Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
  • C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
  • C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen 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
  • C07D203/08—Heterocyclic compounds containing three-membered rings with one nitrogen 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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring nitrogen atom
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
  • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
  • A61P31/04—Antibacterial agents
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
  • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
  • A61P31/10—Antimycotics
• • 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
  • C07D207/04—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 no double bonds between ring members or between ring members and non-ring members
  • C07D207/06—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 no double bonds between ring members or between ring members and non-ring members with radicals, containing only hydrogen and carbon atoms, attached to ring carbon atoms
• • 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
  • C07D207/33—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 ring carbon atoms
  • C07D207/335—Radicals substituted by nitrogen atoms not forming part of a nitro radical
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
  • C07D209/04—Indoles; Hydrogenated indoles
  • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
  • C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
  • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
  • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
  • C07D211/10—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms
  • C07D211/14—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms with hydrocarbon or substituted hydrocarbon radicals attached to the ring nitrogen atom
• • 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
  • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
  • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
  • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
  • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
  • C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
  • C07D223/04—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with only hydrogen atoms, halogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
• • 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
  • C07D233/64—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 substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
• • 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
  • C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
• • 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
  • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
  • C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen 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
  • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
  • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
  • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
  • C07D333/58—Radicals substituted by nitrogen atoms

