DD282242A5 - PROCESS FOR THE RACEMATING OF (1SR, 2RS, 5SR, 6RS) -BICYCLO [3.3.0] OCTAN-2,6-DIOL - Google Patents
PROCESS FOR THE RACEMATING OF (1SR, 2RS, 5SR, 6RS) -BICYCLO [3.3.0] OCTAN-2,6-DIOL Download PDFInfo
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- DD282242A5 DD282242A5 DD32759989A DD32759989A DD282242A5 DD 282242 A5 DD282242 A5 DD 282242A5 DD 32759989 A DD32759989 A DD 32759989A DD 32759989 A DD32759989 A DD 32759989A DD 282242 A5 DD282242 A5 DD 282242A5
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Abstract
Es wird ein Verfahren zur Racematspaltung von * durch enzymkatalysierte Umesterung mit Carbonsaeureestern in organischen Loesungsmitteln unter Bildung von * und * beschrieben. Diese Verbindungen dienen als Ausgangsmaterial fuer die Synthese optisch aktiver Prostaglandine und Prostaglandinderivate.{Racematspaltung; * enzymkatalysierte Umesterung; Carbonsaeureester; * * Prostaglandin}A process is described for the racemate resolution of * by enzyme-catalyzed transesterification with carboxylic acid esters in organic solvents to form * and *. These compounds serve as starting material for the synthesis of optically active prostaglandins and prostaglandin derivatives. {Racemate resolution; * enzyme-catalyzed transesterification; Carbonsaeureester; * * Prostaglandin}
Description
Hierzu 1 Seite FormelnFor this 1 page formulas
Anwendungsgebiet der ErfindungField of application of the invention
Die Erfindung betrifft ein Verführen zur Racematspaltung von (1 SR^RS.SSR.öRSl-BicyclolS.S.Oloctan^e-diol der Formel I in die optischen Antipoden (1 S,2 R,5 S,6 R)-2,6-Diacyloxy-bicyclo[3.3.0loctan (J?r allgemeinen Formel II, in der R1 Wasserstoff, Alkyl oder Aryl bedeutet, und (1 R^S.SR.eSJ-BicyclolS.S.Oloctan^.e-diol der Formel III.The invention relates to a seduction for the racemate resolution of (1 SR) RS.SSR.ÖRSI-bicyclol S .Oloctan ^ e-diol of the formula I in the optical antipodes (1 S, 2 R, 5 S, 6 R) -2, 6-Diacyloxybicyclo [3.3.0loctane (general formula II wherein R 1 is hydrogen, alkyl or aryl, and (1 R 2 S.SR 8SJ-bicyclol S-octane-1-diol) Formula III.
Beide Enantiomere können Ausgangsmaterial für die Synthese optisch aktiver Prostaglandin und Pro aglandinderivate sein, die zur Verhütung und Behandlung von Herz-Kreislauf-Erkrankungen, für gynäkologische Indikationen, zur Verhütung und Behandlung von Magen- und Darmgeschwüren in der Humanmedizin sowie zur Geburten- und Bi unstsynchronisation in tier Tierproduktion verwendbar sind.Both enantiomers can be starting materials for the synthesis of optically active prostaglandin and pro aglandinderivate, which for the prevention and treatment of cardiovascular diseases, for gynecological indications, for the prevention and treatment of gastric and intestinal ulcers in human medicine as well as for birth and bi unsynchronization are useful in animal production.
