DE1443408B - 17,20-dimethyl-18-nor-17alpha-pregn-5,13-diene-3beta, löalpha, 20-triol, its 3-mono- and 3,16-diacetate and process for their preparation - Google Patents
17,20-dimethyl-18-nor-17alpha-pregn-5,13-diene-3beta, löalpha, 20-triol, its 3-mono- and 3,16-diacetate and process for their preparationInfo
- Publication number
- DE1443408B DE1443408B DE1443408B DE 1443408 B DE1443408 B DE 1443408B DE 1443408 B DE1443408 B DE 1443408B
- Authority
- DE
- Germany
- Prior art keywords
- pregn
- dimethyl
- triol
- diacetate
- mono
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 9
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 6
- TUCNEACPLKLKNU-UHFFFAOYSA-N acetyl Chemical compound C[C]=O TUCNEACPLKLKNU-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 230000001548 androgenic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003098 androgen Substances 0.000 description 2
- 210000000056 organ Anatomy 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 210000001625 seminal vesicle Anatomy 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 201000010653 vesiculitis Diseases 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- DNXHEGUUPJUMQT-UHFFFAOYSA-N (+)-estrone Natural products OC1=CC=C2C3CCC(C)(C(CC4)=O)C4C3CCC2=C1 DNXHEGUUPJUMQT-UHFFFAOYSA-N 0.000 description 1
- -1 20-methyl-5-pregnen-20-ol Chemical compound 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 241000700159 Rattus Species 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229940030486 androgens Drugs 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 229960003399 estrone Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 210000002307 prostate Anatomy 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Description
Die Verbindungen nach der Erfindung besitzen die allgemeine FormelThe compounds according to the invention have the general formula
CH3 CH 3
HO — C — CH1 HO - C - CH 1
RORO
worin R sowie R' ein Wasserstoffatom bedeuten oder R sowie R' für den Acetylrest stehen oder R den Acetylrest und R' Wasserstoff bedeutet.where R and R 'represent a hydrogen atom or R and R' represent the acetyl radical or R denotes Acetyl radical and R 'is hydrogen.
Das freie Triol ist eine hormonal wirksame Verbindung mit bei warmblütigen Tieren gesteigerter androgener Aktivität. Das 3-Acetat sowie das 3,16tDiacetat sind hormonal in gleicher Weise wirksam mit verbesserter Lipoidlöslichkeit.The free triol is a hormonally active compound with increased androgenic activity in warm-blooded animals. The 3-acetate and the 3.16t diacetate are hormonally effective in the same way with improved lipoid solubility.
Das erfindungsgemäße Verfahren zur Herstellung dieser Verbindungen ist dadurch gekennzeichnet, daß man eine Verbindung der allgemeinen FormelThe process according to the invention for the preparation of these compounds is characterized in that one is a compound of the general formula
CH3
HO-C-CH3 CH 3
HO-C-CH 3
worin R die vorstehende "Bedeutung hat, in an sich bekannter Weise mit Bortrifluoridätherat bei einer Temperatur zwischen O und 36° C in Gegenwart eines inerten, wasserfreien, organischen Lösungsmittels umsetzt, worauf man gegebenenfalls das erhaltene Produkt in 3ß-Stellung und bzw. oder in 16a-Stellung acetyliert.wherein R has the above "meaning, in a manner known per se with boron trifluoride etherate in a Temperature between 0 and 36 ° C in the presence of an inert, anhydrous, organic solvent, whereupon the product obtained is optionally in the 3β-position and / or in the 16α-position acetylated.
Der Ausdruck »inert« bedeutet hier, daß das Lösungsmittel weder mit den Ausgangsstoffen noch mit dem erwarteten Reaktionsprodukt reagiert. Beispiele für solche inerte Lösungsmittel sind Benzol, n-Pentan, Diäthyläther, Tetrahydrofuran oder Cyclohexan. The term "inert" means here that the solvent neither with the starting materials nor reacts with the expected reaction product. Examples of such inert solvents are benzene, n-pentane, diethyl ether, tetrahydrofuran or cyclohexane.
