DD154899A1 - PROCESS FOR THE PREPARATION OF CARDENOLIDE AND BUFADIENOLIDE-14 BETA-O-URETHANES - Google Patents
PROCESS FOR THE PREPARATION OF CARDENOLIDE AND BUFADIENOLIDE-14 BETA-O-URETHANES Download PDFInfo
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- DD154899A1 DD154899A1 DD22560980A DD22560980A DD154899A1 DD 154899 A1 DD154899 A1 DD 154899A1 DD 22560980 A DD22560980 A DD 22560980A DD 22560980 A DD22560980 A DD 22560980A DD 154899 A1 DD154899 A1 DD 154899A1
- Authority
- DD
- German Democratic Republic
- Prior art keywords
- bufadienolide
- beta
- urethanes
- preparation
- urethane
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- TYYDXNISHGVDGA-UHFFFAOYSA-N Corotoxigenin Natural products CC12CCC3C(CCC4CC(O)CCC34C=O)C1CCC2C5=CC(=O)OC5 TYYDXNISHGVDGA-UHFFFAOYSA-N 0.000 title claims description 3
- JIUWTCXNUNHEGP-GJHPUSIBSA-N cardenolide Chemical compound C1([C@H]2CC[C@@H]3[C@H]4[C@@H]([C@]5(CCCCC5CC4)C)CC[C@@]32C)=CC(=O)OC1 JIUWTCXNUNHEGP-GJHPUSIBSA-N 0.000 title claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 239000012948 isocyanate Substances 0.000 claims abstract description 5
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 5
- 239000012442 inert solvent Substances 0.000 claims abstract description 3
- 150000001652 bufadienolides Chemical class 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 150000003673 urethanes Chemical class 0.000 claims description 3
- HAJGVUYNXHQLER-UHFFFAOYSA-N Bufadienolide Natural products O1C(=O)C=CC(C2C3C(C4C(C5CCCCC5CC4)CC3)CC2)=C1 HAJGVUYNXHQLER-UHFFFAOYSA-N 0.000 claims description 2
- 238000006359 acetalization reaction Methods 0.000 claims description 2
- YBPMPRDOWHIVNA-XTBIJCDISA-N bufadienolide Chemical compound C=1([C@H]2CC[C@@H]3[C@H]4[C@@H]([C@]5(CCCCC5CC4)C)CC[C@@]32C)C=CC(=O)OC=1 YBPMPRDOWHIVNA-XTBIJCDISA-N 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 238000006266 etherification reaction Methods 0.000 claims description 2
- 125000006239 protecting group Chemical group 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- 150000001737 cardanolides Chemical class 0.000 claims 1
- 150000008282 halocarbons Chemical class 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001738 cardenolides Chemical class 0.000 abstract 1
- 230000000747 cardiac effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- XZTUSOXSLKTKJQ-CESUGQOBSA-N digitoxigenin Chemical compound C1([C@H]2CC[C@]3(O)[C@H]4[C@@H]([C@]5(CC[C@H](O)C[C@H]5CC4)C)CC[C@@]32C)=CC(=O)OC1 XZTUSOXSLKTKJQ-CESUGQOBSA-N 0.000 description 2
- SQEBMLCQNJOCBG-HVHJFMEUSA-N (5s)-3-(hydroxymethyl)-5-methoxy-4-methyl-5-[(e)-2-phenylethenyl]furan-2-one Chemical group C=1C=CC=CC=1/C=C/[C@]1(OC)OC(=O)C(CO)=C1C SQEBMLCQNJOCBG-HVHJFMEUSA-N 0.000 description 1
- GRNOZCCBOFGDCL-UHFFFAOYSA-N 2,2,2-trichloroacetyl isocyanate Chemical compound ClC(Cl)(Cl)C(=O)N=C=O GRNOZCCBOFGDCL-UHFFFAOYSA-N 0.000 description 1
- 108091006112 ATPases Proteins 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 102000057290 Adenosine Triphosphatases Human genes 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- MYEJFUXQJGHEQK-ALRJYLEOSA-N Proscillaridin Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1O[C@@H]1C=C2CC[C@H]3[C@@]4(O)CC[C@H](C5=COC(=O)C=C5)[C@@]4(C)CC[C@@H]3[C@@]2(C)CC1 MYEJFUXQJGHEQK-ALRJYLEOSA-N 0.000 description 1
