HRP20180454T1 - Postupak za proizvodnju 3-okso-pregn-4-en-21,17-karbolaktona pomoću bezmetalne oksidacije 17-(3-hidroksipropil)-3,17-dihidroksiandrostana - Google Patents
Postupak za proizvodnju 3-okso-pregn-4-en-21,17-karbolaktona pomoću bezmetalne oksidacije 17-(3-hidroksipropil)-3,17-dihidroksiandrostana Download PDFInfo
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- HRP20180454T1 HRP20180454T1 HRP20180454TT HRP20180454T HRP20180454T1 HR P20180454 T1 HRP20180454 T1 HR P20180454T1 HR P20180454T T HRP20180454T T HR P20180454TT HR P20180454 T HRP20180454 T HR P20180454T HR P20180454 T1 HRP20180454 T1 HR P20180454T1
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- 238000000034 method Methods 0.000 title claims 19
- 238000007254 oxidation reaction Methods 0.000 title claims 9
- 230000003647 oxidation Effects 0.000 title claims 8
- 238000004519 manufacturing process Methods 0.000 title claims 5
- UWBICEKKOYXZRG-LHZXLZLDSA-N (8r,9s,10r,13s,14s,17s)-10,13-dimethylspiro[2,6,7,8,9,11,12,14,15,16-decahydro-1h-cyclopenta[a]phenanthrene-17,5'-oxolane]-2',3-dione Chemical class C([C@H]1[C@H]2[C@@H]([C@]3(CCC(=O)C=C3CC2)C)CC[C@@]11C)C[C@]11CCC(=O)O1 UWBICEKKOYXZRG-LHZXLZLDSA-N 0.000 title claims 3
- BMAXQBBOPJUDSD-OHPXTLHMSA-N (5S,8R,9S,10S,13S,14S)-17-(3-hydroxypropyl)-10,13-dimethyl-1,2,3,4,5,6,7,8,9,11,12,14,15,16-tetradecahydrocyclopenta[a]phenanthrene-3,17-diol Chemical class OCCCC1(CC[C@@H]2[C@]1(C)CC[C@H]1[C@H]2CC[C@H]2CC(CC[C@]12C)O)O BMAXQBBOPJUDSD-OHPXTLHMSA-N 0.000 title 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 18
- 239000001257 hydrogen Substances 0.000 claims 18
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 18
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims 16
- 150000001875 compounds Chemical class 0.000 claims 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 5
- 239000003638 chemical reducing agent Substances 0.000 claims 4
- 125000003700 epoxy group Chemical group 0.000 claims 4
- VUZNLSBZRVZGIK-UHFFFAOYSA-N 2,2,6,6-Tetramethyl-1-piperidinol Chemical class CC1(C)CCCC(C)(C)N1O VUZNLSBZRVZGIK-UHFFFAOYSA-N 0.000 claims 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 3
- 238000006243 chemical reaction Methods 0.000 claims 3
- 239000000203 mixture Substances 0.000 claims 3
- 239000007864 aqueous solution Substances 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims 2
- 239000007800 oxidant agent Substances 0.000 claims 2
- 239000000243 solution Substances 0.000 claims 2
- 239000002904 solvent Substances 0.000 claims 2
- RVWUHFFPEOKYLB-UHFFFAOYSA-N 2,2,6,6-tetramethyl-1-oxidopiperidin-1-ium Chemical compound CC1(C)CCCC(C)(C)[NH+]1[O-] RVWUHFFPEOKYLB-UHFFFAOYSA-N 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims 1
- 239000005708 Sodium hypochlorite Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 229940079826 hydrogen sulfite Drugs 0.000 claims 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims 1
- 235000015497 potassium bicarbonate Nutrition 0.000 claims 1
- 239000011736 potassium bicarbonate Substances 0.000 claims 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 238000010791 quenching Methods 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims 1
- 235000010262 sodium metabisulphite Nutrition 0.000 claims 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J53/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton has been modified by condensation with a carbocyclic rings or by formation of an additional ring by means of a direct link between two ring carbon atoms, including carboxyclic rings fused to the cyclopenta(a)hydrophenanthrene skeleton are included in this class
