FI56965B - FOER FARING FRAMSTAELLNING AV D-PENICILLAMIN - Google Patents
FOER FARING FRAMSTAELLNING AV D-PENICILLAMIN Download PDFInfo
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- FI56965B FI56965B FI3151/73A FI315173A FI56965B FI 56965 B FI56965 B FI 56965B FI 3151/73 A FI3151/73 A FI 3151/73A FI 315173 A FI315173 A FI 315173A FI 56965 B FI56965 B FI 56965B
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- Finland
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- acid
- norephedrine
- penicillamine
- mol
- formylisopropylidene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/04—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D277/06—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Indole Compounds (AREA)
- Medicines Containing Plant Substances (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
Description
ΙΠ^Γ-,Ι ,ftl .... KUULUTUSJULKAISU .. ä [B] <11) UTLÄGGNI NGSSKRIFT 5 696 5 C (45) Patentti myönnetty 12 35 1930 Patent meddelat T (51) KY.ik.*/int.a.* C 07 C 149/243 SUOMI-FINLAND (21) Patanttlhikamut — PK«ttaraMcnlng 3151/73 (22) Hakamitpilvl —Araeknlnpdag 11.10.73 ' * (23) AlkupUvi—GIMfhacsdag 11.10.73 (41) Tullut luikituksi — Bllylt offuntllg 30.05.74ΙΠ ^ Γ-, Ι, ftl .... ADVERTISEMENT .. ä [B] <11) UTLÄGGNI NGSSKRIFT 5 696 5 C (45) Patent granted 12 35 1930 Patent meddelat T (51) KY.ik. * / Int. a. * C 07 C 149/243 SUOMI-FINLAND (21) Patanttlhikamut - PK «ttaraMcnlng 3151/73 (22) Hakamitpilvl —Araeknlnpdag 11.10.73 '* (23) Home - GIMfhacsdag 11.10.73 (41) Has become slipped - Bllylt offuntllg 30.05.74
Patentti· ja rekisterihallitut .............Patents and registries .............
_ x , , , , (44) Nihtivlktlptnon ja kuuLjulkaltun pvm. —_ x,,,, (44) Date of mitigation and date of issue. -
Patent· och registerstyrelsen Antttkm utiagd och uti.*krHt*n public*rad 31.01.80 (32)(33)(31) Pyydetty «uolkuut—BugSrd prtorltet 29.11.72Patent · och registerstyrelsen Antttkm utiagd och uti. * KrHt * n public * rad 31.01.80 (32) (33) (31) Pyydetty «uolkuut — BugSrd prtorltet 29.11.72
Saksan Liittotasavalta-Förbundsrepubliken Tyskland(DE) P 2258411.8 Toteennäytetty-Styrkt (71) Deutsche Gold- und Silber-Scheideanstalt vormals Roessler, Weissfrauen-strasse 9, Frankfurt(Main), Saksan Liittotasavalta-Förbundsrepubliken Tyskland(DE) (72) Friedrich Asinger, Rott, Heribert Offermanns, Grossauheim, Karl-Heinz Gluzek, Alpen, Walter von Bebenburg, Buchschlag, Saksan Liittotasavalta-Förbundsrepubliken Tyskland(DE) (7*0 Oy Kolster Ab (5M Menetelmä D-penisillamiinin valmistamiseksi - Förfarande för framställ-ning av D-penicillaminFederal Republic of Germany-Förbundsrepubliken Tyskland (DE) P 2258411.8 Proof-Styrkt (71) Deutsche Gold- und Silber-Scheideanstalt vormals Roessler, Weissfrauen-Strasse 9, Frankfurt (Main), Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) Rott, Heribert Offermanns, Grossauheim, Karl-Heinz Gluzek, Alpen, Walter von Bebenburg, Buchschlag, Federal Republic of Germany Förbundsrepubliken Tyskland (DE) (7 * 0 Oy Kolster Ab -penicillamin
Keksintö koskee 1-norefedriinln käyttöä D-penisillamllnin valmistamiseksi D,L-penisillami ineista.The invention relates to the use of 1-norephedrine for the preparation of D-penicillamines from D, L-penicillamines.
