DE1643013C3 - Process for the preparation of butenolides - Google Patents
Process for the preparation of butenolidesInfo
- Publication number
- DE1643013C3 DE1643013C3 DE19671643013 DE1643013A DE1643013C3 DE 1643013 C3 DE1643013 C3 DE 1643013C3 DE 19671643013 DE19671643013 DE 19671643013 DE 1643013 A DE1643013 A DE 1643013A DE 1643013 C3 DE1643013 C3 DE 1643013C3
- Authority
- DE
- Germany
- Prior art keywords
- preparation
- reaction
- triphenyl
- butenolides
- phosphonium
- 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
- 238000002360 preparation method Methods 0.000 title claims description 5
- 238000000034 method Methods 0.000 title claims description 4
- 239000002904 solvent Substances 0.000 claims description 5
- VIHAEDVKXSOUAT-UHFFFAOYSA-N 2-Furanone Chemical group O=C1OCC=C1 VIHAEDVKXSOUAT-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- -1 phosphonium halides Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- BZKBCQXYZZXSCO-UHFFFAOYSA-N sodium hydride Chemical compound [H-].[Na+] BZKBCQXYZZXSCO-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-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
- 239000002585 base Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N Triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene dichloride Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical compound [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 description 2
- 150000004714 phosphonium salts Chemical group 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZKXBIMMWFBSXGS-UHFFFAOYSA-N CN(P(=O)(N)N)O Chemical compound CN(P(=O)(N)N)O ZKXBIMMWFBSXGS-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N Nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N Potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N Sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N Triphenylphosphine oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001738 cardenolides Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drugs Drugs 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N n-methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012053 oil suspension Substances 0.000 description 1
- 125000004430 oxygen atoms Chemical group O* 0.000 description 1
- 125000004437 phosphorous atoms Chemical group 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Description
In dem Patent 1643014 ist ein Verfahren zur Herstellung von Cardennoliden angegeben worden, nach dem man Triphenyl-(20-oxo-pregnan-21 -yl-oxycarbonyl-alkyl)-phosphoniumsalze mit starken Basen in einem gegen die Reaktionspartner inerten Lösungsmittel umsetzt.In the patent 1643014 a process for the production of cardenolides has been specified according to the triphenyl (20-oxo-pregnane-21-yo-oxycarbonyl-alkyl) -phosphonium salts with strong bases in a solvent inert to the reactants.
Es wurde nun gefunden, daß man diese Reaktion generell bei Steroiden ausführen kann, die letztlich eine sekundäre a-Ketolstruktur besitzen.It has now been found that this reaction can generally be carried out with steroids, which ultimately have a secondary α-ketol structure.
Die Erfindung betrifft Butenolide der allgemeinenThe invention relates to butenolides in general
Formelformula
worin R1 und R2 zusammen mit den benachbarten C-Atomen 4' und 5' des Butenolidringes einen Steroidrest, der auch substituiert sein kann, bedeuten, und ein Verfahren zu deren Herstellung, dadurch gekennzeichnet, daß man gemäß Hauptpatent 1643 014 Triphenyl-fa-yl-oxy-carbonyl-alkylJ-phosphonium-halogenide von Ketosteroiden in einem gegen die Reaktionspartner inerten Lösungsmittel mit einer starken Base umsetzt.wherein R 1 and R 2 together with the adjacent carbon atoms 4 'and 5' of the butenolide ring signify a steroid radical, which can also be substituted, and a process for their preparation, characterized in that triphenyl-fa -yl-oxy-carbonyl-alkylJ-phosphonium halides of ketosteroids in a solvent inert to the reactants with a strong base.
Als Substituenten am Steroidrest kommen vorzugsweise in Betracht: niedere Acyloxy-, niedere Alkoxy- und niedere Alkylgruppen, die Benzoyloxy- oder Ketogruppe, ein Fluoratom, ein Chloratom an einem doppelt gebundenen C-Atom sowie Kohlcnstoffdoppelbindungen. Preferred substituents on the steroid radical are into consideration: lower acyloxy, lower alkoxy and lower alkyl groups, the benzoyloxy or keto group, a fluorine atom, a chlorine atom on a double bonded carbon atom and carbon double bonds.