Charakteristik des bekannten Standes der TechnikCharacteristic of the known state of the art
Die Racematspaltung von (1 SR,2RS,5SR,6RS)-Bicyclo[3.3.0]octan-2,6-diol (I) wurde bisher, ausgehend von (1 SR,2RS,5SR,6RS)-2,6-Diacetoxy-bicyclo[3.3.0]octan, durch enzymkatalysierte Hydrolyse mit Esterase aus Plexaura homomalla Esper (M.A. Djadchenko, V.I. Mel'nikova, K. K. Pivnitsky; Zh. Obshch. Khim. 56. 2143 [1986) realisiert. Dabei entsteht (1 R,2S,5R,6S)-2,6-Diacetoxy-bicyclo[3.3.0loctan mit einem Enantiomerenüberschuß von 88% in 36% chemischer Ausbeute i.eben 41 % (1 S,2R,5S,6R)-2-Acetoxy-bicyclo[3.3.0]octan-6-ol mit einem Enantiomerenüberschuß von 41 % und 15% (1 a,9R,55,6R)-BiCyCIo[S.3.0]octan-2,6-diol mit einem Enantiomerenüberschuß von 82%, wobei nachteilig ist, daß nur die Produkte, deren Enantiomerenüberschuß >80% beträgt, durch UmkristalMsation noch weiter gereinigt werden könr en. Diese enzymkatalysierte Hydrolyse erfordert darüber hinaus sehr verdünnte wäßrige Substratlösungen (15g Substrat/5I wäßrige Pufferlösung). Diese extreme Verdünnung und Probleme bei der Isolierung der Produkte Jnd ein weiterer Nachteil dieser Verfahrensweise.The racemate resolution of (1 SR, 2RS, 5SR, 6RS) -bicyclo [3.3.0] octane-2,6-diol (I) has hitherto been based on (1 SR, 2RS, 5SR, 6RS) -2,6- Diacetoxy-bicyclo [3.3.0] octane, realized by enzyme-catalyzed hydrolysis with esterase from Plexaura homomalla Esper (MA Djadchenko, VI Melnikova, KK Pivnitsky, Zh. Obshch. Khim., 56, 2143 [1986]). This gives (1 R, 2S, 5R, 6S) -2,6-diacetoxy-bicyclo [3.3.0loctane with an enantiomeric excess of 88% in 36% chemical yield, then 41% (1S, 2R, 5S, 6R) 2-Acetoxy-bicyclo [3.3.0] octan-6-ol with an enantiomeric excess of 41% and 15% (1 a, 9 R, 55.6 R) -BiCyCiO [S.3.0] octane-2,6-diol with an enantiomeric excess of 82%, it being disadvantageous that only the products whose enantiomeric excess is> 80%, could be purified even further by UmkristalMsation. This enzyme-catalyzed hydrolysis, moreover, requires very dilute aqueous noun r atlösungen (15g substrate / 5I aqueous buffer solution). This extreme dilution and problems in the isolation of the products Jnd another disadvantage of this procedure.
Ziel der ErfindungObject of the invention
Das Ziel der Erfindung besteht darin, die Racematspaltung von (1 SR,2 RS,5SR,6RS)-Bicyclo[3.3.0]octan-2,6-diol so zu gestalten, daß (1 S,2R,5S,6R)-2,6-Diacyloxy-bicyclo[3.3.0]octane der allgemeinen Formel Il und das entsprechende Enantiomer (1 R^S.SR^Sl-BicyclolS.S.Oloctan^.ö-diol der Formel III in guter chemischer Ausbeute mit einem hohen Enantiomerenüberschuß in einem organischen Lösungsmittel bei akzeptabler Substratkonzentration entstehen.The object of the invention is to make the racemate resolution of (1S, 2R, 5SR, 6RS) -bicyclo [3.3.0] octane-2,6-diol such that (1S, 2R, 5S, 6R) -2,6-Diacyloxy-bicyclo [3.3.0] octanes of the general formula II and the corresponding enantiomer (1 R ^ S.SR ^ Sl-BicyclolS.S.Octan ^. -Diol of the formula III in good chemical yield with a high enantiomeric excess in an organic solvent at acceptable substrate concentration arise.
Darlegung des Wesens der ErfindungExplanation of the essence of the invention
Aufgabe der Erfindung ist es, ein Verfahren zur Racematspaltung von (1 SR,2RS,5SR,6RS)-Bicyclo[3.3.0]octan-2,6-diol der Formel I in die optischen Antipoden (1S,2R,5S,6R)-2,6-Diacyloxy-bicyclo[3.3.0]octan der allgemeinen Formel II, in der R1 Wasserstoff, Alkyl oder Aryl bedeutet, und (1 R,2S,5R,6S)-Bicyclc[3.3.0]octan-2,6-diol der Formel III durch enzymkatalysierte Umesterung in organischen Lösungsmitteln zu entwickeln. Diese Aufgabe wird gelöst, indem erfindungsgemäßThe object of the invention is a process for the racemate resolution of (1 SR, 2RS, 5SR, 6RS) bicyclo [3.3.0] octane-2,6-diol of the formula I in the optical antipodes (1S, 2R, 5S, 6R ) -2,6-Diacyloxy-bicyclo [3.3.0] octane of the general formula II in which R 1 is hydrogen, alkyl or aryl, and (1 R, 2S, 5R, 6S) -bicyclc [3.3.0] octane -2,6-diol of formula III to develop by enzyme-catalyzed transesterification in organic solvents. This object is achieved by the invention
