PL238289B1 - 3-O-(β-D-4'-O-methylglucopyranosyl)-17-ethinylestr-17β-ol and method of preparation of 3-O-(β-D-4'-O-methylglucopyranosyl)-17-ethinylestr-17β-ol - Google Patents
3-O-(β-D-4'-O-methylglucopyranosyl)-17-ethinylestr-17β-ol and method of preparation of 3-O-(β-D-4'-O-methylglucopyranosyl)-17-ethinylestr-17β-ol Download PDFInfo
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Abstract
Zgłoszenie dotyczy 3-O-(ß-D-4'-O-metyloglukopiranozylo)-17-etynyloestr-17ß-olu i sposobu wytwarzania 3-O-(ß-D-4'-O-metyloglukopiranozylo)-17-etynyloestr-17ß-olu. Zgodnie z rozwiązaniem w wyniku działania układu enzymatycznego zawartego w komórkach szczepu Isaria fumosorosea KCh J2, następuje przyłączenie ß-D-4'-O-metyloglukopiranozy do grupy hydroksylowej substratu. Uzyskany w ten sposób produkt wydziela się z wodnej kultury mikroorganizmu, znanym sposobem, przez ekstrakcję rozpuszczalnikiem organicznym niemieszającym się z wodą (chloroform).The application concerns 3-O-(ß-D-4'-O-methylglucopyranosyl)-17-ethynylester-17ß-ol and a method for producing 3-O-(ß-D-4'-O-methylglucopyranosyl)-17-ethynylester- 17ß-ol. According to the solution, as a result of the action of the enzymatic system contained in the cells of the Isaria fumosorosea KCh J2 strain, ß-D-4'-O-methylglucopyranose is attached to the hydroxyl group of the substrate. The product obtained in this way is isolated from the aqueous culture of the microorganism in a known method, by extraction with an organic solvent immiscible with water (chloroform).
Description
Przedmiotem wynalazku jest sposób wytwarzania 3-O-(β-D-4'-O-metyloglukopiranozylo)-17-etynyloestr-17e-olu.The present invention relates to a process for the preparation of 3-O- (β-D-4'-O-methylglucopyranosyl) -17-ethynyl ester-17e-ol.
Metoda według wynalazku może znaleźć zastosowanie w przemyśle farmaceutycznym do wytwarzania leków antykoncepcyjnych.The method according to the invention may find application in the pharmaceutical industry for the production of contraceptive drugs.
17-etynyloestr-17β-ol jest składnikiem większości leków antykoncepcyjnych stosowanych doustnie (Schramm G, Henske R. Hormonal contraceptive containing a combination of ethinyloestradiol and Chlormadinone acetate. Patent No.: US 9,107,840 B2; Date of Patent: Aug. 18, 2015). Wiele naturalnych związków występuje w formie związanej z jednostką cukrową, co ma istotny wpływ na ich stabilność i rozpuszczalność, a często także wpływa na ich biodostępność i aktywność biologiczną (Wang X. Structure, mechanism and engineering of plant natural product glycosyltransferases. FEBS Lett. 2009; 583(20):3303-9;p Wang L, Han W, Xie C, Hou J, Fang Q, Gu J, et al. Comparing the acceptor promiscuity of a Rosa hybrida glucosyltransferase RhGT1 and an engineered microbial glucosyltransferase OleDPSA toward a small flavonoid library. Carbohydr Res. 2013; 368:73-7; Pandey RP, Gurung RB, Parajuli P, Koirala N, Tuoi LT, Sohng JK. Assessing acceptor substrate promiscuity of YjiC-mediated glycosylation toward flavonoids. Carbohydr Res. 2014;393:26-31).17-ethinylestr-17β-ol is an ingredient of most oral contraceptives (Schramm G, Henske R. Hormonal contraceptive containing a combination of ethinyloestradiol and Chlormadinone acetate. Patent No .: US 9,107,840 B2; Date of Patent: Aug. 18, 2015) . Many natural compounds exist in a form related to the sugar unit, which has a significant impact on their stability and solubility, and often also affects their bioavailability and biological activity (Wang X. Structure, mechanism and engineering of plant natural product glycosyltransferases. FEBS Lett. 2009 ; 583 (20): 3303-9; p Wang L, Han W, Xie C, Hou J, Fang Q, Gu J, et al. Comparing the acceptor promiscuity of a Rosa hybrida glucosyltransferase RhGT1 and an engineered microbial glucosyltransferase OleDPSA toward a small flavonoid library. Carbohydr Res. 2013; 368: 73-7; Pandey RP, Gurung RB, Parajuli P, Koirala N, Tuoi LT, Sohng JK. Assessing acceptor substrate promiscuity of YjiC-mediated glycosylation toward flavonoids. Carbohydr Res. 2014; 393: 26-31).
