US2286892A - Process of preparing oxo compounds of the cyclopentano-polyhydrophenanthrene series - Google Patents
Process of preparing oxo compounds of the cyclopentano-polyhydrophenanthrene series Download PDFInfo
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- US2286892A US2286892A US223857A US22385738A US2286892A US 2286892 A US2286892 A US 2286892A US 223857 A US223857 A US 223857A US 22385738 A US22385738 A US 22385738A US 2286892 A US2286892 A US 2286892A
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- 238000000034 method Methods 0.000 title description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- -1 3-hydroxy-17--chlorylaminoandrostene Chemical compound 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 13
- 150000001412 amines Chemical class 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- 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 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910001916 chloryl Inorganic materials 0.000 description 5
- 235000011118 potassium hydroxide Nutrition 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910000039 hydrogen halide Inorganic materials 0.000 description 4
- 239000012433 hydrogen halide Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- DSGUOXYGJFURLL-RSFJJWEVSA-N [(8R,9S,10S,13R,14S,17R)-16-amino-17-[(2R)-but-3-en-2-yl]-16-[(8R,9S,10S,13S,14S,17R)-17-[(2R)-but-3-en-2-yl]-16-[(8R,9S,10S,13S,14S,17S)-17-[(2R)-but-3-en-2-yl]-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-16-yl]-10,13-dimethyl-1,2,3,4,5,6,7,8,9,11,12,14,15,17-tetradecahydrocyclopenta[a]phenanthren-16-yl]-10,13-dimethyl-1,2,3,4,5,6,7,8,9,11,12,14,15,17-tetradecahydrocyclopenta[a]phenanthren-15-yl] acetate Chemical compound C(C)(=O)OC1C([C@@H]([C@]2(CC[C@@H]3[C@]4(CCCCC4CC[C@H]3[C@H]12)C)C)[C@H](C)C=C)(C1([C@@H]([C@]2(CC[C@@H]3[C@]4(CCCCC4CC[C@H]3[C@@H]2C1)C)C)[C@H](C)C=C)C1[C@@H]([C@]2(CC[C@@H]3[C@]4(CCCCC4CC[C@H]3[C@@H]2C1)C)C)[C@H](C)C=C)N DSGUOXYGJFURLL-RSFJJWEVSA-N 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- AURFZBICLPNKBZ-YZRLXODZSA-N 3alpha-hydroxy-5beta-pregnan-20-one Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)C)[C@@]2(C)CC1 AURFZBICLPNKBZ-YZRLXODZSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- AURFZBICLPNKBZ-UHFFFAOYSA-N Pregnanolone Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(=O)C)C1(C)CC2 AURFZBICLPNKBZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229950007402 eltanolone Drugs 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002987 phenanthrenes Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GMVAAADTMXYSDE-XFNFOBRPSA-N 2-[(8R,9S,10S,13S,14S,17R)-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-17-yl]ethenol Chemical compound OC=C[C@H]1CC[C@H]2[C@@H]3CCC4CCCC[C@]4(C)[C@H]3CC[C@]12C GMVAAADTMXYSDE-XFNFOBRPSA-N 0.000 description 1
- GCYPZXYIBVBYSZ-RPYMUYIPSA-N [(8R,9S,10S,13S,14S,17R)-17-(1-aminopropan-2-yl)-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl] acetate Chemical compound C(C)(=O)OC1CC2CC[C@H]3[C@@H]4CC[C@H](C(CN)C)[C@]4(CC[C@@H]3[C@]2(CC1)C)C GCYPZXYIBVBYSZ-RPYMUYIPSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XOVJAYNMQDTIJD-UHFFFAOYSA-N cyclopentobarbital Chemical class C1CC=CC1C1(CC=C)C(=O)NC(=O)NC1=O XOVJAYNMQDTIJD-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 150000007659 semicarbazones Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J41/00—Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J75/00—Processes for the preparation of steroids in general
Definitions
- the present invention relates to'a process of preparing oxo-compounds of the cyclopen'tanopolyhydro-phenanthrene series.
- the amine has hitherto been transformed into the corresponding alcohol by means of nitrous acid and the alcohol subsequently oxidized to form the 0x0- compound.