Definitions

• This invention relates to propenyl-amines, processes for their production and pharmaceutical compositions containing them.
• the present invention provides a compound of formula I, wherein
• lower alkyl or “lower alkoxy” radical mean containing 1 to 4 carbon atoms, especially 2 or 1 carbon atoms.
• Any alkyl (C 1 ⁇ 12 ) moiety is preferably alkyl (C 2 ⁇ 8 ); phenylalkyl or phenylalkoxy has preferably 7 carbon atoms.
• Any alkenyl or alkynyl radical has preferably 3 to 6 carbon atoms, especially 3 or 4 carbon atoms.
• the multiple bond is in other than the ⁇ , ⁇ position and is conveniently in the remote terminal position.
• An example of an alkenyl group is allyl.
• An example of an alkynyl group is propinyl.
• Cycloalkylalkyl has preferably an alkyl moiety of 1 to 4 carbon atoms, especially 2 or 1 carbon atoms, and a cycloalkyl moiety preferably of 3 to 6 carbon atoms.
• R 4 is cycloalkylalkyl this is especially cyclopentyl alkyl or cyclohexylalkyl.
• R 10 is cycloalkylalkyl this is especially cyclopropylalkyl or cyclobutylalkyl.
• R 7 and R 8 are identical and are both hydrogen.
• R 9 is hydrogen or halogen.
• IIb and IIc the bond to the carbon atom to which R 2 and R 3 are attached is conveniently attached meta to X and para to the ring nitrogen, respectively.
• X is conveniently sulphur, imino or lower alkylamino.
• R 1 is preferably a radical of formula IIb, IIc or IId or especially IIa.
• R 2 is preferably hydrogen.
• R 3 is preferably hydrogen and R 4 is conveniently alkyl.
• R 5 is conveniently hydrogen.
• R 6 when it is a heterocycle, conveniently contains one oxygen or sulphur atom or one or two nitrogen atoms.
• the bond linking R 6 to the vinylene moiety is attached to a ring carbon atom adjacent to a ring heteroatom.
• the ring is unsubstituted or substituted by lower alkyl.
• R 10 is conveniently phenylalkoxy.
• IIIa is conveniently optionally substituted 2 or 4-pyridyl.
• IIIc, IIId, IIIe it is to be appreciated that the bond linking R 6 to the vinylene moiety and R 11 to R 13 may be attached to any of the ring carbon atoms present.
• IIIc is preferably a cycloalk-1-en-1-yl radical.
• R 11 to R 13 are hydrogen.
• q is conveniently 0 or 1. Any double bond in IIIf is conveniently trans.
• R 14 is conveniently alkoxy (C 1 ⁇ 8 ) carbonyl, phenyl or alkyl or phenalkyl.
• R 17 is conveniently halogen and R 18 is conveniently hydrogen.
• R 6 is conveniently IIIc.
• u is conveniently 3, 4 or 5, more conveniently 4.
• m, n, p, q, s, t and v are conveniently chosen to produce a five or six-membered ring.
• the double bond between R 6 and the nitrogen atom preferably has the trans configuration.
• Halogen is conveniently fluorine, or preferably bromine or chlorine.
• R 1 is IIb or IIe and R 6 is IIIa it is to be appreciated that the two radicals R 9 may be the same or different.
• the present invention also provides a process for the production of a compound of formula I, selected from
• Process a) may be effected in conventional manner for the production of tertiary amines by condensation from analogous starting materials.
• the process may be effected in an inert solvent such as a lower alkanol, e.g. ethanol, optionally in aqueous admixture, an aromatic hydrocarbon solvent, e.g. benzene or toluene, a cyclic ether, e.g. dioxane or a carboxylic acid dialkylamide solvent, e.g. dimethylformamide.
• the reaction temperature is conveniently from room temperature to the boiling temperature of the reaction mixture, preferably room temperature.
• the reaction is conveniently effected in the presence of an acid binding agent, such as an alkali metal carbonate, e.g.
• the leaving group A is conveniently iodine or preferably chlorine or bromine, or an organic sulphonyloxy group having 1 to 10 carbon atoms, e.g. alkylsulphonyloxy, preferably having 1 to 4 carbon atoms such as mesyloxy, or alkylphenylsulphonyloxy preferably having 7 to 10 carbon atoms such as tosyloxy.
• Process b) may be effected in conventional manner for catalytic hydrogenation in order to produce a compound of formula I wherein the double bond adjacent to R 6 has the cis configuration.
• the process may be effected in conventional manner for a complex metal hydride reduction in order to produce a compound of formula I wherein the double bond has the trans configuration.
• the catalytic hydrogenation may be effected in a solvent, e.g. methanol, ethanol, methylene chloride, pyridine or ethyl acetate.
• the catalyst is preferably palladium on a carrier material such as BaS0 4 or CaC0 3 .
• the catalyst may be pretreated, e.g. with a lead salt, so as to be partially poisoned (e.g. a Lindlar catalyst).
• the hydrogenation may be effected at room temperature and at normal pressure.
• the metal hydride reduction may be effected in conventional manner for a lithium aluminium -hydride or a diisobutylaluminium hydride reduction.
• the reduction is conveniently effected in an inert solvent such as toluene or benzene.
• the reaction is conveniently effected at room temperature.
• Process c) may be effected in conventional manner for a photochemical isomerisation of a cis alkene.
• the reaction may be effected in a solvent such as benzene, petroleum ether, ethanol, or preferably cyclohexane.
• the solution is conveniently irradiated with light from a mercury high or low pressure lamp.
• the reaction is conveniently effected at room temperature.
• an appropriate sensitizer such as eosine or a catalyst such as diphenyldisulphide may be present.
• Process d) may be effected in manner conventional for the "alkylation" of secondary amines (the term “alkylation” being used here to denote introduction of any of the hydrocarbyl groups R 4 ), for example by direct “alkylation” with an “alkylating” agent, for example a halide or sulphate, or by reductive alkylation, in particular by reaction with an appropriate aldehyde and subsequent or simultaneous reduction.
• Reductive "alkylation” is suitably effected in an inert organic solvent, such as a lower alkanol, e.g. methanol, and at an elevated temperature, in particular at the boiling temperature of the reaction medium.
• the subsequent reduction may be effected with, for example, a complex metal hydride reducing agent, e.g. NaBH 4 or LiAIH 4 .
• a complex metal hydride reducing agent e.g. NaBH 4 or LiAIH 4 .
• the reduction may also be effected simultaneously to the alkylation, for example by use of formic acid which may serve both as reducing agent and as a reaction medium.
• side reactions may occur, e.g. reduction of halogen to hydrogen, reduction of a nitro group to an amino group, reduction of an alkenyl moiety to an alkyl moiety and/or reduction of a keto moiety to a carbinol moiety in processes b) or process d) when reductive alkylation is used, or simultaneous cis/trans isomerisation of any double bond present in R 4 or R 6 when process c) is used.
• the reaction conditions should be chosen to avoid such side reactions, and the desired final product isolated using conventional purification techniques, e.g. thin layer chromatography.
• Free base forms of the compounds of formula I may be converted into salt forms and vice versa.
• Suitable acids for acid addition salt formation include hydrochloric acid, fumaric acid and naphthalene-1,5-disulphonic acid.
• non-cyclic amines of formula IV may be made by condensing a compound of formula VIII, or the corresponding iodide or chloride, with a compound of formula R 4 NH 2 .
• cyclic amines of formula IV may be made as follows:- wherein
• Alk lower alkyl
• the compounds of formula VI are new and may be made by reacting an appropriate amine of formula IV with compounds of formulae R 5 ⁇ CHO and under Mannich reaction conditions.
• the title compound may also be made in analogous manner to Examples 3, 4 and 5.
• the title compound may also be made in analogous manner to Examples 1 and 5.
• the title compound may also be prepared by following Examples 1, 4 and 5.
• the title compound may also be prepared by following Examples 1, 3 and 5.
• the title compound may also be prepared in analogous manner to Examples 1, 3 and 4.
• NMR data on the above-mentioned compounds of formula I, obtained as oils, are given in the following table.
• the compounds of formula I exhibit chemotherapeutic activity.
• they exhibit antimycotic activity, as indicated in vitro with tests against various families and types of mycetes, including Trichophton quinkeanum, Aspergillus fumigatus, Microsporum canis Sporotrychium schenkii and Candida albicans, at concentrations of, for example 0.1 to 100 ⁇ g/ml, and in vivo in the experimental skin mycosis model in guinea pigs. In the latter model, guinea pigs are infected by cutaneous application of Trichophyton quinkeanum.
• test substance is administered daily for 7 days beginning 24 hours after the infection by local application by rubbing the test substance (taken up in polyethylene glycol) on the skin surface, or perorally, the test substance being administered as a suspension.
• the activity is shown on local application at concentrations of from example 0.1 to 2%, in particular 0.1 to 0.6%.
• the oral activity is shown at dosages of, for example, 50 to 100 mg/kg.
• the compounds are therefore indicated for use as anti-mycotic agents.
• daily dose is from 500 to 2000 mg. If desired, this may be administered in divided doses 2 to 4 times a day in unit dosage form containing from about 125 mg to about 1000 mg or in sustained release form.
• the compounds may be used in free base form or in the form of chemotherapeutically acceptable acid addition salts. Such salt forms exhibit the same order of activity as the free base forms.
• the compounds may be admixed with conventional chemotherapeutically acceptable diluents and carriers, and, optionally, other excipients and administered in such forms as tablets or capsules.
• the compounds may alternatively be administered topically in such conventional forms as ointments or creams.
• concentration of the active substance in such topical application forms will of course vary depending on the compound employed, the treatment desired and the nature of the form etc. In general, however, satisfactory results are obtained at concentrations of from 0.05 to 3, in particular 0.1 to 1 wt 96.
• a compound with particularly interesting activity is the compound of Example 4.
• One group of compounds has a formula Ig, wherein
• Another group of compounds comprises those of formula Ih, wherein
• a further group of formula I compounds comprises compounds of formula li, wherein