Nyt on havaittu, että käytettäessä 1-norefedriiniä D-penisillamiinin valmistamiseksi D,L-penisi 1lam!inistä FI-patenttihakemuksen 1403/72 mukaan, on erityisen edullista käyttää 1-norefedriiniä suolana.It has now been found that when using 1-norephedrine to prepare D-penicillamine from D, L-penicillamine according to FI patent application 1403/72, it is particularly advantageous to use 1-norephedrine as a salt.
1-norefedri1ni saostuu yleensä sitä valmistettaessa suoloina. Kun käytetään näitä suoloja välittömästi valmistettaessa D-penisl1lamiinia 1-norefedriinin avulla, vältetään norefedriinin vapaan emäksen valmistaminen.1-Norephedrine usually precipitates when prepared as salts. The immediate use of these salts in the preparation of D-penicillamine with 1-norephedrine avoids the preparation of norephedrine free base.
1-norefedriinin suoloina tulevat ennen kaikkea kysymykseen suolat orgaanisten happojen kanssa, varsinkin suolat sulfonihappojen kanssa ja erittäinkin suolat karboksyylihappojen kanssa. Sulfonihappojen suhteen on kysymys esimerkiksi a 1ifaattisista sulfonihapoista, kuten metaani sulfonihappo, metaani trisulfonihappo ja propaani-2-sulfonlhappo, ta? aromaattisista sulfonihapoista, kuten p-tolueeni-suifonihappo, erittäinkin bentseenisulfonihaposta. KarboksyylIhappoja ovat tyydyttyneet tai tyydyttymättömät, mahdollisesti OH-, NHj-, NHR-, NR^-, 0R-, SH-, SR-tai halogeeniryhmi1lä substituoidut alifaattiset mono- ja polykarboksyylihapot, kuten isovoihappo, maitohappo, oksaalihappo, malonlhappo, adipiinihappo, maleiini- 2 C ύ 9 G £ happo, merlp!hkahappo, viinihappo, sitruunahappo, erityisesti sellaiset, joissa on 1-6 hiiliatomia, kuten muurahaishappo, etikkahappo, propionihappo, tai ara1ifaattiset hapot, kuten fenyylietikkahappo, mantelihappo, kanelihappo, eritteinkin 3~fenyylipropionihappo, tai aromaattiset karboksyylihapot, kuten ftaa 1i-happo, tereftaaiihappo, salisyylihappo, varsinkin bentsoehappo, tai heteroaromaat-tiset hapot, kuten tiofeeni-2-karboksyy1ihappo, tiatsoli-l»-karboksyy 1ihappo, furaani-2-karboksyylihappo, pikoliinihappo, isonikotiinihappo.Suitable salts of 1-norephedrine are, above all, salts with organic acids, in particular salts with sulfonic acids and, in particular, salts with carboxylic acids. With regard to sulfonic acids, there are, for example, aliphatic sulfonic acids, such as methane sulfonic acid, methane trisulfonic acid and propane-2-sulfonic acid, or? aromatic sulfonic acids, such as p-toluenesulfonic acid, especially benzenesulfonic acid. Carboxylic acids are saturated or unsaturated aliphatic mono- and polycarboxylic acids, optionally substituted by OH, NH 3, NHR, NR 4, OR, SH, SR or halogen groups, such as isobutyric acid, lactic acid, maleic acid, malonic acid, malonic acid, malonic acid, 2 C ύ 9 G £ acid, formic acid, tartaric acid, citric acid, especially those having 1 to 6 carbon atoms, such as formic acid, acetic acid, propionic acid, or ariphatic acids, such as phenylacetic acid, mandelic acid, erythionic acid, cinnamic acid, cinnamic acid, cinnamic acid, aromatic carboxylic acids such as phthalic acid, terephthalic acid, salicylic acid, especially benzoic acid, or heteroaromatic acids such as thiophene-2-carboxylic acid, thiazole-1'-carboxylic acid, furan-2-carboxylic acid, picolic acid, picolic acid,
Norefedriinin suoloja käytetään samalla tavalla, samoissa olosuhteissa ja vastaavat määrät kuin 1-norefedriinin vapaata emästä. Suolojen käyttö on osoittautunut erittäin edulliseksi D,L-penisi1lamiinin rasemaatin hajolttamisessa silloin, kun tämä on n-asetyyli- tai edullisesti n-formyy!ijohdannaisena, erityisesti n-formyy1i-2,2,5,5-tetrametyy1itiatsolidiini-^-karboksyyli happona (n-formyyli-Isopropy1ideeni-D,L-penisiliemiini) tai n-formyy1i-2,2-pentametyleeni- 5,5-d1 metyyl1tiatsolid 1ini-^-karboksyylihappona.The salts of norephedrine are used in the same manner, under the same conditions and in the same amounts as the free base of 1-norephedrine. The use of salts has proved to be very advantageous in the decomposition of the D, L-penicillamine racemate when it is an n-acetyl or preferably n-formyl derivative, in particular n-formyl-2,2,5,5-tetramethylthiazolidine-4-carboxylic acid ( n-formyl-isopropylidene-D, L-penicillamine) or n-formyl-2,2-pentamethylene-5,5-d-methylthiazolidine as 4-carboxylic acid.
