CH204844A - Process for the preparation of a pregnen-5-ol-3-one-20 derivative. - Google Patents
Process for the preparation of a pregnen-5-ol-3-one-20 derivative.Info
- Publication number
- CH204844A CH204844A CH204844DA CH204844A CH 204844 A CH204844 A CH 204844A CH 204844D A CH204844D A CH 204844DA CH 204844 A CH204844 A CH 204844A
- Authority
- CH
- Switzerland
- Prior art keywords
- pregnen
- acid
- solution
- derivative
- preparation
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 4
- 239000002253 acid Substances 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 5
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- XXTZHYXQVWRADW-UHFFFAOYSA-N diazomethanone Chemical compound [N]N=C=O XXTZHYXQVWRADW-UHFFFAOYSA-N 0.000 claims description 4
- 238000007127 saponification reaction Methods 0.000 claims description 4
- QRLVDLBMBULFAL-UHFFFAOYSA-N Digitonin Natural products CC1CCC2(OC1)OC3C(O)C4C5CCC6CC(OC7OC(CO)C(OC8OC(CO)C(O)C(OC9OCC(O)C(O)C9OC%10OC(CO)C(O)C(OC%11OC(CO)C(O)C(O)C%11O)C%10O)C8O)C(O)C7O)C(O)CC6(C)C5CCC4(C)C3C2C QRLVDLBMBULFAL-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- UVYVLBIGDKGWPX-KUAJCENISA-N digitonin Chemical compound O([C@@H]1[C@@H]([C@]2(CC[C@@H]3[C@@]4(C)C[C@@H](O)[C@H](O[C@H]5[C@@H]([C@@H](O)[C@@H](O[C@H]6[C@@H]([C@@H](O[C@H]7[C@@H]([C@@H](O)[C@H](O)CO7)O)[C@H](O)[C@@H](CO)O6)O[C@H]6[C@@H]([C@@H](O[C@H]7[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O7)O)[C@@H](O)[C@@H](CO)O6)O)[C@@H](CO)O5)O)C[C@@H]4CC[C@H]3[C@@H]2[C@@H]1O)C)[C@@H]1C)[C@]11CC[C@@H](C)CO1 UVYVLBIGDKGWPX-KUAJCENISA-N 0.000 claims description 3
- UVYVLBIGDKGWPX-UHFFFAOYSA-N digitonine Natural products CC1C(C2(CCC3C4(C)CC(O)C(OC5C(C(O)C(OC6C(C(OC7C(C(O)C(O)CO7)O)C(O)C(CO)O6)OC6C(C(OC7C(C(O)C(O)C(CO)O7)O)C(O)C(CO)O6)O)C(CO)O5)O)CC4CCC3C2C2O)C)C2OC11CCC(C)CO1 UVYVLBIGDKGWPX-UHFFFAOYSA-N 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims 1
- 239000003814 drug Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SOADZZNUBPUHLR-UHFFFAOYSA-N 1,2,3,5,6-oxatetrazin-4-one Chemical compound O1N=NC(=O)N=N1 SOADZZNUBPUHLR-UHFFFAOYSA-N 0.000 description 2
- LUWROZHMGRPGKK-CYVXNRQHSA-N 2-diazo-1-[(8R,9S,10S,13S,14S)-3-hydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15-dodecahydro-1H-cyclopenta[a]phenanthren-17-yl]ethanone Chemical compound [N+](=[N-])=CC(C1=CC[C@H]2[C@@H]3CCC4CC(CC[C@]4(C)[C@H]3CC[C@]12C)O)=O LUWROZHMGRPGKK-CYVXNRQHSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000004702 methyl esters Chemical group 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- OILXMJHPFNGGTO-UHFFFAOYSA-N (22E)-(24xi)-24-methylcholesta-5,22-dien-3beta-ol Natural products C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)C=CC(C)C(C)C)C1(C)CC2 OILXMJHPFNGGTO-UHFFFAOYSA-N 0.000 description 1
- AURFZBICLPNKBZ-SRJHXTLLSA-N 3-hydroxypregnan-20-one Chemical compound C1CC2CC(O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)C)[C@@]1(C)CC2 AURFZBICLPNKBZ-SRJHXTLLSA-N 0.000 description 1
