DE1643022C3 - Process for the preparation of 21-esters of the 11a, 21-dihydroxysteroids with a branched-chain ester residue in the 21-position as well as the corresponding 6α-fluoro-11α-hydroxy-21-acyloxy-16α-methyl-1,4pregnadiene-3.20- dione intermediates - Google Patents
Process for the preparation of 21-esters of the 11a, 21-dihydroxysteroids with a branched-chain ester residue in the 21-position as well as the corresponding 6α-fluoro-11α-hydroxy-21-acyloxy-16α-methyl-1,4pregnadiene-3.20- dione intermediatesInfo
- Publication number
- DE1643022C3 DE1643022C3 DE19671643022 DE1643022A DE1643022C3 DE 1643022 C3 DE1643022 C3 DE 1643022C3 DE 19671643022 DE19671643022 DE 19671643022 DE 1643022 A DE1643022 A DE 1643022A DE 1643022 C3 DE1643022 C3 DE 1643022C3
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- Prior art keywords
- branched
- hydroxy
- fluoro
- acyloxy
- methyl
- 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.)
- Expired
Links
- 230000000875 corresponding Effects 0.000 title claims description 4
- 238000000034 method Methods 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title claims description 3
- 150000002148 esters Chemical group 0.000 title 1
- 239000000543 intermediate Substances 0.000 title 1
- 238000005886 esterification reaction Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene dichloride Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 230000001264 neutralization Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- -1 steroid alcohols Chemical class 0.000 description 3
- PGZVFRAEAAXREB-UHFFFAOYSA-N 2,2-dimethylpropanoyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC(=O)C(C)(C)C PGZVFRAEAAXREB-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M NaHCO3 Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 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
- GUHFLRTWNHWJBS-VLTGGNAYSA-N (8R,9S,10S,13S)-17-acetyl-10,13-dimethyl-1,2,4,5,6,7,8,9,11,12-decahydrocyclopenta[a]phenanthren-3-one Chemical compound C1CC2CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1C1=CC=C(C(=O)C)[C@@]1(C)CC2 GUHFLRTWNHWJBS-VLTGGNAYSA-N 0.000 description 1
- VUAXHMVRKOTJKP-UHFFFAOYSA-N 2,2-dimethylbutyric acid Chemical compound CCC(C)(C)C(O)=O VUAXHMVRKOTJKP-UHFFFAOYSA-N 0.000 description 1
- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-ethylbutanoic acid Chemical compound CCC(CC)C(O)=O OXQGTIUCKGYOAA-UHFFFAOYSA-N 0.000 description 1
- MLMQPDHYNJCQAO-UHFFFAOYSA-N 3,3-dimethylbutyric acid Chemical compound CC(C)(C)CC(O)=O MLMQPDHYNJCQAO-UHFFFAOYSA-N 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N Chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N Isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 229940050176 Methyl Chloride Drugs 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N Pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- AVGAIPMGSIOHFZ-UHFFFAOYSA-N dichloromethane;2-propan-2-yloxypropane Chemical compound ClCCl.CC(C)OC(C)C AVGAIPMGSIOHFZ-UHFFFAOYSA-N 0.000 description 1
- RYPWQHONZWFXBN-UHFFFAOYSA-N dichloromethyl(methylidene)-$l^{3}-chlorane Chemical compound ClC(Cl)Cl=C RYPWQHONZWFXBN-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008079 hexane Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000001665 trituration Methods 0.000 description 1
Description
Es ist bekannt, daß die selektive Veresterung einer 21-Hydroxylgruppe bei gleichzeitiger Anwesenheit einer 1 Ια-Hydroxylgruppe mit geradkettigen Carbonsäuren in technisch brauchbaren Ausbeuten nach den üblichen Veresterungsmethoden nicht möglich ist. Um eine selektive Veresterung in bezug auf die Veresterungsgeschwindigkeit gleichwertiger Hydroxylgruppen zu erzwingen, wurde vorgeschlagen, deutsche Auslegeschrift 11 34 670), die Veresterung in Gegenwart solcher Katalysatoren durchzuführen, die mit der zu veresternden Hydroxylgruppe und einer im Molekül gleichzeitig anwesenden Carbonylgruppe einen Chelatring zu bilden vermögen.It is known that the selective esterification of a 21-hydroxyl group in the simultaneous presence a 1 Ια-hydroxyl group with straight-chain carboxylic acids in technically useful yields according to the usual esterification methods is not possible. A selective esterification with respect to the rate of esterification To enforce equivalent hydroxyl groups has been proposed, German Auslegeschrift 11 34 670) to carry out the esterification in the presence of such catalysts that are to be esterified with Hydroxyl group and a carbonyl group simultaneously present in the molecule form a chelate ring able to form.
