CH242988A - Process for the production of a lactone. - Google Patents
Process for the production of a lactone.Info
- Publication number
- CH242988A CH242988A CH242988DA CH242988A CH 242988 A CH242988 A CH 242988A CH 242988D A CH242988D A CH 242988DA CH 242988 A CH242988 A CH 242988A
- Authority
- CH
- Switzerland
- Prior art keywords
- lactone
- production
- oxy
- dioxy
- digitoxigenin
- Prior art date
Links
- 150000002596 lactones Chemical class 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000000034 method Methods 0.000 title claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 230000010933 acylation Effects 0.000 claims description 2
- 238000005917 acylation reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- 230000008030 elimination Effects 0.000 claims 1
- 238000003379 elimination reaction Methods 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 230000001225 therapeutic effect Effects 0.000 claims 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XZTUSOXSLKTKJQ-UHFFFAOYSA-N Uzarigenin Natural products CC12CCC(C3(CCC(O)CC3CC3)C)C3C1(O)CCC2C1=CC(=O)OC1 XZTUSOXSLKTKJQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- BLAKAEFIFWAFGH-UHFFFAOYSA-N acetyl acetate;pyridine Chemical compound C1=CC=NC=C1.CC(=O)OC(C)=O BLAKAEFIFWAFGH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- QONQRTHLHBTMGP-UHFFFAOYSA-N digitoxigenin Natural products CC12CCC(C3(CCC(O)CC3CC3)C)C3C11OC1CC2C1=CC(=O)OC1 QONQRTHLHBTMGP-UHFFFAOYSA-N 0.000 description 1
- HWJHWSBFPPPIPD-UHFFFAOYSA-N ethoxyethane;propan-2-one Chemical compound CC(C)=O.CCOCC HWJHWSBFPPPIPD-UHFFFAOYSA-N 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J19/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 by a lactone ring
-
- 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)
Description
Verfahren zur Herstellung eines Lactons. Es wurde gefunden, dass man zu einem -ton der Cyelopentanopolyhydrophenan- tnren-Reihe gelangen kann, wenn man ein 3a-Oxy-pregnan-derivat der allgemeinen For mel
EMI0001.0006
wobei Y ein Halogenatom bedeutet, mit Me tallen in Gegenwart eines inerten Lösungs mittels behandelt, die entstandene Organo- metallverbindung mit hydrolysierenden Mit teln zersetzt und das Reaktionsprodukt einer Aeylierung,
Wasserabspaltung und Hydro lyse unterwirft.
Das auf diese Weise erhaltene Lacton, das A20,22-3a,21-Dioxy-nor-cholensäure-lacton
EMI0001.0015
Jung finden oder als Zwischenprodukt zur Herstellung therapeutisch verwendbarer Ver bindungen dienen.
<I>Beispiel:</I> 1 g 3a-Oxy-21-bromacetoxy-pregnan-20-on (erhalten aus 21-Diazo-pregnan-3a-ol-20-on vom F. 174-l78 durch Behandlung mit Bromessigsäure) wird scharf getrocknet und mit 1 g Zinkspänen in Benzollösung zur Re aktion gebracht. Zur Aufarbeitung wird mit Alkohol verdünnt, heiss von unverändertem Zink abfiltriert und das Filtrat in 2-n-Salz- säure gegossen. Man destilliert mit Wasser dampf die Lösungsmittel ab und nimmt den Rückstand in Essigester auf'.
Nach dem Ver dampfen des Lösungsmittels wird das Reak tionsprodukt mit Pyridin- Acetanhydrid unter mässigem Erwärmen acetyliert. Das Acylie- rungsprodukt wird wie üblich aufgearbeitet und chromatographisch getrennt.
Die Benzol-Äther-Eluate enthalten das
EMI0001.0029
den F. 166-167 zeigt, einen stark positiven Legaltest gibt und die für a,ss-ungesättigte Lactone typische U. V. - Absorption (7",@y. = 220 mit) besitzt. Durch saure Verseifung erhält man daraus das 14-Desoxy-digitoxigenin (Lacton der d2o>22_3a,21-Dioxy-nor-cholen- säure) vom F. 225-227 .
Die Äther-Aceton-Eluate enthalten das Lacton der 3a - Acetoxy - 20,21- dioxy - nor - cholansäure vom F. 204-207 , das zwecks Wasserabspaltung mit Acetanhydrid gekocht wird. Das so erhaltene Acetat des Lactons der d 20,22-3a.21-Dioxy-nor-cholensäure (Acetat des 14-Desoxy-digitoxigenins) vom F. 166 bis 167 wird sauer verseift.
