DD241180A3 - PROCESS FOR PREPARING 3,3 ALPHA BETA, 4,5,6,6 ALPHA-BETA HEXAHYDRO-4BETA-FORMYL-5ALPHA-TRIMETHYLSILYLOXY-2H-CYCLOPENTA BETA FURAN-2-ON - Google Patents
PROCESS FOR PREPARING 3,3 ALPHA BETA, 4,5,6,6 ALPHA-BETA HEXAHYDRO-4BETA-FORMYL-5ALPHA-TRIMETHYLSILYLOXY-2H-CYCLOPENTA BETA FURAN-2-ON Download PDFInfo
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- DD241180A3 DD241180A3 DD23937282A DD23937282A DD241180A3 DD 241180 A3 DD241180 A3 DD 241180A3 DD 23937282 A DD23937282 A DD 23937282A DD 23937282 A DD23937282 A DD 23937282A DD 241180 A3 DD241180 A3 DD 241180A3
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- German Democratic Republic
- Prior art keywords
- furan
- cyclopenta
- hexahydro
- beta
- trimethylsilyloxy
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- RHDGNLCLDBVESU-UHFFFAOYSA-N but-3-en-4-olide Chemical compound O=C1CC=CO1 RHDGNLCLDBVESU-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006227 trimethylsilylation reaction Methods 0.000 claims abstract description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 10
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 5
- VTHIKKVKIVQWHV-UHFFFAOYSA-N chromium(6+) oxygen(2-) pyridine Chemical compound [O-2].[O-2].[O-2].[Cr+6].C1=CC=NC=C1 VTHIKKVKIVQWHV-UHFFFAOYSA-N 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 16
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 229940094443 oxytocics prostaglandins Drugs 0.000 abstract description 3
- 230000002997 prostaglandinlike Effects 0.000 abstract description 3
- 150000003180 prostaglandins Chemical class 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 abstract 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000012027 Collins reagent Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 4
- NPRDHMWYZHSAHR-UHFFFAOYSA-N pyridine;trioxochromium Chemical compound O=[Cr](=O)=O.C1=CC=NC=C1.C1=CC=NC=C1 NPRDHMWYZHSAHR-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 125000006239 protecting group Chemical group 0.000 description 3
- -1 tert-butyl-dimethylsilyloxy group Chemical group 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- JPVUWCPKMYXOKW-UHFFFAOYSA-N 4-phenylbenzoyl chloride Chemical compound C1=CC(C(=O)Cl)=CC=C1C1=CC=CC=C1 JPVUWCPKMYXOKW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000005835 Pfitzner-Moffat oxidation reaction Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000002009 allergenic effect Effects 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-HOSYLAQJSA-N cyclopentanol Chemical class O[13CH]1CCCC1 XCIXKGXIYUWCLL-HOSYLAQJSA-N 0.000 description 1
- FDSGHYHRLSWSLQ-UHFFFAOYSA-N dichloromethane;propan-2-one Chemical compound ClCCl.CC(C)=O FDSGHYHRLSWSLQ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Racemisches oder optisch aktives 3,3ab,4,5,6,6ab-Hexahydro-5a-hydroxy-4b-hydroxymethyl-2H-cyclopenta/b/furan-2-on laesst sich nach Trimethylsilylierung der primaeren und sekundaeren Hydroxylgruppe mit einem Chrom(VI)oxid-Pyridin-Komplex in Dichlormethan selektiv und in hoher Ausbeute zu racemischem bzw. optisch aktivem 3,3ab,4,5,6,6ab-Hexahydro-4b-formyl-5a-trimethylsilyloxy-2H-cyclopenta-/b/-furan-2-on oxydieren. Die erfindungsgemaessen Verbindungen stellen wichtige Zwischenprodukte fuer racemische bzw. optisch aktive Prostaglandine und prostaglandinaehnliche Verbindungen dar.Racemic or optically active 3,3ab, 4,5,6,6ab-hexahydro-5a-hydroxy-4b-hydroxymethyl-2H-cyclopenta / b / furan-2-one can be obtained after trimethylsilylation of the primary and secondary hydroxyl groups with a chromium ( VI) oxide-pyridine complex in dichloromethane selectively and in high yield to racemic or optically active 3,3ab, 4,5,6,6ab-hexahydro-4b-formyl-5a-trimethylsilyloxy-2H-cyclopenta / b / - oxidize furan-2-one. The compounds according to the invention are important intermediates for racemic or optically active prostaglandins and prostaglandin-like compounds.