- the reaction of the amine with nitrous acid to form the alcohol is accompanied by a number of secondary reactions so that the yield of the alcohol desired is only very small.
- the further oxidation of the alcohol to form the oxo-compound is also very difficult, particularly in case that there are also other sensitive parts i-n the molecule, such as a double bond.
- amines of the cyclopentano polyhydro phenanthrene series may be transformed in a nearly quantitative reaction into the corresponding halogen-amine compounds with the aid cfhypchalogenous acid and these halogen-aminecom-pounds may readily be hydrolized, while splitting off hydrogen halide, to form the oxo-com pounds by hydrolysis of the imines-produced. It is suitable to perform the hydrolysis by means of dilute acids, for instance of dilute sulfuric acid.
- the process may be carried out by isolating the halogen-amines after the reaction of the amines with hypohalcgenous acid (they are in part well crystallized compounds), splitting off hydrogen halide with the aid of alkalies and then transforming the i-minesproduced into the corresponding oxo-c'omp'ounds by hydrolysis by means of an acid. But the process may likewise be carried out in one operation, for instance by directly subjecting the reaction product from the amine and hypochlorous acid to hydrolysis by an acid or an alkali.
- Hydrogen halide may be split oii from the halogen-amine compounds by means of the usual agents splitting ofi hydrogen, for instance by means of sodium alcoholate, sodium amide, caustic potash solution or pyridine.
- amines of the cyclopentano-polyhydro phenanthrene series especially such compounds having the following general formula R- CH (Clin -N112- wherein R stands for a saturated or unsaturated cyclopentano-polyhydro-phenanthrene residue.
- :1: stands for zero or 1 and 3 stands for zero, for 2.
- the whole is then poured into dilute sulfuric acid and allowed to stand.
- the pregnanolone separates in flakes and is suitably extracted with ether.
- the crude pregnanolone obtained after the ether has been distilled melts at 142 C. After it has been recrystallized from dilute methanol the yield amounts to 14 grams.
- the mixture is then poured into dilute sulfuric acid and allowed to stand for some time while the bisnorcholane aldehyde separates in flakes; it is suitably isolated by extracting it with ether. After the hydroxy-bisnorcholane aldehyde has been recrystallized from dilute methanol it melts at 128 C. The yield is 0.9 gram.
- the solution is at once filtered and evaporated under reduced pressure.
- the residue constitutes 5.4 grams of the corresponding chloryl compound. It is oily but crystallises when triturated. It is ground together with 40 cc. of an alcoholic caustic potash solution of 10 per cent strength in which operation the separation of potassium chloride sets in at once and ammonia is split off. After 24 hours the reaction is finished.
- the solution is poured into water, acidified with sulfuric acid and it is then extracted with ether. residue of the ethereal solution contains 3.5 grams of the desired ketone compound.
- R stands for a member of the group consisting of saturated and unsaturated cyclopentano polyhydro phenanthrene radicals
- X stands for a member selected from the group consisting of 0 and 1
- Y stands for a member selected from the group consisting of 0, 1 and 2 to react with hypochlorous acid, splitting ofi hydrogen chloride from the halogen amine compound thus obtained andhydrolyzing the imine thus formed.
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- 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
Patented June 16, 1942 i PROCESS OF PREPARING OX COMPOUNDS OF THE 'CYCLOPENTANO-POLYHYDRO- PHENANTHR'ENE SERIES Max Bockmiihl,
Gustav Ehrhart,
Heinrich Ruschig, and Walter Aumiiller, Frankfort-on- Germany, assignors to Winthrop Chemical Company, Inc., New York, N. Y., a corporation of New York the Main Hochst,
No Drawing. Application August 9, 1938, Serial 4 Claims.
The present invention relates to'a process of preparing oxo-compounds of the cyclopen'tanopolyhydro-phenanthrene series.
In order to obtain the oxo-compounds corresponding with the amines of the cyclopentanopolyhydro-phenan'threne series the amine has hitherto been transformed into the corresponding alcohol by means of nitrous acid and the alcohol subsequently oxidized to form the 0x0- compound. The reaction of the amine with nitrous acid to form the alcohol is accompanied by a number of secondary reactions so that the yield of the alcohol desired is only very small. The further oxidation of the alcohol to form the oxo-compound is also very difficult, particularly in case that there are also other sensitive parts i-n the molecule, such as a double bond.
