ES362299A1 - Cyclohexene carboxylic acids and cyclohexane carboxylic acids and derivatives thereof and process for their production - Google Patents

Cyclohexene carboxylic acids and cyclohexane carboxylic acids and derivatives thereof and process for their production

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Publication number
ES362299A1
ES362299A1 ES362299A ES362299A ES362299A1 ES 362299 A1 ES362299 A1 ES 362299A1 ES 362299 A ES362299 A ES 362299A ES 362299 A ES362299 A ES 362299A ES 362299 A1 ES362299 A1 ES 362299A1
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ES
Spain
Prior art keywords
acid
hydrogen
converting
alkali metal
group
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.)
Expired
Application number
ES362299A
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Spanish (es)
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.)
Roche Palo Alto LLC
Original Assignee
Roche Palo Alto LLC
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 Roche Palo Alto LLC filed Critical Roche Palo Alto LLC
Publication of ES362299A1 publication Critical patent/ES362299A1/en
Expired legal-status Critical Current

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    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/12—Esters of phosphoric acids with hydroxyaryl 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing aromatic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C335/30—Isothioureas
    • C07C335/32—Isothioureas having sulfur atoms of isothiourea groups bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/18—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with unsaturation outside the aromatic ring
    • C07C39/19—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with unsaturation outside the aromatic ring containing carbon-to-carbon double bonds but no carbon-to-carbon triple bonds
    • 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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy 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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
    • C07C45/292—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with chromium derivatives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C61/12—Saturated polycyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C61/16—Unsaturated compounds
    • C07C61/28—Unsaturated compounds polycyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C62/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C62/08—Saturated compounds containing ether groups, groups, groups, or groups
    • C07C62/12—Saturated compounds containing ether groups, groups, groups, or groups polycyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C62/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C62/30—Unsaturated compounds
    • C07C62/32—Unsaturated compounds containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C62/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C62/30—Unsaturated compounds
    • C07C62/34—Unsaturated compounds containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C62/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C62/30—Unsaturated compounds
    • C07C62/38—Unsaturated compounds containing keto groups
    • 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
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no 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
    • C07D307/20—Oxygen atoms
    • 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
    • C07D307/60—Two oxygen atoms, e.g. succinic anhydride
    • 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
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/88—Benzo [c] furans; Hydrogenated benzo [c] furans with one oxygen atom directly attached in position 1 or 3
    • 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
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no 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
    • C07D309/10—Oxygen atoms
    • C07D309/12—Oxygen atoms only hydrogen atoms and one oxygen atom directly attached to ring carbon atoms, e.g. tetrahydropyranyl ethers