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J53/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton has been modified by condensation with a carbocyclic rings or by formation of an additional ring by means of a direct link between two ring carbon atoms, including carboxyclic rings fused to the cyclopenta(a)hydrophenanthrene skeleton are included in this class
- C07J53/002—Carbocyclic rings fused
- C07J53/004—3 membered carbocyclic rings
- C07J53/008—3 membered carbocyclic rings in position 15/16
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Steroid Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Claims (18)
1. Postupak za proizvodnju 3-okso-pregn-4-en-21,17-karbolaktona s formulom IIIa
[image]
u kojem:
R6a je vodik, ili zajedno s R7a je -CH2 skupina;
R6b je vodik, ili zajedno s R7b je -CH2 skupina, ili dvostruka veza;
R7a je vodik, C1-C4-alkoksikarbonil, C1-C4-tioacil,
R7b je vodik, ili zajedno s R6b je -CH2 skupina;
R9 je vodik, zajedno s R11 je dvostruka veza ili zajedno s R11 je epoksi skupina -O-;
R10 je vodik, ili metil;
R11 je vodik, zajedno s R9 je dvostruka veza ili zajedno s R9 je epoksi skupina -O-;
R15 je vodik, zajedno s R16 je -CH2 skupina ili dvostruka veza;
R16 je vodik, zajedno s R19 je -CH2 skupina ili dvostruka veza;
koji obuhvaća oksidaciju spoja s formulom Ia
[image]
u kojoj
R6a, R6b, R7a, R7b, R9, R10, R11, R15, R16 imaju isto značenje kao u formuli IIIa, da se dobije formula IIa;
[image]
i naknadno uklanjanje vode s prikladnom kiselinom da nastane spoj formule IIa;
naznačen time da se
provodi oksidacija, s najmanje 3 molarna ekvivalenta alkalijskog hipoklorita, organskog hipoklorita ili 2-3 molarna ekvivalenta zemnoalkalijskog hipoklorita kao oksidacijskog sredstva u prisutnosti katalitičkih količina derivata 2,2,6,6-tetrametilpiperidin-N-oksida kod pH od najmanje 8.0, u dvofaznoj smjesi otapalo-voda, pri čemu je otapalo odabrano tako da se oba TEMPO derivat i spojevi s formulom Ia u njemu mogu dobro otopiti.
2. Postupak prema zahtjevu 1 za proizvodnju spoja s formulom IIIb,
[image]
naznačen time da sadrži oksidaciju spoja s formulom Ib
[image]
da nastane spoj s formulom IIb,
[image]
a zatim uklanjanje vode da se dobije spoj formule IIIb.
3. Postupak za proizvodnju 3-okso-pregn-4-en-21,17-karbolaktona s formulom IIa
[image]
u kojoj
R6a je vodik, ili zajedno s R7a je skupina -CH2;
R6b je vodik, ili zajedno s R7b je skupina -CH2, ili dvostruko vezan;
R7a je vodik, C1-C4-alkoksikarbonil, C1-C4-tioacil,
R6b je vodik, ili zajedno s R6b je skupina -CH2;
R9 je vodik, zajedno s R11 je dvostruka veza, ili zajedno sa R11 je epoksi skupina -O-;
R10 je vodik, ili metil;
R11 je vodik, zajedno s R9 je dvostruka veza ili zajedno s R9 je epoksi skupina -O-;
R15 je vodik, zajedno s R16 je skupina -CH2 ili dvostruka veza;
R16 je vodik, zajedno s R15 je skupina -CH2 ili dvostruka veza;
koji obuhvaća oksidaciju spoja formule Ia
[image]
u kojoj
R6a, R6b, R7a, R7b, R9, R10, R11, R15, R16 imaju isto značenje kao u formuli IIa,
naznačen time da
se oksidacija provodi s barem 3 molarna ekvivalenta alkalijskog hipoklorita, organskog hipoklorita ili 2-3 molarna ekvivalenta zemnoalkalijskog hipoklorita kao oksidirajućeg sredstva u prisutnosti katalitičkih količina derivata 2,2,6,6-tetrametilpiperidin-N-oksida uz pH od najmanje 8.0, u dvofaznoj smjesi otapalo-voda, pri čemu se otapalo bira tako da i TEMPO derivat i spojevi formule la mogu u njemu biti dobro otopljeni.