- OQMZNAMGEHIHNN-UHFFFAOYSA-N 7-Dehydrostigmasterol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)C=CC(CC)C(C)C)CCC33)C)C3=CC=C21 OQMZNAMGEHIHNN-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- HZYXFRGVBOPPNZ-UHFFFAOYSA-N UNPD88870 Natural products C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)=CCC(CC)C(C)C)C1(C)CC2 HZYXFRGVBOPPNZ-UHFFFAOYSA-N 0.000 description 1
- OVMHABLOXWFPMV-UHFFFAOYSA-N acetyloxycarbonyl acetate Chemical compound CC(=O)OC(=O)OC(C)=O OVMHABLOXWFPMV-UHFFFAOYSA-N 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- LGJMUZUPVCAVPU-UHFFFAOYSA-N beta-Sitostanol Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(C)CCC(CC)C(C)C)C1(C)CC2 LGJMUZUPVCAVPU-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- DLLJVQNYBYOKGS-UHFFFAOYSA-N ethoxyethane;pentane Chemical compound CCCCC.CCOCC DLLJVQNYBYOKGS-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- BDRTVPCFKSUHCJ-UHFFFAOYSA-N molecular hydrogen;potassium Chemical compound [K].[H][H] BDRTVPCFKSUHCJ-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- JWMFYGXQPXQEEM-WZBAXQLOSA-N pregnane Chemical compound C1CC2CCCC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](CC)[C@@]1(C)CC2 JWMFYGXQPXQEEM-WZBAXQLOSA-N 0.000 description 1
- 150000003130 pregnenes Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- HCXVJBMSMIARIN-PHZDYDNGSA-N stigmasterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)/C=C/[C@@H](CC)C(C)C)[C@@]1(C)CC2 HCXVJBMSMIARIN-PHZDYDNGSA-N 0.000 description 1
- BFDNMXAIBMJLBB-UHFFFAOYSA-N stigmasterol Natural products CCC(C=CC(C)C1CCCC2C3CC=C4CC(O)CCC4(C)C3CCC12C)C(C)C BFDNMXAIBMJLBB-UHFFFAOYSA-N 0.000 description 1
- 229940032091 stigmasterol Drugs 0.000 description 1
- 235000016831 stigmasterol Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J7/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J5/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by a chain of two carbon atoms, e.g. pregnane and substituted in position 21 by only one singly bound oxygen atom, i.e. only one oxygen bound to position 21 by a single bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J75/00—Processes for the preparation of steroids in general
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Steroid Compounds (AREA)
Description
Verfahren zur Herstellung eines Fregnen-5-ol-3-on-20-derivates. Verbindungen, die das Pregnan- oder Pregnenskelett (Bezeichnung siehe Formel I) aufweisen, sind bisher entweder aus Natur produkten isoliert oder durch Abbau höher molekularer Stoffe gewonnen worden. Ver bindungen, die in 21-Stellung mit Halogen oder Sauerstoff, z. B. Hydroxyl, substituiert sind, sind bisher nicht bekannt geworden.
EMI0001.0008
Es wurde nun gefunden, dass man ausge hend von 3-Oxy-äthio-cholan-oder-allocholan- oder -cholensäuren, sowie von gesättigten oder ungesättigten Substitutionsprodukten der selben, die zum Beispiel noch weiteren Sauerstoff in hydrogyl-, äther- oder ogyd- artiger Bindung enthalten können, zu wert vollen Derivaten des Pregnan-3-ol-20-ons ge langen kann, die in 21 Stellung substituiert sind, wenn man die genannten Säuren, unter Schutz der freien Hydroxylgruppen im Ring system (z.