Description
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Die Erfindung betrifft ein Verfahren zur Herstellung von racemischen oder optisch aktivem 3,3a/3,4,5,6,6aß-Hexahydro-4/3-formyl-5a-trimethylsilyloxy-2H-cyclopenta/b/furan-2-on 3, einem wichtigen Zwischenprodukt für die Synthese von racemischen bzw. optisch aktiven Prostaglandinen und prostaglandinähnlichen Verbindungen.The invention relates to a process for the preparation of racemic or optically active 3,3a / 3,4,5,6,6aß-hexahydro-4/3-formyl-5a-trimethylsilyloxy-2H-cyclopenta / b / furan-2-one 3 , an important intermediate for the synthesis of racemic or optically active prostaglandins and prostaglandin-like compounds.
Die Umwandlung von 3,3a/3,4,5/6,6a/3-Hexahydro-5a-hydroxy-4jS-hydroxymethyl-2H-cyclopenta/b/furan-2-on 1 in einen Aldehyd, der wie 3 an der sekundären Hydroxylgruppe eine Schutzgruppe trägt, gelingt in der Weise, daß die primäre Hydroxylgruppe im ersten Schritt selektiv trimethylsilyliert oder trityliert, im zweiten Schritt die noch freie sekundäre Hydroxylgruppe mit Acetanhydrid, Benzoylchlorid oder p-Phenyl-benzoylchlorid acyliert, im dritten Schritt die Schutzgruppe an der primären Hydroxylgruppe selektiv durch saure Hydrolyse entfernt und im vierten Schritt die jetzt freie primäre Hydroxylgruppe zum Aldehyd oxydiert wird (I.Tömösközi, L Gruber, G.Koväcs, I.Szekely und V.Simonidesz, Tetrahedron Letters 1976,4639).The conversion of 3,3a / 3,4,5 / 6,6a / 3-hexahydro-5a-hydroxy-4jS-hydroxymethyl-2H-cyclopenta / b / furan-2-one into an aldehyde, which was prepared as described at 3 carries secondary hydroxyl group protecting group succeeds in such a way that the primary hydroxyl group in the first step selectively trimethylsilylated or tritylated, in the second step the acylated still free secondary hydroxyl group with acetic anhydride, benzoyl chloride or p-phenyl benzoylchlorid, in the third step, the protective group on the The primary hydroxyl group is selectively removed by acid hydrolysis and in the fourth step, the now free primary hydroxyl group is oxidized to the aldehyde (I.Tömösközi, L Gruber, G.Kovacs, I.Szekely and V.Simonidesz, Tetrahedron Letters 1976,4639).