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• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Heterocyclic Compounds Containing Sulfur Atoms (AREA)
• Furan Compounds (AREA)
• Pyridine Compounds (AREA)
• Pyrrole Compounds (AREA)
• Quinoline Compounds (AREA)
• Indole Compounds (AREA)
• Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

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• 1978
  • 1978-08-07 DE DE7878100611T patent/DE2862103D1/de not_active Expired
  • 1978-08-07 EP EP78100611A patent/EP0000896B1/en not_active Expired
  • 1978-08-10 DK DK354678A patent/DK152114C/da not_active IP Right Cessation
  • 1978-08-10 FI FI782446A patent/FI65774C/fi not_active IP Right Cessation
  • 1978-08-17 IE IE1670/78A patent/IE47314B1/en not_active IP Right Cessation
  • 1978-08-17 IL IL55382A patent/IL55382A/xx active IP Right Grant
  • 1978-08-17 NZ NZ188170A patent/NZ188170A/xx unknown
  • 1978-08-17 ES ES472641A patent/ES472641A1/es not_active Expired
  • 1978-08-17 CA CA309,579A patent/CA1111852A/en not_active Expired
  • 1978-08-18 US US06/934,772 patent/US4680291A/en not_active Expired - Lifetime
  • 1978-08-18 PT PT68448A patent/PT68448A/pt unknown
  • 1978-08-18 IT IT26835/78A patent/IT1098253B/it active
  • 1978-08-19 JP JP10137578A patent/JPS5441855A/ja active Granted
• 1985
  • 1985-12-30 MY MY40/85A patent/MY8500040A/xx unknown

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