NO122072B - - Google Patents
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- Publication number
- NO122072B NO122072B NO315368A NO315368A NO122072B NO 122072 B NO122072 B NO 122072B NO 315368 A NO315368 A NO 315368A NO 315368 A NO315368 A NO 315368A NO 122072 B NO122072 B NO 122072B
- Authority
- NO
- Norway
- Prior art keywords
- nitro
- dihydro
- phenyl
- benzodiazepine
- nitrobenzophenone
- Prior art date
Links
- 238000000034 method Methods 0.000 claims description 14
- YEABXHBIQRGGDP-UHFFFAOYSA-N 2-amino-n-(2-benzoyl-4-nitrophenyl)acetamide Chemical compound NCC(=O)NC1=CC=C([N+]([O-])=O)C=C1C(=O)C1=CC=CC=C1 YEABXHBIQRGGDP-UHFFFAOYSA-N 0.000 claims description 13
- KJONHKAYOJNZEC-UHFFFAOYSA-N nitrazepam Chemical compound C12=CC([N+](=O)[O-])=CC=C2NC(=O)CN=C1C1=CC=CC=C1 KJONHKAYOJNZEC-UHFFFAOYSA-N 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- 238000007363 ring formation reaction Methods 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- PZPZDEIASIKHPY-UHFFFAOYSA-N (2-amino-5-nitrophenyl)-phenylmethanone Chemical compound NC1=CC=C([N+]([O-])=O)C=C1C(=O)C1=CC=CC=C1 PZPZDEIASIKHPY-UHFFFAOYSA-N 0.000 description 1
- MAOBFOXLCJIFLV-UHFFFAOYSA-N (2-aminophenyl)-phenylmethanone Chemical compound NC1=CC=CC=C1C(=O)C1=CC=CC=C1 MAOBFOXLCJIFLV-UHFFFAOYSA-N 0.000 description 1
- -1 2-bromoacetamino-5-nitrobenzophenone Chemical compound 0.000 description 1
- IVUAAOBNUNMJQC-UHFFFAOYSA-N 5-phenyl-1,3-dihydro-1,4-benzodiazepin-2-one Chemical compound C12=CC=CC=C2NC(=O)CN=C1C1=CC=CC=C1 IVUAAOBNUNMJQC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D243/00—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms
- C07D243/06—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4
- C07D243/10—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4 condensed with carbocyclic rings or ring systems
- C07D243/14—1,4-Benzodiazepines; Hydrogenated 1,4-benzodiazepines
- C07D243/16—1,4-Benzodiazepines; Hydrogenated 1,4-benzodiazepines substituted in position 5 by aryl radicals
- C07D243/18—1,4-Benzodiazepines; Hydrogenated 1,4-benzodiazepines substituted in position 5 by aryl radicals substituted in position 2 by nitrogen, oxygen or sulfur atoms
- C07D243/24—Oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Fremgangsmåte til fremstilling av 1,3-dihydro-7-nitro-5-fenyl-2H-1,4-benzodiazepin-2-on. Process for the preparation of 1,3-dihydro-7-nitro-5-phenyl-2H-1,4-benzodiazepine-2-one.
Oppfinnelsen vedrører en spesiell fremgangsmåte til fremstilling av l,3-dihydro-7-nitro-5-fenyl-2H-l,4-benzodiazepin-2-on med formel The invention relates to a special method for the preparation of 1,3-dihydro-7-nitro-5-phenyl-2H-1,4-benzodiazepine-2-one with the formula
ved ringslutning av 2-glycylamino-5-nitro-benzofenon by cyclization of 2-glycylamino-5-nitro-benzophenone
Det er kjent at forbindelsen med formel I lar seg fremstille etter forskjellige fremgangsmåter. Således er det ifølge tysk patent nr. 1.145.626 mulig i en en-trinns fremgangsmåte å-bringe 2-amino-5-nitrobenzofenon til omsetning med glycinesterhydroklorid. Utbyttet utgjør imidlertid bare ca. 155? av det teoretiske. Ifølge samme patent er det også mulig først å kondensere 2-amino-benzofenon med glycinesterhydroklorid og å nitrere deretter det dannede 1,3-dihydro-5-f>enyl-2H-l, 4-benzodiazepin-2-on. It is known that the compound of formula I can be prepared by various methods. Thus, according to German patent no. 1,145,626, it is possible in a one-step process to react 2-amino-5-nitrobenzophenone with glycine ester hydrochloride. However, the yield only amounts to approx. 155? of the theoretical. According to the same patent, it is also possible to first condense 2-amino-benzophenone with glycine ester hydrochloride and then to nitrate the 1,3-dihydro-5-phenyl-2H-1,4-benzodiazepine-2-one formed.
