Classifications

• • 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
  • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
  • C07D213/53—Nitrogen atoms
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
  • A61P29/00—Non-central analgesic, antipyretic or antiinflammatory agents, e.g. antirheumatic agents; Non-steroidal antiinflammatory drugs [NSAID]
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
  • A61P9/00—Drugs for disorders of the cardiovascular system
  • A61P9/06—Antiarrhythmics
• • 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
  • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
  • C07D213/46—Oxygen atoms
  • C07D213/50—Ketonic 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
  • C07D233/66—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 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
  • C07D233/84—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
  • C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
  • C07D277/18—Nitrogen 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
  • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole 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
  • C07D277/38—Nitrogen atoms
  • C07D277/40—Unsubstituted amino or imino radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
  • C07D279/04—1,3-Thiazines; Hydrogenated 1,3-thiazines
  • C07D279/06—1,3-Thiazines; Hydrogenated 1,3-thiazines not condensed with other rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
  • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
  • C07D513/04—Ortho-condensed systems

Definitions

• the invention relates to new bicyclic thia-diaza compounds, in particular 1,3-diaza-cyclopent-2-eno [2,1-b] (1-thia-3-aza-cycloalkanes) of the general formula (I) whose 1,3-diaza-cyclopent-2-ene ring may have a further double bond,
• Alk represents lower alkylene which separates the thia from the aza atom by 2-4 carbon atoms
• Ar 1 and Ar 2 independently of one another optionally substituted phenyl, Pyridyl or thienyl and n is 0, 1 or 2, with the proviso that at least one of the radicals Ar 1 and Ar 2 is different from phenyl when alk ethylene and the 1,3-diaza-cyclopent-2-ene ring represents an imidazole ring, and their salts, and processes for their preparation, furthermore pharmaceutical preparations containing these compounds and their use, preferably in the form of pharmaceutical preparations.
• radicals and compounds designated "lower" in connection with the present description preferably contain up to 7 and primarily up to 4 carbon atoms.
• Lower alkylene alk is preferably unbranched, but also branched lower alkylene with 2-4 carbon atoms in the chain between the sulfur and the nitrogen atom.
• Pyridyl is a 2-, 3- or 4-pyridyl and thienyl is a 3- or especially 2-thienyl.
• Substituted phenyl, pyridyl or thienyl is e.g. single, double or multiple substituted.
• Substituents, especially on the phenyl radical include Lower alkyl, lower alkoxy, halogen, trifluoromethyl, lower alkylsulfonyl or nitro.
• Substituents on the pyridyl or thienyl radical are preferably lower alkyl, halogen or trifluoromethyl.
• Lower alkyl is e.g. Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, furthermore n-pentyl, n-hexyl, isohexyl or n-heptyl.
• Lower alkylene is ethylene, and also 1,3-propylene, 1,4-butylene, but can also be 1,2-propylene, 1,2- or 2,3-butylene, 1,3- or 2,4-pentylene or 1, Be 4-pentylene.
• Lower alkoxy is e.g. Methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy or tert-butyloxy.
• Halogen is one with the atomic number up to and 35 and stands for fluorine or bromine, preferably for chlorine.
• Lower alkylsulfonyl is e.g. for methylsulfonyl, ethylsulfonyl or n-propylsulfonyl.
• the compounds according to the invention have valuable pharmacological properties, in particular anti-inflammatory and anti-rheumatic effects, as can be shown in animal experiments. e.g. in the kaolin paw edema test (Helv. Physiol. Acta 25 (1967) 156) on the rat at a dose given from around 10 mg / kg or in the turpentine pleurisy test [Helv. Physiol. Acta 26 (1969) 287) given orally to the rat at a dose of 30 to 100 mg / kg, they show an anti-inflammatory or anti-exudative effect. In particular, the unsaturated compounds also show an excellent effect in the adjuvant arthritis test [Pharmacology 2 (1969) 288] on the rat at a oral dose of 10-30 mg / kg.
• the new compounds are also analgesic, as shown in the phenyl p-benzoquinone test on the mouse (Proc. Soc. Exp. Biol. 95 (1957) 729) at doses of 30 to 100 mg / kg, given orally leaves.
• the tetrahydro compounds additionally show a reinforcing effect in the pertussis edema test (Agents and Actions, vol. 6, 613, 1976) at 5-50 mg / kg / rat.