Seuraavissa esimerkeissä on aineiden kiertokyky annettu ominaiskiertona 20 3 , dimensioina aste.cm /dm.g. Ilmoitetut prosentit ovat painoprosentteja.In the following examples, the rotation of the substances is given as the specific rotation 20 3, in the dimensions degree.cm /dm.g. The percentages given are by weight.
Esimerkki 1 21,7 g (0,1 mol) N-formyy1i-isopropy1ideeni-D,L-penlsi 1lamiinia liuotettiin 60-70°C:n lämpötilassa 80 ml:aan n-butyyliasetaattia. Liuokseen lisättiin sekoittaen 11,7 g (0,06 mol) 1-norefedriiniasetaattia Ja se pidettiin sen jälkeen 30 minuuttia 80-85°C:ssa. Ensin muodostui kirkas liuos; tästä erottui muutamien minuuttien kuluttua N-formyyli-isopropylideeni-D-penisi1lamiinin ja 1-norefedriinin 1iIttymistuote. Sen jälkeen kun oli jäähdytetty hitaasti huoneen lämpötilaan, suodatettiin imulla. Saatu 1?Ittymistuote pestiin 20 ml :11a n-butyyliasetaattia ja kuivattiin sen jälkeen alennetussa paineessa. Sen ominaiskierto oli +3A° ja sulamispiste 200-203°C. Saanto oli 11,5 g, mikä vastaa 63 % laskettuna käytetyn n-formyyli-isopropylideeni-D,L-penis11lami inin määrästä.Example 1 21.7 g (0.1 mol) of N-formylisopropylidene-D, L-penylamine were dissolved in 80 ml of n-butyl acetate at 60-70 ° C. 11.7 g (0.06 mol) of 1-norephedrine acetate were added to the stirred solution, which was then kept at 80-85 ° C for 30 minutes. First, a clear solution formed; after a few minutes, the coupling product of N-formylisopropylidene-D-penicillamine and 1-norephedrine separated. After slowly cooling to room temperature, it was filtered off with suction. The resulting product was washed with 20 ml of n-butyl acetate and then dried under reduced pressure. Its specific rotation was + 3A ° and its melting point was 200-203 ° C. The yield was 11.5 g, corresponding to 63% based on the amount of n-formylisopropylidene-D, L-penisamine used.
11 g N-formyy1i-isopropylideeni-0,L-penisillamiinin ja 1-norefedriinin 1iittymistuotetta suspendoiti In 40 ml:aan vettä. Seoksen pH säädettiin huoneen lämpötilassa väkevällä suolahapolla arvoon 1. Seuraavien 15 minuutin kuluessa erottui N-formyy1i-isopropylIdeeni-D-penisί1lamiini. Se suodatettiin imulla, pestiin 10 ml :11a vettä ja kuivattiin alennetussa paineessa. N-formyyli-iso-propylideeni-D-penisi1lamiinin ominaiskierto oi? +52° ja sulamispiste 182-183°C. Saanto oli 5,8 g, mikä vastaa 90 % laskettuna käytetyn 111ttymistuotteen määrästä.11 g of the coupling product of N-formylisopropylidene-O, L-penicillamine and 1-norephedrine were suspended in 40 ml of water. The pH of the mixture was adjusted to 1 at room temperature with concentrated hydrochloric acid. Over the next 15 minutes, N-formylisopropylidene-D-penicillamine was separated. It was filtered off with suction, washed with 10 ml of water and dried under reduced pressure. N-Formyl-iso-propylidene-D-penicillamine Specific rotation oi? + 52 ° and melting point 182-183 ° C. The yield was 5.8 g, which corresponds to 90% of the amount of the product used.