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

Abstract

The invention comprises compounds of Formula (I): wherein R1 is methyl or ethyl R2' is hydrogen or methyl R3 is methyl, ethyl or isopropyl R4 is hydrogen, lower alkoxy, hydroxy and the hydrolysable carboxylic esters thereof, cyclopentyloxy, cyclohexyloxy, tetrahydropyran-21- yloxy, tetrahydrofuran-21-yloxy, the group OSO 2 OX or the group OPO(OX) 2 , wherein X is hydrogen or an alkali metal atom R5 is hydrogen, lower alkyl, lower alkoxy, hydroxy and the hydrolysable carboxylic esters thereof, cyclopentyloxy, cyclohexyloxy, tetrahydropyran-21-yloxy, tetrahydrofuran-21-yloxy, the group OSO 2 OX or the group OPO(OX) 2 , wherein X is hydrogen or an alkali metal atom R6' is hydroxymethyl or the hydrolysable carboxylic esters thereof, formyl, -COCl, -COF, -CONH 2 or the group -COOR7' in which R7 is hydrogen, lower alkyl or an alkali metal atom and Z and Z1 is a carbon to carbon single bond or double bond provided that at least one of Z and Z1 is a carbon to carbon single bond, provided that when R6' is -COCl or -COF, that each of R4 and R5 is other than the group OSO 2 OX or the group OPO(OX) 2 , provided further that when R3 is ethyl, R4 is lower alkoxy, R5 is H and R6 is -COOR7, then R2' is methyl. Lower alkyl and alkoxy are defined as having 1 to 6 carbon atoms. The invention further comprises a process for the preparation of compounds of the above formula, but wherein R1 is hydrogen, methyl or ethyl and R3 is hydrogen, methyl, ethyl or isopropyl and subject to only the first of the above provisos, wherein (a) to obtain a cyolohex-3-ene carboxylic acid a compound of Formula (II) or the corresponding isothiouroniun acetate is reacted with a compound of Formula (III) in an aqueous solution of a water-miscible organic solvent, followed by acid treatment to yield a compound of Formula (IV) treating said compound with an aqueous watermiscible organic solvent solution of an alkali metal hydroxide followed by carbonyl reduction in a divided electrolysis cell in an electrolyte medium comprising a mineral acid electrolyte, water and an inert water-miscible organic solvent at a current density of from about 0À01 to about 0À2 ampere per square centimeter or (b) for preparing a cyclohexane carboxylic acid, catalytically hydrogenating the thus obtained cyclohex-3-enecarboxylic acid, or (c) for preparing a cyclohex-4-enecarboxylic acid, heating the thus obtained cyclohex-3-enecarboxylic acid with hydrogen chloride in an organic solvent and optionally treating any one of the thus-obtained cyclohex-3-enecarboxylic acid, cyclohexanecarboxylic acid and cyclohex-4-enecarboxylic acid products by any of the following steps: (1) converting to the corresponding acid chloride by treatment with triphenylphosphine in carbon tetrachloride or with thionyl or oxalyl chloride (2) converting to the corresponding acid fluoride with N-(2-chloro-1,1,2- trifluoroethyl)diethylamine, (3) converting to the corresponding amide by sequential treatment with thionyl chloride and anhydrous ammonia, (4) converting to the corresponding alkali metal salt by treatment with an alkali metal hydroxide or bicarbonate solution, (5) converting said alkali metal salt to the corresponding acid ester by treatment with lower alkyl iodide or bromide, (6) converting said acid ester to the corresponding hydroxymethyl compound by treatment with an aluminum hydride reagent, (7) esterifying said hydroxymethyl compound to a corresponding hydrolysable carboxylic ester of the hydroxymethyl group, (8) converting said hydroxymethyl compound to the corresponding aldehyde by treatment with chromium trioxide in pyridine, (9) converting any free ring hydroxy group to a group of the formula OSO 2 OX wherein X is hydrogen or an alkali metal, (10) converting any free ring OH groups to OPO(OX) 2 groups wherein X is H or an alkali metal atom and (11) restoring any acid and/or base labile derivatives of free OH groups which may have been removed during any of the preceding steps (1) to (10). The compounds of Formula (I) admixed with an edible bait are used as anti-fertility agents in the control of rodents.
ES362299A 1968-01-11 1969-01-09 Cyclohexene carboxylic acids and cyclohexane carboxylic acids and derivatives thereof and process for their production Expired ES362299A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US69701068A 1968-01-11 1968-01-11

Publications (1)

Publication Number Publication Date
ES362299A1 true ES362299A1 (en) 1970-12-01

Family

ID=24799417

Family Applications (1)

Application Number Title Priority Date Filing Date
ES362299A Expired ES362299A1 (en) 1968-01-11 1969-01-09 Cyclohexene carboxylic acids and cyclohexane carboxylic acids and derivatives thereof and process for their production

Country Status (5)

Country Link
CA (1) CA924312A (en)
CH (1) CH530952A (en)
DE (1) DE1900668A1 (en)
ES (1) ES362299A1 (en)
GB (2) GB1262491A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9522857B2 (en) * 2011-05-18 2016-12-20 Ube Industries, Ltd. 3,3′,4,4′-tetraalkyl cyclohexylbenzene and method for producing same

Also Published As

Publication number Publication date
CH530952A (en) 1972-11-30
DE1900668A1 (en) 1969-08-28
CA924312A (en) 1973-04-10
GB1262491A (en) 1972-02-02
GB1262492A (en) 1972-02-02

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