Von gleichen Autoren wird weiterhin die Möglichkeit aufgezeigt, das S^ajSAB^^a/S-Hexahydro-Ba-hydroxy^-hydroxymethyl-2H-cyclopenta/b/furan-2-on 1 auch in den entsprechenden chemisch allerdings instabilen Aldehyd mit freier, sekundärer Hydroxylgruppe umzuwandeln (Tetrahedron Letters 1976,4639). Dies erfolgt durch selektive Oxydation der primären Hydroxylgruppe mit Dicyclohexylcarbodiimid in Dimethylsulfoxid nach der Methode von Pfitzner-Moffat. Darüber hinaus ist aus der DE-OS 2618663 bekannt, 2a-(6-Alkoxycarbonyl-hex-2(Z)-enyl)-3/3-hydroxymethyl-4atetrahydropyranyloxy-cyclopentanol durch Umsetzung mit einem Chromtrioxid/Pyridin-Komplex in einem inerten organischen Lösungsmittel, beispielsweise Dichlormethan, bei niedriger Temperatur, vorzugsweise bei 00C, in 2a-(6-Alkoxycarbonyl-hex-2(Z)-enyl)-3/3-formyl-4<*-tetrahydropyranyloxy-cyclopentanol umzuwandeln. Der Nachteil dieses Verfahrens, eine Verbindung mit einer primären und einer sekundären Hydroxylgruppe mit Collins-Reagens unter Erhalt der ungeschützten sekundären Hydroxylgruppe zum entsprechenden Hydroxyaldehyd zu oxydieren, liegt insbesondere in der fehlenden Selektivität und damit verbunden in einer unbefriedigenden Ausbeute, da sekundäre Hydroxylgruppen durch Chrom(VI)-oxid leichter oxydierbar sind als primäre Hydroxylgruppen. Dieses Verfahren ist deshalb für weiterführende Synthesen zur Herstellung von Prostaglandinen und prostaglandinähnlichen Verbindungen nicht geeignet.The same authors continue to show the possibility that the S ^ ajSAB ^^ a / S-hexahydro-Ba-hydroxy ^ -hydroxymethyl-2H-cyclopenta / b / furan-2-one 1 in the corresponding chemically unstable aldehyde with free to convert secondary hydroxyl group (Tetrahedron Letters 1976,4639). This is done by selective oxidation of the primary hydroxyl group with dicyclohexylcarbodiimide in dimethylsulfoxide according to the method of Pfitzner-Moffat. In addition, it is known from DE-OS 2618663, 2a- (6-alkoxycarbonyl-hex-2 (Z) -enyl) -3 / 3-hydroxymethyl-4atetrahydropyranyloxy-cyclopentanol by reaction with a chromium trioxide / pyridine complex in an inert organic Solvent, for example dichloromethane, at low temperature, preferably at 0 0 C, in 2a- (6-alkoxycarbonyl-hex-2 (Z) -enyl) -3 / 3-formyl-4 <* - tetrahydropyranyloxy-cyclopentanol to convert. The disadvantage of this process of oxidizing a compound having a primary and a secondary hydroxyl group with Collins reagent to give the unprotected secondary hydroxyl group to the corresponding hydroxyaldehyde is in particular the lack of selectivity and thus in an unsatisfactory yield, since secondary hydroxyl groups by chromium ( VI) oxide are more easily oxidized than primary hydroxyl groups. This method is therefore unsuitable for further syntheses for the production of prostaglandins and prostaglandin-like compounds.
Ferner ist aus Chem. Comm. 1972,1120 bekannt, bei der Umwandlung eines substituierten Cyclopentanols in das entsprechende Cyclopentanon durch Oxydation mit Collins-Reagens, die weiteren sekundären Hydroxylgruppen, welche nicht oxydiert werden sollen, durch Trimethylsilylierung wirksam vor der Reaktion mit Chrom(VI)-oxid zu schützen.Furthermore, Chem. Comm. 1972,1120, in the conversion of a substituted cyclopentanol into the corresponding cyclopentanone by oxidation with Collins reagent to protect the additional secondary hydroxyl groups which are not to be oxidized by trimethylsilylation effectively from reaction with chromium (VI) oxide.
Auch andere Silyloxygruppen, beispielsweise die tert.-Butyl-dimethylsilyloxygruppe, sind gegenüber Collins-Reagens stabil. Verbindungen, die freie Hydroxylgruppen neben tert.-Butyl-dimethylsilyloxygruppen enthalten, können deshalb unter Erhalt der tert.-Butyl-dimethylsilyloxygruppe mit Collins-Reagens zu Carbonylverbindungen oxydiert werden. Nachteilig ist hierbei, daß ein Verfahren über mehrere Syntheseschritte stets mit Ausbeuteverlusten verbunden ist.Other silyloxy groups, for example the tert-butyl-dimethylsilyloxy group, are also stable to Collins reagent. Compounds containing free hydroxyl groups besides tert-butyl-dimethylsilyloxy groups can therefore be oxidized to carbonyl compounds to give the tert-butyl-dimethylsilyloxy group with Collins reagent. The disadvantage here is that a process over several synthesis steps is always associated with yield losses.