Eine säurekatalysierte Ringöffnung von 16α,17α-Epoxysteroiden ist an sich z. B. aus J. Am. Chem.An acid catalyzed ring opening of 16α, 17α-epoxy steroids is in itself z. B. from J. Am. Chem.
Soc. 81 (1959) S. 6478 ff. und 6483 ff. und aus Gazz. Chim. ital. 92 (1962) S. 1118 ff. sowie aus der französischen Patentschrift 1 161 364 und der deutschen Auslegeschrift 1 004 609 bekannt. Jedoch wurde überraschenderweise gefunden, daß bei der Anwendung dieser an sich bekannten Reaktion auf das erfindungsgemäß verwendete Ausgangsmaterial therapeutisch überlegene Wirkstoffe erhalten werden. So wurden bei einem Vergleichsversuch das 17/3,20-Dimethyl-18-nor-17a-pregn-5,l 3-dien-3/3,l 6a,20"-triol verglichen mit dem bekannten Androgenwirkstoff 5-Pregnen-20-on-3,3,16a-diol. Soc. 81 (1959) pp. 6478 ff. And 6483 ff. And from Gazz. Chim. ital. 92 (1962) p. 1118 ff. as well as from the French Patent specification 1 161 364 and the German Auslegeschrift 1 004 609 known. However, it was surprising found that when applying this known reaction to the invention used starting material therapeutically superior active ingredients can be obtained. So were at a comparative experiment the 17 / 3,20-dimethyl-18-nor-17a-pregn-5, l 3-diene-3/3, l 6a, 20 "-triol compared to the known androgenic active ingredient 5-pregnen-20-one-3,3,16a-diol.
Die beiden Substanzen wurden in Maiskornöl suspendiert, zwei Gruppen von je fünf jugendlichen männlichen Ratten in einer Gesamtdosis von 3 mg/kg subkutan injiziert, und zwar sieben Injektionen an 7 darauf folgenden Tagen. Nach dem 8. Tag wurden die Tiere getötet und die Organe gewogen und mit denjenigen der Kontrollgruppe, welche keine Wirkstoffe erhalten hatten, verglichen. Die Ergebnisse sind in der nachfolgenden Tabelle angegeben:The two substances were suspended in corn kernel oil, two groups of five adolescents each male rats were injected subcutaneously at a total dose of 3 mg / kg, seven injections on 7 following days. After the 8th day, the animals were sacrificed and the organs were weighed and included compared to those of the control group who had not received any active ingredients. The results are indicated in the table below:
Mittlere Gewichtszunahme Medium weight gain
Kontrollgruppe
mgControl group
mg
VergleichssubstanzComparison substance
TestgruppeTest group
mgmg
Effekt
%effect
%
Verbindung gemäß ErfindungCompound according to the invention
Kontrollgruppe
mgControl group
mg
Testgruppe
mgTest group
mg
Effekt
%effect
%
Samenbläschen ..
Ventrale Prostata
Levator ani Seminal vesicles ..
Ventral prostate
Levator ani
22,9
42,1
24,922.9
42.1
24.9
19,6
43,9
23,619.6
43.9
23.6
Die Ergebnisse zeigen, daß die für Androgenwirkstoffe charakteristische Gewichtszunahme der Organe eingetreten ist, wobei jedoch bei der Verbindung gemäß der Erfindung eine starke Gewichtszunahme auch bei den Samenbläschen und dem Levator ani zu bemerken war.The results show that the weight increase in the organs which is characteristic of androgenic agents has occurred, but with the compound according to the invention a large weight gain was also noticeable in the seminal vesicles and the levator ani.
