Classifications

• • 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
  • C07D317/44—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 ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D317/46—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 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
  • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
  • C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring 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 atoms of the carbocyclic ring
  • C07D317/64—Oxygen atoms
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
  • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
  • A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
  • C07C201/06—Preparation of nitro compounds
  • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
• • 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
  • C07C323/10—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 singly-bound oxygen atoms bound to the same carbon skeleton
  • C07C323/11—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 singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
  • C07C323/14—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 singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and unsaturated
• • 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
  • C07C323/10—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 singly-bound oxygen atoms bound to the same carbon skeleton
  • C07C323/11—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 singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
  • C07C323/16—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 singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing 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
  • C07C323/10—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 singly-bound oxygen atoms bound to the same carbon skeleton
  • C07C323/18—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 singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
  • C07C323/20—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 singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton with singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
• • 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
  • C07C323/50—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 carboxyl groups bound to the same carbon skeleton
  • C07C323/62—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 carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring 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
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
  • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
  • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
  • C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
• • 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
  • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
  • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
  • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
  • C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
  • C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
  • C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
• • 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
  • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
  • C07C69/92—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with etherified hydroxyl groups
• • 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
  • C07D317/44—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 ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D317/46—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 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
  • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
  • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
  • C07D317/52—Radicals substituted by halogen atoms or nitro radicals
• • 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
  • C07D317/44—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 ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D317/46—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 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
  • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
  • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
  • C07D317/54—Radicals substituted by oxygen atoms
• • 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
  • C07D317/44—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 ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D317/46—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 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
  • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
  • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
  • C07D317/56—Radicals substituted by sulfur atoms
• • 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
  • C07D317/44—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 ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D317/46—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 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
  • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
  • C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring 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 atoms of the carbocyclic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
  • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated

Definitions

• R to R have various significances including e.g. alkyl, X and Y include 0 and S and s, v and w are whole numbers and Ar is phenyl or substituted phenyl.
• the compounds possess insecticidal properties.
• the present invention relates to ethers and thioethers and more specifically to aromatic ethers and thioethers.
• the present invention provides compounds of formula I,
• W is alkyl of 1 to carbon atoms, fluorine, chlorine or bromine,
• R and R which may be the same or different, are
• R is alkyl of l to 11 carbon atoms, non-cyclic hydrocarbon of up to 11 carbon atoms having one or two double bonds or one triple bond, cycloalkyl of 4 to 7 carbon atoms, alkyl substituted cycloalkyl of 4 to 7 ring carbon atoms the alkyl substituent having 1 to 5 carbon atoms, cycloalkenyl of 4 to 7 carbon atoms, alkyl substituted cycloalkenyl of 4 to 7 ring carbon atoms the alkyl substituent having 1 to 5 carbon atoms, phenyl, Ar which has the same definition as -Ar above wherein Ar and Ar may be the same or different,
• R R R R R R R R and R which may be the same or different, are each hydrogen, alkyl of 1 to 5 carbon atoms or alkenyl of 2 to 6 carbon atoms,
• Y is oxygen or sulphur
• X is oxygen, sulphur, OCH ---or SCH s, v, and w, which may be the same or different, are
• alkyl, alkenyl, alkoxy and non-cyclic hydrocarbon cover both; straight and branched chain configurations thereof.
• Hal is chlorine or bromine
• 'M is hydrogen, potassium or sodium
• Hal is chlorine or bromine
• R and R or R and R are'other than hydrogen
• Ra iv V wherein R ,Y and s are as defined in relation to formula I, and Me is sodium or potassium,
• a compound of formula Ia i.e. a compound of formula I wherein z is l, v+w is 0 or 2, or when v+w,,;is
• R1 R2! R3, R4 R5, R6, R7 R8 R9: Y, w and Z are as defined in relation to formula I, with a compound of formula IIIa Ar 'OH IIIa wherein Ar, is as defined in relation to formula I, in the presence of dicyclohexylcarbodiimide as condensation agent, to produce a compound of formula Ib, i.e. a compound of formula I wherein X is oxygen, or
• a compound of formula III is conveniently reacted in a solvent, for example, a hydrocarbon such as benzene, an ether such as dioxane, 1,2-dimethoxyethane, diethyleneglycol-dimethyl ether, an alcohol such as ethanol, tert. butanol, a ketone such as acetone, a nitrile such as acetonitrile, an acid amide such as dimethylformamide, or in an appropriate solvent mixture, in the presence of an acid binding agent, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, potassium-tert.butoxide, at a temperature between prefer-. ably 0 and about 100 C. with a compound of formula II. Potassium iodide may, conveniently be added in catalytic amounts to the reaction mixture as catalyst.
• a solvent for example, a hydrocarbon such as benzene, an ether such as dioxane, 1,2-dimethoxyethane, diethyleneg
• a compound of formula VIa or V'Ib is reacted, conveniently in an appropriate solvent, for example a hydrocarbon such as benzene, an ether such as 1,2-dimethoxyethane, an alcohol such as ethanol or tert.butanol, a ketone such as acetone, a nitrile such as acetonitrile, an acid amide such as dimethyl formamide, or in an appropriate solvent mixture, in the presence of an acid binding agent, for example sodium hydroxide and potassium hydroxide, at a temperature between and 100 C. with a compound of formula VlII.
• Working up of the reaction product is effect in conventional manner.
• the reaction may be effected in the absence of an acid binding agent.
• the reaction may be effected in an appropriate solvent, such as benzene, tert.butanol, 1,2-dimethoxyethane, dimethylformamide.
• Working up is effected in the usual manner.
• the compounds of formula II employed as starting material in the production of compounds of formula I in accordance with process (a) above, may be produced by a process as follows viz.
• a halide transmitter e.g. hydrobromic acid, thionyl halides or a suitable phosphorous halide in the presence of an acid binding agent to obtain a compound of formula Ila i.e. a compound of formula II, wherein z is 1.
• R R are as defined in relation to formula 1, Hal is chlorine or bromine, each of R R R R R and R is hydrogen, and each of v and w is 0 or 1, with a compound of formula V, to produce a compound of formula IId i.e. a compound of formula II, wherein R and R is hydrogen, and each of v and w is 0.
• reaction temperature and solvent depend on the halide transmitter employed. Thus, with 48% by weight hydrogen bromide or hydrochloric acid no solvent is required and the reaction temperature may be between -20 and 0 C.
• a suitable solvent is ether and a suitable reaction temperature is room temperature.
• phosphorous halides e.g. phosphorous tribromide
• pyridine may be employed as solvent which also serves as acid binding agent and a suitable reaction temperature is between 20 and 0 C.