Es wurde nun gefunden, daß eine selektive Veresterung der 2!-Hydroxylgruppe neben einer gleichzeitig anwesenden 1 Ια-Hydroxylgruppe auch ohne Zusatz der den selektiven Reaktionsablauf katalysierenden Reagentien möglich ist, wenn man die 21-HydroxyI-gruppe statt mit geradkettigen organischen Carbonsäuren mit verzweigtkettigen Carbonsäuren oder deren Säurederivaten verestert.It has now been found that a selective esterification of the 2! -Hydroxyl group in addition to one at the same time 1 Ια-hydroxyl group present even without the addition of the catalyzing the selective course of the reaction Reagent is possible if you have the 21-HydroxyI group instead of straight-chain organic carboxylic acids with branched-chain carboxylic acids or their Esterified acid derivatives.
Die vorliegende Erfindung betrifft somit ein Verfahren zur Herstellung von 1 la-Hydroxy-21-acyloxysteroiden mit verzweigtkettigem 21-Acylrest aus entsprechenden 1 la,21-Dihydroxysteroiden durch Veresterung der 21-Hydroxylgruppe nach an sich bekannten Methoden, dadurch gekennzeichnet, daß man zur Veresterung eine verzweigtkettige Carbonsäure oder deren Säurederivat verwendet.The present invention thus relates to a process for the preparation of 1 la-hydroxy-21-acyloxysteroids with branched 21-acyl radical from corresponding 11a, 21-dihydroxysteroids by esterification of the 21-hydroxyl group according to known ones Methods, characterized in that a branched-chain carboxylic acid or for the esterification their acid derivative is used.
Zur erfindungsgemäßen selektiven Veresterung der vorliegenden 21-Hydroxylgruppe kommen alle gesättigten oder ungesättigten und substituierten, z. B. durch Halogenatome, Hydroxygruppen, oder unsubstituierten Carbonsäuren oder deren Säurederivate mit verzweigter Kohlenstoffkette, wie sie der Fachmann allgemein üblich zur Veresterung von Steroidalkoholen verwendet, in Frage. Als vorzugsweise geeignete verzweigtkettige Carbonsäuren seien beispielsweise Trimethylessigsäure, Dimethylessigsäure, Diäthylessigsäure, t-Butylessigsäure, 2,2-Dimethylbuttersäure und andere Genannt.For the selective esterification of the present 21-hydroxyl group according to the invention, all saturated ones come or unsaturated and substituted, e.g. B. by halogen atoms, hydroxyl groups, or unsubstituted Carboxylic acids or their acid derivatives with a branched carbon chain, as generally known to the person skilled in the art commonly used for the esterification of steroid alcohols in question. As preferably suitable branched chain Carboxylic acids are, for example, trimethyl acetic acid, dimethyl acetic acid, diethyl acetic acid, t-butylacetic acid, 2,2-dimethylbutyric acid and other called.
Der glatte Ablauf der erfindungsgemüßen Veresterung war nicht voraussehbar, nachdem dem Fachmann bekannt ist, daß bei Veresterung eines Ilu,2l-I)ihydroxysteroids mit einer geradkettigen Carbonsäure, wie Essigsäure, das entsprechende I Iu,2!-Diacetat entsteht. Die Durchführung der selektiven Veresterung mit den erfindungsgemäß anwendbaren verzweigtkettigen Carbonsäuren bzw. deren Süurederivatcn ist grundsätzlich nach den Arbeitsmethoden möglich, wieThe smooth course of the esterification according to the invention was not foreseeable, since the person skilled in the art is aware that the esterification of an Ilu, 2l-I) ihydroxysteroids with a straight-chain carboxylic acid, such as acetic acid, the corresponding I Iu, 2! -diacetate is formed. Carrying out the selective esterification with the branched-chain ones that can be used according to the invention Carboxylic acids or their acid derivatives is basically possible according to the working methods, such as
ίο sie zur Veresterung von Steroidalkoholen gebräuchlich sind. Eine bevorzugte Ausführungsform ist es, das 1 la,2l-Dihydroxysteroid in einem mit Wasser nicht mischbaren Lösungsmittel, wie z. B. Äthylenchlorid, Methylenchlorid, Chloroform oder Essigester, mitίο They are used for the esterification of steroid alcohols are. A preferred embodiment is not to use the 1 la, 2l dihydroxysteroid in one with water miscible solvents, such as. B. ethylene chloride, methylene chloride, chloroform or ethyl acetate, with
Anhydrid der gewünschten verzweigtkettigen Carbonsäure in Gegenwart wäßrigen Alkalis, z. B. wäßrige Natronlauge, umzusetzen. Bei Anwendung einer Reaktionstemperatur von etwa 40°C wird die gewünschte selektive Veresterung der 21-Hydroxylgruppe mit einerAnhydride of the desired branched-chain carboxylic acid in the presence of aqueous alkali, e.g. B. aqueous Caustic soda to implement. When using a reaction temperature of about 40 ° C, the desired selective esterification of the 21-hydroxyl group with a
ao Ausbeute von über 90% der Theorie bereits in etwa 30 min erzielt.ao yield of over 90% of theory achieved in about 30 minutes.