Now We have found that the amines of the cyclopentano polyhydro phenanthrene series may be transformed in a nearly quantitative reaction into the corresponding halogen-amine compounds with the aid cfhypchalogenous acid and these halogen-aminecom-pounds may readily be hydrolized, while splitting off hydrogen halide, to form the oxo-com pounds by hydrolysis of the imines-produced. It is suitable to perform the hydrolysis by means of dilute acids, for instance of dilute sulfuric acid.
The process may be carried out by isolating the halogen-amines after the reaction of the amines with hypohalcgenous acid (they are in part well crystallized compounds), splitting off hydrogen halide with the aid of alkalies and then transforming the i-minesproduced into the corresponding oxo-c'omp'ounds by hydrolysis by means of an acid. But the process may likewise be carried out in one operation, for instance by directly subjecting the reaction product from the amine and hypochlorous acid to hydrolysis by an acid or an alkali.
Hydrogen halide may be split oii from the halogen-amine compounds by means of the usual agents splitting ofi hydrogen, for instance by means of sodium alcoholate, sodium amide, caustic potash solution or pyridine.
As starting materials for the process of the present invention there may generally be used amines of the cyclopentano-polyhydro phenanthrene series, especially such compounds having the following general formula R- CH (Clin -N112- wherein R stands for a saturated or unsaturated cyclopentano-polyhydro-phenanthrene residue.
:1: stands for zero or 1 and 3 stands for zero, for 2.
The compounds bearing in 3-position of the cy- In Germany August 12, 1937 clopentano-polyhydro-phenanthrene residue the oXo-group or an esterified or non-esterified hy- .while vigorously shaking, into a solution of 1.66
grams of 3-hydroxyI'I-amino-androstene in "500 cc. of ether. The solution obtained is completely neutral. After having been filtered it is evaporated and the crystalline residue which consists of the 3-hydroxy-17--chlorylaminoandrostene is heated on the water bath for 45' minutes in cc. of absolute alcohol'tog'ether with 1.5 grams of sodium. Then the whole is poured into water containing sulfuric acid and the colloidal mixture is allowed to stand for one day. During this time the crude dehydro-androste'ne separates in flakes. It is introduced into ether and the residue of the ethereal solution which amounts to 1.2 grams is crystallized from ethyl acetate or aqueous alcohol. The final product melts at l36.5 C.
p The acetyl product melts at 167 C. to 168 -C.; the semi-carbazone of the acetyl product decomposes between 273 C. and 275 C.
(2) 13.4 grams of acetoxy-ternorcholenylamine are dissolved in 1.5 liters of ether and the solution is dried with the aid of potassium hydroxide. It is then filtered, some anhydrous sodium sulfate is added and the mixture is cooled to l5 C. Now 250 cc. of an ethereal solution of hypochlorous acid which contains 1.96 grams of hypochlorous acid and is likewise cooled to -15 C. is run in, while stirring. The solution obtained is evaporated under reduced pressure and the well crystallizable residue is the corresponding chloryl compound of the amine obtained in a nearly quantitative yield. The chloryl compound is introduced into 465 cc. of absolute alcohol, an alcoholic solution prepared from 8.8 grams of sodium and cc. of alcohol is added, and the whole is heated for 45 minutes on the water bath. The solution is then poured in water and the colloidal mixture is acidified with sulfuric acid. After some time the pregnenol(-3-)one(20) separates in the form of a white substance. The product is extracted with ether and the residue of the ethereal extract is crystallized from methanol. The yield amounts to 8 grams, the melting point is between 187 C. and 190 C.
(3) 22 grams of acetoxy-ternorcholanylamine are dissolved in methanol, 60 cc. of a methyl alcoholic caustic potash solution of 7.5 per cent strength are. added and ether is added to the whole. The ethereal solution is repeatedly washed with water, dried and in the presence of sodium sulfate 300 cc. of an ethereal solution containing 0.0094 gram of hypochlorous acid in 1 cc. are added. Distillation of the ether leaves the solid chloryl compound. This is dissolved in 320 cc. of absolute methanol without a further purification and the solution is heated to gentle boiling for 45 minutes together with a solution of 16 grams of sodium in 340 cc. of ethanol. The whole is then poured into dilute sulfuric acid and allowed to stand. The pregnanolone separates in flakes and is suitably extracted with ether. The crude pregnanolone obtained after the ether has been distilled melts at 142 C. After it has been recrystallized from dilute methanol the yield amounts to 14 grams.