• the compounds of formula XIII employed as starting material in process (a) above may, for example, be produced by reacting a compound of formula IX,
• R Y, v, and w are as defined in relation to formula I,
• HzC C wherein R is as defined above, and Mt is MgCl, MgBr or Li in organometallic bond,
• the reaction may be effected with or without a solvent.
• a suitable solvent is ether.
• the reaction temperature may vary between 0 and 30 C.
• the starting compounds of formula VIa, wherein z is 3 employed in process (c') and also in process (c) above for the production of some of the compound of formula Ib and in process (d) above for the production, of some of the compounds of formula Ic, may be produced by sodium bromohydride reduction of a compound of formula XVI,
• the compounds of formula XVI may, for example, be obtained by reacting the compounds of formula VIII with alkyl vinyl ethers in the presence of mercury-II- acetate at an elevated temperature, preferably for a period of e.g. 4 days, and subsequent transposition by short heating to l60l90 C., preferably over 1 to 2 hours.
• the production of compounds of formula IId in accordance with process (d') may be effected as follows viz.
• the compounds of formulae V and XIIIa are dissolved in a suitable solvent e.g. an alcohol of formula R (CH OH- or thioalcohol of formula R (CH ,SH wherein R and s correspond to those of formula V, and acid amide e.g. dimethyl formamide, or a sulphoxide e.g. dimethyl sulphoxide and the reaction is effected at a temperature of between 0 and C. preferably between 20 and 30 C.
• a suitable solvent e.g. an alcohol of formula R (CH OH- or thioalcohol of formula R (CH ,SH wherein R and s correspond to those of formula V, and acid amide e.g. dimethyl formamide, or a sulphoxide e.g. dimethyl sulphoxide and the reaction is effected at a temperature of between 0 and C. preferably
• the compounds of formula XIV employed as starting material in process (e') above may be produced by reacting a compound of formula 1X with a Grignard compound of formula XV,
• the compounds of formula VIa when z is 2 may be effected by reacting a compound of formula II wherein z is 2 with potassium acetate, preferably in glacial acetic acid under reflux and hydrolysing the resulting acetate with methanolic potassium hydroxide.
• the compound of formula VIb employed as a starting material in process (d) above for the production of some of the compounds of formula 10, wherein z is 1 or 3 may be produced as follows viz.
• Dysdercus fasciatus (Egyptain cotton worm) Prodenia littura (cotton stainer) Tenebrio molitor (flour beetle) and Tetranychus urticae (red spider) from one development stage thereof to the next, to result either in death or reduced oviposition or inhibition of copulation as indicated by the following tests viz.
• TEST 2 Effect on the development of Prodenia littura larvae (cotton stainer) into adults
• Filter paper is impregnated with a solution of a compound of formula I.
• Partitions, having a size of 3.5 x 5.5 cm., of a plastic box are coated with the filter paper treated in this way.
• One Prodenia caterpillar in the third to fourth larval stage is placed into each partition and a piece of artificial medium is given as food. The insects are kept at The number of the adults which have developed normally after 21 days is determined.
• TEST 3 Effect on the development of Tenebrio molitor chrysales (flour beetle) into adults
• a compound of formula I is used at a concentration of 1% by weight in acetonic solution. 2 ,ul. of the resulting solution, corresponding to 20 micrograms of compound,
• the amount applied to a locus to be treated e.g. a plant culture
• the amount applied to a locus to be treated will of course vary depending on the compound employed, the mode of application, ambient conditions, and the insects to be combated.
• a compound of formula I is applied to the locus in an amount between 1 and 10 kg./hectare, the application being repeated as required.
• the compounds may be applied to the locus with conventional applicator equipment and by conventional methods e.g. strewing, spraying and dusting.
• Compositions may be produced in conventional manner and may comprise a compound of formula I in ad mixture with insecticidal carriers e.g. talc, diatomaceous earth, bentonite and pumice, insecticidal diluents e.g. Water or appropriate organic solvents such as alcohols, petroleum and tar distillates and/ or insecticidal adjuvants e.g. emulsifying agents, solvent aids such as mineral oils and wetting and adhesive agents such as cellulose derivatives.
• insecticidal carriers e.g. talc, diatomaceous earth, bentonite and pumice
• insecticidal diluents e.g. Water or appropriate organic solvents such as alcohols, petroleum and tar distillates and/ or insecticidal adjuvants e.g. emulsifying agents, solvent aids such as mineral oils and wetting and adhesive agents such as cellulose derivatives.
• insecticidal carriers e.g. talc, diatomace