200 g 6a-Fluor-l la,21-dihydroxy-16a-methyl-AM- »5 pregnadien-3,20-dion werden in 2 1 Äthylenchlorid unter gelindem Erwärmen gelöst, die Lösung dann auf 20°C abgekühlt und 500gTrimethylessigsäureanhydrid zugegeben. Man rührt 1 h bei 200C unter N2, erwärmt dann auf 400C und tropft eine Lösung von 215 g NaOH in 1 1 Wasser hinzu. Nach 30 min kühlt man auf 2O0C ab, trennt die organische Phase von der wäßrigen ab. Die organische Phase wird mit Wasser neutral gewaschen, über Na2SO4 getrocknet, filtriert und im Vakuum zur Trockne eingeengt. Der erhaltene Rückstand wird aus Methanol unter Kohlebehandlung umkristallisiert. Man erhält 223 g (91,3% der Theorie) 6a-Fluor - Ha- hydroxy - 21 - trimethylacetoxy -1 όα- methyl-AM-pregnadien-3,20-dion. F. 216 bis 2190C; UV: ε2ί3 = 18 500.200 g of 6a-fluoro-l la, 21-dihydroxy-16a-methyl-A M - »5 pregnadien-3,20-dione are dissolved in 2 1 of ethylene chloride under mild heating, then the solution was cooled to 20 ° C and added 500gTrimethylessigsäureanhydrid . The mixture is stirred for 1 h at 20 ° C. under N 2 , then warmed to 40 ° C. and a solution of 215 g of NaOH in 1 l of water is added dropwise. After 30 min, cooled to 2O 0 C, the organic phase is separated from the aqueous. The organic phase is washed neutral with water, dried over Na 2 SO 4 , filtered and concentrated to dryness in vacuo. The residue obtained is recrystallized from methanol while treating with charcoal. 223 g (91.3% of theory) 6a-fluoro-Ha-hydroxy-21-trimethylacetoxy-1 α-methyl-A M -pregnadiene-3,20-dione are obtained. M.p. 216 to 219 ° C; UV: ε 2ί3 = 18,500.
500 mg 6a-Fluor-l la,21 -dihydroxy-loa-methyl-A1·4-pregnadien-3,20-dion werden in 8 ml Pyridin gelöst, 1 ml Trimethylessigsäureanhydrid zugegeben und unter500 mg of 6a-fluoro-11a, 21-dihydroxy-loa-methyl-A 1 · 4 -pregnadiene-3,20-dione are dissolved in 8 ml of pyridine, 1 ml of trimethyl acetic anhydride is added and under
Rühren und Stickstoff 16 h auf 8O0C erhitzt. Nach Abkühlen rührt man die Reaktionslösung in Eiswasser ein, extrahiert mit Methylenchlorid und wäscht die organische Phase nacheinander mit kalter ln-Schwefelsäure, Wasser, 5%iger Natriumbicarbonatlösung und Wasser aus. Man trocknet über Na2SO4, engt im Vakuum zur Trockne ein und kristallisiert den erhaltenen Rückstand mehrmals aus Methylenchlorid-Isopropyläther um. Man erhält 6a-Fluor-l la-hydroxy-21-trimethylacetoxy-16a-methyl-AM-pregnadien-3,20- dion. F. 210bis214°C.Stirring and nitrogen for 16 h heated to 8O 0 C. After cooling, the reaction solution is stirred into ice water, extracted with methylene chloride and the organic phase is washed out successively with cold 1N-sulfuric acid, water, 5% sodium bicarbonate solution and water. It is dried over Na 2 SO 4 , concentrated to dryness in vacuo and the residue obtained is recrystallized several times from methylene chloride-isopropyl ether. 6a-fluoro-1 la-hydroxy-21-trimethylacetoxy-16a-methyl-A M -pregnadiene-3,20-dione is obtained. Mp 210-214 ° C.