B. durch Acylierung oder Ver- ätherung) in die Säurehalogenide überführt und diese mit Diazomethan behandelt (vergl. Arndt, Eistert und Partale, Ber. Deutsch. Chem. Ges. 60, 1364, 1927). Hierdurch können Pregnenderivate, die in 21-Stellung eine Diazogruppe tragen, gewonnen werden. Diese lassen sich mannigfach umformen.
So kann die Diazogruppe, nach vorheriger alka lischer Verseifung im Ringsystem vorhan dener Acyloxygruppen, durch Einwirkung von organischen Carbonsäuren in Pregnen-ol- on-derivate mit einer Acyloxygruppe in 21- Stellung übergeführt werden.
Gegenstand des vorliegenden Patentes ist ein Verfahren zur Herstellung eines Pregnen-5-ol-3-on-20-deri- vates, welches dadurch gekennzeichnet ist, dass man Acyloxy-3-äthio-cholen-45,6-säure (Formel II), die man z.
B. aus Stigmasterin oder Cholesterin bereiten kann, in das ent sprechende Säure-Halogenid (Formel 11I) überführt, aus diesem durch Einwirkung von überschüssiger Diazomethanlösung das Diazo- keton (Formel IV) herstellt, aus diesem durch alkalische Hydrolyse das freie Oxy- diazoketon (V) gewinnt und letzteres mit konzentrierter Essigsäure, zweckmässig unter Ausschluss von Wasser bei Temperaturen von ungefähr 40 bis 1-90', umsetzt.
Man erhält so die Verbindung von der Formel (VI), welche gegen Alkalien sehr empfind lich ist und alkalische Silberlösung in der Kälte rasch reduziert.
EMI0002.0013
<I>Beispiel:</I> Die als Ausgangsmaterial zu verwen dende Ac5-loxy-3-äthio-cholen-d5,6-säure lässt sich durch oxydativen Abbau der 3-Oxy - bisnorcholen-sä.ure (Fernholz Liebigs Ana- nalen 507, 1?8. <B>1933)</B> über verschiedene Zwischenprodukte gewinnen.
Die freie Oxy- säure bildet farblose Kristalle, die bei 280 bis 288 kor. unter Zersetzung schmelzen (etwas verschieden, je nach Heizgeschwindig- keit) ; ihr Methylester bildet Nadeln aus Me thanol, die bei<B>180'</B> kor. schmelzen. Die acetylierte Säure schmilzt bei 240 bis 242 kor., ihr Methylester bei 153 bis 154' kor.
1 g 3- Acetoxy-äthio-cholen-d5,6-säure wer den mit 5 cm' Benzol und 5 g reinstem Thio- nylchlorid 3 Stunden unter Rückfluss ge kocht. Man dampft unter Feuchtigkeitsaus schluss ein, wobei das Chlorid bald kristalli siert. Das leicht gelblich gefärbte Produkt zeigt keinen eigentlichen Schmelzpunkt, son dern zersetzt sich je nach Heizgeschwindig- keit verschieden. Manchmal kann ein Schmelzpunkt bei 160 beobachtet werden unter Wiedererstarren und eventuell neuem Schmelzen der zersetzten Masse bei über 300 .
Das Chlorid wird in 80 cm' trockenem Äther gelöst und bei - 10 eine trockene ätherische Lösung von zirka 1 bis 1,5g Di- azomethan einlaufen gelassen. Die Mischung lässt man einige Stunden bei 0 , dann noch 6 Stunden bei Zimmertemperatur stehen, engt stark ein und gibt Petroläther zu bis zur Trübung. Das Diazoketon kristallisiert aus. Aus der Mutterlauge werden weitere Mengen analog gewonnen. Insgesamt erhält man so 0,7 g reines Produkt als schwach gelbliche Blättchen, die gegen<B>150</B> (etwas verschie den je nach Heizgeschwindigkeit) unter leb hafter Zersetzung schmelzen.
