IL43992A - Racemic 13beta-ethyl-3-methoxy-8,14-seco-gona-1,3,5(10),8-tetraene-17beta-ol-14-one and a process for the preparation thereof - Google Patents
Racemic 13beta-ethyl-3-methoxy-8,14-seco-gona-1,3,5(10),8-tetraene-17beta-ol-14-one and a process for the preparation thereofInfo
- Publication number
- IL43992A IL43992A IL43992A IL4399274A IL43992A IL 43992 A IL43992 A IL 43992A IL 43992 A IL43992 A IL 43992A IL 4399274 A IL4399274 A IL 4399274A IL 43992 A IL43992 A IL 43992A
- Authority
- IL
- Israel
- Prior art keywords
- ethyl
- gona
- methoxy
- tetraene
- seco
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 11
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000000203 mixture Substances 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 11
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- OSVMTWJCGUFAOD-KZQROQTASA-N formestane Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1O OSVMTWJCGUFAOD-KZQROQTASA-N 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 125000004043 oxo group Chemical group O=* 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000000397 acetylating effect Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000006257 total synthesis reaction Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- FGVNCNTVSHHPTI-UHFFFAOYSA-N butoxyaluminum Chemical compound CCCCO[Al] FGVNCNTVSHHPTI-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 150000003803 gonane derivatives Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 125000003198 secondary alcohol group Chemical group 0.000 description 1
- 150000003338 secosteroids Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 150000003431 steroids Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Racemic 13M-ethyl-3methoxy-8 ,14-seco-gona-l , 3 , 5 (10$ ,8-tetraene- 17β-ο1-14-οηβ and a process for the preparation thereof Richter Gedeon Vegyeszeti Gyar R.T.
This invention relates to racemic 13B-et yl-3- methoxy-8 , 14-seco-gona- ,3,5(10),8-tetraene-17B~ol-1 -one , a novel compound, as well as to a process for the preparation thereof. This compound can be utilized with great advantages in the total synthesis of certain gonane derivatives.
It is known that one of the oxo groups of 13-ethyl-3-methoxy-8, -seco-gona- , 3, 5(10) , 9-tetraene , 14, 17-dione can be selectively reduced with sodium borohydride to form a secondary alcohol group (see U.S. Patent Specification No. j¾ 54-9*673). According to the same reference (see lines 39 to 5 of column 3 and lines 1 to 23 of column 4), in this reaction racemic 3B-ethyl-3-methoxy-8, 4-seco-gona-1}3»5( O),9-tetraene-17 -ol-1 -one is formed exclusively.
This invention is based on the recognition that when reducing l3-ethyl-3-methoxy-8, 4-seco-gona-1 , 3, 5(10) , 9-tetraene-^, 17-dione with sodium borohydride of an amount necessary for the reduction of one of the oxo groups, in the presence of an alkali metal hydroxide and/or alcoholate, a diastereomeric mixture containing racemic 13B-ethyl-3-methoxy-8, -seeo-gona-1 , 3> 5(10) , 9-tetraene-17B-ol-14~one as main product is formed, and if this crude diastereomeric mixture is treated with an organic acid containing 5 to 15 % of water, then the racemic 13fi-ethyl-3-niethoxy-8, 14-seco-gona-1,3,5( O),9-tetraene-17 -ol-14-one by-product quantita^ tively converts into the known racemic 13fl-ethyl-3-methoxy-8,1 -seco-9§ ,1 « -oxido-gona-1,3»5(IO)-triene-17-one, while the main product, that is, the 17B-hydroxy-14-one compound, converts into the novel racemic 3B-ethyl-3-methoxy-8, 14-seco-gona-1,3,5(lO),8-tetraene-17B-ol-1 -one. The compounds obtained in this way greatly differ from each other with respect to their polarities and thus they can be easily separated from each other. Such type of the 9 > 8(9) isomerisation of a double bond was hitherto unknown in the seco-steroid series. e have found further that when acetylating racemic 3B-ethyl-3-methoxy-8, 14-seco-gona-1 , 3, 10) f8-tetraene-17B-ol-14-one and treating, the reaction mixture with an acid, the known racemic 13B-ethyl-3-methoxy-gona-1 , 3, 5(10) ,8, 14-pentaene-17B-ol-acetate can be obtained with an excellent yield. This latter compound is an important starting substance for the preparation of 13B-ethyl-gonane derivatives.