e-diol der Formel I (K. Yu.Chernyuk, V. I. Mel'nikova, K. K. Pivnitsky; Zh. Org. Khim. I8,e-diol of formula I (K. Yu.Chernyuk, V. I. Mel'nikova, K. K. Pivnitsky, Zh. Org. Khim. I8,
577 [1982)) mit Carbonsäureestern der allgemeinen Formel IV, in der R' Wasserstoff, Alkyl oder Aryl, R2 Alkyl, CH2-CH2X, CH2-CHX2, CH2-CX3, wobei X Halogen wie Fluor, Chlor oder Brom ist, oder Aryl bedeuten, in einem wasserfreien organischen Iösungsmittel wie Diethylether, 1,4-Dioxan, Tetrahydrofuran oder Toluen in Gegenwart einer Base wie Pyridin, Triethylamin, 4-N,N-Dimethylaminopyridin oder Imidazol und einer Lipase tierischen, mikrobiellen oder pflanzlichen Ursprungs, vorzugsweise roher Schweinepankreas-Lipase in Form des Präparates Pankreatin, bei Temperaturen zwischen 0 und 800C, vorzugsweise zwischen 20 und 40°C, umgesetzt wird.577 [1982]) with carboxylic acid esters of the general formula IV in which R 'is hydrogen, alkyl or aryl, R 2 is alkyl, CH 2 -CH 2 X, CH 2 -CHX 2 , CH 2 -CX 3 , where X is halogen, such as fluorine Is chlorine or bromine, or aryl, in an anhydrous organic solvent such as diethyl ether, 1,4-dioxane, tetrahydrofuran or toluene in the presence of a base such as pyridine, triethylamine, 4-N, N-dimethylaminopyridine or imidazole and an animal lipase, microbial or plant origin, preferably crude porcine pancreatic lipase in the form of the preparation pancreatin, at temperatures between 0 and 80 0 C, preferably between 20 and 40 ° C, is reacted.
Hierdurch werden nach Trennung durch Chromatographie oder Verteilung (1 S,2R,5S,6R)-2,6-Diacyloxy-bicyclo[3.3.0)octane der Formel Il neben dem entsprechenden (1 R^S.öR.eSl-BicyclolS.S.Oloctan^.e-diol der Formel III erhalten. Entsprechende Monoacyloxy-Verbinclungen werden nur in Mengen um 2% gebildet. Erneute Umsetzung von III unter den erfindungsgemäßen Bedingungen liefert neben Il auch III mit einem Enantiomerenüberschuß von >90%. Die Umsetzung von III mit Acetanhydrid in Pyridin unter üblichen Bedingungen liefert das entsprechende Diacetat von III.As a result, after separation by chromatography or distribution (1 S, 2R, 5S, 6R) -2,6-diacyloxy-bicyclo [3.3.0] octanes of the formula II in addition to the corresponding (1 R ^ S.ÖR.eSl-BicyclolS. Corresponding monoacyloxy compounds are formed only in amounts of about 2% Reactive conversion of III under the conditions according to the invention yields, in addition to II, also III with an enantiomeric excess of> 90% III with acetic anhydride in pyridine under conventional conditions gives the corresponding diacetate of III.
Ausführungsbeispieleembodiments
Eine Lösung von 1,42g (lOmmol) (1 SR^RS.öSR.eRSi-Bicycloß.S.Oloctan^.Fdiol (I), 13,9g (73mmol) 2,2,2-Trichlorethylacetat und 0,72g (7,2mmol) absolutem Triethylamin in 25ml absolutem Tetrahydroturan wird mit 5g roher Schweinepankreas-Lipase in Form des Präparates Pankreatin versetzt und 15,5 Stunden bei einer Temperatur von 23°C gerührt. Danach wird die Suspension filtriert und der Filterrückstand mit Ethylacetat gewaschen. Das Filtrat wird im Vakuum eingeengt. Der Rückstand wird durch Flash-Chromatographie über Kieseigel gereinigt.A solution of 1.42g (10mmol) (1 SR ^ RS.O.SR.eRSi-bicyclodin S.Octane ^ .diol (I), 13.9g (73mmol) 2,2,2-trichloroethyl acetate, and 0.72g (7 , 2 mmol) of absolute triethylamine in 25 ml of absolute tetrahydroturan is mixed with 5 g of crude porcine pancreatic lipase in the form of the preparation pancreatin and stirred for 15.5 hours at a temperature of 23 ° C. The suspension is then filtered and the filter residue is washed with ethyl acetate is concentrated in vacuo and the residue is purified by flash chromatography on silica gel.
Man erhält 826mg (37%) (1 S,2R,5S,6R)-2,6-Diacetoxy- bicyclo[3.3.0]octan Il als farblose Kristalle.826 mg (37%) of (1S, 2R, 5S, 6R) -2,6-diacetoxybicyclo [3.3.0] octane II are obtained as colorless crystals.