4. Postupak prema zahtjevu 3 za proizvodnju spoja formule IIb
[image]
naznačen time da obuhvaća oksidaciju spoja formule Ib;
[image]
5. Postupak prema bilo kojem od zahtjeva 1 do 4, naznačen time da se oksidacija provodi u smjesi diklorometana i vode.
6. Postupak prema bilo kojem od prethodnih zahtjeva, naznačen time da se koristi 1-5 mol% derivata 2,2,6,6-tetrametilpiperidin-N-oksida.
7. Postupak prema bilo kojem od prethodnih zahtjeva, naznačen time da se koristi 1-1.5 mol% 2,2,6,6-tetrametilpiperidin-N-oksida.
8. Postupak prema bilo kojem od prethodnih zahtjeva, naznačen time da se koristi 3-6 molarna ekvivalenta alkalijskog hipoklorita.
9. Postupak prema bilo kojem od prethodnih zahtjeva, naznačen time da se koristi 3-4 molarna ekvivalenta natrijevog hipoklorita.
10. Postupak prema bilo kojem od prethodnih zahtjeva, naznačen time da pH reakcijske otopine je između 8.5 i 10.0.
11. Postupak prema bilo kojem od prethodnih zahtjeva, naznačen time da se pH reakcijske otopine podešava s kalijevim bikarbonatom.
12. Postupak prema bilo kojem od prethodnih zahtjeva, naznačen time da je reakcijska temperatura od 0 do 15°C.
13. Postupak prema bilo kojem od prethodnih zahtjeva, naznačen time da se spoj s formulom IIa ili IIb izolira uz taloženje pomoću dodavanja izopropiletera.
14. Postupak prema bilo kojem od prethodnih zahtjeva, naznačen time da nakon što je okončana reakcija oksidacije, u reakcijsku smjesu se dodaje redukcijsko sredstvo radi gašenja suviška hipokloritnog reagensa.
15. Postupak prema zahtjevu 14, naznačen time da se redukcijsko sredstvo dodaje uz dodatak baze ili bazičnog pufera kod pH od više od 5.
16. Postupak prema bilo kojem od zahtjeva 14 ili 15, naznačen time da se kao redukcijsko sredstvo koristi vodena otopina alkalijskog hidrogen sulfita.
17. Postupak prema bilo kojem od zahtjeva 14 do 16, naznačen time da se kao redukcijsko sredstvo koristi, natrijev hidrogen sulfit ili kalijev hidrogen sulfit u obliku vodene otopine natrijevog disulfita ili kalijevog disulfita.