Process for the production of a lactone. It has been found that one can arrive at a tone of the cyelopentano polyhydrophenant series if one uses a 3a-oxy-pregnane derivative of the general formula
EMI0001.0006
where Y denotes a halogen atom, treated with metals in the presence of an inert solvent, the resulting organometallic compound is decomposed with hydrolyzing agents and the reaction product of an aylation,
Subjects to dehydration and hydrolysis.
The lactone obtained in this way, the A20,22-3a, 21-dioxy-nor-cholenic acid-lactone
EMI0001.0015
Find Jung or serve as an intermediate for the production of therapeutically useful compounds.
<I> Example: </I> 1 g 3a-oxy-21-bromoacetoxy-pregnan-20-one (obtained from 21-diazo-pregnan-3a-ol-20-one from F. 174-178 by treatment with bromoacetic acid ) is sharply dried and brought to reaction with 1 g of zinc shavings in benzene solution. For working up, it is diluted with alcohol, filtered off from unchanged zinc while hot, and the filtrate is poured into 2N hydrochloric acid. The solvent is distilled off with water and the residue is taken up in ethyl acetate.
After the solvent has evaporated, the reaction product is acetylated with pyridine acetic anhydride with moderate heating. The acylation product is worked up as usual and separated by chromatography.
The benzene ether eluates contain this
EMI0001.0029
the F. 166-167 shows, gives a strongly positive legal test and has the UV absorption typical of a, ss-unsaturated lactones (7 ", @ y. = 220 with). Acid saponification gives the 14-deoxy- digitoxigenin (lactone der d2o> 22_3a, 21-dioxy-nor-cholenic acid) from F. 225-227.
The ether-acetone eluates contain the lactone of 3a - acetoxy - 20,21 - dioxy - nor - cholanic acid from F. 204-207, which is boiled with acetic anhydride to split off water. The acetate of the lactone d 20,22-3a.21-dioxy-nor-cholenic acid obtained in this way (acetate of 14-deoxy-digitoxigenin) with a melting point of 166 to 167 is saponified under acidic conditions.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH238516T | 1942-03-16 | ||
| CH242988T | 1942-03-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH242988A true CH242988A (en) | 1946-06-15 |
Family
ID=25728322
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH242988D CH242988A (en) | 1942-03-16 | 1942-03-16 | Process for the production of a lactone. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH242988A (en) |
-
1942
- 1942-03-16 CH CH242988D patent/CH242988A/en unknown
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Scanlan et al. | Action of Lead Tetraacetate upon Hydroxylated Fat Acids and Related Compounds. II. Hydroxylated Ricinoleic Acid and Castor Oil1 | |
| CH242988A (en) | Process for the production of a lactone. | |
| CH242990A (en) | Process for the production of a lactone. | |
| CH242989A (en) | Process for the production of a lactone. | |
| CH243263A (en) | Process for the production of a lactone. | |
| CH240100A (en) | Process for the preparation of a lactone of the cyclopentanopolyhydrophenanthrene series. | |
| CH242274A (en) | Process for the preparation of a lactone of the cyclopentanopolyhydrophenanthrene series. | |
| DE835595C (en) | Process for the production of xanthogenic acid pellets | |
| CH244982A (en) | Process for the production of a lactone. | |
| AT215089B (en) | Process for the preparation of 6-hydroxy-3: 5-cyclopregnan-20-one | |
| DE859617C (en) | Process for the preparation of tetracyclic derivatives of the sterol series | |
| CH556830A (en) | Androstane derivs | |
| AT203004B (en) | Process for the preparation of new esters of piperidyl- (2) -phenylcarbinol and their salts | |
| DE819696C (en) | Process for the production of nuclear-substituted phenylacetic acids | |
| DE651612C (en) | Process for the preparation of ketodicarboxylic acids and their lactones | |
| DE820307C (en) | Process for the preparation of new naphthylpropionic acids and their functional derivatives | |
| DE545853C (en) | Process for the preparation of ª ‡ - (3,4,5-trimethoxyphenyl-) ª ‰ -aminoaethane | |
| AT162906B (en) | Process for the preparation of derivatives of the cyclopentano-polyhydro-phenantren- or the polyhydro-chrysen series | |
| AT251767B (en) | Process for the production of new esters of ascorbic acid with higher unsaturated fatty acids | |
| AT267079B (en) | Process for the preparation of a new estradiol ester | |
| CH199953A (en) | Process for the production of a polynuclear unsaturated ring diketone of the etio-cholan series. | |
| DE1048904B (en) | Process for the production of pure dimethyl terephthalate | |
| DE1013647B (en) | Process for the preparation of substituted 2-acylaminoinden- (2) -onen- (1) | |
| CH240098A (en) | Process for the preparation of a lactone of the cyclopentanopolyhydrophenanthrene series. | |
| CH230407A (en) | Method of preparing a compound of the etiocholanic acid series. |