GB912037A - 11-methylene steroids - Google Patents
11-methylene steroidsInfo
- Publication number
- GB912037A GB912037A GB2241160A GB2241160A GB912037A GB 912037 A GB912037 A GB 912037A GB 2241160 A GB2241160 A GB 2241160A GB 2241160 A GB2241160 A GB 2241160A GB 912037 A GB912037 A GB 912037A
- Authority
- GB
- United Kingdom
- Prior art keywords
- methylene
- formula
- androstan
- carbon atoms
- acid
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract 9
- 125000004432 carbon atom Chemical group C* 0.000 abstract 4
- 150000003431 steroids Chemical class 0.000 abstract 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract 3
- 125000002252 acyl group Chemical group 0.000 abstract 3
- 230000003647 oxidation Effects 0.000 abstract 3
- 238000007254 oxidation reaction Methods 0.000 abstract 3
- XHGAHWBVEAHHJX-YNZDMMAESA-N (3S,5S,8S,9R,10S,13S,14S)-3-hydroxy-10,13-dimethyl-11-methylidene-2,3,4,5,6,7,8,9,12,14,15,16-dodecahydro-1H-cyclopenta[a]phenanthren-17-one Chemical compound O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CCC([C@@]4(C)CC([C@@H]3[C@]2(CC1)C)=C)=O XHGAHWBVEAHHJX-YNZDMMAESA-N 0.000 abstract 2
- ZOQNCHIIPVZBQV-RYMRXWPBSA-N (5S,8S,9R,10S,13S,14S)-3,3-dimethoxy-10,13-dimethyl-11-methylidene-1,2,4,5,6,7,8,9,12,14,15,16-dodecahydrocyclopenta[a]phenanthren-17-one Chemical compound COC1(C[C@@H]2CC[C@H]3[C@@H]4CCC([C@@]4(C)CC([C@@H]3[C@]2(CC1)C)=C)=O)OC ZOQNCHIIPVZBQV-RYMRXWPBSA-N 0.000 abstract 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract 2
- 238000005917 acylation reaction Methods 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 150000002249 furostenes Chemical class 0.000 abstract 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract 2
- 239000001257 hydrogen Substances 0.000 abstract 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 2
- 230000007062 hydrolysis Effects 0.000 abstract 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract 2
- 238000000034 method Methods 0.000 abstract 2
- FCXKURROYSLNIC-INAMJSSCSA-N (5S,8S,9R,10S,13S,14S)-10,13-dimethyl-11-methylidene-1,2,4,5,6,7,8,9,12,14,15,16-dodecahydrocyclopenta[a]phenanthrene-3,17-dione Chemical compound C=C1[C@@H]2[C@]3(CCC(C[C@@H]3CC[C@H]2[C@@H]2CCC([C@@]2(C)C1)=O)=O)C FCXKURROYSLNIC-INAMJSSCSA-N 0.000 abstract 1
- 238000006237 Beckmann rearrangement reaction Methods 0.000 abstract 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 abstract 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- MUCRYNWJQNHDJH-OADIDDRXSA-N Ursonic acid Chemical compound C1CC(=O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C(O)=O)CC[C@@H](C)[C@H](C)[C@H]5C4=CC[C@@H]3[C@]21C MUCRYNWJQNHDJH-OADIDDRXSA-N 0.000 abstract 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 239000003377 acid catalyst Substances 0.000 abstract 1
- 239000003125 aqueous solvent Substances 0.000 abstract 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- OSVMTWJCGUFAOD-KZQROQTASA-N formestane Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1O OSVMTWJCGUFAOD-KZQROQTASA-N 0.000 abstract 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 238000006317 isomerization reaction Methods 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 abstract 1
- 235000015497 potassium bicarbonate Nutrition 0.000 abstract 1
- 239000011736 potassium bicarbonate Substances 0.000 abstract 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 abstract 1
- 235000017557 sodium bicarbonate Nutrition 0.000 abstract 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Steroid Compounds (AREA)
Abstract