18. Postupak prema bilo kojem od zahtjeva 15 do 17, naznačen time da se kao baza ili bazični pufer koristi natrijev fosfat (Na3PO4).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP05090214.7A EP1746101B2 (de) | 2005-07-21 | 2005-07-21 | Verfahren zur Herstellung von 3-Oxo-pregn-4-en-21,17-carbolactonen durch die metallfreie Oxidation von 17-(3-hydroxypropyl)-3,17-dihydroxyandrostanen |
| US11/185,984 US7319154B2 (en) | 2005-07-21 | 2005-07-21 | Process for the production of 3-oxo-pregn-4-ene-21, 17-carbolactones by the metal free oxidation of 17-(3-hydroxypropyl)-3, 17-dihydroxyandrostanes |
| EP12165450.3A EP2527356B1 (en) | 2005-07-21 | 2006-07-20 | Process for the Production of 3-Oxo-pregn-4-ene-21,17-carbolactones by the Metal-Free Oxidation of 17-(3-Hydroxypropyl)-3,17-dihydroxyandrostanes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| HRP20180454T1 true HRP20180454T1 (hr) | 2018-05-04 |
Family
ID=37434272
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| HRP20160853TT HRP20160853T1 (hr) | 2005-07-21 | 2016-07-12 | Postupak za proizvodnju 3-okso-pregn-4-en-21,17-karbolaktona pomoću bezmetalne oksidacije 17-(3-hidroksipropil)-3,17-dihidroksiandrostana |
| HRP20180454TT HRP20180454T1 (hr) | 2005-07-21 | 2018-03-16 | Postupak za proizvodnju 3-okso-pregn-4-en-21,17-karbolaktona pomoću bezmetalne oksidacije 17-(3-hidroksipropil)-3,17-dihidroksiandrostana |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| HRP20160853TT HRP20160853T1 (hr) | 2005-07-21 | 2016-07-12 | Postupak za proizvodnju 3-okso-pregn-4-en-21,17-karbolaktona pomoću bezmetalne oksidacije 17-(3-hidroksipropil)-3,17-dihidroksiandrostana |
Country Status (23)
| Country | Link |
|---|---|
| EP (2) | EP1910403B1 (hr) |
| KR (1) | KR101410583B1 (hr) |
| AU (1) | AU2006271885B8 (hr) |
| BR (1) | BRPI0613679A2 (hr) |
| CA (1) | CA2614804C (hr) |
| CR (1) | CR9669A (hr) |
| DK (2) | DK2527356T3 (hr) |
| EA (1) | EA016411B1 (hr) |
| EC (1) | ECSP088124A (hr) |
| ES (2) | ES2663399T3 (hr) |
| HK (1) | HK1120520A1 (hr) |
| HR (2) | HRP20160853T1 (hr) |
| HU (2) | HUE027858T2 (hr) |
| IL (1) | IL188619A (hr) |
| LT (1) | LT2527356T (hr) |
| MX (1) | MX2008000936A (hr) |
| NO (1) | NO344680B1 (hr) |
| NZ (1) | NZ565247A (hr) |
| PL (2) | PL2527356T3 (hr) |
| PT (2) | PT2527356T (hr) |
| RS (2) | RS56982B1 (hr) |
| SI (2) | SI1910403T1 (hr) |
| WO (1) | WO2007009821A1 (hr) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2057182A2 (en) | 2007-05-01 | 2009-05-13 | Sicor, Inc. | A process for preparing drospirenone and intermediate thereof |
| DE102007030596B3 (de) * | 2007-06-28 | 2009-03-12 | Bayer Schering Pharma Aktiengesellschaft | Verfahren zur Herstellung von 17-(3-Hydroxypropyl)-17-hydroxysteroiden |
| EP2266998B1 (en) * | 2009-06-16 | 2013-07-24 | Crystal Pharma, S.A.U. | Process for obtaining 17-spirolactones in steroids |
| CN102040650B (zh) * | 2010-10-26 | 2014-03-26 | 西安科技大学 | 串联反应构建甾体-6β,7β-亚甲基结构的方法 |
| ITMI20111383A1 (it) | 2011-07-25 | 2013-01-26 | Ind Chimica Srl | Processo per la preparazione di drospirenone |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4069219A (en) | 1976-12-27 | 1978-01-17 | G. D. Searle & Co. | 7ξ-(Alkoxycarbonyl)-6ξ-alkyl/halo-17-hydroxy-3-oxo-17α-pregn-4-ene-21-carboxylic acid γ-lactones and corresponding 21-carboxylic acids, their salts, and esters |
