NO128765B - - Google Patents
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- Publication number
- NO128765B NO128765B NO03087/68A NO308768A NO128765B NO 128765 B NO128765 B NO 128765B NO 03087/68 A NO03087/68 A NO 03087/68A NO 308768 A NO308768 A NO 308768A NO 128765 B NO128765 B NO 128765B
- Authority
- NO
- Norway
- Prior art keywords
- formula
- dichloro
- hydroxy
- steroid
- methylene
- Prior art date
Links
- 150000003431 steroids Chemical class 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000004423 acyloxy group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000005660 chlorination reaction Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- -1 acetoxy, butyroyloxy Chemical group 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NPOMSUOUAZCMBL-UHFFFAOYSA-N dichloromethane;ethoxyethane Chemical compound ClCCl.CCOCC NPOMSUOUAZCMBL-UHFFFAOYSA-N 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 241000283973 Oryctolagus cuniculus Species 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000011888 autopsy Methods 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002357 endometrial effect Effects 0.000 description 1
- 239000000262 estrogen Substances 0.000 description 1
- 229940011871 estrogen Drugs 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001072 progestational effect Effects 0.000 description 1
- 239000000583 progesterone congener Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000003248 secreting effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 210000004291 uterus Anatomy 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/56—Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids
- A61K31/57—Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids substituted in position 17 beta by a chain of two carbon atoms, e.g. pregnane or progesterone
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J5/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by a chain of two carbon atoms, e.g. pregnane and substituted in position 21 by only one singly bound oxygen atom, i.e. only one oxygen bound to position 21 by a single bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J7/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Steroid Compounds (AREA)
Description
Analogifremgangsmåte for fremstilling av progestativt virksomme 4,6-diklor-16-metylen-.,A. ' -pregnadien (og A ' pregnatrien)-3,20-dioner.
Nærværende oppfinnelse vedrorer en analogifremgangsmåte for fremstilling av progestativt virksomme 4,6-diklor-l6-metylen-A4'6-pregnadien (og A1' 4' 6-pregnatrien)-3, 20-dioner med den generelle formel hvor R betyr hydroksy eller alkanoyloksy med inntil 8 karbonatomer
og den punkterte binding i 1,2-stilling er fakultativ.
En alkanoyloksygruppe er for eksempel acetoksy-, butyroyloksy-eller caproyloksygruppen.
Forbindelser med formel I kan finne anvendelse som progestative midler. Når R betyr hydroksy, kan forbindelsene administreres parenteralt, og når R betyr alkanoyloksy, kan forbindelsene administreres oralt eller parenteralt.
Fremgangsmåten ifolge oppfinnelsen er karakterisert ved at man behandler et steroid med formelen
hvor R har foran angitte betydning,
med klor og en protonakseptor og eventuelt dehydroklorerer det som biprodukt oppstående 2,4-diklorsteroid med formelen
eller at man forestrer et steroid med formelen I, hvor R er hydroksy.
Kloreringen utfores hensiktsmessig ved innledning av klor i
et reaksjonsmedium som inneholder utgangssteroidet med formel II. Kloreringen kan gjennomfores i nærvær av en protonakseptor, for eksempel et N, N-di-lavere-alkyl-lavere-alkanoyl-amid, som dimetylformamid eller dimetylacetamid; et lavere-alkylenoksyd, som etylenoksyd eller propylenoksyd, i et opplosningsmiddel, som en lavere-alkankarboksylsyre, f.eks. propionsyre eller eddiksyre. På den annen side kan proton-akseptoren tilfores i tilslutning til behandlingen av utgangssteroidet med klor. I dette tilfelle oppnås som primært kloreringsprodukt en forbindelse med formelen
Dette mellomprodukt kan uten ytterligere rensning dehydro-kloreres ved behandling med en protonakseptor, som en nitrogen-holdig, heterocyklisk base, f.eks. picolin eller pyridin.
Hvis protonakseptoren er tilstede ved begynnelsen av kloreringen, kan den også tjene som opplosningsmiddel for utgangssteroidet med formel II. På den annen side og fortrinnsvis inneholder reak-sjon smediet andre opplosningsmidler. Som opplosningsmiddel egner seg de vanlige inerte organiske opplosningsmidler, f.eks. etere, som lavere-alkyletere, f.eks. etyleter eller dioksan; klorerte hydrokarboner som kloroform eller karbontetraklorid. Kloret kan innfores på i og for seg kjent måte i reaksjons-blandingen, f.eks. i form av en oppløsningen i en lavere-alkankarboksylsyre, som propionsyre. Kloreringen gjennomfores hensiktsmessig ved lavere temperaturer, fortrinnsvis mellom -40° og romtemperatur, spesielt mellom -30° og 0°. Kloreringen kan også gjennomfores med en opplosning av klor i karbontetraklorid under anvendelse av kloroform som opplosningsmiddel for utgangssteroidet ved temperaturer mellom 0° og romtemperatur, hvorpå opplosningsmidlet fjernes og slutter seg til en behandling med en protonakseptor.