Videre kan man ifølge øst-tysk patent nr. 41256 bringe 2- bromacetamino-5-nitrobenzofenon til omsetning med ammoniakk. Denne fremgangsmåte har imidlertid den ulempe at ved siden av l,3_dihydro-7-nitro-5-fenyl-2H-l,4-benzodiazepin-2-on oppstår alltid 2-glycylamino-5-nitro-benzofenon og dessuten dannes vekslende mengder av 3- amino-l,2-dihydro-6-nitro-4-fenyl-chinolon-(2) (L.H. Sternbach og medarbeider J.org. Chemistry 27 /"19627 3788). Furthermore, according to East German patent no. 41256, 2-bromoacetamino-5-nitrobenzophenone can be reacted with ammonia. However, this method has the disadvantage that next to 1,3-dihydro-7-nitro-5-phenyl-2H-1,4-benzodiazepine-2-one always occurs 2-glycylamino-5-nitro-benzophenone and, moreover, varying amounts of 3-amino-1,2-dihydro-6-nitro-4-phenyl-quinolone-(2) (L.H. Sternbach et al. J.org. Chemistry 27 /"19627 3788).
Endelig er det også mulig å overføre 2-glycylamino-5_ nitrobenzofenon ved dehydratiserende cyklisering til 1,3-dihydro-7-nitro-5-fenyl-2H-lj4-benzodiazepin-2-on. Tilsvarende DDR-patent nr. 41256 bevirkes dette ved materialets oppvarmning med eller uten oppløsningsmidler eller ifølge DDR-patent nr. 40504 ved at man bringer 2-glycylamino-5-nitrobenzofenon til en pH-verdi på minst 7. Angivelse og utbyttene er ikke mulig ved de sistnevnte fremgangsmåter, da det spesielle tilfelle av cyklisering av 2-glycylamino-5-nitrobenzofenon til l,3-dihydro-7-nitro-5-fenyl-2H-l,4-benzodiazepin-2-on ikke er omtalt i litteraturen med utbytte og angivelser. Dette synes å være begrunnet i at ved denne cykliseringsprosess ble det iakttatt dannelse av 3-amino-l,2-dihydro-6-nitro-4-fenyl-chinolin-(2) som tydeligvis oppstår i større mengder (L.H. Sternbach og medarbeidere J.org. Chemistry 27, (1962) 3793> R.I. Pryer og medarbeidere J.chem.Soc. Finally, it is also possible to transfer 2-glycylamino-5-nitrobenzophenone by dehydrating cyclization to 1,3-dihydro-7-nitro-5-phenyl-2H-lj4-benzodiazepine-2-one. Corresponding to DDR patent no. 41256, this is effected by heating the material with or without solvents or according to DDR patent no. 40504 by bringing 2-glycylamino-5-nitrobenzophenone to a pH value of at least 7. Indication and yields are not possible by the latter methods, as the special case of cyclization of 2-glycylamino-5-nitrobenzophenone to 1,3-dihydro-7-nitro-5-phenyl-2H-1,4-benzodiazepine-2-one is not discussed in the literature with dividend and information. This seems to be justified by the fact that during this cyclization process the formation of 3-amino-1,2-dihydro-6-nitro-4-phenyl-quinoline-(2) was observed, which clearly occurs in larger quantities (L.H. Sternbach and co-workers J .org. Chemistry 27, (1962) 3793> R.I. Pryer et al. J.chem.Soc.
(London) 1964, 3097). (London) 1964, 3097).