- XZTUSOXSLKTKJQ-UHFFFAOYSA-N Uzarigenin Natural products CC12CCC(C3(CCC(O)CC3CC3)C)C3C1(O)CCC2C1=CC(=O)OC1 XZTUSOXSLKTKJQ-UHFFFAOYSA-N 0.000 description 1
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- WRJWRGBVPUUDLA-UHFFFAOYSA-N chlorosulfonyl isocyanate Chemical compound ClS(=O)(=O)N=C=O WRJWRGBVPUUDLA-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- QONQRTHLHBTMGP-UHFFFAOYSA-N digitoxigenin Natural products CC12CCC(C3(CCC(O)CC3CC3)C)C3C11OC1CC2C1=CC(=O)OC1 QONQRTHLHBTMGP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000005907 ketalization reaction Methods 0.000 description 1
- 230000009090 positive inotropic effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229930190098 proscillaridin Natural products 0.000 description 1
- 229960003584 proscillaridin Drugs 0.000 description 1
- MYEJFUXQJGHEQK-UHFFFAOYSA-N proscillaridin A Natural products OC1C(O)C(O)C(C)OC1OC1C=C2CCC3C4(O)CCC(C5=COC(=O)C=C5)C4(C)CCC3C2(C)CC1 MYEJFUXQJGHEQK-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000005147 toluenesulfonyl group Chemical group C=1(C(=CC=CC1)S(=O)(=O)*)C 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Die Erfindung hat das Ziel, ein Verfahren zur Herstellung von herzwirksamen 14beta-O-Urethanen von Cardenoliden und Bufadienoliden zu entwickeln. Das erfindungsgemaesse Verfahren ist dadurch gekennzeichnet, dass 14beta-OH-Cardenolide oder -Bufadienolide mit einem relativen Isocyanat in einem inerten Loesungsmittel umgesetzt werden, nachdem sonstige OH-Gruppen im Molekuel - soweit sie nicht in ein Urethan ueberfuehrt werden sollen - in an sich bekannter Weise geschuetzt wurden. Das Verfahren fuehrt in guter Ausbeute z.B. zu 3-Acetyl-digitoxigenin-14beta-O-(N-trichloracetyl)-urethan.The invention aims to develop a process for the preparation of cardiac active 14beta-O-urethanes of cardenolides and bufadienolides. The inventive method is characterized in that 14beta-OH-cardenolides or -Bufadienolide be reacted with a relative isocyanate in an inert solvent, after other OH groups in the molecule - as far as they are not to be converted into a urethane - in a conventional manner were protected. The process results in good yield e.g. to 3-acetyl-digitoxigenin-14beta-O- (N-trichloroacetyl) urethane.
Description
-ι-- 2 2 5 6 03-ι-- 2 2 5 6 03
R. Megges I. Eschholz R. Hintsche R. SchwensowR. Megges I. Eschholz R. Hintsche R. Schwensow
VERFAHREN ZUR HERSTELLUNG VON CARDSNOLID- UND BUFADIENOLID- 14ß-0-URETHANSN ; PROCESS FOR THE PREPARATION OF CARDSNOLIDE AND BUFADIENOLIDE 14ß-0- URETHANSN ;
Die Erfindung betrifft ein Verfahren zur Herstellung von Cardenolid- und Bufadienolid-i4ß-0- urethanen der allgemeinen Formel I (s.Anlage).The invention relates to a process for the preparation of cardenolide and Bufadienolid-i4ß-0 urethanes of general formula I (s.Anlage).
Anwendungsgebiet der Erfindung ist die pharmazeutische Industrie.Field of application of the invention is the pharmaceutical industry.