Das Ziel der Erfindung besteht darin, S^a/iAS^^a^Hexahydro-Ba-hydroxy^/J-hydroxymethyl^H-cyclopenta/b/furan^-on 1 in racemischer oder optisch aktiver Form in ein für weitere Umsetzungen ausreichend stabiles Derivat des 3,3a/3,4,5,6,6a/3-Hexahydro-4^-formyl-5o:-hydroxy-2H-cyclopenta/b/furan-2-ons umzuwandeln. Dabei ist der Einsatz des Allergien hervorrufenden Dicyclohexylcarbodiimids zu vermeiden, die Zahl der notwendigen Synthesestufen zu vermindern und die Gesamtausbeute der Umwandlung zu erhöhen.The object of the invention is to provide S ^ a / iAS ^^ a ^ hexahydro-Ba-hydroxy ^ / J-hydroxymethyl ^ H-cyclopenta / b / furan ^ -one 1 in racemic or optically active form in a solution sufficient for further reactions stable derivative of 3,3a / 3,4,5,6,6a / 3-hexahydro-4 ^ -formyl-5o: -hydroxy-2H-cyclopenta / b / furan-2-one convert. The use of the allergenic dicyclohexylcarbodiimide should be avoided, the number of synthesis steps required to be reduced and the overall yield of the conversion increased.
Dieses Ziel wird dadurch erreicht, daß man erfindungsgemäß racemisches oder optisch aktives 3,3aß,4,5,6,6a/3-Hexahydro-5ahydroxy^/S-hydroxymethyl^H-cyclopenta/b/furan^-on 1 mit einem geeigneten Trimethylsilylierungsmittel in racemisches oder optisch aktives S^a/SAS.e^a/S-Hexahydro-Ba-trimethylsilyloxy^/S-trimethylsilyloxymethyl^H-cyclopenta/b/furan^-on 2 überführt und dieses in Dichlormethan mit einem Chrom(VI)oxid-Pyridin-Komplex oxydierte Damit gelingt es überraschenderweise, nach Einführung gleichartiger Schutzgruppen an der primären und der sekundären Hydroxylgruppe selektiv nur die primäre Hydroxyfunktion zu oxydieren. Diese völlig selektiv verlaufende Oxydation liefert den Aldehyd 3 in hohen Ausbeuten.This object is achieved in that according to the invention racemic or optically active 3,3aß, 4,5,6,6a / 3-hexahydro-5ahydroxy ^ / S-hydroxymethyl ^ H-cyclopenta / b / furan ^ -one 1 with a suitable Trimethylsilylierungsmittel in racemic or optically active S ^ a / SAS.e ^ a / S-hexahydro-Ba-trimethylsilyloxy ^ / S-trimethylsilyloxymethyl ^ H-cyclopenta / b / furan ^ -one 2 converted and this in dichloromethane with a chromium (VI Oxidized Oxidation-Pyridine Complex Surprisingly, after the introduction of similar protective groups on the primary and secondary hydroxyl groups, it is possible to selectively oxidize only the primary hydroxyl function. This completely selective oxidation provides the aldehyde 3 in high yields.
Die Trimethylsilylierung wird in an sich bekannter Weise durch Erhitzen mit Hexamethyldisilazan, Umsetzung mit Trimethylchlorsilan/Hexamethyldisilazan/Pyridin oder Trimethylchlorsilan/Triethylamin durchgeführt.The trimethylsilylation is carried out in a manner known per se by heating with hexamethyldisilazane, reaction with trimethylchlorosilane / hexamethyldisilazane / pyridine or trimethylchlorosilane / triethylamine.