• Concentrate forms of the compositions may generally contain between 2 and preferably between 5 and 50% by weight, of a compound of formula I.
• compositions may generally contain between 0.01 and 0.1%, by weight of a compound of formula I.
• EXAMPLE 1 2-(3-Ethyl-5-sec.butoxy-2-pentenyloxy)-benzaldehyde (according to process (a)) 10 1-bromo-3-ethyl-5-sec;butoxy-2-pentene is added without purification to 6.1 g. (0.05 mol) of salicylic aldehyde and 2.8 g. (0.05 mol) of potassium hydroxide in 80 cc. of 1,2-dimethoxy ethane. The mixture is stirred.
• the obtained 2-(3 ethyl-5-sec.butoxy -i2 pentenyloxy)- benzaldehyde may be purified by chromatography on silica gel with hexane/ethyl acetate l:1 as elant. ⁇ 1 1.5090.
• CiaH2a04 320-4 -511 66 10 4-(3-ethyl-5-isopropoxy-2-pentenyloxy)benzoic methyl ester iaHz
• EXAMPLE 36 5 (4-Isobutoxy-2-methyl-2-butenyloxy)-1,3-benzodioxol (according to process (a)) 2.21 g. (0.01 mol) of 1-bromo-4-isobutoxy-Z-methyl-Z- butene are added at 0 during the course of 5 minutes to 1.38 g. (0.01 mol) of 3,4-methylendioxy-phenol and 0.56 g. (0.01 mol) of potassium hydroxide in cc. of 1,2-dimethoxyethane. After stirring the reaction mixture at room temperature for 24 hours it is filtered and the solvent is distilled off at reduced pressure.
• EXAMPLE 37 5-(6-Isopropoxy-4-methyl-3-hexenyloxy)-1,3-benzodioxol (according to process (a)) 2.35 g. (0.017 mol) of potassium carbonate and 50 mg. of potassium iodide are added to a solution of 4.0 g. (0.017 mol) of 1-bromo-6-isopropoxy-4-methyl-3-hexene and 2.35 g. (0.017 mol) of 3,4-methylendioxy-phenol in 120 cc. of acetone. The suspension is boiled under reflux during the course of 20 hours, is then filtered and liberated from acetone in a vacuum.
• EXAMPLE 39 5 (5 -Isoprop oxy-2-pentenyloxy) 1,3 -benzodioxol Analysis: C H O (molecular weight: 264.3). Calc.: C, 68.2%; H, 7.6%; O, 24.2%. Found: C, 68.4%; 8.0%; O, 24.1%.
• EXAMPLE 40 4- 5-Isopropoxy-2-pentenylthio -methyl] -chorobenzol (according to process (a)) 8.1 g. (0.05 mol) of 1-chloro-5-isopropoxy-2-pentene are added dropwise at 20-25 during the course of 10 minutes and while stirring to a solution of 7.9 g. (0.05 mol) of 4-chloro-benzylmercaptan and 5.6 g. (0.05 mol) of potassium tert.butoxide in 150 cc. of tert.butanol. The solution which is rendered turbid during the addition is stirred at 60 during the course of 1 hour and is then cooled and filtered.
• EXAMPLE 41 (5-Isopropoxy-3-methyl-2-pentenyloxy)-methyl] 1,3- benzodioxol (according to process (a)) 15.8 g. (0.1 mol) of 5-isopropoxy-3-methyl-1-penten-3- 01 are added dropwise at 5 during the course of 15 minutes and while stirring to 40 cc. of 48% hydrobromic acid. After 30 minutes at 0-5 the mixture is extracted with ether, the ether extract is extracted with soda solution and subsequently with saturated salt solution, is
• EXAMPLE 43 5-[ 5-Isopropoxy-3-methyl-2-pentenyloxy -methyl] 1,3-benzodioxol (according to process (a)) 8.0 g. (0.2 mol) of sodium hydroxide are added to' a solution of 30.4 g. (0.2 mol) of3,4-methylendioxy-benzylalcohol in 300 cc. of benzene. The mixture is heated while stirring vigorously and kept at reflux temperature Whereby the water condensing in a refrigerator is separated by means of a water separator. After 24 hours 35.3 g. (0.2 mol) of 1-chloro-'5-isopropoxy-3-methyl-2-pentene are added dropwise during the course of 1 hour and the mixture is stirred underreflux for a further 16 hours.
• the product is identical with the compound produced in accordance with Example 41.
• EXAMPIJE 44- 5-(4-Isobutoxy-3-methyl-2-butenyloxy) 1,3- benzodioxol (according to process (b)) 1.6 g. (0.01 65 mol) of sodium-isobutylate in 75 cc; 01' isobutanol are added dropwise at 70 during the course of 15 minutes to 4.3 g. (0.015 mol) of 5-(4-bromo-3- methyl-2-butenyloxy)-1,3-benzodi0xol which is dissolved in 130 cc. of isobutanol. After 3 hours at this temperature the reaction mixture is filtered, the solvent is distilled 01f at reduced pressure and the residue is dissolved in ether.
• EXAMPLE 46 4'-(4-Isobutoxy-3-methyl-2-butenyloxy)-acetophenone Analysis: C H O (molecular weight: 276.4). Calc.: C, 73.8%; H, 8.7%; O, 17.3%. Found: C, 73.4%; H, 9.1%; O, 18.1%.
• EXAMPLE 49 4'-(4-Benzylthio-3-methyl-2-butenyloxy)-acetophenone (according to process (b)) 14.15 g. (0.05 mol) of 4'-(4-bromo-3-methyl-2-butenyloxy)-acetophenone are added at -15 during the course of 1 hour to 7.3 g. (0.05 mol) of sodium salt of benzylmercaptan which is dissolved in 120 cc. of dimethylformamide. The mixture is stirred at -25" for 20 hours, is subsequently filtered and the filtrate is evaporated at reduced pressure. The residue is dissolved in ether, is extracted with saturated salt solution and the ether solution is evaporated.
• EXAMPLE 50' 5- (4-Isobutylthio-3-methyl-2-butenyloxy) 1,3-benzodioxol (according to process (b) A solution of 4.3 g. (0.015 mol) of 5-(4-bromo-3- methyl-2-butenyloxy)-1,3-benzodioxol in 50 cc. of benzene is added at to 1.7 g. (0.015 mol) of sodium-isobutylthio alcoholate in cc. of benzene. The mixture is kept at reflux temperature for 13 hours, is subsequently filtered, washed with saturated salt solution and evaporated.