Verbindungen der Formel I sind bisher unbekannt. Bekannt sind lediglich analoge Vsrbindungen:ein Cyclocarbonat eines 7ß»i4ß-0H- Cardenolides (J.pharmac.Soc.Jap.>8j[,8O5(196i)) bzw. Cyclosulfite, Cycloborate und Cycloaryl- sowie Cyclodiarylborate von 7ß, I4ß- OH- und I4ß, I6ß-OH-Cardenoliden (HeIv.Chim.Acta 44,1063(1961), WP 77489, Coll.Czech. Chem.Commun. 22,2985(1962), J.Chromatog.,154, 197(1978),ibid.1^,169 (1978). Daneben ist die Acetylierung der I4ß- OH -Grupp© bekannt:Compounds of the formula I are hitherto unknown. Known are only analogous Vsrbindungen: a cyclocarbonate of a 7ß »i4ß-0H- Cardenolides (J.Pharmac.Soc.Jap. > 8j [, 8O5 (196i)) or Cyclosulfite, Cycloborate and Cycloaryl- and Cyclodiarylborate of 7ß, I4ß- OH and I4ß, I6ß-OH-Cardenoliden (HeIv.Chim.Acta 44, 1063 (1961), WP 77489, Coll.Czech Chem.Commun. 22, 2985 (1962), J. Chromatog., 154, 197 (1978 ), ibid., 169 (1978). In addition, the acetylation of the I4β-OH group © is known:
a) durch Einsatz von 4-N-Dimethylaminopyridin als Katalysator unter gleichzeitiger Umsetzung am Butenolidring (WP 94616)a) by using 4-N-dimethylaminopyridine as catalyst with simultaneous reaction at the butenolide ring (WP 94616)
b) durch Umsetzung mit Acetonenolacetat unter Säurekatalyse (WP 116614),b) by reaction with acetoneol acetate under acid catalysis (WP 116614),
Die Erfindung hat das Ziel, ein Herstellungsverfahren für Verbindungen der allgemeinen Formel I zu finden.The invention has the aim of finding a preparation process for compounds of general formula I.
Darlegung des Wesens der Erfindung Explanation of the essence of the invention
Erfindungsgemäß werden Verbindungen der allgemeinen Formel I erhalten durch Umsetzung von Verbindungen der allgemeinen Formel II mit einem reaktiven Isocyanat R - NCO* (III). R ist dabei ein Rest mit starkem— I- Effekt wie z.B. CC1J20-, ClSOp- oder Toluolsulfonyl^OH-Gruppen im Molekül von II außer I4ß-OH, die nicht in Urethane umgewandelt werden sollen, werden vor der Umsetzung in an sich bekannter Weis© geschützt durch Veresterung und/oder Verätherung und/oder KetalisierungAccording to the invention, compounds of general formula I are obtained by reacting compounds of general formula II with a reactive isocyanate R - NCO * (III). R is a radical with a strong I effect, such as CC1J20-, ClSOp- or toluenesulfonyl ^ OH groups in the molecule of II other than I4β-OH, which are not to be converted into urethanes, are protected before the reaction in a manner known per se by esterification and / or etherification and / or ketalization
_2_ 225609_ 2 _ 225609
und/oder Acetalisierung. Ggf. werden diese Schutzgruppen nach der Umsetzung teilweise oder vollständig in an sich bekannter Weise wieder abgespalten. Die Umsetzung erfolgt in einem inerten Lösungsmittel wie einem Kohlenwasserstoff, einem Halogenkohlenwasserstoff oder Geraischen davon bei Temperaturen zwischen +20 C und -70 C unter Einsatz von 1-5 Äquivalenten Isocyanat/OH-Gruppe in 5bis 15 Minuten,Die Isolierung von I erfolgt in an sich bekannter Weise durch Ausfällen und/oder Eindampfen und/oder Kristallisieren« überraschend ist bei dem Verfahrran, daß die Umsetzung rasch und trotzdem ohne Bildung von 14—Anhydroderivaten erfolgt, und daß der Lactonring oder Doppelbindungen im Molekül dabei nicht angegriffen werden. ^and / or acetalization. Possibly. these protective groups are split off after the reaction partially or completely in a conventional manner again. The reaction is carried out in an inert solvent such as a hydrocarbon, a halohydrocarbon or Geraischen thereof at temperatures between +20 C and -70 C using 1-5 equivalents of isocyanate / OH group in 5 to 15 minutes, The isolation of I takes place in known manner by precipitation and / or evaporation and / or crystallization «is surprising in the Verfahrran that the reaction is rapid and still without formation of 14-anhydro derivatives, and that the Lactonring or double bonds in the molecule are not attacked. ^
Verbindungen des Typs I wirken positiv inotrop beurteilt nach ihrer Hemmwirksamkeit im ATPase-Test (Arzneimittelforschung 14-, 1073(1964·)) oder sind als Zwischenprodukte der Synthese biologisch aktiver Verbindungen interessant.Type I compounds have a positive inotropic effect on their inhibitory activity in the ATPase assay (Arzneimittelforschung 14- , 1073 (1964)) or are of interest as intermediates in the synthesis of biologically active compounds.