• the new compounds can therefore be used as anti-inflammatory agents, for example for the treatment of rheumatic, arthritic and other inflammations Diseases in particular, rheumatoid arthritis or as analgesics, for example to treat painful conditions.
• the invention relates in particular to compounds of the formula I in which Ar 1 and Ar 2 independently of one another are a phenyl radical which is optionally substituted by lower alkyl, lower alkoxy, halogen or trifluoromethyl, a pyridyl such as a 2-, 3- or 4-pyridyl or thienyl , in particular represent a 2-thienyl radical, alk is a lower alkylene radical which connects the sulfur and nitrogen atoms via 2-3 carbon atoms, primarily an unbranched lower alkylene radical and n is especially 0, furthermore also 1 or 2, and their salts.
• the invention relates primarily to compounds of the formula II in which Ar 1 and Ar 2 independently of one another represent a phenyl radical which is optionally substituted by lower alkoxy, such as methoxy or halogen, in particular chlorine, and m is primarily 1, furthermore also 2, and their salts.
• the invention particularly relates to compounds of the formula III wherein Ar 1 and Ar 2 independently of one another, optionally by lower alkoxy, such as methoxy or halogen, ins special chlorine-substituted phenyl radical and m is primarily 1, furthermore also 2, and their salts.
• the invention relates to the new compounds described in the examples.
• the new compounds can be obtained by methods known per se.
• Reactively esterified hydroxy is especially one with a strong inorganic acid, e.g. Hydrogen halide, especially hydrogen chloride, or sulfuric acid, or with a strong organic acid, such as with a lower alkanesulfonic acid, e.g. Methane or ethanesulfonic acid or a benzenesulfonic acid optionally substituted by lower alkyl, lower alkoxy or halogen, e.g. p-Toluenesulfonic acid or p-bromobenzenesulfonic acid esterified hydroxy group.
• a strong inorganic acid e.g. Hydrogen halide, especially hydrogen chloride, or sulfuric acid
• a strong organic acid such as with a lower alkanesulfonic acid, e.g. Methane or ethanesulfonic acid or a benzenesulfonic acid optionally substituted by lower alkyl, lower alkoxy or halogen,
• the ring closure is preferably carried out under acid-releasing conditions. This is done primarily in a low-boiling solvent, such as dimethylformamide or acetone, an alcohol, e.g. Methanol or ethanol, if desired, in the presence of a base, e.g. an inorganic base, such as an alkali or alkaline earth hydroxide, hydroxide or carbonate, primarily sodium hydride, sodium hydroxide or sodium carbonate, or an organic base, preferably a nitrogen base, such as tri-lower alkylamine, e.g. Trimethylamine, triethylamine, dimethylisopropylamine, or pyridine.
• a base e.g. an inorganic base, such as an alkali or alkaline earth hydroxide, hydroxide or carbonate, primarily sodium hydride, sodium hydroxide or sodium carbonate, or an organic base, preferably a nitrogen base, such as tri-lower alkylamine, e.g. Trimethyl
• the starting materials can be obtained if a corresponding diaza-2-mercapto compound is reacted with a dihydroxyalkylene in which at least one of the two hydroxyl groups has been reactively esterified, if appropriate the mercapto group is oxidized to the sulfinyl or sulfonyl group and then, if necessary, the second hydroxyl group reactively esterified.
• the reactive esterified hydroxyl groups correspond to the above-mentioned conditions as well as the condensation conditions. In this reaction, in particular if both hydroxyl groups are esterified in a reactive manner, the starting materials of the formula IV can be obtained in situ, which are closed to form a ring in the same reaction.
• the new compounds of the formula I which have a further double bond can also be obtained if compounds of the formula Va or Vb or ring-closes their tautomers and, if desired, in optionally obtained compounds in which n is 0, the thia atom is oxidized to the sulfinyl or sulfonyl group and / or, if desired, converts the free compounds obtained into their salts or salts obtained into the free ones Converting compounds and / or separating an isomer mixture obtained according to the process into the individual isomers.
• the ring closure takes place under water-releasing conditions, such as by heating, e.g. from about 50 ° to about 150 °, preferably in the presence of a solvent such as acetonitrile or an alcohol, e.g. Methanol or ethanol.
• a solvent such as acetonitrile or an alcohol, e.g. Methanol or ethanol.