(4) 1.4 grams of acetoxy-bisnorcholanylamine are dissolved in absolute ether and, while cooling with ice, the calculated quantity of an absolute ether solution of hypochlorous acid is run in. After the reaction has ceased and the ether has been distilled the chloryl compound of the 3-acetoxy-bisnorcholanylamine is obtained in a quantitative yield in the form of an amorphous substance. 200 cc. of absolute ethanol and a sodium ethylate solution prepared from 1.25 grams of sodium and 30 cc. of ethanol are added and the whole is boiled under reflux for 40 minutes. The mixture is then poured into dilute sulfuric acid and allowed to stand for some time while the bisnorcholane aldehyde separates in flakes; it is suitably isolated by extracting it with ether. After the hydroxy-bisnorcholane aldehyde has been recrystallized from dilute methanol it melts at 128 C. The yield is 0.9 gram.
(5) 6 grams of acetoxy-ternorcholenylamine are dissolved in 1.5 liters of ether and the solution is rapidly dried by means of potassium hydroxide. The solution is then filtered, some anhydrous sodium sulfate is added and the mixture is cooled to 15 C. The calculated quantity of the ethereal solution of hypochlorous acid which is likewise cooled to -15 C. is now slowly run in. By this operation first a small quantity of the hydrochloride of acetoxy-ternorcholenylamine separates. After addition of the calculated quantity of hypochlorous acid the at first strongly alkaline reaction of the solution becomes neutral. About 59 cc. of an ethereal solution of hypochlorous acid containing 14.8 milligrams of hypochlorous acid in 1 cc. are required.
The solution is at once filtered and evaporated under reduced pressure. The residue constitutes 5.4 grams of the corresponding chloryl compound. It is oily but crystallises when triturated. It is ground together with 40 cc. of an alcoholic caustic potash solution of 10 per cent strength in which operation the separation of potassium chloride sets in at once and ammonia is split off. After 24 hours the reaction is finished. The solution is poured into water, acidified with sulfuric acid and it is then extracted with ether. residue of the ethereal solution contains 3.5 grams of the desired ketone compound.
(6) 64 cc. of an ice-cold ethereal solution of hypochlorous acid containing 0.62 gram of hypochlorous acid are run, while vigorously shaking, at -5 C. and in the presence of sodium sulfate into a solution of 3.32 grams of 3-oxo-l'7-aminoandrostene in 1 liter of absolute ether. The solution has a neutral reaction. It is evaporated under reduced pressure, the residue is heated under reflux for 45 minutes with a sodium alcoholate solution prepared from 3 grams of sodium and 210 cc. of absolute alcohol, the reaction solu- The tion is poured into water acidified by means of sulfuric acid and the colloidal mixture is allowed to stand for 24 hours. The whole is then etherified, the residue is distilled under a strongly reduced pressure from the ethereal solution (boiling point C. to 210 C. under a pressure of 0.05 millimeter) and the distillate is redissolved in aqueous acetone. The androstendionemelts at 167 C.
We claim:
1. The process which comprises causing an amine of the following general formula:
[CH3 R- (3H (Climb-BN1 wherein R stands for a member of the group consisting of saturated and unsaturated cyclopentano polyhydro phenanthrene radicals, X stands for a member selected from the group consisting of 0 and 1, and Y stands for a member selected from the group consisting of 0, 1 and 2 to react with hypohalogenous acid, splitting off hydrogen halide from the halogen amine compound thus obtained and hydrolyzing the imine thus formed.