It was already known that when reducing 13-ethyl-3-methoxy-8, 4-seco-gona- , 3 » 5(10) j 9-tetraene-14, 17-dione with lithium tri-tert.butoxy aluminium hydride, besides the main product, i.e., racemic 3£-etyhl-3-methoxy-8, 14-seco-gona-1, 3 > 5( 0) , 9-tetraene-17<<-ol-14-one, also a diastereomeric by-product, i.e., racemic 13B-ethyl-3-methoxy-8,14-seco-gona- , 3» 5( 10) , 9-tetraBne-17B-ol-l4-one is formed (J. Med. Ohem. 1j?, 360 /1972/) . According to the practice, however, neither this mixture, nor the diastereomeric mixture of racemic 3fl-ethyl-3-methoxy-gona-1 * 3» (10),8,14-pentaene-17« -ol-acetate and of the corrsponding 17B-compound, prepared by acetylating the former mixture and subjecting the products of acetylation to ring closure, can be used for carrying out further stereospecific reactions, and the diastereomers of steroid skeleton can be separated from each other only with great difficulties (J. Med. Chem. 360 / 72/) .
The racemic 13B-ethyl-3-methoxy-8, 14-seco-gona- 1 » 3 , 5(10),8-tetraene-17B-Ql-1 -oiie is prepared according to the invention as follows: one of the oxo groups of 13-ethyl» 3-methoxy-8, 4~seco-gona- , 3, 5(10) , 9-tetraene-1 , 17-dione is deduced with sodium borohydride in the presence of an alkali metal hydroxide and/or alcoholate, the obtained liastereomeric mixture, consisting mainly of racemic 13B~ 3thyl-3-methoxy-8,1 -seco-gona-1»3,5( O),9-tetraene-17B-ol~~ 14~one, is reacted with an organic acid, preferably with a C^_6 aliphatic carboxylic acid, and the obtained 13B-ethyl-3-methoxy-8, 1 -seco-gona-1 , 3, 5(10) ,8-tetraene- 7B-ol-1 -one is, separated from the reaction mixture.
The above reactions are preferably carried out by reducing 3-ethyl-3-methoxy-8, 1 -seco-gona-1 , 3, 5(10) , 9-tetraene-1 , 17-dione, dissolved in 0.1 n methanolic sodium hydroxide, with sodium borohydride, wherein the latter reactant is used in an amount sufficient to reduce only one of the oxo groups. The reaction is carried out preferably at a temperature between +20° and +60°; within this range the room temperature is the most preferred. The diastereo-meric mixture of the 1 -S-hydroxy-1 -one and 17«C -hydroxy-1 -one compounds, obtained after processing the above reaction mixture, is treated at room temperature with acetic acid containing 5 to 15 of water, thereafter the reaction, mixture is evaporated to dryness. The residue is subjected to column chromatography, to yield the syrup-like racemic 13fi-ethyl-3-methoxy-8,1 -seco-gona-1 ,3, (10) ,8-tetraene-17£-ol-1 -one.
The main advantages of the process according to the invention are as follows; a) Using this modified sodium borohydride reduction of 13-ethyl-3-methoxy-8, 1 -seco-gona-l , , (10) ,9-tetraene- 14,17-dione, the 3B-ethyl-3-methoxy-8, 14-seco-gona-1 , 3, 5( 19. tetraene-17B-ol-14-one is obtained as main product, instead of the 17 eC -compound. b) When treating the diastereomeric mixture of the t 17B- and 17 eC -hydroxy-14-one compounds with an organic acid, both of the isomers convert into the different corresponding products which, due to their highly different polarities, can readily be separated from each other. In this latter reaction the 17B-hydroxy-14-one compound converts into a new derivative, that is, into racemic 13B-e l-3-methoxy- 8,1 -seco-gona-1,3,5(10),8-tetraene-17fl-ol-14-one- which is a valuable intermediate for the total synthesis of 13B-ethyl- gonane derivatives, since it can be converted, even in crude state, into racemic 13B-ethyl-3-methoxy-gona-1,3,5(10) ,8,14-5 pentaene-17B-ol-acetate with excellent yields.