Esimerkki 2Example 2
Meneteltiin kuten esimerkissä 1, mutta saatettiin 21,7 (0,1 mol) N-formyyli-isopropylideeni-D,L-penisi1lamiinia reagoimaan 21 g:n (0,1 mol) kanssa 1-norefedri iniasetaattia 100 mlrssa etikkahapon etyyliesteriä. Saadulla 1iittymistuotteellaThe procedure was as in Example 1, but 21.7 (0.1 mol) of N-formylisopropylidene-D, L-penicillamine was reacted with 21 g (0.1 mol) of 1-norephedrine acetate in 100 ml of ethyl acetate. With the obtained joining product
3 i>S96S3 i> S96S
oli ominaiskierto +32° ja sulamispiste 199“201°C. Saanto oli 15 g, mikä vastaa 82 %.had a specific rotation of + 32 ° and a melting point of 199 “201 ° C. The yield was 15 g, corresponding to 82%.
Esimerkki 3Example 3
Meneteltiin kuten esimerkissä 1, mutta saatettiin *»3,6 g (0,2 mol) N-formyy1i-isopropy1ideenl-D,L-penisi 1lamiintä reagoimaan 180 mlrssa tolueenia 2*»,8 g:n (0,11 mol) kanssa 1 -norefedri inipropionaattia . SaadullaN-formyyli-tsopropylideeni-D-penisi1lamiinin ja 1-norefedriinin Iiittymistuotteeila oiΪ omina!skierto +30° Ja sulamispiste 201 -20*»°C. Saanto oli 2*t g, mikä vastaa 65 %.The procedure was as in Example 1, but 3.6 g (0.2 mol) of N-formylisopropylidene-D, L-penicillamine were reacted with 180 g of toluene in 8 ml of 8 g (0.11 mol). 1-norephedrine inipropionate. The resulting N-formyl-isopropylidene-D-penicillamine and 1-norephedrine coupling products had a characteristic rotation of + 30 ° and a melting point of 201-20 ° C. The yield was 2 * t g, corresponding to 65%.
Esimerkki *♦Example * ♦
Meneteltiin kuten esimerkissä 1, mutta saatettiin 21,7 g (0,1 mol) N-formyyli-isopropylideeni-D,L-penisi1lamiinia reagoimaan 11,5 g:n (0,02 mol) kanssa 1-norefedriinimaleaattia 80 ml:ssa etikkahapon etyyliesteriä . Saadulla N-formyyli-isopropy1ideeni-D-penis!1lamiinin ja 1-norefedriInin 1iittymistuotteella oli ominaiskierto +27° ja sulamispiste 199-201°C. Saanto oli 9,*» g, mikä vastaa 51 *.The procedure was as in Example 1, but 21.7 g (0.1 mol) of N-formylisopropylidene-D, L-penicillamine were reacted with 11.5 g (0.02 mol) of 1-norephedrine maleate in 80 ml of acetic acid. ethyl ester. The resulting N-formylisopropylidene-D-penicillamine and 1-norephedrine fusion product had a specific rotation of + 27 ° and a melting point of 199-201 ° C. The yield was 9 * »g, which corresponds to 51 *.