2 g lla,17,21-Trihydroxy-4-pregnen-3,20-dion werden in 20 ml Äthylenchlorid suspendiert, man gibt 5 ml Trimethylessigsäureanhydrid zu und rührt 1 h bei Raumtemperatur unter Stickstoff. Dann erwärmt man auf 400C, tropft eine Lösung von 2,15 g Ätznatron in 10 ml Wasser hinzu und rührt 1 h bei 35°C. Danach wird die abgetrennte organische Phase mit Wasser2 g of IIIa, 17,21-trihydroxy-4-pregnen-3,20-dione are suspended in 20 ml of ethylene chloride, 5 ml of trimethyl acetic anhydride are added and the mixture is stirred for 1 h at room temperature under nitrogen. Then heated to 40 0 C, dropwise added a solution of 2.15 g of sodium hydroxide in 10 ml of water and stirred for 1 h at 35 ° C. Then the separated organic phase is washed with water
neutral gewaschen, über Natriumsulfat getrocknet, filtriert und im Vakuum bis zur Trockne eingeengt. Der Rückstand wird mit Pentan ausgerührt und dann aus Methanol unter Kohlebehandlung umkristallisiert.washed neutral, dried over sodium sulfate, filtered and concentrated to dryness in vacuo. the The residue is stirred with pentane and then recrystallized from methanol while treating with charcoal.
Man erhall 1,941 g 1 iu,17-Dihydmxy-2l-trimelhylacetoxy-4-pregnen-3,20-üion; F. 250 bis 251 C; UV: ew ■--·-- 16 000.1.941 g of 1 iu, 17-Dihydmxy-2l-trimelhylacetoxy-4-pregnen-3,20-üion are obtained; M.p. 250 to 251 C; UV: e w ■ - · - 16,000.
2 g 11α,17,21-Τιϋΐ3'αΓοχ>'-4-ρΐ·ί.·!;ηοη-3,20-ι1ϊοη weiden in 50 ml Methylenchlorid suspendiert, 10,5 ml Trimethylessig.säureanhydricl zugegeben und unter Rühren und in Gegenwart einer Stickstoffatmosphüre mit einer Lösung von 6 g NaOH in 30 ml Wasser bei Raumtemperatur versetzt. Nach I6stündigem Rühren bei Raumtemperatur wird die organische Phase abgetrennt, mit Wasser neutral gewaschen, getrocknet über Na2SO4 und im Vakuum zur Trockne eingeengt. Durch Verreiben des Rückstandes mit Pentan erhält man 2,2945 g 1 In, 17- Dihydroxy-21-trimethylacetoxy-4-pregnen-2 g of 11α, 17,21-Τιϋΐ3'αΓοχ>'- 4-ρΐ · ί In the presence of a nitrogen atmosphere, a solution of 6 g of NaOH in 30 ml of water is added at room temperature. After stirring for 16 hours at room temperature, the organic phase is separated off, washed neutral with water, dried over Na 2 SO 4 and concentrated to dryness in vacuo. By triturating the residue with pentane, 2.2945 g of 1 In, 17-dihydroxy-21-trimethylacetoxy-4-pregnen-
:i,20-dion (97,8% der Theorie); F. 244 bis 248"C; UV: f..ia ■-■ 16 000. : i, 20-dione (97.8% of theory); F. 244 to 248 "C; UV: f .. ia ■ - ■ 16 000.
1 g I la,l7,2l-Trihydroxy-4-prcgnen-3,20-dion werden in 13 ml Methylcnchlorid gelöst. Untre Rühren und in Gegenwart einer Stickstoffatmosphäre werden dieser Lösung 2,5 ml a-Methyl-u-äthyl-capronsüurechlorid und 1,5 g NaOIl in 7,5 ml Wasser zugeset/.t.1 g of I la, 17,2l-trihydroxy-4-pregnen-3,20-dione dissolved in 13 ml of methyl chloride. With stirring and in the presence of a nitrogen atmosphere this solution 2.5 ml of a-methyl-u-ethyl-caproic acid chloride and 1.5 g NaOIl in 7.5 ml water added / .t.
ίο Nach I6stündigem Rühren bei Raumtemperatur wird die organische Phase abgetrennt, mit Wasser neutral gewaschen, getrocknet über Na2SO., und im Vakuum zur Trockne eingeengt. Durch Verreiben des Rückstandes mit Hexan erhält man 1,0305 g 11«, 17-Dihydroxy-2l-(u-methyl-a-äthylhcxanoyl-oxy)-4-prcg- nen-3,20-dion; F. 82 bis 1130C; UV: e213 = !5 460.ίο After stirring for 16 hours at room temperature, the organic phase is separated off, washed neutral with water, dried over Na 2 SO., and concentrated to dryness in vacuo. Trituration of the residue with hexane gives 1.0305 g of 11,17-dihydroxy-2l- (u-methyl-α-ethylhexanoyl-oxy) -4-pregnen-3,20-dione; M.p. 82 to 113 0 C; UV: e 213 =! 5,460.
Claims (4)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DESC040711 | 1967-05-13 |
Publications (1)
Publication Number | Publication Date |
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DE1643022C3 true DE1643022C3 (en) | 1977-08-25 |
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