Til grunn for oppfinnelsen ligger den oppgave å fremstille l,3-dihydro-7-nitro-5-fenyl-2H-l,4-benzodiazepin-2-on med formel I i meget gode utbytter og med høy renhet. The invention is based on the task of producing 1,3-dihydro-7-nitro-5-phenyl-2H-1,4-benzodiazepine-2-one of formula I in very good yields and with high purity.
Oppfinnelsen vedrører altså en fremgangsmåte til fremstilling av l,3-dihydro-7-nitro-5-fenyl-2H-l,4-benzodiazepin-2-on ved ringslutning av 2-glycylamino-5-nitro-benzofenon, idet fremgangsmåten er karakterisert ved at ringslutningen foretas i nærvær av uorganiske eller organiske syrer i et indifferent organisk eller vandig organisk oppløsningsmiddel. The invention therefore relates to a process for the production of 1,3-dihydro-7-nitro-5-phenyl-2H-1,4-benzodiazepine-2-one by cyclization of 2-glycylamino-5-nitro-benzophenone, the process being characterized in that the ring closure is carried out in the presence of inorganic or organic acids in an indifferent organic or aqueous organic solvent.
Fremgangsmåten ifølge oppfinnelsen er overraskende i flere henseende da det for det første ikke var å vente at en cyklisering av 2-glycylamino-5_nitrobenzofenon finner sted under pH-verdien 7, da det ifølge DDR-patent nr. 40504 hertil kreves en nedre begrens-ning av pH-verdien til 7. Videre forløper fremstillingen av 1,3~ dihydro-7-nitro-5-fenyl-2H-l, 4-benzodiazepin-2-on ved fremgangsmåten ifølge oppfinnelsen uten dannelse av biprodukter, spesielt er også dannelsen av det ellers alltid iakttatte 3-amino-l,2-dihydro-6-nitro-4-fenyl-chinolon-(2) unngått. The method according to the invention is surprising in several respects as, firstly, it was not expected that a cyclization of 2-glycylamino-5-nitrobenzophenone would take place below the pH value 7, as according to DDR patent no. 40504 a lower limit is required for this of the pH value to 7. Furthermore, the production of 1,3~ dihydro-7-nitro-5-phenyl-2H-1,4-benzodiazepine-2-one proceeds by the method according to the invention without the formation of by-products, in particular the formation of the otherwise always observed 3-amino-1,2-dihydro-6-nitro-4-phenyl-quinolone-(2) is avoided.
Det er også meget godt mulig å sammenknytte fremstillings-prosessen av det som utgangsprodukt anvendte 2-glycylamino-5-nitrobenzofenon (som lett lar seg fremstille og i meget gode utbytter og høy renhet av 2-(0-arylsulfonyl-glykoloylamino)-5-nitrobenzofenon og ammoniakk) med cykliseringsfremgangsmåten ifølge oppfinnelsen, idet man ikke isolerer det dannede 2-glycylamino-5-nitrobenzofenon, men underkaster med en gang deretter for den sure cykliseringsfremgangs-måte ifølge oppfinnelsen. For dette formål blir etter avslutning av gasstilførselen til 2-(O-arylsulfonyl-glykoloylamino)-5-nitrobenzofenon med ammoniakk f.eks. i dioksan som oppløsningsmiddel, en luft-strøm blåst gjennom reaksjonsblandingen for mest mulig å fjerne overskytende ammoniakk. Deretter surgjør man reaksjonsblandingen hvorved cykliseringen utføres ifølge oppfinnelsen. It is also very well possible to link the production process of the starting product 2-glycylamino-5-nitrobenzophenone (which can be easily produced and in very good yields and high purity of 2-(0-arylsulfonyl-glycoloylamino)-5- nitrobenzophenone and ammonia) with the cyclization method according to the invention, not isolating the formed 2-glycylamino-5-nitrobenzophenone, but immediately subjecting it to the acidic cyclization method according to the invention. For this purpose, after completion of the gas supply to 2-(O-arylsulfonyl-glycoloyamino)-5-nitrobenzophenone with ammonia e.g. in dioxane as solvent, an air current is blown through the reaction mixture to remove excess ammonia as much as possible. The reaction mixture is then acidified, whereby the cyclization is carried out according to the invention.