Der für die Oxydation erforderliche Chrom(VI)oxid-Pyridin-Komplex wird entweder als Substanz eingesetzt oder in situ aus Chrom(VI)oxid und Pyridin erzeugt. Es wird bei Temperaturen zwischen 0 und 40°C, vorzugsweise bie 20 bis 25°C, oxydiert.The required for the oxidation of chromium (VI) oxide-pyridine complex is either used as a substance or generated in situ from chromium (VI) oxide and pyridine. It is oxidized at temperatures between 0 and 40 ° C, preferably from 20 to 25 ° C.
Ausführungsbeispiele Beispiel 1Exemplary embodiments Example 1
20g (±)-3,3a/3,4,5,6,6y3-Hexahydro-5a;-hydroxy-4/3-hydroxymethyl-2H-cyclopenta/b/furan-2-on 1 werden in 100ml absolutem Pyridin gelöst und nacheinander mit 20ml Hexamethyldisilazan und 10 ml Trimethylchlorsilan versetzt. Nach 1 h bei Raumtemperatur wird der Ansatz von 200 ml Ether versetzt und nacheinander mit einer 5%igen Natriumhydrogencarbonatlösung und mit Wasser ausgeschüttelt. Die etherische Phase wird mit Natriumsulfat getrocknet, filtriert und das Filtrat im Vakuum eingeengt. Der verbleibende Rückstand wird im Vakuum destilliert.20 g (±) -3.3a / 3,4,5,6,6y3-hexahydro-5a; -hydroxy-4/3-hydroxymethyl-2H-cyclopenta / b / furan-2-one 1 are dissolved in 100 ml of absolute pyridine and 20 ml of hexamethyldisilazane and 10 ml of trimethylchlorosilane were added successively. After 1 h at room temperature, the batch of 200 ml of ether is added and shaken out in succession with a 5% strength sodium bicarbonate solution and with water. The ethereal phase is dried with sodium sulfate, filtered and the filtrate is concentrated in vacuo. The remaining residue is distilled in vacuo.
Ausbeute: 32g (82,2% d.Th.);Yield: 32 g (82.2% of theory);
Kp104bis106°C/7- 10~3Torr;Bp104 to 106 ° C / 7-10 -3 Torr;
C14H28O4Si2 316,44C 14 H 28 O 4 Si 2 316.44
1H-NMR: 3,6ppm(d,2H, R-CH2-OSiMe3) 1 H-NMR: 3.6 ppm (d, 2H, R-CH 2 -OSiMe 3 )
4,15ppm(m, 1H,5-CH)4.15ppm (m, 1H, 5-CH)
5,0ppm(m,1H,6a-CH)5,0ppm (m, 1H, 6a-CH)
Optisch aktive 3,3aj8,4,5,6,6a/3-Hexahydro-5a:-trimethylsilyloxy-4/3-trimethylsilyloxymethyl-2H-cyclopenta/b/furan-2-one In gleicherweise wie im Beispiel 1 werden ( 2H-cyclopenta/b/furan-2-on und (-^,Sa/SA cyclopenta/b/furan-2-on aus den entsprechenden optisch cyclopenta/b/furan-2-onen gewonnen.Optically Active 3,3aj8,4,5,6,6a / 3-hexahydro-5a: -trimethylsilyloxy-4/3-trimethylsilyloxymethyl-2H-cyclopenta / b / furan-2-ones In the same manner as in Example 1, (2H- cyclopenta / b / furan-2-one and (- ^, Sa / SA cyclopenta / b / furan-2-one were obtained from the corresponding optically cyclopenta / b / furan-2-ones.