The invention is. further illustrated by the aid of the following, non-limiting Example.
Example Step (a) ; Preparation of racemic 13B-ethyl-3-methoxy- 8, 4-seco-gona- , 3, 5(10) ,8-tetraene-17B-ol-14-one 50 g. of 13-ethyl-3-methoxy-8, 4-seco-gona-1,3,5(10),9- tetraene-14,17-dione (prepared according to the method described in J. Org. Ohem. j£, 3126 /1968/) are dissolved in 2.5 litres, of 0.1 n methanolic sodium hydroxide, and 2.5 g. of sodium borohydride are added to the solution at 20 °C.
After 0.5 hours of stirring the mixture is neutralized with glacial acetic acid and evaporated to dryness. The dry residue is dissolved in a mixture of water and ethyl acetate, then the organic phase is separated and evaporated to dry- ness. The thus-obtained residue (50 g.), consisting of racemic 3B-ethyl-3-methoxy-8 , 14~seco-gona- , 3 , 5(10) ,9-tetraene-17B-ol-14-one and racemic 13B-ethyl-3-methoxy-8, 14-seco-gona-1, 3 , 5(10) , 9-tetraene-17<< -ol-14-one, is dissolved in 2.5 litres of a 9:1 mixture of acetic acid and water, and the obtained solution is left to stand at room temperature for 72 hours* Thereafter the reaction mixture is evaporated to dryness at 3 °0, under reduced pressure. The obtained oily residue ( 9 g.) is dissolved in benzene and subjected to chromatography on a silica gel column. The elution is started with benzene containing 2.5 of ethyl acetate.
The obtained effluent is evaporated to yield the racemic 13B-ethyl-3-methoxy-8,14-seco-9'l) ,14«C -oxido-gona- * 3j (10)-triene-17-one by-product. The elution is continued with benzene containing" 5 # of ethyl acetate, and the effluent is evaporated. In this way 30 g. of a syrup-like residue is obtained, consisting of crude racemic 13fi-ethyl<~ 3-methoxy-8,14-seco-gona- , 3, 5(10) , 8-tetraene-17B-ol-14-one .
A small portion of this product is purified by chromatography for analytical purposes. As adsorbent, a 1:1 mixture of Kieselgel ^2^-366 (Merck) and Kieseleel G (Merck) is used, and development is carried out with a 98:1:1 mixture of chloroform, acetone and methanol, The spot appearing at Hf - 0.31 is eluted, and the eluate is evaporated. Syrup-like, pure, uniform 3B-ethyl-3-methoxy-8,14-seco-gona-1, 3, 5(10) , 8-tetraene-17B-ol-14-one is obtained, λ e hanol 270 ( . - 10, 500) max, Λ IS (film): > - 3440 (OH), 1720 (G-0), 1602, 1565, W6 cm" (aromatic 0*0).
NMR: cT = 0.90 (t, CH3/CH2/); 3.77 (s, CH^) $ 4.24 (t, 0-17 H, J - 5.5 Hz); 5-7 (t, C-8 H, J = 4 Hz); 6.6 to 6.8 (m,, 0-4 H and 0-2 H, Jmeta - 2.5 Hz, Jortho . 9-5v Hz); 7.15 (d, 0-1 H, J = 9.5 Hz) ppm.