Eksempel 1. Example 1.
12,9 g 2-glycylamino-5_nitrobenzofenon ble under rysting eller omrøring oppløst ved værelsetemperatur i 60 ml 30$-ig eddik-syre. Etter 5 til 10 minutter klarfiltreres det og hensettes til krystallisering. Krystallutskillelsen begynner etter ca. 30 til 60 minutter, og er avsluttet etter 20 til 24 timer. Det utskilte 1,3-dihydro-7_nitro-5_fenyl-2H-l,4-benzodiazepin-2-on frasuges og vaskes med 10 ml alkohol og 10 ml eddikester. Man får 9,7 g (tilsvarende 82J5 av det teoretiske) gulaktig l,3-dihydro-7-nitro-5-fenyl-2H-l,4-benzodiazepin-2-on med smp. 220 til 224°C. Etter omkrystallisering fra eddikester er produktet omtrent hvitt, smp. 12.9 g of 2-glycylamino-5-nitrobenzophenone were dissolved under shaking or stirring at room temperature in 60 ml of 30% acetic acid. After 5 to 10 minutes, it is clearly filtered and set aside for crystallization. Crystal precipitation begins after approx. 30 to 60 minutes, and is finished after 20 to 24 hours. The separated 1,3-dihydro-7_nitro-5_phenyl-2H-1,4-benzodiazepine-2-one is suctioned off and washed with 10 ml of alcohol and 10 ml of acetic acid. 9.7 g (corresponding to 82% of the theoretical) of yellowish 1,3-dihydro-7-nitro-5-phenyl-2H-1,4-benzodiazepine-2-one with m.p. 220 to 224°C. After recrystallization from acetic acid, the product is approximately white, m.p.
226 til 228°C. 226 to 228°C.
Eksempel 2. Example 2.
5,4 g 2-glycylamino-5-nitrobenzofenon omrøres eller rystes med 95 ml dioksan og 4 ml l-n saltsyre i 20 timer ved værelsetemperatur. Det bortfiltreres fra en liten uklarhet og fil-tratet blandes porsjonsvis med 250 ml vann. Av denne melkeaktige uklare væske utskiller det seg l,3-dihydro-nitro-5~fenyl-2H-l,4- 5.4 g of 2-glycylamino-5-nitrobenzophenone is stirred or shaken with 95 ml of dioxane and 4 ml of 1-n hydrochloric acid for 20 hours at room temperature. It is filtered away from a slight turbidity and the filtrate is mixed in portions with 250 ml of water. From this milky cloudy liquid, 1,3-dihydro-nitro-5~phenyl-2H-1,4-
benzodiazepin-2-on med en gang krystallinsk. Utbyttet av brun-aktige krystaller utgjør 3,2 g svarende til 63% av det teoretiske, smp. 219 til 226°C. Etter omkrystallisering fra eddiksyreetylester ligger smeltepunktet av de omtrent hvite krystaller ved 226 til 228,5°C. benzodiazepine-2-one immediately crystalline. The yield of brownish crystals amounts to 3.2 g corresponding to 63% of the theoretical, m.p. 219 to 226°C. After recrystallization from acetic acid ethyl ester, the melting point of the approximately white crystals is 226 to 228.5°C.
Eksempel 3. Example 3.