The invention comprises (1) a process for the preparation of a steroid of the formula <FORM:0912037/IV (b)/1> (wherein R is (OMe)2 and R1 is hydrogen) which comprises reacting 3b -hydroxy- or a 3b -acyloxy-11-methylene-5a ,25D-spirostan with an acylating agent under conditions which will effect isomerization of the spiroketal system to give the corresponding 26-acyloxy-furost-20(22)-ene derivative of the formula <FORM:0912037/IV (b)/2> (wherein R and R1 are acyl groups containing at most 8 carbon atoms), subjecting this to oxidation and hydrolysis and, if necessary, re-acylation to give a steroid of the formula <FORM:0912037/IV (b)/3> (wherein R is an acyl group containing at most 8 carbon atoms), treating this with hydroxylamine to form the corresponding 20-oxime, subjecting this to the Beckmann rearrangement and hydrolysing to form 3b -hydroxy - 11 - methylene-5a -androstan-17-one, oxidizing this to the 3,17-dione, treating this with methanol and an acid catalyst to give 3,3 - dimethoxy - 11 - methylene-5a -androstan-17-one, and reducing the 17-oxo-group; and, if desired, acylating the product to form a 17-ester and/or treating with a catalytic quantity of an acid in an aqueous organic solvent to form a 3-ketone; and (2) as new compounds, steroids of the first general formula above wherein R is (OMe)2 and R1 is hydrogen, acetyl or propionyl; 3b - hydroxy-11-methylene-5a -androstan-17-one and its 3-acetate; 11-methylene - 5a - androstane - 3,17 - dione and 3,3-dimethoxy - 11 - methylene-5a -androstan-17-one. Suitable acylating agents for the first stage of the above process are carboxylic acid anhydrides of 2 to 8 carbon atoms, used at a temperature between 160 DEG and 220 DEG C. Oxidation of the furostene may be effected by chromic acid in aqueous acetic acid or hydrogen peroxide in acetic acid, and hydrolysis by refluxing in acetic acid, or by using sodium or potassium bicarbonate, carbonate or hydroxide in aqueous solvents in which case re-acylation must be effected. Detailed examples are provided. In the Provisional Specification the oxidation product of the furostene is stated to be a steroid of the formula <FORM:0912037/IV (b)/4> (wherein R and R1 are acyl groups containing at most 8 carbon atoms). Specification 912,036 is referred to.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB2241160A GB912037A (en) | 1960-06-27 | 1960-06-27 | 11-methylene steroids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB2241160A GB912037A (en) | 1960-06-27 | 1960-06-27 | 11-methylene steroids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB912037A true GB912037A (en) | 1962-12-05 |
Family
ID=10178937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB2241160A Expired GB912037A (en) | 1960-06-27 | 1960-06-27 | 11-methylene steroids |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB912037A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1042352A4 (en) * | 1997-11-26 | 2004-12-22 | Res Triangle Inst | ANDROGENIC STEROID COMPOUNDS AND METHOD OF MANUFACTURE AND USE THEREOF |
| WO2015075693A1 (en) | 2013-11-25 | 2015-05-28 | Richter Gedeon Nyrt. | Process for the synthesis of (11 beta.17alpha)-17-acetoxy-1 1 -methyl-19-norpregn-4-en-3.20-dione |
-
1960
- 1960-06-27 GB GB2241160A patent/GB912037A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1042352A4 (en) * | 1997-11-26 | 2004-12-22 | Res Triangle Inst | ANDROGENIC STEROID COMPOUNDS AND METHOD OF MANUFACTURE AND USE THEREOF |
| WO2015075693A1 (en) | 2013-11-25 | 2015-05-28 | Richter Gedeon Nyrt. | Process for the synthesis of (11 beta.17alpha)-17-acetoxy-1 1 -methyl-19-norpregn-4-en-3.20-dione |
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