Esimerkki 5Example 5
Meneteltiin kuten esimerkissä 1, mutta saatettiin *»3,5 g (0,2 mol) N-formyyli-isopropylideeni-D,L-penlsi1lamiinia reagoimaan 30 g:n (0,11 mol) kanssa 1-norefedriinibentsoaattia. Saadun 1iittymistuotteen ominaiskierto oii +30° ja sulamispiste 200-203°C. Saanto oli 2*» g, mikä vastaa 65 %.The procedure was as in Example 1, but 3.5 g (0.2 mol) of N-formylisopropylidene-D, L-penylamine was reacted with 30 g (0.11 mol) of 1-norephedrine benzoate. The obtained coupling product has a specific rotation of + 30 ° and a melting point of 200-203 ° C. The yield was 2 * »g, corresponding to 65%.
Esimerkki 6Example 6
Meneteltiin kuten esimerkissä 1, mutta saatettiin 21,7 g (0,1 mol) N-formyyli-isopropylideeni-D,L-penisi 1lamiinia reagoimaan 10,8 g:n (0,06 mol) kanssa 1-norefedriin?formiaattIa. Saadun 1iittymistuotteen ominaiskierto oii +32° ja sulamispiste 198-201°C. Saanto oli 11 g, mikä vastaa 60 %.The procedure was as in Example 1, but 21.7 g (0.1 mol) of N-formylisopropylidene-D, L-penicillamine were reacted with 10.8 g (0.06 mol) of 1-norephedrine-formate. The obtained coupling product has a specific rotation of + 32 ° and a melting point of 198-201 ° C. The yield was 11 g, corresponding to 60%.
Esimerkki 7Example 7
Meneteltiin kuten esimerkissä 1, mutta saatettiin 21,7 g (0,1 mol) N-formyyli-isopropy1ideenl-D,L-penisi 1lamiinia reagoimaan 16,5 g:n (0,06 mol) kanssa 1-norefedri?ni-3-fenyylipropionaattia. Saadun 1iittymistuotteen ominaiskierto oii +32° ja sulamispiste 198-202°C. Saanto oli 11,5 g, mikä vastaa 62 %.The procedure was as in Example 1, but 21.7 g (0.1 mol) of N-formylisopropylidene-1-D, L-penicillamine were reacted with 16.5 g (0.06 mol) of 1-norephedrine-3 -fenyylipropionaattia. The obtained coupling product has a specific rotation of + 32 ° and a melting point of 198-202 ° C. The yield was 11.5 g, corresponding to 62%.
Esimerkki 8Example 8
Meneteltiin kuten esimerkissä 1, mutta saatettiin 21,7 g (0,1 mol) N-formyyli-isopropylideeni-D,L-penisi1lamiinia reagoimaan 33 g:n (0,11 mol) kanssa 1-norefedriini-bentseenisulfonaattia. Saadun 1ίittymistuotteen ominaiskierto oli +31° ja sulamispiste 197-199°C. Saanto oli 1*» g, mikä vastaa 76 %.The procedure was as in Example 1, but 21.7 g (0.1 mol) of N-formylisopropylidene-D, L-penicillamine were reacted with 33 g (0.11 mol) of 1-norephedrine benzenesulfonate. The obtained rotation product had a specific rotation of + 31 ° and a melting point of 197-199 ° C. The yield was 1 * »g, corresponding to 76%.
Esimerkki 9Example 9
Meneteltiin kuten esimerkissä 1, mutta saatettiin 21,7 g (0,1 mol) N-formyy11-isopropy1ideeni-D,L-penIsillamiinia reagoimaan 21,5 q:n (0,03 mol) kanssa 4 56965 1-norefedriInisitraattia. Saadun 1i1ttymistuotteen omi nai skierto oil +30° Ja sulamispiste 198-200°C. Saanto oli 13 g, mikä vastaa 70 %.The procedure was as in Example 1, but 21.7 g (0.1 mol) of N-formyl-isopropylidene-D, L-penicillamine were reacted with 21.5 g (0.03 mol) of 4,56965 1-norephedrine citrate. The obtained coupling product has a viscosity of + 30 ° and a melting point of 198-200 ° C. The yield was 13 g, corresponding to 70%.