Als starke Basen für die erfindungsgemäße Rcaktion kommen z.B. in Frage: Alkalimetallhydride, vorzugsweise Natriumhydrid, Alkalimetallalkoholate, vorzugsweise Kalium-tcrt.-butylat, Alkalimetallhydroxide vorzugsweise Natrium- und Kal.umhydroxid, oder Alkalimetallamide, wie Natnumamid. Als merte Lösungsmittel können beispielsweise bcnut/i werden: Dimethylsulfoxid. Dimcihyliormamid. Dimcthylacctarnid, N-Mcthylpyrrolidon oder Hcxamcthylphosnhorsäuretriamid. . .Possible strong bases for the reaction according to the invention are, for example: alkali metal hydrides, preferably sodium hydride, alkali metal alcoholates, preferably potassium tert-butoxide, alkali metal hydroxides preferably sodium and potassium hydroxide, or alkali metal amides, such as sodium amide. As merte Solvents can for example be bcnut / i: Dimethyl sulfoxide. Dimcihyliormamid. Dimcthylacctarnid, N-methylpyrrolidone or hydroxy-methylphosphoric acid triamide. . .
Die Reaktion verläuft im allgemeinen bei Temperaturen von etwa 100 C mit optimaler Ausbeute. Die Reaktion kann auch bei tieferen Temperaturen durchgerührt werden, es ist dann jedoch die Abspaltung des Triphenylphosphinoxids aus dem Rcaktionskomplex erschwert. Bei höheren Temperaturen ,st unter Umständen mit Nebenreakt.onen zu rechnenThe reaction generally takes place at temperatures of about 100 C with optimal yield. The reaction can also take place at lower temperatures be carried out, but it is then the split-off of the triphenylphosphine oxide from the reaction complex made difficult. At higher temperatures, st side reactions are to be expected under certain circumstances
Es ist zweckmäßig, die Reaktion unter Ausschluß von Luftsauerstoff vorzunehmen, da durch Luftsauerstoff Nebenreaktionen begünstigt werden.It is advisable to carry out the reaction with the exclusion of atmospheric oxygen, since atmospheric oxygen Side reactions are favored.
Es war nicht zu erwarten, daß sich diese heterocyclischen Verbindungen so leicht nach der Willig-Methode bilden würden, da be. der Wittig-Reaktion in einem solchen Fall ein Bicyclus als Zwischenstufe auftritt Die Ausbildung eines solchen B.cyclus. in dem dazu die miteinander reagierenden Phosphor- und Sauerstoff-Atome eine ganz bestimmte räumliche Stellung zueinander einnehmen müssen, ist normalerweise sehr erschwert.It was not to be expected that these heterocyclic compounds would form so readily by the Willig method that be. the Wittig reaction in such a case a bicycle occurs as an intermediate stage The formation of such a B. cycle. in that the reacting phosphorus and oxygen atoms have to take a very specific spatial position to one another, is usually very difficult.
Die Herstellung der Tnphenyl-(«-yl-oxycarbonylalkvD-phosphoniumsalze und deren Derivate kann erfolgen durch Veresterung von „-Hydroxy-ketosteroiden mit „-Halogencarbonsäuren und anschließendem Austausch des Halogenatoms gegen den Phosphoniumsalzrest. Die crfindungsgcmaß herstellbaren Substanzen sind wertvolle Arzneimittel.The preparation of the phenyl- ("- yl-oxycarbonylalkvD-phosphonium salts and their derivatives can take place by esterification of -hydroxy-ketosteroids with "-halocarboxylic acids and subsequent exchange of the halogen atom for the Phosphonium salt residue. The determinations that can be made Substances are valuable medicines.
Beispiele A. Herstellung der AusgangsmaterialienExamples A. Preparation of raw materials
lOmMol des „-Hydroxy-zi-keto-steroides werden in 50 ml absolutem Dioxan aufgenommen und mit 1 -> ml (l5mMol) Pyridin versetzt. Dazu tropft man im Verlauf einer Stunde 1,1 ml(12 mMol) Bromacctylbromid in 25 ml absolutem Äther gelöst, und rührt die Mischung etwa 15 Stunden bei Raumtemperatur. Man verdünnt mit Äther, wäscht dreimal mit Wasser, trocknet die Ätherphase, zieht das Lösungsmittel im Vakuum ab und kristallisiert bzw. FdIIt den Ester um. Die Ausbeuten betragen etwa 90%. Entsprechend lassen sich andere Halogenderivate herstellen.lOmMol of the "-hydroxy-zi-keto-steroid taken up in 50 ml of absolute dioxane and with 1 -> ml (15 mmol) of pyridine were added. 1.1 ml (12 mmol) of bromoacctyl bromide are added dropwise over the course of one hour dissolved in 25 ml of absolute ether, and the mixture is stirred for about 15 hours at room temperature. It is diluted with ether, washed three times with water, the ether phase is dried, the solvent is drawn off in the Vacuum and crystallize or FdIIt the ester. The yields are about 90%. Other halogen derivatives can be produced accordingly.
