GB813845A - Improvements in cyclopentanophenanthrene compounds - Google Patents
Improvements in cyclopentanophenanthrene compoundsInfo
- Publication number
- GB813845A GB813845A GB9567/56A GB956756A GB813845A GB 813845 A GB813845 A GB 813845A GB 9567/56 A GB9567/56 A GB 9567/56A GB 956756 A GB956756 A GB 956756A GB 813845 A GB813845 A GB 813845A
- Authority
- GB
- United Kingdom
- Prior art keywords
- diol
- androstene
- androsten
- acetic acid
- acetate
- 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
- 150000001875 compounds Chemical class 0.000 title abstract 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 10
- CVCDJRPXEWJAAY-UVSUZTNJSA-N 5-Androstene-3beta,16alpha-diol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1C[C@@H](O)C[C@@]1(C)CC2 CVCDJRPXEWJAAY-UVSUZTNJSA-N 0.000 abstract 8
- CVCDJRPXEWJAAY-DSEYRMEUSA-N 5-Androstene-3beta,16beta-diol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1C[C@H](O)C[C@@]1(C)CC2 CVCDJRPXEWJAAY-DSEYRMEUSA-N 0.000 abstract 8
- -1 cyclopentylpropionyl Chemical group 0.000 abstract 6
- 229910052783 alkali metal Inorganic materials 0.000 abstract 4
- 230000003301 hydrolyzing effect Effects 0.000 abstract 4
- DBPIAVXIWZCTGQ-BDPHEOEISA-N (8S,9S,10R,13R,14S,16S)-10,13-dimethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-16-ol Chemical compound C[C@@]12C[C@H](C[C@H]1[C@@H]1CC=C3CCCC[C@]3(C)[C@H]1CC2)O DBPIAVXIWZCTGQ-BDPHEOEISA-N 0.000 abstract 3
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 abstract 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 abstract 3
- 238000000034 method Methods 0.000 abstract 3
- 239000001632 sodium acetate Substances 0.000 abstract 3
- 235000017281 sodium acetate Nutrition 0.000 abstract 3
- MXJJBDZZXUZFIX-YACACONYSA-N [(3s,8s,9s,10r,13r,14s,16r)-16-acetyloxy-10,13-dimethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1h-cyclopenta[a]phenanthren-3-yl] acetate Chemical compound C1C=C2C[C@@H](OC(C)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1C[C@@H](OC(=O)C)C[C@@]1(C)CC2 MXJJBDZZXUZFIX-YACACONYSA-N 0.000 abstract 2
- 150000002009 diols Chemical class 0.000 abstract 2
- 150000002148 esters Chemical class 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 2
- 229910000033 sodium borohydride Inorganic materials 0.000 abstract 2
- 239000012279 sodium borohydride Substances 0.000 abstract 2
- LYFPAZBMEUSVNA-DYKIIFRCSA-N (3s,8s,9s,10r,13s,14s)-10,13-dimethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1h-cyclopenta[a]phenanthren-3-ol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CCC[C@@]1(C)CC2 LYFPAZBMEUSVNA-DYKIIFRCSA-N 0.000 abstract 1
- DBPIAVXIWZCTGQ-NYLIBXOJSA-N (8S,9S,10R,13R,14S,16R)-10,13-dimethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-16-ol Chemical compound C[C@@]12C[C@@H](C[C@H]1[C@@H]1CC=C3CCCC[C@]3(C)[C@H]1CC2)O DBPIAVXIWZCTGQ-NYLIBXOJSA-N 0.000 abstract 1
- IEUIUMLODMQJQY-SPOLIRPYSA-N (8s,9s,10r,13r,14s)-10,13-dimethyl-1,2,3,4,7,8,9,11,12,14,15,17-dodecahydrocyclopenta[a]phenanthren-16-one Chemical compound C1C=C2CCCC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC(=O)C[C@@]1(C)CC2 IEUIUMLODMQJQY-SPOLIRPYSA-N 0.000 abstract 1
- SBNLPRGISFUZQE-VMXHOPILSA-N (8s,9s,10r,13s,14s)-10,13-dimethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1h-cyclopenta[a]phenanthrene Chemical compound C1C=C2CCCC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CCC[C@@]1(C)CC2 SBNLPRGISFUZQE-VMXHOPILSA-N 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- DDJZPGVSQFALQY-QCPSMULASA-N [(3S,8S,9S,10R,13R,14S,16R)-3-hydroxy-10,13-dimethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-16-yl] acetate Chemical compound C(C)(=O)O[C@H]1C[C@]2(C)[C@@H](C1)[C@@H]1CC=C3C[C@H](CC[C@]3(C)[C@H]1CC2)O DDJZPGVSQFALQY-QCPSMULASA-N 0.000 abstract 1
- LWKLYTSESQYTHU-GBAHDIBCSA-N [(3S,8S,9S,10R,13R,14S,16S)-10,13-dimethyl-16-(4-methylphenyl)sulfonyloxy-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-yl] 4-methylbenzenesulfonate Chemical compound C1(=CC=C(C=C1)S(=O)(=O)O[C@@H]1CC2=CC[C@H]3[C@@H]4C[C@@H](C[C@@]4(C)CC[C@@H]3[C@]2(CC1)C)OS(=O)(=O)C1=CC=C(C=C1)C)C LWKLYTSESQYTHU-GBAHDIBCSA-N 0.000 abstract 1
- HBYODKLFEGHOHT-MKDSLVHESA-N [(3S,8S,9S,10R,13R,14S,16S)-3-hydroxy-10,13-dimethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-16-yl] 4-methylbenzenesulfonate Chemical compound C1(=CC=C(C=C1)S(=O)(=O)O[C@@H]1C[C@]2(C)[C@@H](C1)[C@@H]1CC=C3C[C@H](CC[C@]3(C)[C@H]1CC2)O)C HBYODKLFEGHOHT-MKDSLVHESA-N 0.000 abstract 1
- 230000000397 acetylating effect Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 229910000091 aluminium hydride Inorganic materials 0.000 abstract 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 abstract 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract 1
- 125000001312 palmitoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 abstract 1
- 239000001117 sulphuric acid Substances 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 125000003944 tolyl group Chemical group 0.000 abstract 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract 1