Esimerkki 10Example 10
Meneteltiin kuten esimerkissä 1, mutta saatettiin 25,7 g (0,1 mol) D,L" N-formyylJ-2,2-pentametyleeni-5,5“d imetyylf tiatsolidi ini-l*-karboksyylihappoa reagoimaan 10,8 g:n (0,06 moi) kanssa 1-norefedrlIni form!aattia. Saadulla D-N-formyy 11 -2,2-pentametyleeni-5,5-dImetyyl Itiatsol id 1 ini-li-karboksyyl ihapon ja 1-norefedriInin 111ttymlstuottee1 la oli ominaisklerto +25° ja sulamispiste 190-191°C. Saanto oli 16,5 g, mikä vastaa 81 %. Li Ittymistuotteen hajottaminen tapahtui kuten esimerkissä 1. Tällöin saadun D-N-formyyli-2,2-pentametyleeni-5,5_ dimetyyl1tiatsolidiIn 1-^-karboksyylihapon ominalskierto oli +62,8° ja sulamispiste 190-191°C. Saanto oli 9,2 g, mikä vastaa 90 I.The procedure was as in Example 1, but 25.7 g (0.1 mol) of D, L "N-formyl] -2,2-pentamethylene-5,5'-dimethylpthiazolidine-1 * carboxylic acid were reacted with 10.8 g: 1 (nor6-mol) of 1-norephedrine formate The resulting DN-formyl-11,2,2-pentamethylene-5,5-dimethylthiazolidin-1-ylcarboxylic acid and 1-norephedrine had a specific cleavage + 25 DEG C. and melting point 190 DEG-191 DEG C. The yield was 16.5 g, corresponding to 81%, and the decomposition product was decomposed as in Example 1. The resulting DN-formyl-2,2-pentamethylene-5,5-dimethyl-thiazolidine-1- the specific rotation of the carboxylic acid was + 62.8 ° and the melting point 190-191 ° C. The yield was 9.2 g, which corresponds to 90 I.
Esimerkki 11Example 11
Meneteltiin kuten esimerkissä 1, mutta saatettiin 25,7 g (0,1 mol) D,L-N-formyyl1-2,2-pentametyleeni-5,5-dimetyyli tiatsolidiinl-l»-karboksyylihappoa reagoi -maan 16,5 g:n (0,06 mol) kanssa 1-norefedrlIni-bentseenisulfonaattIa. Saadun 1iittymistuotteen ominaisklerto oli +2^° ja sulamispiste 189~191°C. Saanto oli 1^,5 g, mikä vastaa 71 %·The procedure was as in Example 1, but 25.7 g (0.1 mol) of D, LN-formyl-1,2,2-pentamethylene-5,5-dimethylthiazolidine-1'-carboxylic acid were reacted to give 16.5 g ( 0.06 mol) with 1-norephedrine benzenesulfonate. The obtained coupling product had a specific cleavage of + 2 ° and a melting point of 189 ~ 191 ° C. The yield was 1.5 g, corresponding to 71% ·
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2258411 | 1972-11-29 | ||
| DE2258411A DE2258411C3 (en) | 1972-11-29 | 1972-11-29 | Process for obtaining D-penicillamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| FI56965B true FI56965B (en) | 1980-01-31 |
| FI56965C FI56965C (en) | 1980-05-12 |
Family
ID=5863013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FI3151/73A FI56965C (en) | 1972-11-29 | 1973-10-11 | FOERFARANDE FOER FRAMSTAELLNING AV D D-PENICILLAMIN |
Country Status (24)
| Country | Link |
|---|---|
| JP (1) | JPS5512423B2 (en) |
| AR (1) | AR203731A1 (en) |
| BE (1) | BE806378R (en) |
| BR (1) | BR7309342D0 (en) |
| CA (1) | CA1003853A (en) |
| CH (1) | CH590182A5 (en) |
| CS (1) | CS183693B2 (en) |
| DD (1) | DD109215A6 (en) |
| DE (1) | DE2258411C3 (en) |
| DK (1) | DK146414C (en) |
| ES (1) | ES418693A2 (en) |
| FI (1) | FI56965C (en) |