• EXAMPLE 53 4-Is obutoxy-2-butenyloxy -1,3-benzodioxol (according to process (b)) 1.9 g. (0.02 mol) of sodium-isobutylate in 30 cc. of isobutanol are added dropwise at 50 during the course of 2 hours to a solution of 5.4 g. (0.02 mol) of 5-(4-bromo-2- butenyloxy)-1,3-benzodioxol in 100 cc. of isobutanol. After stirring the reaction mixture at 50 for 6 hours it is filtered and the solvent of the filtrate is distilled olf at reduced pressure.
• EXAIVHLE 54 4-(4-Isobutoxy-2-butenyloxy)-acetophenone Analysis: C H O (molecular weight: 262.3). Calc.: C, 73.3%; H, 8.5%. Found: C, 73.5%; H, 8.6%.
• EXAMPLE 56 5 (7-Isopropoxy-5 -methyl-4-heptenyloxy -1, 3- benzodioxol (according to process (0)) A mixture of 2.5 g. (0.013 mol) of 7-isopropoxy-5- methyl-4-cis,trans-heptenol, 1.25 g. (0.009 mol) of 3,4
• the remaining vinyl-bromide solution is added dropwise at such afratethat the reaction mixture maintains a temperature of 4 516 50 (approximately 1 to 1% hours). Then the 'mix-ture -is stirred at 50 for 1 hour and 1 subsequentlycoole'd 'to 0, 52 g. (0.4 mol) of 4 isopropoxy-2 butanone in 100 cc. of absolute tetrahydrofurane are addeddropwise 'duiing the course of 45 minutes and while stir ring vigorously; the reaction mixture is subsequently stirred at room temperature during the course of 16hours. After this period 250 cc. of a 20% ammonium chloride solution are added during the course of 15 minutes to the reaction mixture which is cooled to 5-10.
• CioHruOS 188.3 8689/0.85 1.4844 18.; 2 4-sec.butylthio-2-butanone.
• the compounds of general formula II may be produced in accordance with the following Example:
• EXAMPLE 84 1 1-Chloro-S-isopropoxy-Z-pentene 13 g. (0.24 mol) of butadiene are introduced at l015 during the course of 1% hours and while stirring into a suspension of 0.8 g. of newly melted zinc chloride in 21.7 g. (0.2 mol) of chloromethyl-isopropylether. The mixture which has now turned yellow is stirred at for 1 hour. After this period 20 cc. of 10% sodium car- 'bonate solution are added dropwise, 100 cc. of benzene are added and the aqueous phase is separated in a separatory funnel. The benzene solution is washed with 10% sodium carbonate solution and subsequently with water, is" dried with magnesium sulphate and evaporated at reduced pressure. The residue is distilled at 90 mm. B.P.
• EMMPLE 87 4- (4-Bromo-3-methyl-2-butenyloxy)-benzoic methyl ester Analysis: C H Br O (molecular Weight: 299.2). Calc.: C, 52.2%; H, 5.1%; Br, 26.7%. Found: C, 52.3%; H, 5.1%; Br, 26.4%.
• EXAMPLE 88 5-[(4-Bromo-3-methyl-2-butenyloxy)-methyl]- 1,3-benzodioxol 8.7 g. (0.05 mol) of sodium salt of the 3,4-methylendioxybenzylalcohol are added at 0 during the course of 15 minutes and while stirring to 12.5 g. (0.055 mol) of 1,4-dibromo-2-methyl-2-butene which is dissolved in 100 cc. of 1,2-dimethoxyethane. The mixture is stirred at 2025 for 16 hours and at 50 for 15 minutes. The solvent is then distilled off at reduced pressure and 100 cc. amounts of water and ether are added to the residue.
• EXAMPLE 89 5- (4-Bromo-2-butenyloxy) -1,3-b enz"odioxol 6.4g. (0.04 mol) of sodium salt of 3,4-methylendioxyphenol are added at 20 to a solution of'8L6 g. (0.04 mol) of 1,4-dibr'omo-2-butene in 100 cc. of 1,2-dimethoxyethane. The mixture is stirred at 0 for 3 hours and subsequently at room temperature for 1 hour. The'solve'nt is distilled off at reduced-pressure and the residue is taken up in ether. Theether solution is extracted with saturated salt solution, is dried with sodium sulphate and evaporated.
• the compounds of general formula VI may be produced inaccordance with the following Example:
• the reaction mixture is extracted with ether, the ether extract is washed with saturated salt solution, is dried with sodium sulphate and the ether is evaporated.
• the residue is fractionated at 16 mm., whereby the 5-isopropoxy-2-penten-l-thiol is obtained as malodorous oil which is uniform according to gas-chromatography; it has a B.P. of 87-89/16 mm.
• I I v.ZI is alkyl of 1 to 5 carbon atoms,.alkenyl of 2to ,12 Q ,carbonatoms, alkoxy of 1 to 5 carbon atoms, alkenyloxy of 2 to 12 carbon .atoms'formyl, alky'l' carbonyl h '1.
• I bromine, cyano or nitro I H R and'R which may bethe same or diifereiit, are
• R represents a single R is alkyl of 1 to 11 carbon atoms or an acyclic hydrocarbon of up to 11 carbon atoms having one or two double bonds or one triple bond,
• R R R R R R R R and R which may be the same or different, are each hydrogen, alkyl of 1 to 5 carbon atoms or alkenyl of 2 to 6 carbon atoms,
• Y is oxygen or sulphur
• X is oxygen, sulphur, -OCH or SCH s, v and w, which may be the same or different, are
• z is 1, 2 or 3.
• DONALD G. DAUS Primary Examiner I. H. TURNIPSEED, Assistant Examiner US. Cl. X.R. 260340.3, 473 R, 592, 609 R, 611 A; 424-282

