test Objective The test procedure is designed to determine the ability of an experimental compound to block the epinastic growth response induced by ethylene in tomato plants when the experimental compound is administered either as a volatile gas or as a component of a spray solution.
  • Treatment chambers are of an appropriate size for the test plants and are airtight. Each is fitted with a reusable septum to be used for injection of ethylene.
  • Test plants are Patio variety tomato seedlings planted two plants per three inch square plastic pot.
  • Volatile gas treatment entails placing two pots of Patio var. tomatoes into a polystyrene 4.8L volume treatment chamber along with one-half (upper or lower section) of a 50 X 9 mm plastic Petri dish containing a Gelman filter pad.
  • the appropriate amount of experimental compound, dissolved in 1.0 ml acetone, is pipetted onto the filter pad and the chamber immediately sealed. Four hours later ethylene gas equal to 10 ppm v/v final concentration is injected into the sealed chamber.
  • Spray application treatment entails using a DeVilbiss atomizer to completely cover all foliage and stems of two pots of Patio var. tomato plants with the appropriate amount of experimental compound dissolved in 10% acetone / 90% water with 0.05%> Silwett L-77 surfactant. Plants are air-dried in a drying hood for four hours then transferred to a 4.8L polystyrene chamber which is sealed.
  • Ethylene gas equal to 10 ppm v/v final concentration is injected into the sealed chamber. Sixteen hours later the chambers are opened in an exhaust hood, allowed to air and the plants scored visually for the degree of protection against ethylene-induced epinasty conferred by the experimental compound when compared to ethylene treated and untreated controls on a scale of 0 to 10. A rating of 10 means complete protection. A rating of 0 means no protection from the effects of ethylene.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
  • Furan Compounds (AREA)
  • Pyridine Compounds (AREA)
  • Pyrrole Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

L'invention concerne en général des procédés d'inhibition des réponses de l'éthylène chez des végétaux et dans des substances végétales, et plus précisément des procédés d'inhibition de différentes réponses de l'éthylène, notamment une maturation et dégradation des végétaux, par exposition des végétaux à des dérivés de cyclopropène et des compositions de ceci, dans lesquels: 1) au moins un substituant sur l'anneau du cyclopropène renferme un anneau carbocyclique ou hétérocyclique ou 2) un substituant renferme du silicium, du soufre, du phosphore ou du bore ou 3) au moins un substituant renferme entre un et quatre atomes non-hydrogène et au moins un substituant renferme plus de quatre atomes non-hydrogène.
EP02707944A 2001-02-26 2002-02-25 Procede d'inhibition de reponses de l'ethylene chez des vegetaux Withdrawn EP1409440A4 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
US27159001P 2001-02-26 2001-02-26
US27158801P 2001-02-26 2001-02-26
US27159101P 2001-02-26 2001-02-26
US271591P 2001-02-26
US271590P 2001-02-26
US271588P 2001-02-26
PCT/US2002/006339 WO2002068367A1 (fr) 2001-02-26 2002-02-25 Procede d'inhibition de reponses de l'ethylene chez des vegetaux

Publications (2)

Publication Number Publication Date
EP1409440A1 EP1409440A1 (fr) 2004-04-21
EP1409440A4 true EP1409440A4 (fr) 2005-09-14

Family

ID=27402393

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02707944A Withdrawn EP1409440A4 (fr) 2001-02-26 2002-02-25 Procede d'inhibition de reponses de l'ethylene chez des vegetaux

Country Status (5)

Country Link
EP (1) EP1409440A4 (fr)
JP (1) JP4785169B2 (fr)
KR (1) KR100921196B1 (fr)
CN (2) CN1463263A (fr)
WO (1) WO2002068367A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2002254251A1 (en) * 2001-02-26 2002-09-12 North Carolina State University A method to inhibit ethylene responses in plants
US7041625B2 (en) 2003-08-21 2006-05-09 Rohm And Haas Company Method to inhibit ethylene responses in plants
UA85690C2 (ru) * 2003-11-07 2009-02-25 Басф Акциенгезелльшафт Смесь для применения в сельском хозяйстве, содержащая стробилурин и модулятор этилена, способ обработки и борьбы с инфекциями в бобовых культурах
EP1609359A3 (fr) * 2004-06-24 2011-10-05 Rohm and Haas Company Procédé pour traiter des plantes ou des parties de plantes
AU2005242218A1 (en) * 2005-01-14 2006-08-03 Rohm And Haas Company Plant growth regulation
US20070117720A1 (en) * 2005-11-18 2007-05-24 Jacobson Richard M Compositions with cyclopropenes
US8093430B2 (en) * 2007-06-22 2012-01-10 North Carolina State University Methods of inhibiting ethylene responses in plants using cyclopropene amine compounds
IL184729A0 (en) * 2007-07-19 2008-01-20 Yissum Res Dev Co Compositions and methods for blocking ethylene response in plants using 3-cyclopropyl-1-enyl-propanoic acid salt
KR101429554B1 (ko) 2010-04-22 2014-08-14 (주)이룸바이오테크놀러지 시클로프로펜 화합물 및 이를 농작물에 부가하는 방법
CN103524434B (zh) * 2013-09-29 2015-08-12 北京大学 植物乙烯合成途径的小分子抑制剂吡嗪酰胺及其应用
US20180325106A1 (en) * 2015-11-03 2018-11-15 Curtin University Of Technology Method of retarding an ethylene response
CN106478507A (zh) * 2016-09-28 2017-03-08 重庆大学 一种2‑（1,3,5‑三芳基‑1‑h‑吡唑‑4‑基）丙二腈的制备方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8407195D0 (en) * 1984-03-20 1984-04-26 Cadbury Schweppes Plc Microbial desaturase enzyme inhibitors
DE3523862A1 (de) * 1985-07-04 1987-01-08 Basf Ag Mittel zur regulierung des pflanzenwachstums
US5123951A (en) * 1986-03-31 1992-06-23 Rhone-Poulenc Nederland B.V. Synergistic plant growth regulator compositions
US5100462A (en) 1991-04-01 1992-03-31 North Carolina State University Method of counteracting ethylene response by treating plants with diazocyclopentadiene and derivatives thereof
US5395958A (en) * 1992-09-30 1995-03-07 Mitsubishi Kasei Corporation Cyclopropene derivatives
US5518988A (en) 1994-06-03 1996-05-21 North Carolina State University Method of counteracting an ethylene response in plants
US6017849A (en) * 1998-08-20 2000-01-25 Biotechnologies For Horticulture, Inc. Synthesis methods, complexes and delivery methods for the safe and convenient storage, transport and application of compounds for inhibiting the ethylene response in plants
JP4690624B2 (ja) * 1999-11-23 2011-06-01 ノース・キャロライナ・ステイト・ユニヴァーシティ シクロプロペン誘導体を用いる植物のエチレン応答を遮断する方法
US6194350B1 (en) * 1999-11-23 2001-02-27 North Carolina State University Methods of blocking ethylene response in plants using cyclopropene derivatives