Für die Her stellung des freien 21-Diazo-pregnen-3-ol-20- ons werden 1 g des obigen Acetates in 30 cm' Methanol suspendiert, mit 16 cm' einer 5- prozentigen Lösung von Kaliumhydrogyd in Methanol versetzt und unter öfterem Um schwenken 6 Stunden bei Zimmertemperatur stehen gelassen. Die Kristalle gehen dabei nach etwa. einer halben Stunde in Lösung.
Nach Zusatz von etwas Wasser wird im Va kuum stark eingeengt, wobei das Oxy-diazo- keton auskristallisiert. Es wird abgenutscht, mit Wasser gewaschen, im Vakuum getrock net und aus Xther-Petroläther umkristalli siert, wodurch es in leicht gelblichen, glän zenden Körnern erhalten wird, die bei 144' unter lebhafter Zersetzung schmelzen; bei langsamem Erhitzen kann der Schmelzpunkt um mehrere Grade tiefer gefunden werden. Die Ausbeute ist fast quantitativ.
Das Pro dukt gibt zum Unterschied gegenüber dem acetylierten Diazoketon mit Digitonin in 80- bis 90prozentigem Alkohol eine Fällung.
0,2 g 21-Diazo-pregnen-3-ol-20-on werden mit 2 cm3 reinstem Eisessig zirka 30 Mi nuten auf 95 erwärmt, worauf die Gas abspaltung beendet ist. Nach dem Erkalten kristallisiert ein Teil des Acetoxy-ketons aus in Form schöner Nadeln. Es wird abge- nutscht und mit Äther-Pentan gewaschen. Aus der Mutterlauge wird der Rest nach Ein engen im Vakuum analog gewonnen. Die Ausbeute beträgt 0,21 g. Die Nadeln ent halten Kristallösungsmittel, sie werden beim Erwärmen gegen<B>80'</B> opak und schmelzen bei 180 bis 182 kor.
Sie besitzen nach ge hörigem Trocknen die Zusammensetzung C"SH840°, geben mit Digitonin eine Fällung und reduzieren alkalische Silberlösung.
Process for the preparation of a Fregnen-5-ol-3-one-20 derivative. Compounds that have the Pregnan or Pregnant skeleton (for the designation see formula I) have so far either been isolated from natural products or obtained by breaking down higher molecular weight substances. Ver compounds that are in the 21-position with halogen or oxygen, for. B. hydroxyl, are substituted, have not become known.
EMI0001.0008
It has now been found that starting from 3-oxy-ethio-cholanic or -allocholanic or -cholenic acids, as well as from saturated or unsaturated substitution products of the same, which, for example, contain further oxygen in hydrogyl-, ether- or ogyd- can contain like bond, to valuable derivatives of the pregnan-3-ol-20-one ge, which are substituted in the 21 position, if you use the acids mentioned, with protection of the free hydroxyl groups in the ring system (z.
B. by acylation or etherification) converted into the acid halides and these treated with diazomethane (see Arndt, Eistert and Partale, Ber. Deutsch. Chem. Ges. 60, 1364, 1927). Pregnene derivatives which carry a diazo group in the 21-position can be obtained in this way. These can be shaped in many ways.
For example, the diazo group, after previous alkali saponification in the ring system, can be converted into pregnen-ol-one derivatives with an acyloxy group in the 21 position by the action of organic carboxylic acids.
The present patent relates to a process for the preparation of a pregnen-5-ol-3-one-20 derivative, which is characterized in that acyloxy-3-ethio-cholen-45,6-acid (formula II) that one z.