Ved kloreringen av 1(2)-mettede utgangssteroider kan som biprodukter 2,4,6-triklor-steroider med formel III oppnås0
Den progestationale aktivitet for A, B, C, D og E ble undersokt: A : 4, 6-diklor-17oc-hydroksy-16-metylenpregna-4, 6-dien-3, 20-
dionacetat.
B : 4, 6-diklor-17oc-hydroksy-16-metylen-pregna-l, 4, 6-trien-3, 20-dionacetat.
C : 4, 6-diklor-17oc-hydroksypregna-4, 6-dien-3, 20-dionacetat.
D : 4,6-diklor-17a-hydroksy-16a-metylpregna-4,6-dien-3,20-dionacetat .
E : 4, 6-diklor-17cx-hydroksypregna-l, 4, 6-trien-3, 20-dionacetat.
Den progestative aktivitet for forannevnte forbindelser ble bestemt ved å administrere forbindelsene i fem på hverandre folgende dager til estrogen-forbehandlede, umodne hun-kaniner. Ved autopsi fjernes uterus og det histologiske preparat fremstilles fra uterin-tverrsnittet. Det histologiske snitt vurde-res mikroskopisk for formålet progestativ aktivitet som fastslås ved et endometrialt response av sekretorisk type. Denne prove ble utfort ved forskjellige dosenivåer for å bestemme den laveste dose hvor vesentlig progestativ aktivitet ble iakttatt.
Resultater
Utgangsmaterialene er overveiende kjente forbindelser eller tilhorer kjente forbindelsesklasser. De kan fremstilles etter i og for seg kjente metoder, for eksempel i analogi til de i de nedenstående eksempler for visse tilfeller utforte fremgangs-måter. Alle temperaturer er angitt i Celsiusgrader.
EKSEMPEL 1
Til en opplosning av 3,9 g 6-klor-17oc-acetoksy-16-metylen-pregna-4,6-dien-3,20-dion i 25 ml alkoholfri kloroform dryppes ved 0° 11,3 ml av en 0,87 molar opplosning av klor i karbontetraklorid. Den resulterende opplosning rores om i en time ved 0°, hvorpå opplosningsmidlene fjernes under forminsket trykk. Det erholdte skum behandles med 10 ml torr pyridin og rores i 2 timer ved romtemperatur. Etter tilsetning av 200 ml eter ekstraheres blandingen to ganger hver gang med 150 ml l-n saltsyre. Den eteriske opplosning torkes, rives med eter og gir 2,4 g råprodukt, som kromåtograferes på 100 g silicagel. Eluering med 2 %'ig etylacetat i benzen gir 2a,4,6-triklor-17a-acetoksy-16-metylenpregna-4,6-dien-3,20-dion, som etter krystallisasjon fra metylenklorid-eter smelter ved 235 - 233°
(begynnende spaltning ved 225°).
Ytterligere eluering med 5 %' ig etylacetat i benzen gir 4,6-di-klor-17oc-acetoksy-16-metylenpregna-4, 6-dien-3, 20-dion, smelte-punkt 218-219° (fra metylenklorid-eter).
EKSEMPEL 2
En opplosning av 0,250 g 2a, 4, 6-triklor-17oc-acetoksy-16-metylen-pregna-4,6-dien-3,20-dion, 0,1 g litiumklorid og 3 ml torr dimetylformamid oppvarmes en 1/2 time under nitrogen under tilbakelop. Opplosningen avkjoles og helles i lOO ml isvann. Bunnfallet filtreres og torkes i luft. Det således erholdte råprodukt kromatogreferes på 6 g noytralt aluminiumoksyd (aktivitet I). Eluering med petroleter (60 - 90°) og metylenklorid (1:1) og deretter med metylenklorid alene gir 4,6-diklor-17oc-acetoksy-16-metylenpregna-l,4,6-trien-3,20-dion som etter krystallisasjon fra eter-metylenklorid smelter ved 225 - 228°.