3-O-(β-D-4'-O-metyloglukopiranozylo)-17-etynyloestr-17β-ol znany jest ze zgłoszenia patentowego DE2326084.3-O- (β-D-4'-O-methylglucopyranosyl) -17-ethynyl ester-17β-ol is known from patent application DE2326084.
Z opisu zgłoszenia wynalazku P.416996 znany jest szczep Isaria fumosorosea KCh J2.From the description of the application of the invention P.416996 the strain Isaria fumosorosea KCh J2 is known.
Istota wynalazku polega na tym, że do podłoża odpowiedniego dla grzybów strzępkowych wprowadza się szczep Isaria fumosorosea KCh J2. Po upływie co najmniej 48 godzin do hodowli wprowadza się substrat, którym jest 17-etynyloestr-17e-ol o wzorze 1, rozpuszczony w rozpuszczalniku organicznym mieszającym się z wodą. Transformację prowadzi się w temperaturze od 20 do 30 stopni Celsjusza, przy ciągłym wstrząsaniu, co najmniej 9 godzin. Kolejno produkt ekstrahuje się rozpuszczalnikiem organicznym niemieszającym się z wodą i oczyszcza chromatograficznie.The essence of the invention consists in introducing the Isaria fumosorosea KCh J2 strain into a medium suitable for filamentous fungi. After at least 48 hours, the substrate 17-ethynyl ester-17e-ol of formula I, dissolved in a water-miscible organic solvent, is introduced into the culture. The transformation is carried out at a temperature of 20 to 30 degrees Celsius with continuous shaking for at least 9 hours. Subsequently, the product is extracted with a water-immiscible organic solvent and purified by chromatography.
W wyniku regioselektywnego przyłączenia e-D-4'-O-metyloglukopiranozy (wytworzonej przez układ enzymatyczny biokatalizatora) do grupy hydroksylowej obecnej przy węglu C-3 w cząstce substratu, otrzymuje się 3-O-(e-D-4'-O-metyloglukopiranozylo)-17-etynyloestr-17e-ol, a reakcję prowadzi się w wodnej kulturze szczepu Isaria fumosorosea KCh J2.As a result of regioselective attachment of eD-4'-O-methylglucopyranose (produced by the biocatalyst enzyme system) to the hydroxyl group present at C-3 carbon in the substrate particle, 3-O- (eD-4'-O-methylglucopyranosyl) -17 is obtained -ethynyl ester-17e-ol and the reaction is carried out in an aqueous culture of the strain Isaria fumosorosea KCh J2.
Korzystnie jest, gdy stosunek masy dodawanego substratu do objętości hodowli wynosi 0,2 g : 1 L.Preferably, the ratio of the mass of the added substrate to the culture volume is 0.2 g: 1 L.
Korzystnie także jest, gdy proces prowadzi się w temperaturze 25 stopni Celsjusza.It is also preferred that the process is carried out at a temperature of 25 degrees Celsius.
Korzystnie jest również, gdy transformację prowadzi się przez 72 godziny.It is also preferred that the transformation is carried out for 72 hours.