5,3 g 2-glycylamino-5_nitrobenzofenon ryster eller rører man med 110 ml dimetylformamid og 2 ml 2-n svovelsyre. Etter 24 timer blander man den klare oppløsning etterhvert med tilsammen 200 ml vann. Ved friksjon med en glass-stav utskiller det seg l,3-dihydro-7-nitro- 5-fenyl-2H-l,4-benzodiazepin-2-on krystallinsk. Man fra-suger, vasker med 25 ml vann, 10 ml alkohol og 5 ml eddikester, utbytte 3>3 gs svarende til 66$ av det teoretiske. Smp. 215 til 223°C. Etter omkrystallisering fra butanol ligger smeltepunktet ved 225 til 227,5°C, svakt gulaktige krystaller. 5.3 g of 2-glycylamino-5-nitrobenzophenone is shaken or stirred with 110 ml of dimethylformamide and 2 ml of 2-n sulfuric acid. After 24 hours, the clear solution is gradually mixed with a total of 200 ml of water. On friction with a glass rod, 1,3-dihydro-7-nitro-5-phenyl-2H-1,4-benzodiazepine-2-one separates out crystalline. It is suctioned off, washed with 25 ml of water, 10 ml of alcohol and 5 ml of vinegar, yield 3>3 gs corresponding to 66$ of the theoretical. Temp. 215 to 223°C. After recrystallization from butanol, the melting point is 225 to 227.5°C, slightly yellowish crystals.
Eksempel 4. Example 4.
50 g 2-(0-p-klorbenzolsulfonyl-glykoloylamino)-5_nitrobenzofenon suspenderes i 500 ml dioksan og under omrøring innføres ved værelsetemperatur i 8 timer ammoniakkgass. Deretter hensetter man reaksjonsblandingen natten over. Man fjerner overskytende oppløst ammoniakk idet man i 15 minutter blåser gjennom en luftstrøm. Deretter surgjør man med 50 ml iseddik, hensetter i 24 timer under om-røring av og til og utfeller det dannede l,3-dihydro-7-nitro-5-fenyl-2H-1,4-benzodiazepin-2-on med tilsetning av 1500 ml vann. Man suger fra, vasker med 200 ml vann, 40 ml metanol og 25 ml eddiksyreetylester. Utbyttet utgjør 18,4 g svarende til 63% av det teoretiske. Etter omkrystallisering f.eks. fra klorbenzol ligger smeltepunktet ved 225°C. 50 g of 2-(0-p-chlorobenzenesulfonyl-glycoylamino)-5-nitrobenzophenone are suspended in 500 ml of dioxane and, with stirring, ammonia gas is introduced at room temperature for 8 hours. The reaction mixture is then allowed to stand overnight. Excess dissolved ammonia is removed by blowing through an air stream for 15 minutes. It is then acidified with 50 ml of glacial acetic acid, allowed to stand for 24 hours with occasional stirring and the 1,3-dihydro-7-nitro-5-phenyl-2H-1,4-benzodiazepine-2-one formed is precipitated by adding of 1500 ml of water. Aspirate, wash with 200 ml of water, 40 ml of methanol and 25 ml of acetic acid ethyl ester. The yield amounts to 18.4 g, corresponding to 63% of the theoretical amount. After recrystallization e.g. from chlorobenzene, the melting point is 225°C.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD12841267 | 1967-11-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO122072B true NO122072B (en) | 1971-05-18 |
Family
ID=5479606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO315368A NO122072B (en) | 1967-11-20 | 1968-08-10 |
Country Status (7)
| Country | Link |
|---|---|
| AT (1) | AT287721B (en) |
| CH (1) | CH506540A (en) |
| DK (1) | DK116512B (en) |
| FI (1) | FI49167C (en) |
| NO (1) | NO122072B (en) |
| SE (1) | SE347264B (en) |
| YU (1) | YU192368A (en) |
-
1968
- 1968-07-12 AT AT677168A patent/AT287721B/en not_active IP Right Cessation
- 1968-08-06 FI FI221568A patent/FI49167C/en active
- 1968-08-06 DK DK377368A patent/DK116512B/en unknown
- 1968-08-10 NO NO315368A patent/NO122072B/no unknown
- 1968-08-13 YU YU192368A patent/YU192368A/en unknown
- 1968-09-13 SE SE1242568A patent/SE347264B/xx unknown
- 1968-10-08 CH CH1498368A patent/CH506540A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FI49167C (en) | 1975-04-10 |
| YU192368A (en) | 1973-04-30 |
| DK116512B (en) | 1970-01-19 |
| FI49167B (en) | 1974-12-31 |
| CH506540A (en) | 1971-04-30 |
| AT287721B (en) | 1971-02-10 |
| SE347264B (en) | 1972-07-31 |
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