GB868897A - Improvements in or relating to 9ª--halosteroids - Google Patents
Improvements in or relating to 9ª--halosteroidsInfo
- Publication number
- GB868897A GB868897A GB16113/59A GB1611359A GB868897A GB 868897 A GB868897 A GB 868897A GB 16113/59 A GB16113/59 A GB 16113/59A GB 1611359 A GB1611359 A GB 1611359A GB 868897 A GB868897 A GB 868897A
- Authority
- GB
- United Kingdom
- Prior art keywords
- dione
- pregnene
- give
- hydroxy
- methyl
- 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
- 238000010438 heat treatment Methods 0.000 abstract 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 abstract 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract 2
- 230000032050 esterification Effects 0.000 abstract 2
- 238000005886 esterification reaction Methods 0.000 abstract 2
- 150000002148 esters Chemical class 0.000 abstract 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 2
- VBTQNRFWXBXZQR-UHFFFAOYSA-N n-bromoacetamide Chemical compound CC(=O)NBr VBTQNRFWXBXZQR-UHFFFAOYSA-N 0.000 abstract 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 abstract 2
- 150000003431 steroids Chemical class 0.000 abstract 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 abstract 1
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 abstract 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract 1
- 241000235546 Rhizopus stolonifer Species 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract 1
- 230000000397 acetylating effect Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 150000008065 acid anhydrides Chemical class 0.000 abstract 1
- 125000004423 acyloxy group Chemical group 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 abstract 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052794 bromium Inorganic materials 0.000 abstract 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract 1
- 239000005018 casein Substances 0.000 abstract 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 abstract 1
- 235000021240 caseins Nutrition 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 238000004587 chromatography analysis Methods 0.000 abstract 1
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 abstract 1
- 238000006356 dehydrogenation reaction Methods 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 239000012433 hydrogen halide Substances 0.000 abstract 1
- 229910000039 hydrogen halide Inorganic materials 0.000 abstract 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 abstract 1
- -1 hydroxymethylene Chemical group 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 235000011056 potassium acetate Nutrition 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract 1
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 abstract 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 abstract 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 abstract 1
- 239000008096 xylene Substances 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J5/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by a chain of two carbon atoms, e.g. pregnane and substituted in position 21 by only one singly bound oxygen atom, i.e. only one oxygen bound to position 21 by a single bond
-
- 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)
- Steroid Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention comprises steroids of the formula: <FORM:0868897/IV (b)/1> (wherein R is an alkyl group of at most 6 carbon atoms, X is carbonyl, hydroxymethylene or alkanoyloxymethylene, the hydroxy or alkanoyloxy group being in the b -configuration and containing at most 3 carbon atoms, Y is -CH2-CH2-, -CH=CH-, -CH(CH3)-CH2- or -C(CH3)=CH-, the 6-methyl group when present being in the a -configuration and Hal is bromine, chlorine or fluorine); and their preparation either by esterification of the 17a -hydroxy compounds, using either a solution of the appropriate acid anhydride in the same acid or using the appropriate acid chloride, or by mixing a 9b : 11b -epoxy-17a -acyloxy-4-pregnene-30:20-dione with a hydrogen halide in a suitable solvent and, if desired, oxidising the 11b -hydroxysteroid so obtained to the corresponding 11-oxo steroid. In the esterification referred to above, when the starting material is an 11b : 17a -diol the product is commonly a mixture of the 11b -hydroxy-17a -acylate and the 11b : 17a -diacylate, which may be separated by chromatography. Examples illustrating these processes are given. Further examples describe the dehydrogenation of various steroids of the invention saturated in the 6 : 7-position by heating with chloranil and p-toluene-sulphonic acid in xylene to give the corresponding D 4:6-steroids. 6a - Methyl- 9a - fluoro- 17a - hydroxy- 4-pregnene-3 : 11 : 20-trione is prepared by inoculating a mixture of 6a -methyl-17a -hydroxy-4-pregnene-3 : 20-dione and casein digest medium with a culture of Rhizopus nigricans to give 6a -methyl-11a :17a -dihydroxy-4-pregnene-3 : 20-dione, reacting this with p-toluene-sulphonyl chloride to give the p-toluene sulphonic ester thereof, heating this ester in collidine to give 6a -methyl-17a -hydroxy-4 : 9(11)-pregnadiene-3 : 20-dione, re-acting this with N-bromo-acetamide in presence of perchloric acid to give 6a -methyl-9a -bromo-11b :17a - dihydroxy-4- pregnene- 3 : 20-dione, heating this with potassium acetate in ethanol to give 6a -methyl-9b : 11b -epoxy-17a -hydroxy-4-pregnene-3 : 20-dione, reacting this with hydrofluoric acid to give 6a -methyl-9a -fluoro- 11b : 17a - dihydroxy-4- pregnene- 3 : 20-dione, and oxidizing this with chromic anhydride in pyridine. 9b : 11b - Epoxy- 17a - acetoxy- 4- pregnene-3 : 20-dione is prepared by acetylating 17a -hydroxy-4 : 9(11)-pregnadiene-3 : 20-dione to give 17a -acetoxy-4 : 9(11)-pregnadiene-3 : 20-dione, reacting this with N-bromo-acetamide in presence of perchloric acid to give 9a -bromo-11b - hydroxy-17a - acetoxy-4-pregnene-3:20-dione and heating this with sodium carbonate in aqueous tetrahydrofuran and then with acetic acid.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US868897XA | 1958-05-19 | 1958-05-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB868897A true GB868897A (en) | 1961-05-25 |
Family
ID=22201557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB16113/59A Expired GB868897A (en) | 1958-05-19 | 1959-05-11 | Improvements in or relating to 9ª--halosteroids |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB868897A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107540719A (en) * | 2016-06-26 | 2018-01-05 | 浙江仙琚制药股份有限公司 | A kind of 17 α acetoxyl groups（8,13）The preparation method of the α hydroxyl progesterones of alkene 11 |
-
1959
- 1959-05-11 GB GB16113/59A patent/GB868897A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107540719A (en) * | 2016-06-26 | 2018-01-05 | 浙江仙琚制药股份有限公司 | A kind of 17 α acetoxyl groups（8,13）The preparation method of the α hydroxyl progesterones of alkene 11 |
| CN107540719B (en) * | 2016-06-26 | 2020-02-21 | 浙江仙琚制药股份有限公司 | A kind of preparation method of 17α-acetoxy-(8,13)-ene-11α-hydroxyprogesterone |
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