Postępując zgodnie z wynalazkiem, w wyniku działania układu enzymatycznego zawartego w komórkach szczepu Isaria fumosorosea KCh J2, następuje przyłączenie β-D-4'-O-metyloglukopiranozy do grupy hydroksylowej substratu. Uzyskany w ten sposób produkt wydziela się z wodnej k ultury mikroorganizmu, znanym sposobem, przez ekstrakcję rozpuszczalnikiem organicznym niemieszającym się z wodą (octan etylu). Zasadniczą zaletą wynalazku jest otrzymanie 3-O-(β-D-4'-O-metyloglukopiranozylo)-17-etynyloestr-17e-olu, z wydajnością izolowaną na poziomie 30% (konwersja według NMR = 80%), w temperaturze pokojowej i przy pH naturalnym dla szczepu.By following the invention, β-D-4'-O-methylglucopyranose is attached to the hydroxyl group of the substrate by the action of the enzyme system contained in the cells of the Isaria fumosorosea KCh J2 strain. The product obtained in this way is isolated from the water of the microorganism in a known manner by extraction with a water-immiscible organic solvent (ethyl acetate). The main advantage of the invention is the preparation of 3-O- (β-D-4'-O-methylglucopyranosyl) -17-ethynyl ester-17e-ol with an isolated yield of 30% (conversion according to NMR = 80%), at room temperature and at the natural pH of the strain.
Wynalazek jest bliżej objaśniony na przykładzie wykonania.The invention is explained in more detail using an exemplary embodiment.
PrzykładExample
Do kolby Erlenmajera o pojemności 2000 cm3, w której znajduje się 500 cm3 sterylnej pożywki zawierającej 5 g aminobaku i 15 g glukozy, wprowadza się szczep Isaria fumosorosea KCh J2. Po 72 godzinach jego wzrostu dodaje się 100 mg 17-etynyloestr-17e-olu o wzorze 1, rozpuszczonego w 1 cm3 DMSO. Transformację prowadzi się w 25 stopniach Celsjusza przy ciągłym wstrząsaniu przez 24 godziny. Następnie mieszaninę poreakcyjną ekstrahuje się trzykrotnie octanem etylu, osusza bezwodnym siarczanem magnezu i odparowuje rozpuszczalnik. Otrzymany ekstrakt oczyszcza się chromatograficznie, używając jako eluentu mieszaniny chloroform i metanol 9 : 1.To the Erlenmeyer flask with a capacity of 2,000 cm 3, which is 500 cm 3 of a sterile medium containing 5 g aminobaku and 15 g of glucose, the strain is introduced Isaria fumosorosea SDS J2. After 72 hours of its growth, 100 mg of 17-ethynyl ester-17e-ol of formula 1, dissolved in 1 cm 3 of DMSO, are added. The transformation is carried out at 25 degrees Celsius with continuous shaking for 24 hours. The reaction mixture was then extracted three times with ethyl acetate, dried with anhydrous magnesium sulfate and the solvent was evaporated. The extract obtained is purified by chromatography using a 9: 1 mixture of chloroform and methanol as eluent.
Na tej drodze otrzymuje się 40 mg 3-O-(e-D-4'-O-metyloglukopiranozylo)-17-etynyloestr-17e-olu, (konwersja według NMR = 80%).In this way, 40 mg of 3-O- (e-D-4'-O-methylglucopyranosyl) -17-ethynylester-17e-ol are obtained (conversion by NMR = 80%).