Das Verfahren wird durch die nachstehenden Beispiele beschrieben ohne dadurch eingeschränkt zu werden.The process is described by the following examples without being limited thereby.
-3- 22 56 09-3- 22 56 09
500mg 3-Acstyl-'digitoxigenin (Ha) werden in 230ml alkohol-und wasserfreiem Chloroform gelöst, die Lösung auf 70ml eingeengt und nach Kühlung mit Sis/NaCl mit 0,2ml Trichloracetylisocyanat (HIa) versetzt. Nach 15 Min. stehan bei 200C wird 3-Acetyl~digitoxigenin-i4ß-0-(N-trichloracetyl)~urethan (Ia) durch Zugabe von Pentan ausgefällt. Ausbeute :464mg Fp: 185-213°C (Zars.) NMR (CDCl,, ^): 8,50 (NH) u.a. 3190,;500 mg of 3-acyltridigoxigenin (Ha) are dissolved in 230 ml of alcoholic and anhydrous chloroform, the solution is concentrated to 70 ml and after cooling with sis / NaCl mixed with 0.2 ml of trichloroacetyl isocyanate (HIa). After 15 min. Standing at 20 0 C, 3-acetyl-digitoxigenin-i4ß-0- (N-trichloroacetyl) urethane (Ia) is precipitated by the addition of pentane. Yield: 464 mg. Fp: 185-213 ° C (Tsars.) NMR (CDCl ,, ^): 8.50 (NH) inter alia 3190;
850 (ccio850 (ccio
IR:(KBr,cm"*1): u.a. 3190,3260 (NH), 1750 (C=O), I5OO (Amid),IR: (KBr, cm -1 ): inter alia 3190.3260 (NH), 1750 (C = O), 150 (amide),
200mg Digitoxigenin (Hb) werden analog Beispiel 1 mit 0,15ml IHa umgesatzt zu Digitoxigenin-3ß»1^ß-0-bis-(N-trichlorac$tyl)-urethan (Ib). NMR (CDCl,,, $ ); 8,59 und 8,57 (NH)200 mg of digitoxigenin (Hb) are converted analogously to Example 1 with 0.15 ml of IHa to give digitoxigenin-3β1-β-O-bis (N-trichloroacetic) urethane (Ib). NMR (CDCl ,,, $); 8.59 and 8.57 (NH)
300mg ProscillaridinA-2l3l^:-triacotat (lic) werden analog Beispiel 1 mit 0,06ml IHa umgesetzt zu Proscillaridin A-2l3l4l-triacetat-1^ß-0-(N-trichloracetyl)-urethan (Ic),300mg ProscillaridinA-2 l 3 l ^ : -triacotate (lic) are reacted analogously to Example 1 with 0.06 ml of IHa to Proscillaridin A-2 l 3 l 4 l -triacetate-1 ^ ß-0- (N-trichloroacetyl) urethane (Ic)
NMR (CDCl3,£): u.a. 8,30 (NH)NMR (CDCl 3 , £): inter alia 8.30 (NH)
200mg Ha v/erden analog Beispiel 1 umgesetzt mit 0,05 ml Chlorsulfonylisocyanat(HIb) zu 3-Ac®tyldigitoxigenin-1zi-ß-0-(N-chlorsulfonyl)-urethan(Id).200 mg of Ha / earth analogously to Example 1 reacted with 0.05 ml of chlorosulfonyl isocyanate (HIb) to 3-Ac®tyldigitoxigenin-1 z i-ß-0- (N-chlorosulfonyl) urethane (Id).
NMR (CDCl3, <£): 8,85 (NH)NMR (CDCl3, <£): 8.85 (NH)
200mg lö-Anhydrogitoxigenin-tetra-acetat v/erden analog Beispiel 1 in Methylenchlorid unter anfänglicher Trockeneis/Alkohol-Kühlung mit 0,03ral HIa umgesetzt zu i6-Anhydrogitoxin-tetra-acetat-i4-ß-0-(N-trichloracetyl)-urethan (Ie).200 mg of anhydrogitoxigenin tetra-acetate in vitro analogously to Example 1 in methylene chloride with initial dry ice / alcohol cooling with 0.03ral HIa converted to i6-anhydrogitoxin-tetra-acetate-i4-β-O- (N-trichloroacetyl) - urethane (Ie).