- 229920002554 vinyl polymer Chemical group 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
-
- 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)
Abstract
The invention comprises cyclopentanophenanthrene compounds of the general formula <FORM:0813845/IV (b)/1> wherein X represents hydrogen or a methyl, ethyl, propyl, butyl, amyl, isoamyl, vinyl, cyclopentylpropionyl, palmitoyl, benzyl, tolyl or naphthyl radical, and the preparation thereof by reducing D 5-androsten-3b -ol-16-one or the required 3-carboxylic ester or ether thereof with an alkali metal borohydride or an alkali metal aluminium hydride. The above process may be modified in that the D 5-androsten-3b ,16b -diol is subsequently acylated or etherified in the 3- and 16-positions or a 3-carboxylic ester or ether of D 5-androstene-3b ,16b -diol may be acylated or etherified in the 16-position. The above process may also be modified in that the D 5-androstene-3b ,16b -diol is reacted with an aryl sulphonyl halide to form D 5-androstene-3b ,16b - diol - di - arylsulphonate, the di-arylsulphonate is selectively hydrolysed with dilute sulphuric acid to form D 5-androstene-3b ,16b -diol-16-arylsulphonate, the 16-arylsulphonate is reacted with an alkali metal acetate in acetic acid to form the 16-acetic acid ester of D 5-androstene-3b ,16a -diol which is then hydrolysed to form D 5-androstene-3b ,16a -diol, or the 3-carboxylic ester or ether of D 5-androstene-3b ,16b -diol is reacted with an aryl sulphonyl halide to form the corresponding 16-arylsulphonic acid ester, this ester is reacted with an alkali metal acetate in acetic acid to form the corresponding 16-acetic acid ester of the 3-carboxylic ester or ether of D 5-androstene-3b ,16a -diol which is then hydrolysed to form D 5-androstene-3b ,16a -diol or to the 3-ether thereof. The additional modified processes referred to above may be extended by acylating or etherifying D 5 - androstene - 3b ,16a - diol in the 3-and 16-positions, or by acylating or etherifying a 3-ether of D 5-androstene-3b ,16a -diol in the 16-position. In the examples: (1) D 5-androstene-3b ,16b -diol is prepared by reducing D 5-androsten - 3b - ol - 16 - one with sodium borohydride and is converted into the corresponding diacetate and dibenzoate; (2) D 5-androstene - 3b ,16a - diol is prepared by reacting D 5 - androstene - 3b ,16b - diol with p-toluene sulphonyl chloride to form D 5-androstene - 3b ,16b - diol - di - p - toluene sulphonate, partially hydrolysing the di-sulphonate to form D 5-androstene-3b ,16b -diol-16-p-toluene sulphonate, epimerizing the monosulphonate by heating with acetic acid and sodium acetate to form D 5 - androstene - 3b ,16a - diol - 16 - acetate and hydrolysing the 16-acetate; (3) D 5 - androstene - 3b ,16a - diol is prepared by acetylating D 5-androsten-b -ol-16-one to form 3b -acetoxy- D 5-androsten-16b -ol, treating this compound with p-toluenesulphonyl chloride to form D 5 - androstene - 3b ,16b - diol - 3 - acetate-16 - p - toluenesulphonate, heating this compound with sodium acetate and acetic acid to form D 5 - androstene - 3b ,16a - diol - diacetate and acetic acid to form D 5-androstene-3b ,16a -diol-diacetate and then hydrolysing this product to form the required diol, and, if necessary, esterifying the diol to form the diacetate or dibenzoate thereof; (4) 3b -methoxy- D 5-androsten-16b -ol is prepared by reducing 3-methoxy-D 5-androsten-16-one with sodium borohydride; (3) 3b - methoxy - D 5 - androsten - 16a - ol is prepared by treating 3b -methoxy- D 5-androsten-16b -ol with p-toluenesulphonyl chloride to form the corresponding 16-p-toluenesulphonate, fusing the sulphonate with sodium acetate in acetic acid to form 3b -methoxy-16a -acetoxy-D 5-androstene, and hydrolysing this compound to form the desired 16a -ol. Specification 813,333 is referred to.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US813845XA | 1955-08-01 | 1955-08-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB813845A true GB813845A (en) | 1959-05-27 |
Family
ID=22163804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9567/56A Expired GB813845A (en) | 1955-08-01 | 1956-03-27 | Improvements in cyclopentanophenanthrene compounds |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB813845A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3939186A (en) * | 1973-12-29 | 1976-02-17 | Mitsubishi Chemical Industries Limited | Process for producing ethers of steroids |
| US6187925B1 (en) | 1997-12-23 | 2001-02-13 | Merck & Co., Inc. | Intermediates and process for the synthesis of azasteroids |
-
1956
- 1956-03-27 GB GB9567/56A patent/GB813845A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3939186A (en) * | 1973-12-29 | 1976-02-17 | Mitsubishi Chemical Industries Limited | Process for producing ethers of steroids |
| US6187925B1 (en) | 1997-12-23 | 2001-02-13 | Merck & Co., Inc. | Intermediates and process for the synthesis of azasteroids |
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