Uzyskany produkt charakteryzuje się następującymi danymi spektralnymi:The obtained product is characterized by the following spectral data:
1H NMR (600 MHz) (ppm) (DMSO) δ: 0.75 (s, 3H, 18-H); 1.22-1.35 (m, 4H, 7-Ha, 8-H, 11-Ηβ, 15-Ηβ); 1.59 (dd, 1H, J = 10.9, 7.7 Hz, 14-H); 1.62-1.68 (m, 2H, 12-Ha, 15-Ha); 1.75-1.82 (m, 2H, 7-Ηβ, 12-Ηβ); 1.86 (td, 1H, J = 13.1, 3.5 Hz, 16-Ha); 2.06-2.13 (m, 2H, 9-H, 16-Ηβ); 2.32 (dq, 1H, J = 13.5, 3.0 Hz, 11-Ha); 2.72-2.78 (m, 2H, 6-Ha, 6-Ηβ); 3.01 (t, 1H, J = 9.3 Hz, 4-H'); 3.20 (ddd, 1H, 1 H NMR (600 MHz) (ppm) (DMSO) δ: 0.75 (s, 3H, 18-H); 1.22-1.35 (m, 4H, 7-Ha, 8-H, 11-Ηβ, 15-Ηβ); 1.59 (dd, 1H, J = 10.9, 7.7Hz, 14-H); 1.62-1.68 (m, 2H, 12-Ha, 15-Ha); 1.75-1.82 (m, 2H, 7-Ηβ, 12-Ηβ); 1.86 (td, 1H, J = 13.1, 3.5 Hz, 16-Ha); 2.06-2.13 (m, 2H, 9-H, 16-Ηβ); 2.32 (dq, 1H, J = 13.5, 3.0 Hz, 11-Ha); 2.72-2.78 (m, 2H, 6-Ha, 6-Ηβ); 3.01 (t, 1H, J = 9.3Hz, 4-H '); 3.20 (ddd, 1H,
PL 238 289 B1PL 238 289 B1
J = 8.8, 8.0, 5.2 Hz, 2-H'); 3.30 (ddd, 1H J = 9.6, 4.9, 2.0 Hz, 5-H'); 3.36-3.39 (m, 1H, 3-H'); 3.44 (s, 3H, -OCH3); 3.45-3.51 (m, 1H, one of 6-H'); 3.61 (ddd, 1H, J = 11.9, 4.7, 1.6 Hz, one of 6-H'); 4.68 (t, 1H, J = 5.7 Hz, C'6-OH); 4.78 (d, 1H, J = 6.7 Hz, 1-H'); 5.21 (d, 1H, J = 5.4 Hz, C'3-OH); 5.32 (d, 1H, J = 5.3 Hz, C'2-OH); 5.34 (s, 1H, C17-OH); 6.69 (d, 1H, J = 2.6 Hz, 4-H); 6.77 (dd, 1H, J = 8.6, 2.6 Hz, 2-H); 7.16 (d, 1H, J = 8.7 Hz, 1-H).J = 8.8, 8.0, 5.2 Hz, 2-H '); 3.30 (ddd, 1H J = 9.6, 4.9, 2.0 Hz, 5-H '); 3.36-3.39 (m, 1H, 3-H '); 3.44 (s, 3H, -OCH3); 3.45-3.51 (m, 1H, one of 6-H '); 3.61 (ddd, 1H, J = 11.9, 4.7, 1.6 Hz, one of 6-H '); 4.68 (t, 1H, J = 5.7Hz, C'6-OH); 4.78 (d, 1H, J = 6.7Hz, 1-H '); 5.21 (d, 1H, J = 5.4Hz, C'3-OH); 5.32 (d, 1H, J = 5.3Hz, C'2-OH); 5.34 (s, 1H, C17-OH); 6.69 (d, 1H, J = 2.6Hz, 4-H); 6.77 (dd, 1H, J = 8.6, 2.6 Hz, 2-H); 7.16 (d, 1H, J = 8.7 Hz, 1-H).
13C NMR (151 MHz) (ppm) (DMSO) δ: 126.18 (C-1); 113.83 (C-2); 155.24 (C-3); 116.30 (C-4); 137.44 (C-5); 29.35 (C-6); 26.95 (C-7); 39.12 (C-8); 43.45 (C-9); 133.52 (C-10); 26.12 (C-11 ); 32.65 (C-12); 46.74 (C-13); 49.09 (C-14); 22.53 (C-15); 38.85 (C-16); 78.23 (C-17); 12.79 (C-18); 89.01 (C-20); 75.11 (C-21); 100.40 (C-1'); 73.54 (C-2'); 76.39 (C-3'); 79.14 (C-4'); 75.63 (C-5'); 60.36 (C-6'); 59.71 (-OCH3). 13 C NMR (151 MHz) (ppm) (DMSO) δ: 126.18 (C-1); 113.83 (C-2); 155.24 (C-3); 116.30 (C-4); 137.44 (C-5); 29.35 (C-6); 26.95 (C-7); 39.12 (C-8); 43.45 (C-9); 133.52 (C-10); 26.12 (C-11); 32.65 (C-12); 46.74 (C-13); 49.09 (C-14); 22.53 (C-15); 38.85 (C-16); 78.23 (C-17); 12.79 (C-18); 89.01 (C-20); 75.11 (C-21); 100.40 (C-1 '); 73.54 (C-2 '); 76.39 (C-3 '); 79.14 (C-4 '); 75.63 (C-5 '); 60.36 (C-6 '); 59.71 (-OCH3).
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