[Q]0 35 + 104,9° (e ---- 2,003, CHCI3).[Q] 0 35 + 104.9 ° (e ---- 2.003, CHCl 3 ).
Enantiomerenüberschuß 92%.Enantiomeric excess 92%.
Weiterhin erhält man 725mg (52%) (1 R,2S,5R,6S)-Bicyclo[3.3.0]octan-2,6-diol (III) als farbloses Öl.Furthermore, 725 mg (52%) of (1R, 2S, 5R, 6S) bicyclo [3.3.0] octane-2,6-diol (III) are obtained as a colorless oil.
[a]D 25 + 32,4° (c = 2,087, CHCI3).[a] D 25 + 32.4 ° (c = 2.087, CHCl 3 ).
Enantio rerenüberschuß 66%.Enantio surplus 66%.
Eine Lösung von 0,142g (1 mmol) (1 R^S.öR.eSJ-Bicyclop.S.Oloctan^.e-diol (III) mit einem Enantiomerenüberschuß von 68%, 1,39g (7,3mmol) 2,2,2-Trichlorethylacetat und 0,072g (0,72mmol) absolutem Triethylamin in 2,5ml absolutem Tetrahydrofuran wird mit 0,5g roher Schweinepankreas-Lipase in Form des Präparates Pankoatin 23,5 Stunden bei einer Temperatur von 23CC gerührt. Danach wird wie im Beispiel 1 aufgearbeitet.A solution of 0.142 g (1 mmol) (1 R 2 S.O. R eS.sub.J-Bicyclop.S-octane-1-diol (III) with an enantiomeric excess of 68%, 1.39 g (7.3 mmol) of 2,2 , 2-trichloroethyl acetate and 0.072 g (0.72 mmol) of absolute triethylamine in 2.5 ml of absolute tetrahydrofuran is stirred with 0.5 g crude porcine pancreatic lipase in the form of the preparation Pankoatin 23.5 hours at a temperature of 23 C C. Thereafter, as worked up in Example 1.
Man erhält 16mg (7%) (1 S,2R,5S,6R)-2,6-Diacetoxy-bicyclo[3.3.0]octan (II) als farblose Kristalle.16 mg (7%) of (1S, 2R, 5S, 6R) -2,6-diacetoxy-bicyclo [3.3.0] octane (II) are obtained as colorless crystals.
[a]D 25 + 110,2° (c = 1,375,CHCI3).[a] D 25 + 110.2 ° (c = 1.375, CHCl 3 ).
Enantiomerenüberschuß 97%.Enantiomeric excess 97%.
Weiterhin erhält man 106mg (75%) (1 R^S^R.eSl-Bicyclop.S.Oloctan^.e-diol (III) als farbloses Öl.Furthermore, 106 mg (75%) of (1 R 1 S 2 R 8Sl-bicyclop.-s-octane-1-diol (III) are obtained as a colorless oil.
[a]D 25 + 44° (c = 2,122,CHCI3).[a] D 25 + 44 ° (c = 2.122, CHCl 3 ).
Enantiomerenüberschuß 90%.Enantiomeric excess 90%.
106mg (0,75i.Tnol) (1 R,2S,5R,6S)-Bicyclo[3.3.0]octan-2,6-diol (III) mit einem Enantiomerenüberschuß von 90% werden in 1 ml Pyridin gelöst, n.i 0,5ml Acetanhydrid versetzt und 16 Stunden bei 23°C stehengelassen. Einengen im Vakuum und Kugelrohr-Destillation (100°C, 5 · 10~2 Torr) liefert 168mg (99%) (1 R,2S,5R,6S)-2,6-Diacetoxy-bicyclo[3.3.0.)octan als farblose Kristalle. [al0-6 - 102,5° (c = ?,082, CHCI3). Enantiomerenüberscpuß 90%.106mg (0.75i.Tnol) (1R, 2S, 5R, 6S) -bicyclo [3.3.0] octane-2,6-diol (III) with an enantiomeric excess of 90% are dissolved in 1 ml of pyridine, ni 0 , 5ml acetic anhydride added and allowed to stand for 16 hours at 23 ° C. Concentration in vacuo and kugelrohr distillation (100 ° C, 5 × 10 -2 Torr) provides 168mg (99%) of (1 R, 2S, 5R, 6S) -2,6-diacetoxy-bicyclo [3.3.0.) Octane as colorless crystals. [al 0 - 6 - 102.5 ° (c =?, 082, CHCl 3 ). Enantiomeric excess 90%.