10 mMol des so erhaltenen Esters werden mit 3,2 g (12 mMoDTriphenylphosphin in 200 ml Nitromcthan 48 Stunden bei Raumtemperatur gerührt. Man engt im Vakuum ein und fällt anschließend das Phosphoniumsalz mit absolutem Äther aus. Die Ausbeute beträgt etwa 90%.10 mmol of the ester obtained in this way are mixed with 3.2 g (12 mmol of triphenylphosphine in 200 ml of nitromethane Stirred for 48 hours at room temperature. It is concentrated in vacuo and the phosphonium salt is then precipitated with absolute ether. The yield is about 90%.
B. Beispiel 1B. Example 1
Man suspendiert 744 mg Natrium-Ölsuspension (55%ig) in 20 ml Dimethylsulfoxid und tropft unter Stickstoff bei 60 "C eine Lösung von 10 g Triphenyl-(3 - oxo - 5u - cholestan - 2« - yloxycarbonylmethyl)-phosphoniumbromid (erhalten aus 5«-Cholestan-2«-ol-3-on-acetat durch Verseifung und anschließende Umsetzung gemäß A. in 140 ml Dimethylsulfoxid im Verlauf von 3 Stunden hinzu. Man rührt weitere 4 Stunden bei 6O0C gießt in essigsaure Kochsalzlösung ein, filtriert den öligen Niederschlag ab, nimmt ihn, nachdem man mit Wasser gewaschen hat. in Methylenchlorid auf, wäscht die Lösung mit Kochsalzlösung, trocknet sie und engt sie zur Trockne ein.744 mg of sodium oil suspension (55%) are suspended in 20 ml of dimethyl sulfoxide and a solution of 10 g of triphenyl (3-oxo-5u-cholestane-2 ”-yloxycarbonylmethyl) phosphonium bromide (obtained from 5 «cholestane-2" -ol-3-one-acetate by saponification and subsequent reaction according to A. in 140 ml of dimethyl sulfoxide in the course of 3 hours added. stirring is continued for 4 hours at 6O 0 C is poured into an acetic acid solution of sodium chloride, filtered the oily precipitate is removed, it is taken up in methylene chloride after washing with water, the solution is washed with sodium chloride solution, dried and concentrated to dryness.
Nach dem Chromatographieren an Silicagc! erhalt man 1,1 g öliges 3-(Carboxymethy)en)-5«-cholestan-2l3b^2ft After chromatography on silica gel! 1.1 g of oily 3- (Carboxymethy) en) -5 "-cholestane-2l3b ^ 2ft are obtained
Man löst 630 mg 50%ige Natriumhydridsuspension in 25 ml Dimcthylsulfoxid unter Stickstoffatmosphüre bei 100 C und tropft unter Rühren im Verlauf einer Stunde eine Lösung von 7,44 g Triphenyl-(3-methoxy-16-oxo-I' λ 5lU"-östratrien - 17/;'-yloxycarbonylme-• hyl)-phosphoniumbromid (Schmelzpunkt 121 bis 123 C) in 100 ml Dimelhylsulfoxid hinzu. Man rührt weitere 4 Stunden bei 100 C unter Stickstoff, kühlt ab und gießt in angesäuerte Kochsalzlösung ein. Man filtriert ab. wäscht mit Wasser, trocknet, reinigt das Butenolid durch Chromatographie an Silicagel und kristallisiert aus Essigsüureäthylestcr um. Man erhält KvCarboxymethylen-östradioW-methyläther-16b -'17-UiCtOn vorn Schmelzpunkt 231 bis 234 C.630 mg of 50% strength sodium hydride suspension is dissolved in 25 ml of dimethyl sulfoxide under a nitrogen atmosphere at 100 ° C. and a solution of 7.44 g of triphenyl (3-methoxy-16-oxo-1 ' λ 5lU "oestratriene is added dropwise with stirring over the course of one hour - 17 /; '- yloxycarbonylmethyl) phosphonium bromide (melting point 121 to 123 ° C.) in 100 ml of dimethyl sulfoxide. The mixture is stirred for a further 4 hours at 100 ° C. under nitrogen, cooled and poured into acidified sodium chloride solution. Washes with water, dries, purifies the butenolide by chromatography on silica gel and recrystallizes from ethyl acetate. Kv-carboxymethylene-estradioW-methylether-16b -'17-UiCtOn with a melting point of 231 to 234 ° C. is obtained.
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DESC040363 | 1967-03-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1643013C3 true DE1643013C3 (en) | 1977-12-08 |
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