Claims (1)
- Analogifremgangsmåte for fremstilling av progestativt virksomme 4, 6-diklor-16-metylen-A4'^-pregnadien (og A^'<4>'^- pregnatrien)-3,20-dioner med den generelle formelhvor R betyr hydroksy eller alkanoyloksy med inntil 8 karbonatomer,og den punkterte binding i 1,2-stilling er fakultativ, karakterisert ved at man behandler et steroid med formelenhvor R har foran angitte betydning.med klor og en protonakseptor og eventuelt dehydroklorerer det som biprodukt oppstående 2, 4-diklorsteroid med formeleneller at man forestrer et steroid med formelen I, hvor R er hydroksy.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US65860267A | 1967-08-07 | 1967-08-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO128765B true NO128765B (no) | 1974-01-07 |
Family
ID=24641922
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO03087/68A NO128765B (no) | 1967-08-07 | 1968-08-06 | |
| NO03088/68A NO128766B (no) | 1967-08-07 | 1968-08-06 |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO03088/68A NO128766B (no) | 1967-08-07 | 1968-08-06 |
Country Status (17)
| Country | Link |
|---|---|
| JP (2) | JPS5021474B1 (no) |
| AT (4) | AT290031B (no) |
| BE (2) | BE719050A (no) |
| CH (10) | CH544073A (no) |
| DE (1) | DE1793063A1 (no) |
| DK (2) | DK126187B (no) |
| ES (2) | ES356956A1 (no) |
| FI (2) | FI45321C (no) |
| FR (4) | FR8417M (no) |
| GB (2) | GB1217530A (no) |
| IE (2) | IE32397B1 (no) |
| IL (2) | IL30491A (no) |
| MY (1) | MY7100216A (no) |
| NL (2) | NL6811217A (no) |
| NO (2) | NO128765B (no) |
| SE (2) | SE351633B (no) |
| YU (2) | YU33190B (no) |
-
1968
- 1968-07-17 CH CH418771A patent/CH544073A/de not_active IP Right Cessation
- 1968-07-17 CH CH418971A patent/CH544074A/de not_active IP Right Cessation
- 1968-07-17 CH CH418871A patent/CH544072A/de not_active IP Right Cessation
- 1968-07-17 CH CH418571A patent/CH541549A/de not_active IP Right Cessation
- 1968-07-17 CH CH419071A patent/CH541550A/de not_active IP Right Cessation
- 1968-07-17 CH CH418671A patent/CH544075A/de not_active IP Right Cessation
- 1968-07-17 CH CH1070568A patent/CH565198A5/xx not_active IP Right Cessation
- 1968-07-17 CH CH1070668A patent/CH555329A/xx not_active IP Right Cessation
- 1968-07-17 CH CH419171A patent/CH544081A/de not_active IP Right Cessation
- 1968-07-17 CH CH419271A patent/CH544076A/de not_active IP Right Cessation
- 1968-07-30 DE DE19681793063 patent/DE1793063A1/de active Pending
- 1968-08-05 AT AT08882/69A patent/AT290031B/de not_active IP Right Cessation
- 1968-08-05 YU YU1858/68A patent/YU33190B/xx unknown
- 1968-08-05 AT AT760368A patent/AT285832B/de not_active IP Right Cessation
- 1968-08-05 IL IL6830491A patent/IL30491A/en unknown
- 1968-08-05 BE BE719050D patent/BE719050A/xx unknown
- 1968-08-05 AT AT888169A patent/AT290030B/de not_active IP Right Cessation
- 1968-08-05 AT AT760468A patent/AT285833B/de not_active IP Right Cessation
- 1968-08-05 YU YU01857/68A patent/YU185768A/xx unknown
- 1968-08-05 IL IL30492A patent/IL30492A/xx unknown
- 1968-08-05 BE BE719049D patent/BE719049A/xx unknown
- 1968-08-06 GB GB37509/68A patent/GB1217530A/en not_active Expired
- 1968-08-06 ES ES356956A patent/ES356956A1/es not_active Expired
- 1968-08-06 NO NO03087/68A patent/NO128765B/no unknown
- 1968-08-06 NO NO03088/68A patent/NO128766B/no unknown
- 1968-08-06 JP JP43055307A patent/JPS5021474B1/ja active Pending
- 1968-08-06 FR FR162043A patent/FR8417M/fr not_active Expired
- 1968-08-06 FR FR1588548D patent/FR1588548A/fr not_active Expired
- 1968-08-06 FR FR162042A patent/FR7921M/fr not_active Expired
- 1968-08-06 DK DK379168AA patent/DK126187B/da unknown
- 1968-08-06 ES ES356957A patent/ES356957A1/es not_active Expired
- 1968-08-06 FR FR1588547D patent/FR1588547A/fr not_active Expired
- 1968-08-06 IE IE950/68A patent/IE32397B1/xx unknown
- 1968-08-06 GB GB37510/68A patent/GB1215752A/en not_active Expired
- 1968-08-06 IE IE949/68A patent/IE32344B1/xx unknown
- 1968-08-06 DK DK379268AA patent/DK122606B/da unknown
- 1968-08-07 FI FI682233A patent/FI45321C/fi active
- 1968-08-07 SE SE10631/68A patent/SE351633B/xx unknown
- 1968-08-07 FI FI682234A patent/FI45322C/fi active
- 1968-08-07 NL NL6811217A patent/NL6811217A/xx unknown
- 1968-08-07 JP JP43055539A patent/JPS5010859B1/ja active Pending
- 1968-08-07 NL NL6811218A patent/NL6811218A/xx unknown
- 1968-08-07 SE SE10630/68A patent/SE351632B/xx unknown
-
1971
- 1971-12-30 MY MY216/71A patent/MY7100216A/xx unknown
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