Die neuen Verbindungen sind deshalb auch besonders wertvolle Androgenwirkstoffe, da sie in ihrer chemischen Struktur von den anderen bekannten Androgenen abweichen, die bekanntlich zur Bildung von Stoffwechselprodukten, wie östron, führen.The new compounds are therefore also particularly valuable androgenic substances, as they are in their chemical structure differ from the other known androgens that are known to form of metabolic products such as oestrone.
Die Erfindung wird an Hand nachstehender Beispiele näher erläutert.The invention is explained in more detail by means of the following examples.
B e i s ρ i e 1 1B e i s ρ i e 1 1
3/3-Acetoxy-17/?,20-dimethyl-l 8-nor-17a-pregn-5,13-dien-16a,20-diol 3/3-acetoxy-17 / ?, 20-dimethyl-l 8-nor-17a-pregn-5,13-diene-16a, 20-diol
Einer Lösung von 2,85
20-methyl-5-pregnen-20-ol [beschrieben von W. C ο 1 e und Mitarbeiter in J. Org. Chem., Bd. 19, S. 131 (1953)]
in 125 ml Diäthyläther wurden 1,0 ml frisch destilliertes Bortrifluorid-ätherat zugesetzt. Das Gemisch wurde
-14,4A solution of 2.85
20-methyl-5-pregnen-20-ol [described by W. C o 1e and coworkers in J. Org. Chem., Vol. 19, p. 131 (1953)] in 125 ml of diethyl ether were 1.0 ml freshly distilled boron trifluoride etherate added. The mixture became -14.4
+42,8+42.8
-5,2-5.2
27,1
34,6
33,027.1
34.6
33.0
30,8
47,4
35,630.8
47.4
35.6
+ 13,7+ 13.7
+ 37,0+ 37.0
+7,9+7.9
umgeschüttelt und 20 Minuten bei 25° C stehengelassen, worauf man 100 ml Wasser, die 2,0 g Kaliumcarbonat enthielten,zusetzte. Nach dem Schütteln des Gemisches wurde die Ätherschicht abgetrennt, mit Wasser gewaschen, mit wasserfreiem Magnesiumsulfat getrocknet und der Äther abdestilliert. Das Rohprodukt, welches 2,72 g wog, wurde in 10 ml Benzol aufgenommen und an 100 g neutralem Aluminiumoxyd der Aktivitätsstufe III chromatographiert. Das mit Benzol, welches 1 bis 10% Diäthyläther enthielt, eluierte Material wurde aus Petroläther (Kp. 60 bis 680C) kristallisiert, wobei man 0,50 g 3^-Acetoxy-17/3,20 - dimethyl - 18 - nor - 17α - pregn - 5,13 - dien-16a,20-diol, mit dem Fp. 148 bis 15.00C, erhielt.shaken and allowed to stand at 25 ° C. for 20 minutes, whereupon 100 ml of water containing 2.0 g of potassium carbonate were added. After shaking the mixture, the ether layer was separated off, washed with water, dried with anhydrous magnesium sulfate and the ether was distilled off. The crude product, which weighed 2.72 g, was taken up in 10 ml of benzene and chromatographed on 100 g of neutral aluminum oxide of activity level III. The benzene containing 1 to 10% diethyl ether, eluted material was crystallized from petroleum ether (b.p. 60 to 68 0 C.) To give 0.50 g of 3-acetoxy-^ 17 / 3,20 - dimethyl - 18 - NOR - 17α - pregn - 5,13 - dien-16a, 20-diol, of mp 148 to 15.0 0 C, obtained..
Analytisch fand man 74,29% C und 9,25% H in guter Übereinstimmung mit den für die empirische Formel C24H36O4 berechneten Werten.Analytically, 74.29% C and 9.25% H were found in good agreement with the values calculated for the empirical formula C 24 H 36 O 4.