| FR (1) | FR2207886B2 (en) |
| GB (1) | GB1413038A (en) |
| HU (1) | HU168379B (en) |
| IE (1) | IE38489B1 (en) |
| IL (1) | IL43567A (en) |
| IT (1) | IT1045950B (en) |
| NL (1) | NL163786C (en) |
| NO (1) | NO138948C (en) |
| RO (1) | RO71923A7 (en) |
| SE (1) | SE382048B (en) |
| SU (1) | SU535900A4 (en) |
| ZA (1) | ZA738498B (en) |
-
1972
- 1972-11-29 DE DE2258411A patent/DE2258411C3/en not_active Expired
-
1973
- 1973-03-14 HU HUDE811A patent/HU168379B/hu unknown
- 1973-09-12 ES ES418693A patent/ES418693A2/en not_active Expired
- 1973-09-20 NO NO3693/73A patent/NO138948C/en unknown
- 1973-09-24 DD DD173640A patent/DD109215A6/xx unknown
- 1973-09-25 CH CH1372973A patent/CH590182A5/xx not_active IP Right Cessation
- 1973-10-11 FI FI3151/73A patent/FI56965C/en active
- 1973-10-22 BE BE6044338A patent/BE806378R/en not_active IP Right Cessation
- 1973-10-23 AR AR250649A patent/AR203731A1/en active
- 1973-10-31 GB GB5061473A patent/GB1413038A/en not_active Expired
- 1973-11-05 ZA ZA738498A patent/ZA738498B/en unknown
- 1973-11-05 IE IE1989/73A patent/IE38489B1/en unknown
- 1973-11-05 IL IL43567A patent/IL43567A/en unknown
- 1973-11-23 IT IT53884/73A patent/IT1045950B/en active
- 1973-11-27 FR FR7342210A patent/FR2207886B2/fr not_active Expired
- 1973-11-27 DK DK638973A patent/DK146414C/en not_active IP Right Cessation
- 1973-11-27 JP JP13297873A patent/JPS5512423B2/ja not_active Expired
- 1973-11-28 CS CS7300008188A patent/CS183693B2/en unknown
- 1973-11-28 SU SU1973450A patent/SU535900A4/en active
- 1973-11-28 SE SE7316110A patent/SE382048B/en unknown
- 1973-11-28 RO RO7376809A patent/RO71923A7/en unknown
- 1973-11-28 BR BR9342/73A patent/BR7309342D0/en unknown
- 1973-11-29 CA CA186,936A patent/CA1003853A/en not_active Expired
- 1973-11-29 NL NL7316344.A patent/NL163786C/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DE2258411A1 (en) | 1974-06-06 |
| DK146414B (en) | 1983-10-03 |
| NL163786B (en) | 1980-05-16 |
| DD109215A6 (en) | 1974-10-20 |
| DE2258411B2 (en) | 1980-01-24 |
| SE382048B (en) | 1976-01-12 |
| JPS4982627A (en) | 1974-08-08 |
| FI56965C (en) | 1980-05-12 |
| IT1045950B (en) | 1980-06-10 |
| CS183693B2 (en) | 1978-07-31 |
| DE2258411C3 (en) | 1981-01-22 |
| BR7309342D0 (en) | 1974-08-29 |
| IE38489L (en) | 1974-05-29 |
| SU535900A4 (en) | 1976-11-15 |
| CA1003853A (en) | 1977-01-18 |
| DK146414C (en) | 1984-03-12 |
| RO71923A7 (en) | 1981-07-30 |
| AR203731A1 (en) | 1975-10-15 |
| NL163786C (en) | 1980-10-15 |
| ZA738498B (en) | 1974-10-30 |
| NO138948C (en) | 1978-12-13 |
| ES418693A2 (en) | 1977-11-01 |
| IL43567A (en) | 1976-04-30 |
| GB1413038A (en) | 1975-11-05 |
| IE38489B1 (en) | 1978-03-29 |
| NL7316344A (en) | 1974-05-31 |
| JPS5512423B2 (en) | 1980-04-02 |
| BE806378R (en) | 1974-02-15 |
| FR2207886A2 (en) | 1974-06-21 |
| HU168379B (en) | 1976-04-28 |
| AU6244773A (en) | 1975-05-15 |
| CH590182A5 (en) | 1977-07-29 |
| NO138948B (en) | 1978-09-04 |
| FR2207886B2 (en) | 1978-01-06 |
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