• the starting materials can be obtained if a compound of the formula VI with a compound of formula VII or their tautomers.
• Reactively esterified hydroxy groups X are in particular the above.
• this reaction is also carried out under water-releasing conditions, for example with heating in a solvent such as acetonitrile or an alcohol, the starting material of the formula Va or Vb can be obtained in situ, which closes under these reaction conditions.
• a solvent such as acetonitrile or an alcohol
• the oxidation of the thia atom to the sulfinyl or sulfonyl group can be carried out in a manner known per se, e.g. with peroxides such as hydrogen peroxide or peracids e.g. carry out an optionally substituted by lower alkyl, lower alkoxy, halogen or another carboxyl group, such as benzoperic acid itself or phthalmonoperacid, or an alkane percarboxylic acid such as peracetic acid or a periodate such as sodium periodate.
• This reaction is usually carried out at low temperatures in a solvent such as glacial acetic acid or acetone.
• the new compounds can be in the form of acid addition salts, especially pharmaceutically acceptable, non-toxic salts, e.g. with organic acids, such as hydrochloric, hydrobromic, sulfuric or phosphoric acid, or with organic, such as aliphatic, cycloaliphatic, cycloaliphatic-aliphatic, aromatic, araliphatic, heterocyclic or heterocyclic-aliphatic carbon or sulfonic acid, e.g.
• organic acids such as hydrochloric, hydrobromic, sulfuric or phosphoric acid
• organic such as aliphatic, cycloaliphatic, cycloaliphatic-aliphatic, aromatic, araliphatic, heterocyclic or heterocyclic-aliphatic carbon or sulfonic acid, e.g.
• Salts of this type can e.g. can be obtained by treating the free compounds, with the acids or with suitable anion exchange resins.
• the free compounds or the salts are also to be understood as meaningful and expedient, if appropriate, the corresponding salts or free compounds.
• the new compounds can be present as isomer mixtures, such as racemates or diastereoisomer mixtures, or in the form of the pure isomers, such as optically active components.
• the separation of isomer mixtures obtained into the pure isomers can be carried out by the known methods. Racemates can e.g. due to physico-chemical differences, e.g. Separate those of solubility, their diastereomeric salts, or by fractional crystallization from an optically active solvent, or by chromatography, in particular thin-layer chromatography, on an optically active carrier material, into the optically active antipodes.
• the pharmacologically more effective or less toxic pure isomer is advantageously isolated, in particular the more effective or less toxic active antipode.
• the process also includes those embodiments according to which compounds obtained as intermediates are used as starting materials and the remaining process steps are carried out with them, or the process is terminated at any stage; furthermore, starting materials in the form of derivatives can be used or formed during the reaction.
• the invention also relates to the new compounds of the general formula Va or Vb obtainable as intermediates or. or their tautomers, where Alk is lower alkylene, which separates the thia from the aza atom by 2-4 carbon atoms, Ar 1 and Ar 2 independently of one another are optionally substituted phenyl, pyridyl or thienyl and n is 0, 1 or 2, and their Salts.
• Alk is lower alkylene, which separates the thia from the aza atom by 2-4 carbon atoms
• Ar 1 and Ar 2 independently of one another are optionally substituted phenyl, pyridyl or thienyl and n is 0, 1 or 2, and their Salts.
• they are approximately as effective as the dihydro compounds of the formula I and can be used as anti-inflammatory agents, for example for the treatment of rheumatic arthritis.
• the new compounds of the present invention can be used, for example, for the production of pharmaceutical preparations which contain an effective amount of the active substance together or in a mixture with inorganic or contain organic, solid or liquid, pharmaceutically usable excipients which are suitable for enteral or parenteral administration.
• tablets or gelatin capsules which contain the active ingredient together with diluents, for example lactose, dextrose, sucrose, mannitol, sorbitol, cellulose and / or glycerol, and lubricants, for example silica, talc, stearic acid or salts thereof, such as magnesium or calcium stearate. and / or polyethylene glycol; Tablets also contain binders, e.g.
• magnesium aluminum silicate starches such as corn, wheat, rice or arrowroot starch, gelatin, tragacanth, methyl cellulose, sodium carboxymethyl cellulose and / or polyvinylpyrrolidone, and, if desired, disintegrants, e.g. starches, agar, alginic acid or a salt thereof, such as sodium alginate, and / or effervescent mixtures, or adsorbents, colors, flavors and sweeteners.