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 89, no. 5, 1978, Columbus, Ohio, US; abstract no. 42600p, L.S. SURMINA ET AL.: "skeletal rearrangement during the dehydrochlorination of 1,1-dichloro-2-benzylcyclopropane." page 558; column 1; XP002335566 *
E. SCHAUMANN: "(2+1) cycloaddition of chloro(phenylthio)carbene to vinyl silanes.", TETRAHEDRON., vol. 45, no. 10, 1989, NLELSEVIER SCIENCE PUBLISHERS, AMSTERDAM., pages 3163 - 3170, XP002335558 *
M. BAIRD: "a new approach to cyclopropene fatty acids involving 1,2-deiodination", JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 1., vol. 17, 1993, GBCHEMICAL SOCIETY. LETCHWORTH., pages 1547 - 1548, XP009028225 *
MARK BAIRD: "an unusual rearrangement in the iodination of some 1-alkyl- and 1-benzylcyclopropenes.", TETRAHEDRON LETTERS., vol. 36, no. 52, 1995, NLELSEVIER SCIENCE PUBLISHERS, AMSTERDAM., pages 9541 - 9542, XP000402668 *
MARK BAIRD: "highly functionalised methylenecyclopropanes from cyclopropenes.", JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 1., vol. 17, 1993, GBCHEMICAL SOCIETY. LETCHWORTH., pages 1945 - 1946, XP002335559 *
See also references of WO02068367A1 *
ZH. ORG. KHIM., vol. 14, no. 4, 1978, ussr, pages 883 *

Also Published As

Publication number Publication date
KR100921196B1 (ko) 2009-10-13
WO2002068367A1 (fr) 2002-09-06
JP2004532191A (ja) 2004-10-21
CN1463263A (zh) 2003-12-24
CN101979394B (zh) 2013-04-03
CN101979394A (zh) 2011-02-23
KR20030076561A (ko) 2003-09-26
EP1409440A1 (fr) 2004-04-21
JP4785169B2 (ja) 2011-10-05

Similar Documents

Publication Publication Date Title
US20110190137A1 (en) Method to inhibit ethylene responses in plants
US7741245B2 (en) Method for treating plants or plant parts
US6548448B2 (en) Delivery systems for cyclopropenes
JP4306806B2 (ja) 有害生物防除性 ３―（置換フェニル）―５―（チエニルまたはフリル）―１，２，４―トリアゾール
JP4964789B2 (ja) 植物のエチレン応答の阻害方法
WO2002068367A1 (fr) Procede d'inhibition de reponses de l'ethylene chez des vegetaux
US7041625B2 (en) Method to inhibit ethylene responses in plants
US20040072694A1 (en) Method to inhibit ethylene responses in plants
PL157467B1 (pl) Sposób wytwarzania nowych pochodnych ditianu PL PL PL PL
KR101040122B1 (ko) 안정한 에틸렌 억제 화합물 및 그 제조방법
EP1408752B1 (fr) Methode d'inhibition des reponses a l'ethylene chez des vegetaux
AU8106691A (en) Ethynylbenzothiophene pesticides
US4647698A (en) Novel compositions
US20100184600A1 (en) Stable Ethylene Inhibiting Compounds and Methods for Their Preparation

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20040109

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

RIN1 Information on inventor provided before grant (corrected)

Inventor name: EVANS, KAREN, ANDERSON

Inventor name: WEHMEYER, FIONA, LINETTE

Inventor name: KELLY, MARTHA, JEAN

Inventor name: JACOBSON, RICHARD, MARTIN

RIC1 Information provided on ipc code assigned before grant

Ipc: 7C 07C 13/04 B

Ipc: 7A 01N 57/00 B

Ipc: 7A 01N 55/00 B

Ipc: 7A 01N 43/00 B

Ipc: 7A 01N 33/00 B

Ipc: 7A 01N 31/00 B

Ipc: 7A 01N 29/00 B

Ipc: 7A 01N 27/00 B

Ipc: 7C 07C 13/00 A

A4 Supplementary search report drawn up and despatched

Effective date: 20050728

17Q First examination report despatched

Effective date: 20060809

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20140901