Wurde bei obigem Verfahren das Material in einer kleinen Menge Äther vor der chromatographischen Trennung aufgenommen und mit dem 10- bis 20fachen Volumen Petroläther (Kp. 60 bis 680C) verdünnt, dann schied sich ein öl ab. Die Lösung wurde abdekantiert und konzentriert und das Konzentrat fürThe material was taken up in a small amount of ether prior to chromatographic separation and diluted with the 10- to 20-fold volume of petroleum ether (bp. 60 to 68 0 C) in the above process, then separated out as an oil. The solution was decanted and concentrated and the concentrate for
das Chromatogramm verwendet, wobei man eine viel schärfere Trennung erzielte.the chromatogram was used, obtaining a much sharper separation.
Zur weiteren Charakterisierung wurde eine Lösung von 3jS-Acetoxy-17/3,20-dimethyl-18 -nor-17a-pregn-5,13-dien-16a,20-diol und 0,37 g Kaliumcarbonat in 17 ml 88%igem wäßrigem Methanol 4 Stunden rückfließend sieden gelassen. Das Material wurde durch Zusatz von 15 ml Wasser zur Kristallisation gebracht, abfiltriert und aus Toluol umkristallisiert, wobei man 0,16 g n/S^O-Dimethyl-lS-nor-na-pregn-S.n-3/3,16a,20-triol erhielt, welches bei 200 bis 2030C schmolz. Analytisch wurden 76,46% C und 9,84% H gefunden in guter Übereinstimmung mit den für die empirische Formel C22HmO3 berechneten Werten.A solution of 3jS-acetoxy-17 / 3,20-dimethyl-18-nor-17a-pregn-5,13-diene-16a, 20-diol and 0.37 g of potassium carbonate in 17 ml of 88% strength was used for further characterization Aqueous methanol is allowed to reflux for 4 hours. The material was made to crystallize by adding 15 ml of water, filtered off and recrystallized from toluene, 0.16 gn / S ^ O-dimethyl-IS-nor-na-pregn-Sn-3 / 3.16a, 20- triol obtained, melting at 200-203 0 C. Analytically, 76.46% C and 9.84% H were found in good agreement with the values calculated for the empirical formula C 22 HmO 3.
- ίο- ίο
3β,ί oa-Diacetoxy-Ha^O-dimethyl-l 8-nor-17a-pregn-5,l 3-dien-20-ol 3β, ί oa-diacetoxy-Ha ^ O-dimethyl-l 8-nor-17a-pregn-5, l 3-dien-20-ol
Ein Gemisch aus 48,1 mg 3^-Acetoxy-17/J,20-dimethyl-18-nor-17a-pregn-5,13-dien-16/3,20-diol (erhalten nach Beispiel 1), 1,2 ml Essigsäureanhydrid und 2,3 ml Pyridin wurde über Nacht bei Raumtemperatur stehengelassen. Hierauf fügte man eine kleine Menge Eis zur Zersetzung des überschüssigen Essigsäureanhydrids zu. Dann setzte man Wasser zu, worauf das S/Uoa-Diacetoxy-n/S^O-dimethyl-lS-nor-17a-pregn-5,13-dien-20-ol kristallisierte. Die Verbinbindung schmolz bei 125 bis 126° C. Analytisch wurden 72,50% C und 8,89% H gefunden in guter Übereinstimmung mit den für die empirische Formel C26H38O5 berechneten Werten.A mixture of 48.1 mg 3 ^ -acetoxy-17 / J, 20-dimethyl-18-nor-17a-pregn-5,13-diene-16 / 3,20-diol (obtained according to Example 1), 1, 2 ml of acetic anhydride and 2.3 ml of pyridine were left to stand overnight at room temperature. A small amount of ice was then added to decompose the excess acetic anhydride. Then water was added, whereupon the S / Uoa-diacetoxy-n / S ^ O-dimethyl-IS-nor-17a-pregn-5,13-dien-20-ol crystallized. The compound melted at 125 to 126 ° C. Analytically, 72.50% C and 8.89% H were found in good agreement with the values calculated for the empirical formula C 26 H 38 O 5.
Claims (2)
Family
ID=
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