• disintegrants e.g. starches, agar, alginic acid or a salt thereof, such as sodium alginate, and / or effervescent mixtures, or adsorbents, colors, flavors and sweeteners.
• the new pharmacologically active compounds can be used in the form of injectable, for example intravenously administrable, preparations or infusion solutions.
• Such solutions are preferably isotonic aqueous solutions or suspensions, these being able to be prepared, for example, from lyophilized preparations which contain the active substance on their own or together with a carrier material, for example mannitol.
• the pharmaceutical preparations can be sterilized and / or contain auxiliaries, for example preservatives, stabilizers, wetting agents and / or emulsifiers, solubilizers, salts for regulating the osmotic pressure and / or buffers.
• the present pharmaceutical preparations which, if desired, may contain other pharmacologically valuable substances, are produced in a manner known per se, for example by means of conventional mixing, granulating, confectioning, dissolving or lyophilizing processes and contain from about 0.1% to 100%, in particular from about 1% to about 50%, of lyophilisates up to 100% of the active ingredient.
• the single dose for a warm-blooded animal weighing approximately 70 kg is between 0.1 and 0.75 g, the daily dose between 0.2 and 1.0 g.
• a suspension of 7 ml of 1,2-dibromoethane, 7 g of sodium carbonate and 55 ml of isopropanol is stirred at room temperature and within one hour with the suspension of 4.7 g of 4,5-diphenyl-imidazolidin-2-thione in 110 ml of l, 5% sodium hydroxide solution added.
• the reaction mixture is refluxed for 7 hours, then the isopropanol and the dibromoethane are removed on a rotary evaporator and the remaining suspension is extracted with toluene.
• the toluene extract is washed with brine, dried over sodium sulfate and evaporated. The residue is chromatographed on silica gel.
• a suspension of 3.5 ml of 1,2-dibromoethane, 3.5 g of sodium carbonate and 30 ml of isopropanol is stirred in with the suspension of 3 g of 4,5-di-anisyl-2-mercapto-imidazole in at room temperature for one hour 50 ml of 1.5% sodium hydroxide solution are added.
• the reaction mixture is refluxed for 6 hours, then the isopropanol and the dibromoethane are removed on a rotary evaporator and the remaining suspension is mixed with 10 ml of 20% potassium hydroxide solution and extracted with ethyl acetate. The organic phases are washed with brine, dried with sodium sulfate and evaporated.
• the starting material can e.g. are prepared: 2.5 g of sodium are dissolved in 220 ml of ethanol. 35 g of 4,5-dianisyl-imidazolin-2-thione are added. A suspension is obtained. For this purpose, 15.7 ml of 2-chloroethanol are added dropwise at room temperature (stirring). The mixture is stirred for 1 hour at 60 ° and 4 hours at reflux. The weak suspension is then evaporated to dryness. The residue is purified from acetone / water.
• the starting material used can e.g. received as follows:
• the 2-mercapto-4,5-di-p-chlorophenylimidazole with 2-chloroethanol is the 2- (2-hydroxyethylthio) -4,5-di-p-chlorophenylimidazole from F. 197-199 ° and from it by cyclization with thionyl chloride the 5,6-di-p-chlorophenyl-imidazo [2,1-b] dihydro-thiazole of mp 199-204 °.
• the 5,6-di-p-methoxyphenyl-4H-imidazo [2,1-b] dihydro-thiazole can also be prepared analogously.
• the hydrobromide of 5,6-di- (p-methoxyphenyl) imidazo [2, l-b] dihydro-thiazole can be obtained from the mother liquor, mp. 200-210 °.
• the L-5,6-di-p-anisyl-2,3,5,6-tetrahydro-4H-imidazo [2,1-b] thiazole N-benzenesulfonyl L (+) - glutamate is filtered off with a little Washed water, suspended in water and decomposed with dilute sodium hydroxide solution. From this, the L-5,6-di-p-anisyl-2,3,5,6-tetrahydro-4H-imidazo [2,1-b] thiazole is extracted with ethyl acetate.
• sucrose, calcium dihydrate and the active ingredient are mixed and granulated with a 10% gelatin solution.
• the moist granules are sieved, dried, mixed with the starch, talc and stearic acid, sieved and compressed into tablets.

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• 1977
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