Step (b): Preparation of racemic 13B-ethyl-3-methoxy»-gona- ,3, ( 10) , 8 , 14-pentaene-17B-ol-acetate 3 g. of crude racemic 3B-ethyl-3-methoxy-8, 14-seco-gonarl ,3» ( 10) , 8-tetraene-17B-ol-14-one (prepared as described in Step /a/) are boiled for 12 hours in a mixture of 270 ml. of abs. benzene*, 35 ml. of pyridine and 30 ml. of acetic anhydride. The reaction mixture is extracted with 3x100 ml, of 2.5 % aqueous hydrochloric acid, then with 2x100 ml. of 5 ^ aqueous sodium- hydrocarbonate solution, and finally with 100 ml.. of water. The benzene solution is dried by distilling off 80 ml. of benzene, thereafter 1 .4 g. of p-toluenesulfonic acid are added to the residue, and the mixture is boiled for 5 hours under a water separator. The reaction mixture is cooled, washed until neutral with 190 ml. of 5 % aqueous sodium hydrocarbonate solution and then with 100 ml. of water, dried over sodium sulfate, and evaporated to dryness. The oily residue ( 29.5 g.) is treated with methanol to form 22.0 g. of a uniform, crystalline product.
The obtained racemic 1^B-ethyl-3-methoxy-gona-1 , 3, 5(10) , 8 , 14- , „ , nn O, 1 methanol pentaene-17B-ol-acetate melts at 87 to 89 C? λ maXe = 314T¾n ( £ = 28, 950) .
Claims (7)
1. Racemic 13p-ethyl-3-methoxy-8, 14-eeco-gona-l, 3, 5(10) ,8- tetraene-17p-ol-14-one .
2. A process for the preparation of racemic 13p-ethyl-3-methoxy- 8,14-seco-gona-l,3,5(10) , 8-tetraene-17p-ol-14-one , in which one of the oxo groups of 13-ethyl-3-methoxy-8, 14-seco-gona- l,3,5(l0),9-tetraene-14,17-dione is reduced with sodium borohydride in the presence of an alkali metal hydroxide and/or alcoholate, the obtained diastereomeric mixture, containing racemic 13p-ethyl-3-methoxy-8,14-seco-gona--l,3, 5 (10) ,9-tetraene-17p-ol-14-one as main component, is reacted with an organic acid, and the obtained racemic 13p-ethyl- 3-methoxy-8 , 14-seco-gona-1 , 3 , 5 ( 10) , 8-tetraene-17f>-ol-14- one is separated from the reaction mixture.
3. A process as claimed in claim 2, in which the organic acid is a aliphatic carboxylic acid.
4. A process as claimed in claim 3, in which the aliphatic . carboxylic acid is acetic acid.
5. Racemic 13p-ethyl-3-methoxy-8,14-seco-gona-l,3,5(10) ,8- tetraene-17p-ol-14-one, whenever prepared by a process as claimed in claim 2, or by an obvious chemical equivalent thereof.
6. A process as claimed in any of claims 2 to 4, for preparing racemic 13p-ethyl-3-methoxy-8, 14-seco-gona-l,3, 5(10) ,8- tetraene-17p-ol-14-one .