| DE3026783C2 (de) | 1980-07-11 | 1982-07-29 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Verfahren zur Herstellung von 5β-Hydroxy-δ↑6↑-steroiden |
| DE3042136A1 (de) | 1980-11-03 | 1982-06-09 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Verfahren zur herstellung von 3 (beta), 7 (beta) -dihydroxy- (delta) (pfeil hoch)5(pfeil hoch) -steroiden |
| ATE15206T1 (de) | 1981-09-21 | 1985-09-15 | Schering Ag | 3-beta,7-beta,15-alpha-trihydroxy-5-androsten-1 - one, ihre 3,15-trimethylessigsaeure-ester und ihre herstellung. |
| DE19633685C1 (de) | 1996-08-12 | 1997-10-09 | Schering Ag | Verfahren zur Herstellung von Drospirenon (6beta,7beta;15 beta,16beta-Dimethyl-en-3-oxo-17alpha-pregn-4-en-21,17-carbolacton, DRSP) sowie 7alpha-(3-Hydroxy-1-propyl)-6beta,7beta;15beta, 16beta-dimethylen-5beta-androstan-3beta,5,17beta-triol (ZK 92836) und 6beta,7beta;15beta,16beta-dimethylen-5beta-hydroxy-3-oxo-17alpha-androstan-21,17-carbolacton (90965) als Zwischenprodukte des Verfahrens |
| ES2271636T3 (es) * | 2002-08-16 | 2007-04-16 | PHARMACIA & UPJOHN COMPANY LLC | Intermediarios de 5 androsten-3-ol esteroides y procedimientos para su preparacion. |
| ITMI20040367A1 (it) * | 2004-03-01 | 2004-06-01 | Ind Chimica Srl | Processo per la preparazione di drospirenone |
| ITMI20042338A1 (it) * | 2004-12-06 | 2005-03-06 | Ind Chimica Srl | Processo per la preparazione di drospirenone |
-
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- 2006-07-20 NZ NZ565247A patent/NZ565247A/en unknown
- 2006-07-20 DK DK12165450.3T patent/DK2527356T3/en active
- 2006-07-20 MX MX2008000936A patent/MX2008000936A/es active IP Right Grant
- 2006-07-20 CA CA2614804A patent/CA2614804C/en active Active
- 2006-07-20 PL PL12165450T patent/PL2527356T3/pl unknown
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- 2006-07-20 EP EP06762786.9A patent/EP1910403B1/en active Active
- 2006-07-20 ES ES12165450.3T patent/ES2663399T3/es active Active
- 2006-07-20 SI SI200632075A patent/SI1910403T1/sl unknown
- 2006-07-20 SI SI200632250T patent/SI2527356T1/en unknown
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- 2006-07-20 EA EA200800326A patent/EA016411B1/ru not_active IP Right Cessation
- 2006-07-20 PL PL06762786.9T patent/PL1910403T3/pl unknown
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- 2006-07-20 BR BRPI0613679-6A patent/BRPI0613679A2/pt not_active Application Discontinuation
- 2006-07-20 KR KR1020087003999A patent/KR101410583B1/ko active IP Right Grant
- 2006-07-20 LT LTEP12165450.3T patent/LT2527356T/lt unknown
- 2006-07-20 DK DK06762786.9T patent/DK1910403T3/en active
- 2006-07-20 WO PCT/EP2006/007287 patent/WO2007009821A1/en active Application Filing
- 2006-07-20 EP EP12165450.3A patent/EP2527356B1/en active Active
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- 2008-01-07 IL IL188619A patent/IL188619A/en active IP Right Grant
- 2008-01-17 CR CR9669A patent/CR9669A/es unknown
- 2008-01-18 EC EC2008008124A patent/ECSP088124A/es unknown
- 2008-02-20 NO NO20080894A patent/NO344680B1/no unknown
- 2008-12-25 HK HK08113989.8A patent/HK1120520A1/xx unknown
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2016
- 2016-07-12 HR HRP20160853TT patent/HRP20160853T1/hr unknown
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2018
- 2018-03-16 HR HRP20180454TT patent/HRP20180454T1/hr unknown
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