B. can prepare from stigmasterol or cholesterol, converted into the corresponding acid halide (formula 11I), from this by the action of excess diazomethane solution the diazo ketone (formula IV) is produced, from this the free oxydiazoketone by alkaline hydrolysis ( V) wins and the latter with concentrated acetic acid, expediently with the exclusion of water at temperatures of about 40 to 1-90 ', is reacted.
The compound of formula (VI) is thus obtained, which is very sensitive to alkalis and rapidly reduces alkaline silver solution in the cold.
EMI0002.0013
<I> Example: </I> The Ac5-loxy-3-ethio-cholene-d5,6-acid to be used as starting material can be broken down by oxidative degradation of the 3-oxy-bisnorcholic acid (Fernholz Liebig's ana nalen 507, 1? 8. <B> 1933) </B> through various intermediate products.
The free oxy acid forms colorless crystals, which at 280 to 288 cor. melt with decomposition (slightly different, depending on the heating speed); Its methyl ester forms needles from methanol, which at <B> 180 '</B> cor. melt. The acetylated acid melts at 240 to 242 cor., Its methyl ester at 153 to 154 'cor.
1 g of 3-acetoxy-ethio-cholen-d5,6-acid are refluxed for 3 hours with 5 cm of benzene and 5 g of the purest thionyl chloride. It is evaporated with the exclusion of moisture, the chloride soon crystallizing. The slightly yellowish colored product does not actually have a melting point, but decomposes differently depending on the heating speed. Sometimes a melting point of 160 can be observed with re-solidification and possibly renewed melting of the decomposed mass above 300.
The chloride is dissolved in 80 cm 'of dry ether and a dry, ethereal solution of about 1 to 1.5 g of diazomethane is allowed to run in at -10. The mixture is left to stand for a few hours at 0, then for a further 6 hours at room temperature, it is concentrated strongly and petroleum ether is added until it becomes cloudy. The diazoketone crystallizes out. Further amounts are obtained from the mother liquor analogously. A total of 0.7 g of pure product is thus obtained as pale yellowish flakes which melt towards <B> 150 </B> (slightly different depending on the heating rate) with vigorous decomposition.
For the manufacture of the free 21-diazo-pregnen-3-ol-20-one, 1 g of the above acetate is suspended in 30 cm 'of methanol, 16 cm' of a 5 percent solution of potassium hydrogen in methanol are added, and with frequent order swirl for 6 hours at room temperature. The crystals go after about. half an hour in solution.
After adding a little water, the mixture is concentrated strongly in vacuo, the oxydiazo ketone crystallizing out. It is suction filtered, washed with water, getrock net in a vacuum and recrystallized from Xther petroleum ether, whereby it is obtained in slightly yellowish, glossy grains that melt at 144 'with vigorous decomposition; with slow heating the melting point can be found several degrees lower. The yield is almost quantitative.
In contrast to the acetylated diazoketone with digitonin in 80 to 90 percent alcohol, the product precipitates.
0.2 g of 21-diazo-pregnen-3-ol-20-one are heated to 95 minutes with 2 cm3 of the purest glacial acetic acid for about 30 minutes, whereupon the splitting off of gas is complete. After cooling, part of the acetoxy-ketone crystallizes out in the form of beautiful needles. It is filtered off with suction and washed with ether-pentane. The remainder of the mother liquor is obtained in an analogous manner after narrowing in a vacuum. The yield is 0.21 g. The needles contain crystal solvents, they become opaque when heated to <B> 80 '</B> and melt at 180 to 182 cor.
After drying they have the composition C "SH840 °, give a precipitation with digitonin and reduce alkaline silver solution.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH204844T | 1937-03-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH204844A true CH204844A (en) | 1939-05-31 |
Family
ID=4444340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH204844D CH204844A (en) | 1937-03-22 | 1937-03-22 | Process for the preparation of a pregnen-5-ol-3-one-20 derivative. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH204844A (en) |
-
1937
- 1937-03-22 CH CH204844D patent/CH204844A/en unknown
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