Ausbeute: VimgYield: Vimg
Fp: 171-17öOC (Zers.)Fp: 171-17o O C (Zers.)
nMR (CDCl <f): u.a. 8,16 (NH)nMR (CDCl <f): i.a. 8,16 (NH)
IR (K^r,cm"1): 3100,3200 (NH),I63O (C=O), I58O (Amid),820 (-CCl3)IR (K ^ r, cm "1): 3100.3200 (NH), I63O (C = O), I58O (amide), 820 (CCl 3)
Hierzu ein Blatt FormelnFor this a sheet of formulas
2258 092258 09
Anlag«anlag "
O-CO-NH-RO-CO-NH-R
,14, 14
: R^ = -OH,: R 1 = -OH,
1 -ONOg, AIk^l- 1 -ONOg, AIk ^ l-
(Zucker) ,n= 1-4·(Sugar), n = 1-4 ·
R1*= CCl CO-, ClSO2-, CH3C6H4SO2-, CF3CO. R17=R 1 * = CCl CO-, ClSO 2 -, CH 3 C 6 H 4 SO 2 -, CF 3 CO. R 17 =
,22, 22
R^y= -CH , -CH2OH, -CHOR ^ y = -CH, -CH 2 OH, -CHO
21a 21b 22 R und/oder R und/oder R = H, Halogen, Psaudohalogen, -0N0„21a 21b 22 R and / or R and / or R = H, halogen, psaudohalogen, -0N0 "
-OAcyl,-OAcyl,
Eine bzw. mehrere OH-Gruppen können sich an den Positionen C., C-, C,., C.., C-o, C.g, C-o befinden und können ebenso wie die OH-Gruppen an der Zuckerkette verestert und/oder veräthert und/oder acetalisiert und/oder ketalisiert sein. Ferner können im Molekül Doppelbindungen zwischen C, und C,. oder C,.,- und C^17 vorhanden sein.One or more OH groups may be located at the positions C., C, C,..., C .., Co, Cg, Co and may, like the OH groups on the sugar chain, be esterified and / or etherified and / or or acetalated and / or ketalized. Furthermore, in the molecule double bonds between C, and C ,. or C,..., and C ^ 17 are present.
II : si, aber mit 14B-0HII: si, but with 14B-0H
Claims (4)
Bufadienolidreihe vom Typ I dadurch gekennzeichnet, daß Cardanolidex)
Bufadienolide series of type I characterized in that cardanolides
oder Bufadienolide vom Typ II in einem inerten Lösungsmittel mitχ)
or Bufadienolide type II in an inert solvent with
einem reaktiven Isocyanat R -NCO ' umgesetzt werden.14x)
a reactive isocyanate R -NCO 'be implemented.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD22560980A DD154899A1 (en) | 1980-12-01 | 1980-12-01 | PROCESS FOR THE PREPARATION OF CARDENOLIDE AND BUFADIENOLIDE-14 BETA-O-URETHANES |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD22560980A DD154899A1 (en) | 1980-12-01 | 1980-12-01 | PROCESS FOR THE PREPARATION OF CARDENOLIDE AND BUFADIENOLIDE-14 BETA-O-URETHANES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DD154899A1 true DD154899A1 (en) | 1982-04-28 |
Family
ID=5527540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DD22560980A DD154899A1 (en) | 1980-12-01 | 1980-12-01 | PROCESS FOR THE PREPARATION OF CARDENOLIDE AND BUFADIENOLIDE-14 BETA-O-URETHANES |
Country Status (1)
| Country | Link |
|---|---|
| DD (1) | DD154899A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995008559A1 (en) * | 1993-09-24 | 1995-03-30 | The Procter & Gamble Company | Novel urethane-containing aminosteroid compounds |
-
1980
- 1980-12-01 DD DD22560980A patent/DD154899A1/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995008559A1 (en) * | 1993-09-24 | 1995-03-30 | The Procter & Gamble Company | Novel urethane-containing aminosteroid compounds |
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