7. A process for the preparation of racemic 13p-ethyl-3-methoxy- 8 , 14-seco-gona-l ,3,5(10),8-tetraene-17p-ol-14-one , substantially as hereinbefore described with reference to the Example.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HUGO1230A HU170147B (en) | 1973-01-31 | 1973-01-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL43992A0 IL43992A0 (en) | 1974-05-16 |
| IL43992A true IL43992A (en) | 1977-07-31 |
Family
ID=10996741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL43992A IL43992A (en) | 1973-01-31 | 1974-01-10 | Racemic 13beta-ethyl-3-methoxy-8,14-seco-gona-1,3,5(10),8-tetraene-17beta-ol-14-one and a process for the preparation thereof |
Country Status (18)
| Country | Link |
|---|---|
| JP (1) | JPS5641610B2 (en) |
| AT (1) | AT346505B (en) |
| BE (1) | BE810381A (en) |
| BG (1) | BG23904A3 (en) |
| CS (1) | CS165309B2 (en) |
| DE (1) | DE2403985C2 (en) |
| DK (1) | DK138314B (en) |
| ES (1) | ES422607A1 (en) |
| FR (1) | FR2216275B1 (en) |
| GB (1) | GB1420892A (en) |
| HU (1) | HU170147B (en) |
| IL (1) | IL43992A (en) |
| IT (1) | IT1043869B (en) |
| NL (1) | NL7401256A (en) |
| RO (1) | RO67880A (en) |
| SE (1) | SE400977B (en) |
| SU (1) | SU561515A3 (en) |
| YU (1) | YU35750B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE541390C2 (en) * | 2017-12-20 | 2019-09-10 | Scania Cv Ab | System and Method for Controlling a Motor Vehicle to Drive Autonomously |
| SE541389C2 (en) * | 2017-12-20 | 2019-09-10 | Scania Cv Ab | System and Method for Controlling a Motor Vehicle to Drive Autonomously |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3549673A (en) * | 1967-03-09 | 1970-12-22 | Takeda Chemical Industries Ltd | Total synthesis of 13beta-substituted gonapolyen-17alpha-ols |
-
1973
- 1973-01-31 HU HUGO1230A patent/HU170147B/hu unknown
-
1974
- 1974-01-10 IL IL43992A patent/IL43992A/en unknown
- 1974-01-14 GB GB162874A patent/GB1420892A/en not_active Expired
- 1974-01-14 YU YU103/74A patent/YU35750B/en unknown
- 1974-01-17 AT AT38374A patent/AT346505B/en not_active IP Right Cessation
- 1974-01-19 RO RO7477336A patent/RO67880A/en unknown
- 1974-01-22 BG BG025563A patent/BG23904A3/en unknown
- 1974-01-25 ES ES422607A patent/ES422607A1/en not_active Expired
- 1974-01-25 IT IT19776/74A patent/IT1043869B/en active
- 1974-01-25 CS CS491A patent/CS165309B2/cs unknown
- 1974-01-28 FR FR7402683A patent/FR2216275B1/fr not_active Expired
- 1974-01-29 SE SE7401140A patent/SE400977B/en not_active IP Right Cessation
- 1974-01-29 DE DE2403985A patent/DE2403985C2/en not_active Expired
- 1974-01-29 JP JP1154774A patent/JPS5641610B2/ja not_active Expired
- 1974-01-30 NL NL7401256A patent/NL7401256A/xx not_active Application Discontinuation
- 1974-01-30 BE BE140361A patent/BE810381A/xx not_active IP Right Cessation
- 1974-01-30 SU SU1991803A patent/SU561515A3/en active
- 1974-01-30 DK DK48374AA patent/DK138314B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| NL7401256A (en) | 1974-08-02 |
| JPS5641610B2 (en) | 1981-09-29 |
| YU10374A (en) | 1980-10-31 |
| GB1420892A (en) | 1976-01-14 |
| ES422607A1 (en) | 1977-04-16 |
| IL43992A0 (en) | 1974-05-16 |
| DE2403985C2 (en) | 1984-03-01 |
| AT346505B (en) | 1978-11-10 |
| DK138314B (en) | 1978-08-14 |
| CS165309B2 (en) | 1975-12-22 |
| FR2216275A1 (en) | 1974-08-30 |
| DE2403985A1 (en) | 1974-08-08 |
| JPS5046653A (en) | 1975-04-25 |
| BG23904A3 (en) | 1977-11-10 |
| IT1043869B (en) | 1980-02-29 |
| FR2216275B1 (en) | 1977-09-23 |
| SU561515A3 (en) | 1977-06-05 |
| DK138314C (en) | 1979-02-05 |
| BE810381A (en) | 1974-05-16 |
| ATA38374A (en) | 1978-03-15 |
| RO67880A (en) | 1980-12-30 |
| SE400977B (en) | 1978-04-17 |
| YU35750B (en) | 1981-06-30 |
| HU170147B (en) | 1977-04-28 |
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