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Plant Pathology (AREA)
• Pest Control & Pesticides (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Agronomy & Crop Science (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Priority Applications (3)

Applications Claiming Priority (4)

Related Child Applications (3)

Publications (1)

Family

ID=27429504

Family Applications (1)

Country Status (15)

Cited By (4)

Families Citing this family (2)

• 1971
  • 1971-12-09 DE DE19712161150 patent/DE2161150A1/de active Pending
  • 1971-12-10 NL NL7117017A patent/NL7117017A/xx unknown
  • 1971-12-10 GB GB5737971A patent/GB1377219A/en not_active Expired
  • 1971-12-13 BR BR8246/71A patent/BR7108246D0/pt unknown
  • 1971-12-13 RO RO69041A patent/RO61639A/ro unknown
  • 1971-12-13 IT IT32325/71A patent/IT943901B/it active
  • 1971-12-13 DD DD164091A patent/DD99574A5/xx unknown
  • 1971-12-13 PL PL1971158176A patent/PL89039B1/pl unknown
  • 1971-12-13 DK DK608671A patent/DK131987C/da active
  • 1971-12-13 US US00207633A patent/US3829442A/en not_active Expired - Lifetime
  • 1971-12-13 HU HUSA2524A patent/HU166922B/hu unknown
  • 1971-12-13 HU HUSA2287A patent/HU164504B/hu unknown
  • 1971-12-13 BE BE776621A patent/BE776621A/fr unknown
  • 1971-12-13 RO RO7100078038A patent/RO62717A/fr unknown
  • 1971-12-13 IL IL38345A patent/IL38345A0/xx unknown
  • 1971-12-13 DD DD159537A patent/DD95486A5/xx unknown
  • 1971-12-14 AU AU36870/71A patent/AU3687071A/en not_active Expired
  • 1971-12-14 FR FR7144934A patent/FR2131931B1/fr not_active Expired

Also Published As

Similar Documents