2. The process which comprises causing an amine of the following general formula:
(EH3 R-LCH om)..Nm wherein R stands for a member of the group consisting of saturated and unsaturated cyclopentano-polyhydro-phenanthrene radicals bearing in 3-position a member of the group consisting of oxygen, hydroxyl and esterified hydroxyl, X stands for a member selected from the group consisting of 0 and 1, and Y stands for a member selected from the group consisting of 0, 1 and 2 to react with hypochlorous acid, splitting off hydrogen chloride from the halogen amine compound thus obtained and hydrolyzing the imine thus formed.
3. The process which comprises causing an amine of the following general formula:
wherein R stands for a member of the group consisting of saturated and unsaturated cyclopentano polyhydro phenanthrene radicals, X stands for a member selected from the group consisting of 0 and 1, and Y stands for a member selected from the group consisting of 0, 1 and 2 to react with hypochlorous acid, splitting ofi hydrogen chloride from the halogen amine compound thus obtained andhydrolyzing the imine thus formed.
4. The process which comprises causing an amine of the following general formula:
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2286892X | 1937-08-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2286892A true US2286892A (en) | 1942-06-16 |
Family
ID=7993690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US223857A Expired - Lifetime US2286892A (en) | 1937-08-12 | 1938-08-09 | Process of preparing oxo compounds of the cyclopentano-polyhydrophenanthrene series |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2286892A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2697107A (en) * | 1951-06-20 | 1954-12-14 | Hoechst Ag | Process of preparing chloramines of the steroid series |
| US2852538A (en) * | 1955-11-16 | 1958-09-16 | Upjohn Co | 2-lower alkyl steroidal compounds |
| US2989549A (en) * | 1955-11-16 | 1961-06-20 | Upjohn Co | 2-lower-alkyl and 2, 17alpha-di-lower-alkyl derivatives of testosterone and of 19-nortestosterone, and intermediates therefor |
-
1938
- 1938-08-09 US US223857A patent/US2286892A/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2697107A (en) * | 1951-06-20 | 1954-12-14 | Hoechst Ag | Process of preparing chloramines of the steroid series |
| US2852538A (en) * | 1955-11-16 | 1958-09-16 | Upjohn Co | 2-lower alkyl steroidal compounds |
| US2989549A (en) * | 1955-11-16 | 1961-06-20 | Upjohn Co | 2-lower-alkyl and 2, 17alpha-di-lower-alkyl derivatives of testosterone and of 19-nortestosterone, and intermediates therefor |
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| SU422142A3 (en) | METHOD FOR OBTAINING STEROID DERIVATIVES 1 The invention relates to a new method for producing steroid derivatives having a hydrocarbon residue in the 17a position, saturated or unsaturated, substituted or unsubstituted, or a dicloalkyl radical, and having physiological activity. a prenatal radical, for example, compounds of 3-oxo-13p-ethyl-17a-ethynyl-17, p-oxygone — 4,9,11-triene, consisting in the fact that 3-ethylenedioxy-17-oxo-13 is prepared first | 3-ethylgon- 4,9,1 i-triene which is reacted with an ethynylation reagent followed by hydrolysis of the ketal group at the 3 G7a-ethynyl derivative position. However, the ketalization of the 3-oxo group of the corresponding 3,17-dioxosteroid is not selective, with a low yield of the intermediate 3-ketal, which reduces the yield of the target product. In addition, in the known method, a 4,9,11-trienoic steroid with a closed ring A is used as a starting product, which can be obtained with the complete synthesis of a steroid only from an intermediate with an open Ring A. The purpose of the proposed method is to eliminate these drawbacks and increase the yield of the target product. The above objective is achieved due to the fact that a 9,11-diene steroid with an open ring 5 C, which is easily available during steroid synthesis, is used as a starting product. which is ketalized predominantly in the presence of lower alkyl orthoformate, the resulting 3,5-bisethylen-dioxy-13p-alkyl-17-oxo-4,5-secogon-9,11-diene is reacted with a metal-10 organic reagent, formed with A compound that has a hydrocarbon residue in position 17a and is 3,5-diketal hydrolyzes ketal groups and closes ring A in an alkaline medium.15 The invention describes a method for producing steroid derivatives of the general formula 2025 In which R represents an alkyl radical containing from 1 to 4 carbon atoms; X is a saturated or unsaturated, substituted or unsubstituted 30 hydrocarbon residue containing from 1 to 6 carbon atoms, or cycloalkyl radicals | |
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