153 mg (1 S,2R,5S,6R)-2,6-Diacetoxy-bicyclo[3.3.0]octan (II) mit einem Enantiomerenüberschuß von 86% werfen in Hexan umkristallisiert.153 mg (1S, 2R, 5S, 6R) -2,6-diacetoxy-bicyclo [3.3.0] octane (II) with an enantiomeric excess of 86% are recrystallized in hexane.
Man erhält 117mg (77%) Il vom Schmelzpunkt 37,5-39°C.117 mg (77%) of melting point 37.5-39 ° C are obtained.
[a]D 25 + 105,6° (c = 2,314, CHCI3).[a] D 25 + 105.6 ° (c = 2.314, CHCl 3 ).
Enantior.ierenüberschuß 93%.Enantioriere surplus 93%.
Eine Lösung von 0,142g (1 mmol) (1 SR^RS.BeSR.eRSi-BicycloIS.S.Oloctan-S.ö-diol (I), 1,39g (7,3rr>mol) 2,2,2-Trichlorethylacetat und 0,072g (0,72mmol) absolutem Triethylamin in 2,5ml absolutem Tetrahydrofuran wird mit 0,5g roher Schweinepankreas-Lipase in Form des Fräparates Pankreatin versetzt und 10,5 Stunden bei 40°C gerührt. Danach wird wie im Beispiel 1 aufgearbeitet.A solution of 0.142g (1mmol) (1 SR ^ RS.BeSR.eRSi-bicycloIS.S.Oloctan-S-diol (I), 1.39g (7,3rr> mol) 2,2,2- Trichloroethyl acetate and 0.072 g (0.72 mmol) of absolute triethylamine in 2.5 ml of absolute tetrahydrofuran are mixed with 0.5 g of raw porcine pancreatic lipase in the form of the preparation pancreatin and stirred for 10.5 hours at 40 ° C. Thereafter, the reaction is carried out as in Example 1 ,
Man erhält 68mg (30%) (1 S,2R,5S,6R)-2,6-Diacetoxy-bicyclo[3.3.0]octan (I!) als farblose Kristalle. !a]D 25 + 113,0° (c = 2,260, CHCI3). Enantiomerenüberschuß 99%.This gives 68mg (30%) (1S, 2R, 5S, 6R) -2,6-diacetoxy-bicyclo [3.3.0] octane (I!) As colorless crystals. ! a] D 25 + 113.0 ° (c = 2.260, CHCl 3 ). Enantiomeric excess 99%.
Weiterhin erhält man 124mg (55%) (1 R^S.öR.eSt-BicyclolS.S.OIoctan^e-diol (III) als farbloses öl. [a]D 25 + 28,8° (c = 2,005, CHCI3). Enantiomerenüberschuß 59%.Furthermore, 124 mg (55%) (1%) of ethyl acetate (III) as a colorless oil are obtained. [Α] D 25 + 28.8 ° (c = 2.005, CHCl 3 ) Enantiomeric excess 59%.
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Application Number | Priority Date | Filing Date | Title |
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DD32759989A DD282242A5 (en) | 1989-04-13 | 1989-04-13 | PROCESS FOR THE RACEMATING OF (1SR, 2RS, 5SR, 6RS) -BICYCLO [3.3.0] OCTAN-2,6-DIOL |
SU894723046A SU1680685A1 (en) | 1989-04-13 | 1989-07-28 | Method for splitting of racemic (1sr, 2 rs, 5r, 6rs)-bicyclo(3 |
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DD32759989A DD282242A5 (en) | 1989-04-13 | 1989-04-13 | PROCESS FOR THE RACEMATING OF (1SR, 2RS, 5SR, 6RS) -BICYCLO [3.3.0] OCTAN-2,6-DIOL |
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DD32759989A DD282242A5 (en) | 1989-04-13 | 1989-04-13 | PROCESS FOR THE RACEMATING OF (1SR, 2RS, 5SR, 6RS) -BICYCLO [3.3.0] OCTAN-2,6-DIOL |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0561321A3 (en) * | 1992-03-20 | 1995-01-11 | Eastman Kodak Co | Additive assisted enzymatic esterification of 1,2-diol monosulfonates |
-
1989
- 1989-04-13 DD DD32759989A patent/DD282242A5/en not_active IP Right Cessation
- 1989-07-28 SU SU894723046A patent/SU1680685A1/en active
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0561321A3 (en) * | 1992-03-20 | 1995-01-11 | Eastman Kodak Co | Additive assisted enzymatic esterification of 1,2-diol monosulfonates |
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