3,2g (10mmol)(±)-3,3a/S,4,5,6,6aß-Hexahydro-5a-trimethylsilyloxy-4/3-trimethylsilyloxymethyl-2H-cyclopenta/b/furan-2-on2 werden in einer Suspension von 5g Chrom(VI)-oxid (50 mmol) in 200 ml absolutem Dichlormethan und 8,2 ml absolutem Pyridin (105mmol) unter Rühren gelöst. Nach einer Stunde bei Raumtemperatur ist dünnschichtchromatographisch kein Ausgangsmaterial mehr nachweisbar (Kieselgel G/Dichlormethan-Aceton wie 9,7:0,3). Der Ansatz wird über Seesand filtriert und das Filtrat im Vakuum eingeengt. Der Rückstand wird in Essigester aufgenommen, nochmals über Seesand/Celite filtriert und das Filtrat im Vakuum eingeengt3.2g (10mmol) (±) -3.3a / S, 4,5,6,6a-hexahydro-5a-trimethylsilyloxy-4/3-trimethylsilyloxymethyl-2H-cyclopenta / b / furan-2-one are in one Suspension of 5 g of chromium (VI) oxide (50 mmol) dissolved in 200 ml of absolute dichloromethane and 8.2 ml of absolute pyridine (105 mmol) with stirring. After one hour at room temperature, no starting material is detectable by thin-layer chromatography (silica gel G / dichloromethane-acetone such as 9.7: 0.3). The mixture is filtered through sea sand and the filtrate is concentrated in vacuo. The residue is taken up in ethyl acetate, filtered again over sea sand / Celite and the filtrate concentrated in vacuo
Ausbeute: 2,1 g (90% d.TH.); 1H-NMR (CDCI3): 9,86ppm (s, 1H1-CHO)Yield: 2.1 g (90% d.TH.); 1 H-NMR (CDCl 3 ): 9.86 ppm (s, 1H 1 -CHO)
Optisch aktive S^a/öAB^eaß-HexahyOptically active S ^ a / öAB ^ eaß-Hexahy
In gleicherweise wie im Beispiel 3 werdenIn the same way as in Example 3
furan-2-on und (-(-S.Sa/S^^^^a/S-Hexahydro^ß-formyl-Ba-trimethylsilyloxy^H-cyclopenta/b/furan^-on aus den entsprechenden optisch aktiven 3,3a/3,4,5,6,6aß-Hexahydro-4/3-trimethylsilyloxymethyl-5a-trimethylsilyloxy-2H-cyclopenta/b/ furan-2-onen gewonnen.furan-2-one and (- (- S.Sa / S ^^^^ a / S-Hexahydro) -β-formyl-ba- trimethylsilyloxy-1H-cyclopenta / b / furan -one from the corresponding optically active 3, 3a / 3,4,5,6,6-hexahydro-4/3-trimethylsilyloxymethyl-5a-trimethylsilyloxy-2H-cyclopenta / b / furan-2-ones.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD23937282A DD241180A3 (en) | 1982-04-28 | 1982-04-28 | PROCESS FOR PREPARING 3,3 ALPHA BETA, 4,5,6,6 ALPHA-BETA HEXAHYDRO-4BETA-FORMYL-5ALPHA-TRIMETHYLSILYLOXY-2H-CYCLOPENTA BETA FURAN-2-ON |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD23937282A DD241180A3 (en) | 1982-04-28 | 1982-04-28 | PROCESS FOR PREPARING 3,3 ALPHA BETA, 4,5,6,6 ALPHA-BETA HEXAHYDRO-4BETA-FORMYL-5ALPHA-TRIMETHYLSILYLOXY-2H-CYCLOPENTA BETA FURAN-2-ON |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DD241180A3 true DD241180A3 (en) | 1986-12-03 |
Family
ID=5538206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DD23937282A DD241180A3 (en) | 1982-04-28 | 1982-04-28 | PROCESS FOR PREPARING 3,3 ALPHA BETA, 4,5,6,6 ALPHA-BETA HEXAHYDRO-4BETA-FORMYL-5ALPHA-TRIMETHYLSILYLOXY-2H-CYCLOPENTA BETA FURAN-2-ON |
Country Status (1)
| Country | Link |
|---|---|
| DD (1) | DD241180A3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3730423A (en) * | 1970-05-22 | 1973-05-01 | G Coulson | Mineral dressing centrifuge |
-
1982
- 1982-04-28 DD DD23937282A patent/DD241180A3/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3730423A (en) * | 1970-05-22 | 1973-05-01 | G Coulson | Mineral dressing centrifuge |
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